PROCEEDINGS
              FIRST US-FRANCE  CONFERENCE
                            ON
       PHOTOCHEMICAL OZONE/OXIDANTS  POLLUTION
                     March 27-28, 1980
             USEPA Environmental Research Center
               Research Triangle Park, NC, USA
US DELEGATION

8. Dimitriades,  EPA-ESRL, Chairman
J. Bufalini,  EPA-ESRL
K. Demerjian, EPA-ESRL
M. Dodge, EPA-ESRL
T. Ellestad,  EPA-ESRL
W. Herget, EPA-ESRL
K. Krost, EPA-ESRL
J. Mulik, EPA-ESRL
R. Patterson, EPA-ESRL
R. Paur, EPA-ESRL
L. Stockburger,  EPA-ESRL
FRENCH DELEGATION

J. C. Oppeneau,  ME,  Chairman
Y. Barbry,  ENSM-SE
D. DiBenedetto,  ENSM-SE
D. DuVold,  ME
J. Page, SB&C
C. Hennequin, INRCA
6. LeBras,  CNRS
R. Lesclaux,  CNRS
G. Madelalne, CEA
R. Nadal, DII
                        COMPILED BY
         ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
            U.  S.  ENVIRONMENTAL PROTECTION AGENCY
           RESEARCH TRIANGLE PARK, NC, 277V,,  USA

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U.S» Ixnrlvewtental Protection
Library, Room 2404  PM-211-A
401 M Street, S.VD.
Washington, DC   20460

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                                PROCEEDINGS
                       FIRST US-FRANCE  CONFERENCE
                                     ON
                PHOTOCHEMICAL OZONE/OXIDANTS  POLLUTION
N
is
                              March 27-28, 1980
                      USEPA  Environmental Research Center
                        Research Triangle Park, NC, USA
         US DELEGATION

         B. Dimitriades,  EPA-ESRL, Chairman
         J. Bufalini,  EPA-ESRL
         K. Demerjian, EPA-ESRL
         M. Dodge,  EPA-ESRL
         T. Ellestad,  EPA-ESRL
         W. Herget, EPA-ESRL
         K. Krost,  EPA-ESRL
         J. Mulik,  EPA-ESRL
         R. Patterson, EPA-ESRL
         R. Paur,  EPA-ESRL
         L. Stockburger,  EPA-ESRL
FRENCH DELEGATION

J. C.  Oppeneau,  ME,  Chairman
Y. Barbry,  ENSM-SE
D. DiBenedetto,  ENSM-SE
D. DuVoid,  ME
J. Page,  SB&C
C. Mannequin,  INRCA
G. LeBras,  CNRS
R. Lesclaux, CNRS
G. Madelaine,  CEA
R. Nadal, DII
                                 COMPILED BY
                  ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
                     U.  S.  ENVIRONMENTAL PROTECTION AGENCY
                    RESEARCH TRIANGLE PARK, NC, 27711,  USA

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                                  Reproduced in January 1981
                                             by the
                             US  Environmental Protection Agency
                            Research Triangle Park,  NC  27711  USA
        PROCEEDINGS—PAGE 11
    First US-France Conference on
Photochemical Pzone/Oxidants  Pollution

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                            PREFACE

     This Conference  constitutes  a first activity in a cooperative
research program  informally negotiated and agreed upon by the Research
Office of the U.  S. Environmental  Protection Agency and the French
Ministry of the Environment.   The purpose of the cooperative program  is
to develop environmental  awareness and to promote cooperation between
the US and France in  the  effort to identify, understand, and reduce
environmental pollution problems.   The purpose of this Conference is  to
describe research efforts currently underway in the two countries in  the
area of photochemical  ozone/oxidants pollution and to identify specific
research areas of mutual  interest upon which to focus future cooperative
efforts.  Within  the  confines  of  the US-France Cooperative Program, this
activity establishes  the  Photochemical Ozone/Oxidants Group presently
headed by Drs. Basil  Dimitriades  (USA) and Jean Claude Oppeneau  (France).
                                                      PROCEEDINGS--PAGE iii
                                                   First US-France Conference on
                                               Photochemical Ozone/Oxidants Pollution

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                       TABLE OF CONTENTS
Introducti on  .............................................    V1 ]


Agenda [[[     1 x


Joint Communique  .........................................     X1


Presentations

     US Session

     1.   U. S. Leaislation  on  Photochemical  Air
          Pollution,  EPA,  OEPER-Air,  ESRL
          Structure/Mission  (Dimitriades) ................      1

     2.   Photochemical Air  Quality Simulation
          (Demerjian)  ....................................     ^

     3.   Photochemical Kinetics  Modeling
          Program  ( Dodge)  ................................     33

     4,   Importance  of Natural Hydrocarbons  in Air
          Pollution (Bufalini)  ...........................     43

     5.   Aerosol  Research Branch Programs
          (Stockburger) ..................................     5?

     5.   Visibility  (Ellestad) ..........................     65

     6.   Assessment  of Secondary Aerosol Formation
          Potential from New Energy Sources  (Patterson) ..     75

     7.   Kosovo Ambient Air Monitoring  Program
          (Patterson)  ................ '....". ..............     91

     8.   Inorganic Air Pollutant Analysis Branch
          Research Programs  (Stevens )  ....................     99

     9.   Calibration  of Ozone  Instruments in the
          U. S. (Paur) ...................................    Ill
                                                        PROCEEDINGS—PAGE v
                                                    First US-France Conference on

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                  10.   The Collection and Analysis of Hazardous
                       Organic Emissions from Industrial
                       Sources (Krost) 	   117

                  11.   Ion Chromatography (Mulik) 	   153

                  12.   Overview of the Environmental Protection
                       Agency (EPA)  Programs for Ground-Based Remote
                       Sensing of Air Pollution (Herget) 	   169


                  French _S_e_ssjij)n_

                  1.    Installations Registered for Purposes of
                       Environmental Protection (Oppeneau) 	   179

                  2.    Reglementation de la Pollution de L'Air
                       en  France (Duvoid) 	   227

                  3.    Pre-alarm and Prevision Aid System for
                       Ambiant Air Monitoring Networks  (Page) 	   247

                  4.    Atmospheric Chemical Kinetics (LeBras) 	   255

                  5.    Reaction Kinetics of NhL Radicals and Fate
                       of  Ammonia in the Atmosphere (Lesclaux) 	   269

                  6.    Recherche dans le domaine de la  Physique
                       des Aerosols  Atmospheriques (Madelaine) 	   287

                  7.    Etude  de la Pollution Oxydante sur la
                       Facade Mediterraneenne (Barbry)  	   303

                  8.    The Main Characteristics of the  Oxidant
                       Pollution Problem on the Mediterranean
                       Front  (Barbry) 	   328

                  9.    A Portable System for the Calibration of
                       Atmospheric Pollution Analysers  Installed
                       in  Stations (Di Benedetto) 	   346
       PROCEEDINGS—PAGE v1
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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                         INTRODUCTION

     Dr. Alfred Ellison,  Director of USEPA's Environmental Sciences
Research Laboratory  {ESRL},  welcomed the delegates and discussed briefly
the missions and organizations  of ESRL and of the parent Offices in the
Washington Headquarters  of  the  Agency.   Mr.  Jean Claude Oppeneau, Head
of the French Delegation, responded thanking the Conference hosts and
stressing the interest of the  French Ministry of the Environment in this
cooperative activity.  Dr.  Basil  Dimitriades, Head of the US Delegation,
discussed briefly the background  activities that culminated with this
cooperative agreement between  the USA and France, and the Conference
objectives agreed upon by the  two delegations.   Such objectives are to
expose current research  programs  and interests  of the two countries, and
to identify specific research  areas in which to focus future cooperative
efforts.
                                                        PROCEEDINGS—PAGE vii
                                                     First US-France Conference on
                                                 Photochemical Ozone/Oxidants Pollution

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                                 AGENDA
              FIRST FRANCE-USA CONFERENCE ON  PHOTOCHEMICAL
                        OZONE/OX IDANTS  POLLUTION
Classroom 3
EPA Research Center
Research Triangle Park, NC
                                   March  27-28,  1980
Thursday, March 27, 1980

     9:00 - 9:10 A.M.    Welcome

     9:10 - 9:30 A.M.
               Session Chairman:   B.  Dimitriades,  USA
                                     A.  Ellison,  USA
     9:30 - 9:45 A.M.
     9:45 A.M. -
       5:00 P.M.
Introductions, election of
Conference Chairmen, approval
of Conference Agenda

U.S. Legislation on Photochemical
Air Pollution, EPA, OEPER-Air,
ESRL Structure/Mission

On-Going Photochemical Air
Pollution Research in the U.S.

1.  Photochemical Air Quality
    Simulation Modeling

2.  Kinetic Modeling of
    Photochemical Smog

3.  Importance of Natural
    Hydrocarbons in Air Pollution

Lunch

4.  Aerosol Research Branch
    Programs

5.  Visibility

6.  Assessment of Secondary
    Aerosol Formation Potential
    from New Energy Sources

7.  Kosovo Ambient Air
    Monitoring Program

8.  Inorganic Pollutant Analysis
    Branch Research Programs

9.  Calibration of Ozone
    Instruments
B. Dimitriades, USA



U.S. Delegation


K. Demerjian, USA


M. Dodge, USA


J. Bufalini, USA




L. Stockburger, USA


T. Ellestad, USA

R. Patterson, USA



R. Patterson, USA


R. Stevens, USA


R. Paur, USA
                                                               PROCEEDINGS—PAGE ix
                                                            First US-France Conference on
                                                        Photochemical Ozone/Oxidants Pollution

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                                  10.  The  Collection  and
                                       Analysis  of  Hazardous
                                       Organic Emissions from
                                       Industrial Sources

                                  11.  Ion  Chromatograohy

                                  12.  Overview  of  the  Environmental
                                       Protection Agency (EPA)
                                       Ground-Based Remote  Sensing
                                       of Air Pollution
                                      K.  Krost,  USA
                                      J.  Mulik,  USA

                                      W.  Herget, USA
         Friday, March 28, 1980

              9:00 - 9:15 A.M.
              9:15 A.M. -
                3:00 P.M.
               Sessjon Chairman:  J.  C.  Oppeneau,  France
              3:00 - 4:00 P.M.

              4:00 - 5:00 P.M.
       PROCEEDINGS—PAGE x
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution
Introductory Remarks
Installations Registered for
Purposes of Environmental Protection

On-Going Photochemical Air
Pollution Research in France
1.   Reglementation de la
     Pollution de L'Air en
     France

2.   Pre-alarm and Prevision
     Aid System for Ambiant Air
     Monitoring Networks

3.   Atmospheric Chemical Kinetics

A.   Reaction Kinetics of NH2
     Radicals and Fate of Ammonia
     in the Atmosphere

5.   Atmospheric Aerosol Physics

6.   Why the Mediterranean Sea
     Shore Has Been Chosen

7.   The Main Characteristics of
     the Oxidant Pollution
     Problem on the Mediterranean
     Front

8.   A Portable System for the
     Calibration of Atmospheric
     Pollution Analysers Installed
     in Stations

Plans for Future Activities

Preparation of Joint Communique
J. C. Oppeneau, France



French Delegation


D. Duvoid, France



J. Fage, France



G. LeBras, France

R. Lesclaux, France



G. Madelaine, France

R. Madal, France


Y. Barbry, France




0. Di Benedetto, France

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                            JOINT COMMUNIQUE


The First France-USA Conference on Photochemical Ozone/Oxidants  Pollution
was held in Research Triangle Park, NC, USA, on March  27-28,  1980,  at
the U.S. Environmental Protection Agency  (USEPA) Environmental Research
Center auditorium.

The French delegation included:  Mr. J. C. Oppeneau, Head of  French
delegation, Ministry of the Environment (ME); Mr. Yves Barbry  {ENSM/SE);
Mr. Dominique Di Benedetto (ENSM/SE); Mr. Daniel Duvoid  (ME);  Mr. Jean-
Michel Page (SB&C); Mr. Claude Hennequin  (INRCA); Mr.  Georges  Le Bras
(CNRS); Mr. Robert Lesclaux (CNRS); Mr. Guy Madeleine  (CEA);  and Mr.
Robert Nadal (Oil).

The United States delegates were:  Dr. Basil Dimitriades, Head of US
delegation, Dr. Kenneth Demerjian, Dr. Joseph Bufalini,  Dr. William
Herget, Dr. Marcia Dodge, Dr. Robert Paur, Dr. Leonard Stockburger, Mr.
Thomas Ellestad, Mr. Ronald Patterson, Mr. Stanley  Kopczynski, Mr.
Kenneth Krost, and Mr, James Mulik, all with the US Environmental Protection
Agency.

In addition to the two-day Conference, the French delegation  spent  an
additional two days visiting the Environmental Research  Center.

Purpose of the Conference was to familiarize the two delegations with
the research programs currently underway  in the two countries  in the
area of photochemical air pollution.  Specific subjects  of presentation
and discussions included:

          Current laboratory and field studies in the  US and  France for
          modeling ambient 0., and aerosols
          Acid pollution and visibility related research in US and
          France
          Current methods for in-situ, sample-collection-type, and
          remote analysis of inorganic and organic  pollutants
          Photochemical pollution-related legislation/regulations in
          France and the US

The two delegations explored possibilities for future  cooperative activities
including:

          yearly conferences for in-depth discussions  of selected subjects
          of mutual interest
          collaboration in field studies
          conduct of training courses or  seminars on selected  subjects by
          selected experts traveling overseas
          information exchange on subjects of unilateral or mutual  interest
          exchange of scientific personnel
                                                          PROCEEDINGS—PAGE xi
                                                      First US-France Conference on
                                                   Photochemical Ozone/Oxidants Pollution

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        Agreement was  reached in having at least one  rrench  scientist and a
        French Sodar system participate in the NEROS-PEPPE field study to be
        conducted by USEPA-ESRL during July-August 1980.

        Tentative agreement was also reached in organizing the  Second Conference
        in France in the  spring or early summer of 1981.  The two delegations
        agreed to exchange  suggestions on Second Conference  objectives and to
        formulate a final agenda by the end of 1980.
        Dr. Basil Dimitriades,  Head,
        U.S. Delegation
Mr. I. C, Oppeneau,  Head,
French Delegation
        Date:  March 28,  1980
       PROCEEDINGS—PAGE xii
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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U. S.  LEGISLATION  ON PHOTOCHEMICAL AIR POLLUTION
         presented by  Basil Dimitriades




         Environmental  Protection  Agency

                   United  States
                                                     PROCEEDINGS—PAGE 1
                                                 First US-France Conference on
                                             Photochemical Ozone/Oxidants  Pollution

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      U. S. Legislation on Photochemical Air Pollution

                                             Basil Dimitriades, USA
     The U. S. Legislation in the air pollution area is the Clean Air
Act of 1977, a law which was first enacted in 1963, and was subsequently
amended several times, the last time being in 1977.  This law authorizes
and requires of EPA to conduct research and issue control regulations
for the purpose of preventing and controlling air pollution.

     The process by which EPA is identifying and solving air pollution
problems is as follows:  EPA is conducting continuous research on the
nature and extent of air pollution and on effects from such pollution.
When sufficient evidence is accumulated that implicates a pollutant in a
problem, the pollutant is declared as "criteria pollutant", that is, a
pollutant of concern, and this declaration is the first step in the
process to take corrective action.  The second stejT7s~the preparation
of a "criteria document", that is, a document in which EPA compiles and
analyzes all evidence available on the pollutant and its effects.  The
third step is to develop and promulgate a National Ambient Air Quality
Standard (NAAOS) with respect to this pollutant.  The fourth and last
step is to issue guidance documents describing optimum strategies ami
specific control methods that could be used to reduce the ambient concen-
trations of the pollutant.

     As of today, EPA has identified problems and issued air quality
standards and nation-wide regulations for 5 pollutants:  0^, N0?, CO,
SCu, and Total Suspended Paniculate (TSP).  Emission controls are
enforced on two or more levels.  At the national level, controls are
applied through promulgation and enforcement of emission standards,
e.g., for automobile emissions.  Such controls alleviate the problem
but, as a rule, are not sufficient, especially in heavily polluted
areas, e.g., Los Angeles.  In those areas, additional controls are
promulgated and enforced by the States.  These State controls, however,
must be checked by EPA and found to be sufficiently stringent to achieve
the MAAQS's.  The States are obligated to abide by the Federal NAAQS's
and control regulations, but can, with the approval of EPA, impose more
stringent or additional regulations.  For example, California has air
quality standards and controls addressed to lead and H9S also.  Furthermore,
the California air quality standard to S0? is 0.04 ppm (24-avg) as
compared to 0.14 ppm for the National standard.  Auto emission standards
also are more stringent in California than the Federal Government standards.

     It should be mentioned, that in addition to the NAAOS's for NOP,
0-, CO, S0~, and TSP, there is currently a peculiar NAAQS for Non-Methane
Hydrocarbon (NMHC).  The peculiarity is that, unlike the other NAAQS's,
the one for NMHC is not to be enforced; it is simply to be used for the
purpose of calculating the degree of MMHC control needed in order to
achieve the flAAQS for 0.,.

     Finally, I should mention that the entire process of reviewing
evidence available and developing air quality standards is required by
law to be done periodically every 5 years.   Right now, in fact, we are
                                                        PROCEEDINGS—PASE 3
                                                     First US-France Conference on
                                                 Photochemical taone/OxIdants Pollution

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             in the process  of reconsidering the NAAQS's for NCL, CO, S02, and TSP;
             reconsideration and revision of the CL-NAAQS was done last year.  The
             area where we expect there will be suDstantial changes in terms of
             NAAQS's and  control regulations is the area of aerosol pollution.  We
             expect to change our NAAQS-TSP and control policies to place the emphasis
             on the health effects of the inhalable portion of ambient aerosols and
             on the portion  that causes visibility reduction.

                  For these  reasons,  it is imperative that we, in the US, continue
             research for those pollution problems for which we already have controls
             under way and undertake  new research for the new pollution problems  for
             which air quality standards and control strateqies do not exist yet.
             This will be reflected in the presentations of this Conference.
       PROCEEDINGS—PAGE 4
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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                                                                 First US-France  Conference on
                                                           Photochemical Ozone/Oxidants  Pollution

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              PROCEEDINGS—PAGE 8
        First  US-France  Conference  on
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                                                                           PROCEEDINGS—PAGc 9
                                                                       First US-Prince Conference on
                                                                  Photochemical Ozone/Oxidants  Pollution

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PHOTOCHEMICAL AIR  QUALITY SIMULATION MODELING
       presented  by Kenneth  L.  Demerjian




        Environmental Protection Agency

                  United States
                                                  PROCEEDINGS—PAGE 11
                                               First US-France Conference on
                                          Photochemical Ozone/Oxidants  Pollution

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               PHOTOCHEMICAL AIR  QUALITY  SIMULATION MODELING

                                                               K.  L. Demerjian
1.  Introduction


     Pollutants  emitted into  the atmosphere are transported  dispersed, trans-


formed and deposited via complex  physical and chemical processes.  The PAQSM is


a set of mathematical  equations that relate  pollutant emissions  to ambient air


quality through theoretical descriptions  of  the chemical and physical processes


occurring  in the atmosphere.   Under the mandate of  the Clean Air Act  and its


amendments  regulatory  actions  leading  to emissions reductions are required to


meet specific air quality  standards.   The  PAQSM provides  a  viable scientific


method for  evaluating  the  impact of various  control  strategy options on future


air quality.


     The concentration of  a pollutant  species at some  fixed  point in time and


space after  being emitted from a source  at a given distance  away is dependent


upon four  fundamental  factors.   These  factors are as  follows:   1)  emission—


the rate of pollutant emitted  and  the  configuration of  its source;  2)   trans-


formation—the  chemical  and  physical   reaction processes  which convert  one


pollutant  species to  another;  3)   transport  and  diffusion—the  movement and


dilution of  a pollutant species  through  time and space  as  a  result  of  various


meteorological  variables;   and  4}    deposition—the  removal of a  pollutant


species through their  interaction with  land  and water  surfaces (dry deposition)


and through  interaction with  rain  droplets  or  cloud condensation nuclei  (wet


deposition).   The  interaction of  these  four  factors  and  their  contributing


processes are  schematically illustrated  in  Figure  1.  and represent  the ideal-


ized air quality simulation model.


     Historically research and  development in photochemical  air quality simula-


tion modeling has focused  on  the  urban scale,  that  is,  modeling  domains of the


order  of   50X50  kilometers.    This occurred  predominatly  because  ozone  was
                                                            PROCEEDINGS—PAGE  13
                                                         First US-France Conference on
                                                     Photochemical Ozone/Oxidants Pollution

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 thought to originate  and reside  in  the vicinity of the  high  emission density

 urban areas.   Ozone  production through secondary  reaction  processes involving

 urban emissions  is still a dominant  factor  in accounting  for  ozone levels in

 U.S.  cities.   But new evidence has shown  that  ozone and its precursors are not

 necessarily  isolated  to the confines of the  urban  complex,  but are transported

 over  scales of hundreds of kilometers and  time periods of several days in many

 instances.   Therefore,  this  contribution must  be  taken  into  consideration in

 applying  the  urban model with  associated  control strategy  options for meeting

 the ozone air  quality standard.   The  impact of  long distance transport of ozone

 and ozone  precursors  is  considered  in the urban models through the specifica-

 tion  of boundary  condition concentrations  at  the  inflow side and  top  of the

 modeling region.   What cannot be  assessed  is how these boundary concentrations

 will  change  under various  control strategy  options.   Hence,  in  recent years,

 research  and  development  has  begun  in  the  area of regional/long  distance

 transport  photochemical  air  quality  simulation  modeling, which will  allow

 assessments of region wide control  strategy options  and will  provide predic-

 tions  of inflow  boundary concentrations  for  all  cities  within  the  modeling

 domain.   Regional models have  spatial domains of  the  order of 1000 km  X 1000

 km.

     Urban  scale PACSM  have been under  research  and  development within the

 Environmental  Sciences Research Laboratory since the early 1970fs.  The work on

 this scale reached a plateau  in 1978 with  the development of "so called"  second

generation models.    It  was apparent  at this  stage that further  research and

development was  not warranted  until  the new generation of models were  adequ-

 ately evaluated and verified.
        PROCEEDINGS—PAGE  14
     First US-France Conference on
 Photochemical Ozone/Oxidants Pollution

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     The St. Louis  Regional Air Pollution Study  (RAPS)  has provided the highly

resolved spatial and temporal  emission and  ground monitoring  air  quality and

meteorological data necessary for urban PAQSM evaluation and verification.  In

the past,  verification studies have  been  limited  in nature  due to the lack of

adequate air monitoring data bases  against  which  to test models.   The unveri-

fied status of PAQSMs has proved  a considerable  deterrent in their application,

both in terms  of the rather extensive data  resources  required in operating the

models and the  unknown  accuracy of  their performance.    Uncertainty limits on

model prediction inaccuracies caused by all sources  of  error  can  be obtained

through extensive comparision  of model concentration predictions  and ambient

measurements.

     A status  report on urban scale PAQSM and  the RAPS model  evaluation and

verification program is  discussed in Demerjian 1978 and  will not be considered

here.

     The  focus  of   this  paper will  be to  review the   Environmental  Sciences

Research Laboratory research program in regional  scale  (1000 km) photochemical

air pollution modeling.
                                                              PROCEEDINGS—PAGE 15
                                                           First US-France Conference on
                                                       Photochemical Ozone/Oxidants Pollution

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                              HETEROGENEOUS
                                PROCESSES
                          HOMOGENEOUS
                           PROCESSES
          DEPOSITION
              &
        RESUSPENSIQN
                     PHOTOCHEMICAL
                       REACTIONS
ANTHROPOGENIC
   EMISSIONS
   NATURAL
   EMISSIONS
  AOVECTEO
  POLLUTANTS
              THERMOCHEMICAL
                 REACTIONS
 AEROSOL
PROCESSES
                        TRANSFORMATION
SOURCES
                 TOPOGRAPHY
                  ROUGHNESS
                       MATHEMATICAL MODEL
                                                     TRANSPORT
                                                    TURBULENCE
                                        INVERSION
                                         HEIGHT
                                                     RADIATION
                          TEMPERATURE
                        CLOUD
                        COVER
          SCAVENGING
   SINK
PROCESSES
                     PREDICTED
                   CONCENTRATION
                                                                                            PRECIPITATION
                                                                       WIND
             Figure 1.  A schematic of the major components contributing to the photochemical air quality
             simulation problem.
        PROCEEDINGS—PAGE  16
     First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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2.  Regional Scale (1000 tan) Photochemical Air Quality Simulation Modeling

     The  significance of the  transport of ozone  and  its precursors over  long

distances  in  the environment  has been  recognized  for  several  years.   In

1975, EPA sponsored  the Northeast  Oxidant Study,  a  field program designed  to

establish  a qualitative  understanding  of  the nature  and extent of  regional

ozone.  This program  was successful  in showing that ozone  and  its precursors  do

travel and  spread over distances of several hundreds of kilometers.  With this

qualitative  information work  began  late  in  1976  to develop  a  regional  scale

photochemical  air  quality simulation  model.   It  was  becoming apparent that  a

regional  model would be  necessary  in assessing  region  wide  strategies for

oxidant control.   This was confirmed  with  the passing of the Clean Air Act  as

amended in  1977 which stated  in Sec. 127 (a) Title I, Part C  that the  adminis-

trator  is  required   to  complete a  study and  report to  the Congress on the

progress made  in carrying  out  part C of title I of the Clean  Air Act (relating

to significant deterioration  of air quality) and  the  problems associated  with

carrying  out  such section,  including  recommendations  for legislative changes

necessary to  implement strategies for  controlling photochemical oxidants  on  a

regional  or multistate  basis.   The  regional model  provides inflow  boundary

conditions  of  ozone  and  its  precursors  from major  upwind  emission  centers

(usually other urban  areas) to the urban scale model used  in  assessing control

plans within the  urban  area  and thereby allowing decision makers to  evaluate

the  impact of oxidant  control  plans  of  individual cities  from  a  regional

prospective as well  as provides the opportunity  to assess a  regional  approach

to oxidant control planning.

     In 1979 the  Northeast Regional  Oxidant Study, a multi-year research and

development program   in regional scale modeling,  was  initiated.   The  programs
                                                           PROCEEDINGS—PAGE 17
                                                        First US-France Conference on
                                                    Photochemical Ozone/Oxidants Pollution

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objectives  were  to  evaluate,  refine and  verify a  first generation regional

PAQSM  and  its  sub-components  and  apply  the model  in  cooperation with  the

regulatory  arm of the  agency,  the Office of Air Quality Planning and Standards,

for the  assessment of oxidant control plans on  regionally transport ozone and

ozone  precursors  from one  urban center  to another.   The  area  initially of

greatest  interest was  the Northeastern urban corridor  of  the county  (i.e., the

Baltimore-Washington to  Boston area).

     The program was designed to provide rigorous testing of the model through

comparative  studies  with field  data gathered under judiciously designed field

studies.   This  not only is expected  to enhance the scientific quality of the

model, but  also  to  provide  significant support  to  the  credibility of agency

decisions made in conjunction with the  application of  the model.  The program,

not only draws upon  our experience of the  Northeast  Oxidant Study of 1975, but

more  importantly  draws  from  our knowledge  of  the  first generation regional

scale PAQSM and  its preliminary performance tests.
        PROCEEDINGS—PAGE 18
     First US-France Conference on
 Photochemical Ozone/Oxidants Pollution

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3.  Description of the Regional  Model

     The  regional  scale  photochemical  model has  been  designed  to simulate

short-term  (1-3 hour averaged) mean concentration of NO, NC>2, 03, CO, S02/ 804,

PAN  and  several  classes of  volatile  organic  compounds  (VOC)  over  regions

roughly  1000 km  on a  side.   In order  to take  into account  earth curvature

effects  and to  interface easily  with meteorological  observations  as  well as

various  other  data  sets  available  in  one or  more of  the commonly used map

projections, the  model  is set up  in  curvilinear  {latitude - longitude) coordi-

nates.   The horizontal  resolution  is  l/4o  longitude by l/6o latitude, which is

roughly  18  x 18  kilometers.   The modeling  domain as it is presently configured

for the Northeast Regional Oxidant study is illustrated in Figure 2.
  Figure 2.   Northeast Regional Oxidant Study Modeling  Domain
                                                               PROCEEDINGS—PAGE 19
                                                            First US-France Conference on
                                                        Photochemical Ozone/Oxidants Pollution

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     The  model  treats the  vertical extent of  the  atmosphere via four dynamic


layers.   The surfaces  that separate each  of  the layers  are variable in both


space  and tijne, and they are  calculated in a manner  that allows the model  to


take into account  in an optimum manner each of  the following  physical  processes


(not necessarily in order of importance):


 1.  Horizontal transport;


 2.  Photochemistry, including the  very  slow reactions;


 3.  Nighttime chemistry  of  the  products and  precursors of photochemical


     reactions;


 4.  Nighttime  wind  shear,  stability stratification, and  turbulence  "episodes"


     associated with the nocturnal  jet;


 5.  Cumulus cloud effects  - venting pollutants from the mixed layer, perturb-


     ing  photochemical  reaction  rates  in  their  shadows,  providing   sites  for


     liquid  phase  reactions,  influencing  changes  in  the mixed  layer  depth,


     perturbing horizontal  flow;


 6.  Mesoscale  vertical motion induced by terrain and horizontal divergence  of


     the large scale flow;


 7.  Mesoscale  eddy effects   on  urban  plume  trajectories  and  growth  rates;


 8.  Terrain effects, on horizontal  flows, removal,  diffusion;


 9.  Subgrid scale chemistry processes—resulting  from emissions from sources


     smaller than the model's grid  can resolve;


10.  Natural sources of hydrocarbons, NOx and stratospheric ozone;


11.  Wet and dry removal processes,  e.g., washout and deposition.
       PROCEEDINGS—PAGE 20
    First US-France Conference on
Photochemical Ozone/Oxidants  Pollution

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     A schematic  of the dynamic layer structure  of  the model and the phenomena

each  layer  is designed  to  treat  is  illustrated  for  daytime  and nighttime

conditions  in  Figure 3 and 4 respectively,  Lamb  (1981).   A detailed discussion

on  the  theoretical  formulation  of  the  model  is  presented  in  Lamb   (1981).

     The  regional scale modeling  program has  been  designed  in  a manner which

allows for  the logical development, refinement,  evaluation and verification of

the  model  and its  subcomponents  and provides  a  framework  from  which model

research  and  development  can  evolve  to meet  future regulatory  requirements

concerning  long-range transport of pollutant species.   The theoretical formu-

lation and   its associated mathematical  framework constitutes the  backbone of

EPA's regional long-range  transport modeling research.  The model has been cast

in a generalized  form with modular  components describing  the various physical

and  chemical  processes occurring  on  the regional  scale.   Such  a framework

allows for  refinements, deletions and additions  of  phencmenological processes

with no retooling of the basic  model.
                                                           PROCEEDINGS—PAGE 21
                                                        First US-France Conference on
                                                    Photochemical  Ozone/Oxidants Pollution

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                                                                                                1. Downwind transport  of
                                                                                                    stratospheric  azor.e
                                                                                                2. Upward  trar.scort  Dy
                                                                                                    cumulus clouss
                                                                                                3. Liquid  and  gas  phase
                                                                                                    pnotochemistry
                                                                                                4. Long range  transport
                                                                                                    Dy fi'e atmosohere

                                                                                                1. Gas phase photochemistry
                                                                                                2. Turbulence  anc  .vino shear
                                                                                                    effects on  transport and
                                                                                                    diffusion
                                                                                                3.  Deposition  pn -nountains
                                                                                                4.  Lake  and tr.arir.s layers

                                                                                                1.  Effect on reaction rate
                                                                                                    sf sec-esatici of fresh
                                                                                                    and  aced pol' ..tants
                                                                                                2.  Ground seposition
                                                                                                3.  Spatial  variation in mean
                                                                                                    concentrations due to line
                                                                                                    point and area sources
     Figure   . ,  Schematic illustration of the  "dyna-.ic"  layer str^ctj'
                  o*" the -eqiona! scale nodel  ana  the daytime p-ienonena
                  each laj'er is designed to treat.
                                ime.
                                                                                                  Lo.yer  Functions
                                                                                                  1. Downward flux 3"
                                                                                                      stratcSDheric ozone.
                                                                                                  I. Trans:or*. of liquid
   Figure    '..  Same as   2  except nighttime phenomena
                                                                                                            reaction products
                                                                                                      and reactar.ts
                                                                                                  3. Dark gas phase cnemist*y
                                                                                                    Transport of aged gas p
                                                                                                     reactants and products
                                                                                                2.  Dark gas phase chemistry
                                                                                               ji.  Transport  of  aged pol'jtjnt
                                                                                                    anc  reactants by nocturnal
                                                                                                    jet.
                                                                                               "2.  Transscrt  of  .nighttime e~is
                                                                                                    sions  ?Vc
-------
4.  Northeast Regional Oxidant Study Field Programs
     Extensive  field study  programs were  planned for  the summer of  1979 and
1980.   The primary emphasis  of the 1979 program  was  regional  air mass charac-
terization, where  field  experiments were designed to  test,  evaluate and verify
the model's overall large  scale performance and provide information to substan-
tiate or refine assumptions  and parameterizations  used in the model.
     Specific experiments were designed to  study and elucidate  the following
 phenomena:
         o     Day - Night Transport
         o     Chemistry of  Aged Proecursors
         o     Subsidence  Inversion Dynamics
         o     Dry Deposition Rates
         o     Nocturnal Jet Characterization
         o     Cloud Induced Pollutant  Fluxes
         o     Cloud Induced Chemical Processes
         o     Natural (Biogenic)  Emissions
     In addition, as part  of the overall program a considerable effort has been
made to develop a data base  which will  support the testing, evaluation, verifi-
cation  and  future application of  the  regional  model.    Specific data  base
developments include:
         o     Emission  Inventory
         o     Air Quality Surface Monitoring
         o     Vertical/Burden Monitoring
         o     Upper Air Meteorological Monitoring
         o     Selective Detailed  Analysis
               -  Organic  (Gas Phase)
               -  Inorganics  (Gas  Phase)
               -  Aerosol/Composition/Size  Distribution
         o     Land Use  Inventory
                                                              PROCEEDINGS—PAGE 23
                                                           First US-France Conference on
                                                       Photochemical Ozone/Oxidants Pollution

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        Participants in the  NEEDS 1979 program  and their areas  of responsibility

   are shown  in Figure 5.    The 1979  field  study  provided measurements  in five

   major areas  including:    day-night  transport;  cloud  and boundary layer  03

   fluxes?  vertical and layer  averaged pollutant burdens; surface air quality and

   special  studies;  and  supplemental  upper air  meteorological  soundings.   Fixed

   monitoring  sites, both those  currently in place as part  of  local,  state and

   federal  networks, and  supplemental locations  added during  the intensive field

   study period  provided  data  for  comparison  with  daytime  near surface model

   predictions for evaluation and verification purposes.



I
i
DAY/NIGHT i
TRANSPORT j
i
'•- BNL/GARBER
j- rt'SL/UtSTBERG
i
i- NOAA/DicKSON
:- EPA/FAA
i
i
i









NEROS
REGIONAL AIR MASS
CHARACTFRIZATICN
SUMMER 197y STUDY




PHENOHENOLOGICAL
STUDIES















CLOUD BOUNDARY
LAYER 0? FLUXES













REGIONAL MODEL 1
VERTIFICATION/DATA ;
EASE DEVELOPMENT 1








VERTICAL/EURDEM \ SuRFACE AlR L UPPER A!R
MONITORING |QUALITY/SPECIAL JI-IETEOROLOGICAL
STUDIES ! /CNITORING
- UNIV. "ICH/STEDIW
- NOAA/EEAN
































- UNIV. HICH/CHANEYJ - SA.ROAD
- EMA'AUGrN
- NASA/LANSLEY/JPL
- RTI/TOKMERDAHL




- ERA3S/EPRI
- EPA/ORD
- WSU/V/ESTBERG
- HSU/ROBINSON
- E,v I /VAUGHN
- NASA/LANG LEY
- ANL/WESELEY
- NVfS
- PSU/THOMPSON
- PSU/ANTHES



    Figure  5.   Participant and Study Areas  in  the NEROS 1979 Summer Field Program


       PROCEEDINGS—PAGE 2«
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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     A  Lagrangian air  parcel  marking  system was developed  and deployed  with

accompanying sampling  aircraft to monitor pollutant air masses  over day-night-

day periods  to study  nighttime transport, dark  chemical  reaction  process and

second day aged precursor chemistry.

     A  turbulence measurement  aircraft  was  outfitted with  a  newly  developed

fast response ozone monitor to  make direct measurements of the flux gradient of

ozone  i.e.,  C^'w'.   This  system was  deployed  to study  ozone transfer  above

the planetary boundary  layer by venting through cumloform  clouds.   Simultaneous

measurements of turbulent velocities,  liquid  water content,  and  ozone have been

made at several altitudes along horizontal paths  intersecting cloud clusters to

determine  vertical  ozone  fluxes.    These  measurements  in  conjunction  with

satelite imagery  and  surface  cloud observation data will  be  used  to parameter-

ize the treatment of this phenomenon within the model.

     Upper air  soundings from  the National  Weather  Service  rawinsonde  network

were supplemented  to measure  vertical winds and temperature  every  six hours in

the modeling domain,  rather  than the routine twice  per day frequency.    The

additional meteorological  data will be used  to  evaluate wind analysis  schemes

and the overall treatment of transport in the model.

     The primary  emphasis  of  the  1980  field  study program is the  characteriza-

tion of urban  plumes on the  regional  scale.   The program has been designed to

test and evaluate physical and  chemical modular components within  the model for

treating the plume phenomenon.

     Urban areas  are  the  primary source of anthropogenic  03 and  its  precur-

sors.    These area wide emissions, often up  to 50 km or more  in diameter,  form

an urban plume which  is then  transported, diffused, and chemically transformed

over  distances of hundreds  of  kilometers  and  in many instances  impact  on
                                                            PROCEEDINGS-PAGE 25
                                                         First US-France Conference on
                                                     Photochemical Ozone/Oxidants Pollution

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  downwind cities.  The  combined plumes of many cities  feed  into the background

  air  mass burden and in stagnating air masses  can return to impact the original

  source area.

       The character  of  the  urban plume  is strongly dependent on  the  diurnal

  cycle/ for  example,  during the convective period  it will be well mixed through

  the  planetary boundary layer.   Experiments have been designed  to  measure the

  dispersion  of large area sources at  long  downwind distances  from  the  city in

  terms of model  parameters.    Studies  of  the  urban  plume oxidant  precursor

  budget,  and chemical  transformation processes  over  and  downwind of  the  city

  will  be considered to  identify that portion of  the pollutants lost to deposi-

  tion  at  the surface  and passed  through the  top of the  mixed layer.

       During the  night the urban plume becomes  decoupled from the surface and an

  instantaneous  picture  of the  plume during this period  shows  large  downwind

  variation  in plume  composition and structure due  to its  past history.   The

  upper 2/3  of a well-mixed  daytime  03 plume  can be sheared  laterally and

  transported by  the nocturnal low  level  jet,  and mixed to the  surface  at rela-

  tively large  distances  from  its  source  area  by convective mixing,  (i.e.,

  fumigation  during the  following  morning).   Ozone  precursor emissions  from an

  urban area  during the  night will be contained  in the atmosphere about 100 to

  300 m above the  surface and be sheared, transported,  and eventually fumigated.

  Experiments have been designed  to document:  1)   the dark chemical reactions of

  both  the new and  aged  portion of the nocturnal plume,  2)   the  structure and

 parameterization of  the   nocturnal  wind  and   temperature  profiles and  their

  effect on long distance transport and shear diffusion,  3)   nocturnal deposition

  and  vertical  fluxes  of  03  and precursors.   Experiments also  have been  de-

  signed to investigate the meteorological and chemical processes associated  with
       PROCEEDINGS-PAGE 26
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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the  interaction of  plumes  from  different  urban  areas,  and of  different ages,

i.e.,  the interaction of a  new urban plume with an air mass burden representing

the  accumulation of numerous urban plumes over several days.

      In the early stages of planning and experimental design for the NEROS 1980

field  program,   it  became quite  apparent  that another  EPA field  study  program

within the Laboratory, PEPE-Persistent  Elevated Pollution  Episodes, had  similar

meteorological   requirements  and  could  benefit   from  the  NERDS  experimental

design.   The PEPE  program  will  focus  on the  characterization  and tracking of

the  stagnating  air systems.   A combined NEROS/PEPE  1980  field  measurements
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                                                               PROCEEDINGS-PAGE 27
                                                            First US-France Conference on
                                                        Photochemical  Ozone/Oxidants Pollution

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 program was  developed  (for  details see Vaughan,  (1980)) for  operation out of

 the Columbus,  Ohio  area.   Ihe  program would  be more  cost effective  in the

 combined approach,  as  a  result of sharing  common data  requirements,  and as a

 result  allowed consideration of  additional  needed research.    A preliminary

 organizational chart for  the combined  field study  program to be carried out

 from July 14 to August  15, 1980  is  presented in Figure 6.

      Several field study  experimental designs will be implemented  in NERDS/PEPE

 program.   Figure  7  illustrates the general geopgraphic location and scale of

 the experimental  strategies  to be  considered.    The  Baltimore  urban  plume

 study, an  element of the NERDS program which was not combined with PEPE, has

 been specifically designed to investigate:   the chemical and  physical proper-

 ties of the  Baltimore  plume and its impact on northeast corridor cities; the

 interaction of the  Baltimore and Washington urban plumes;  the Baltimore urban

 plume under stagnant meteorological conditions.
       PROCEEDINGS—PAGE 28
    First US-France Conference on
Photochemical Ozorte/Oxidants Pollution

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                                                   RAMC - REGIONAL AIR MASS CHARACTERIZATION
                                                   RUPC - REGIONAL URBAN PLUME CHARACTERIZATION
                                                   REAL - REGIONAL ATMOSPHERIC LAGRANGIAN
                                                   PEPE - PERSISTENT ELEVATED POLLUTANT EPISODE
                                                   CPS  - COLUMBUS PLUME STUDY
                                                   BPS  ~ BALTIMORE PLUME STUDY
                                                     D - NECRMP
                                                     6. - UPPER AIR STATIONS
Figure  7.   Geographic Location and Scale  of NEFOS/PEPE Experimental  Strategies
                                                                       PROCEEDINGS—PAGE 29
                                                                   First US-France Conference on
                                                              Photochemical  Ozone/Oxidants  Pollution

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 5.   Summary

      The regional scale modeling  program is designed  in  a manner which allows

 for the  logical development,  refinement, evaluation  and verification  of the

 model and its subcomponents and provides a  framework from which model research

 and development  can evolve to  meet future regulatory requirements concerning

 long range transport  and  transformation  of  pollutant species.   The model has

 been cast in a generalized form with modular  components describing the various

 physical and  chemical  processes  occurring on  the  regional scale.    Such a

 framework allows for  refinements, deletions and  additions of phenomemological

 processes with no retooling of the basic model.

      The Northeast  Regional Oxidant Study and  its associated  field programs

 will provide data  to evaluate, refine  and  verify the  regional  model with the

 intent of  applying  it for  state  implementation plans  in the  assessment of

 oxidant control strategies for urban areas  residing in the northeastern corri-

 dor of the  United States.

      The NEROS  1979  and  the  NEROS/PEPE 1980  field  studies are  expected to

 provide extensive data to  address technical questions  related to the adequacy

 of  the model's  theoretical treatment  of the  chemical and  physical processes

 occurring in the atmosphere over the time and space scales of  interest.

      The data  sets  will also  be  used  for  evaluation and  verification of the

 regional oxidant model in  its  entirety  for  the Northeastern portion of U.S.

 6.   References

 Demerjian,  K.  L.,  Oxidant Modeling Status.    Transportation Research Record

     Series   670,  Transportation  Research  Board, National  Research  Council,

     Washington,  D.C. (1978).
       PROCEEDINGS—PAGE 30
    First US-France Conference on
Photochemical Ozone/Oxidants  "Dilution

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Lamb,  R.  G.,  A Regional Scale  (1000 km).   Model  Photochemical  Air Pollution

    Part  I:   Theoretical  Formulation,  EPA Technical Report  in  press (1981).

Vaughan, W,  Draft Field  Plan for the Summer  1980 PEPE/NEROS  Field Measurements

    Program.   EPA Contract  Quarterly Report, Contract No. 68-02-3411  February

    1980  Environmental Measurements,  Inc.
                                                              PROCEEDINGS—PAGE 31
                                                           First US-France Conference on
                                                       Photochemical Ozone/Oxidants Pollution

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r
                                  PHOTOCHEMICAL KINETICS MODELING PROGRAM
                                       presented by Mareia C. Dodge




                                      Environmental Protection Agency

                                                United States
                                                                              PROCEEDINGS—PAGE 33
                                                                           First US-France Conference on
                                                                       Photochemical  Ozone/Oxldants Pollution

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                  Photochemical Kinetics Modeling Program


                                                      Marcia C. Dodge

     The Environmental Sciences Research Laboratory  in  1972 initiated a

computer modeling program to elucidate  the  chemistry of photochemical

smog formation.  The overall objective  of this  research effort is to

develop chemical kinetic submodels  for  use  in Air Quality  Simulation Models

(AQSM's) and the Empirical Kinetics Modeling Approach (EKMA).   Both of

these models will be used by states in  their State Implementation Plan


(SIP) development to estimate  the reductions in ozone precursors  that


are needed to attain the 0.12  ppm ozone National Air Quality  Standard.

     A number of major accomplishments  have been achieved  since the

initiation of this modeling effort.  Highly sophisticated,  detailed

kinetic mechanisms have been developed  for  both the  olefinic  and

paraffinic hydrocarbons.  These mechanisms  are  able  to  reproduce  ozone

yields obtained in smog chamber studies of  olefin, paraffin and NO
                                                                   X

mixtures.  Condensed, or lumped, mechanisms have also been developed for

use in AQSM's.  In these mechanisms, all organics and organic free

radicals are grouped according to structure in  order to limit the number

of reactions and species contained  in the mechanisms.  The mechanism


that is presently being used in the AQSM's  is called the Carbon Bond

Mechanism (CBM) .  In this mechanism all organics are divided into four


groups based on the type of carbon  bonding  found in  the various classes

of organics.  The CBM has been used successfully to  explain ozone yields

observed in smog chamber studies of multi-component  hydrocarbon and

NO  mixtures.
  X
                                                          PROCEEDINGS—PAGE 35
                                                       First US-France Conference on
                                                   Photochemical Ozone/Oxidants Pollution

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     Another major accomplishment of the modeling program has been  the



development of the EKMA method  for ozone control.   In  the EKMA method,



measured ambient levels of hydrocarbon and NO  are  used  to  predict
                                             x


relative changes in air quality that will be achieved  if a  given



emission control strategy is  implemented.  EKMA  is  a very simple



moving-box model that contains  a detailed chemical  mechanism developed



to reproduce measured 0. yields obtained in a smog  chamber  study  of



irradiated auto exhaust and NO  mixtures.  The mechanism was used to
                              x

                                    2
generate a series of ozone isopleths  as a function of 6-9  AM levels



of NMHC and NO  (see Figure 1).  These isopleths can be  used to calculate
              A


the amount of hydrocarbon control needed to achieve the  0.  air quality



standard.  To demonstrate the use of this method, suppose that the  6-9



am NMHC-to-NO  ratio for a given urban area is determined to be 8.
             A


Suppose also that the peak afternoon 0_ level measured downwind of  this area



is 0.30 ppm.  These two pieces  of data define a  point  on the diagram



indicated as point A.  The amount of hydrocarbon control needed to



reduce ozone from the existing  value of 0.30 ppm to the  standard  of 0.12



ppm is indicated along the line from point A to  point  B. In this par-



ticular example, NMHC must be reduced from a level  of  1.0 ppmC to about



0.3 ppraC in order to achieve  the ozone standard.  This corresponds  to a



reduction in NMHC emissions of  70%.  This approach  is currently  being



used by the states to determine what hydrocarbon emission reductions are



needed to achieve the ozone standard.



     The major thrust of the  photochemical modeling program is to improve



the chemical mechanisms that  are currently contained in  the AQSM's  and



EKMA.  The mechanism presently  used in EKMA contains propylene and  butane
       PROCEEDINGS—PAGE 36

    First US-France Conference on

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as the only hydrocarbon species.  Aromatics  are  not  included in EKMA



because, at the time EKMA was developed,  it  was  impossible to construct



a kinetics mechanism for aromatics.  Too  little  was  known about the



chemistry of this important class of hydrocarbons.   Aromatics are



included in the Carbon Bond Mechanism, but they  are  treated in an



 mexact, empirical fashion.  The major goal  of our modeling program,



therefore, is to elucidate the chemistry  of  aromatics  so  that sound



kinetic mechanisms for this hydrocarbon class can be incorporated into



EKMA and the AQSM's.



     The Environmental Sciences Research  Laboratory  is conducting a



number of studies directed towards  elucidating the kinetics and



mechanism of aromatics hydrocarbon  reactions.  Smog  chamber studies of



aromatics are being conducted in both an  indoor  and  outdoor smog chamber



facility.  The objective of thes studies  is  to obtain  carbon and



nitrogen balances for the aromatic  hydrocarbon/NO  systems.  The data
                                                 X


obtained in these studies are used  to test the kinetic mechanisms under



development for the aromatics.  Kinetic and  mechanistic studies are also



being conducted to determine rate constants  and  products  formed in the



oxidation of aromatic hydrocarbons.



     Recently there has been a breakthrough  in our efforts to model



aromatic hydrocarbons.  For the first time it is now possible to fit  smog



chamber data obtained during the irradiation of  toluene and NO  mixtures.
                                                               A


For quite awhile modelers had attempted to fit chamber data by assuming



that the major products of the reaction of toluene with OH radicals were



benzaldehyde and cresol.  These were the  products detected in a kinetic



study conducted at low total pressure.  In this  study  it  was found



that OH abstracts a hydrogen from toluene 15% of the time to yield a
                                                         PROCEEDINGS—PAGE 37

                                                      First US-France Conference on

                                                  Photochemical Ozone/Oxidants Pollution

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free radical that ultimately  reacts  to  form benzaldehyde.   The remaining

852 of the time OH adds  to  the ring  to  form a  complex.   At low total

pressure, oxygen then abstracts  a  hydrogen from this complex to produce

cresol:
                      OH +
                                                    HO-
Very recently it was discovered  that this cresol-forming reaction occurs

to only a small extent at  atmospheric pressure.   At high pressure oxygen

adds to the ring to form the  complex shown in Figure 2.  The subsequent
                                                   4
reactions of this O.-adduct can  only be speculated  at present, but

ultimately the ring falls  apart  to yield some very reactive dialdehydes.

For toluene, the suspected products are methyl glyoxal and 2-butene-l, 4-dial,

a highly reactive olefin with carbonyl groups at each end.

     A detailed kinetic mechanism, based on the reaction scheme shown in

Figure 2, has been constructed  and is being used with good results to

model smog chamber data obtained in the indoor chamber facility at the

University of California at Riverside.   An example of the type of fits

being obtained with this mechanism is shown in Figure 3.  The points are
                                                        PROCEEDINGS—PAGE 33
                                                     First US-France Conference on
                                                 Photochemical Ozone/Oxidants Pollution

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the experimental data;  the  solid  lines  are the computer profiles.   The


mechanism is able  to  reproduce  the  experimental data obtained for


toluene, NO, N0_,  0_, PAN,  formaldehyde and benzaldehyde.   This


mechanism is still in the preliminary stages of development.   The


initial results, however, appear  promising and it is anticipated that,


in the near future, reliable mechanisms for aromatic hydrocarbons  will


be available for use  in EKMA and  the AQSM's,


References


1.   G.Z. Whitten,  J. P. Killus and H.  Hogo, "Modeling  of  Simulated


     Photochemical Smog with Kinetic Mechanisms," U.S.  Environmental


     Protection Agency  Report,  EPA-600/3-80-028a, Research Triangle


     Park, North Carolina,  February 1980.


2.   M. C. Dodge,,  "Combined Use  of Modeling Techniques and Smog Chamber


     Data to Derive Ozone-Precursor Relationships,"  In: Proceedings of


     the International  Conference on Photochemical Oxidant Pollution


     and Its Control, U.S.  Environmental Protection  Agency Report,


     EPA-600/3-77-001b, Research  Triangle  Park,  NC,  June 1977.


3.   "Uses, Limitations and Technical Basis of Procedures  for Quantifying


     Relationships Between  Photochemical Oxidants and Precursors,"  U.S.


     Environmental Protection Agency Report,  EPA-450/2-77-021a,  Research


     Triangle Park, North Carolina, November 1977.


4.   R. Atkinson, W.P.L. Carter,  K.R. Darnall,  A.M.  Winer  and J. N.


     Pitts, "A Smog Chamber and Modeling Study of the Gas  Phase  NO  -


     Air Photooxidations of Toluene and the Cresols," Submitted  to


     Int.  J.  Chemical Kinetics, 1980.


5.   J.N.  Pitts, K. Darnall, W.P.L. Carter,  A.M.  Winer  and R.  Atkinson,


     "Mechanisms of Photochemical Reactions in Urban Air," U.S.  Environmental


     Protection Agency  Report, EPA-600/3-79-110,  Research  Triangle  Park, NC,


     November 1979.

                                                        PROCEEDINGS—PAGE 39
                                                     First US-France Conference on
                                                 Photochemical  Ozone/Oxidants Pollution

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W
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               PROCEEDINGS—PAGE *0
          First US-France Conference on
     Photochemical  Ozone/Oxidants Pollution

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       Figure  2.   Ring Cleavage  in the Toluene-OH Reaction
                       «3   „        \   Oh   „

           H   0,   Y-VOH    02   VTV-OH
                                        NO
CH,
 CH
       H
H  0  0
H     H
                       H-C-C-C-H  +  0-C-C-C-C-O + H-
                          H
                      H     H
                                                            HO,
                       METHYGLYOXAL       2-BUTENE-l,4-D1AL
                                                 PROCEEDINGS—PAGE *1
                                              First US-France Conference on
                                          Photochemical Ozone/Oxidants Pollution

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                 Figure  3.  Predicted  and Observed  Profiles  Obtained
                             in the UCR Smog  Chamber Study  of the
                             Toluene/NO  System
   0.80
  0.80
  0.40
  o.eo
  0.00
           \     I    f   I     »    I    I
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                 TINE CN1NUTES)
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                                                   i
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                                                     0.90
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    0   BO  100 ISO 200  250 900 350  400
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                                   I    I    T   I    I
                                  PUN    •
                                  MCHI   *
                                  •ZR    *
                                          TINE ININUTES)
        PROCEEDINGS-PAGE &2
    First US-France Conference on
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r
                           IMPORTANCE  OF NATURAL  HYDROCARBONS  IN AIR POLLUTION
                                     presented by Joseph J. Bufalini



                                     Environmental  Protection Agency

                                               United  States
                                                                             PROCEEDINGS—PAGE 43
                                                                          First US-France Conference on
                                                                      Photochemical Ozone/Oxidants Pollution

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               Importance of Natural Hydrocarbons  in Air Pollution
                               Joseph  J. Bufalini
        Environmental Protection Agency, ESRL,  Research Triangle Park,  NC

         Presented at the First France-USA Conference on Photochemical
     Ozone/Oxidant Pollutants, March 25-28,  1980,  Research Triangle Park, NC

INTRODUCTION
     The involvement of hydrocarbons in the  formation of photochemical  smog
is well documented (1-4).  Also generally  accepted is that both the type
and the amount of hydrocarbon are  important  in  the formation of photochemical
smog.  If ozone is taken as the indicator  for smog formation, at a favorable
hydrocarbon to NO  ratio, olefins  are  found  to  produce ozone most quickly,
                 X
followed by the substituted aromatics  and  then  the slow reacting paraffins.
     Natural hydrocarbons, i.e., isoprene  and the  monoterpenes, are olefinic
compounds (Figure 1} and are expected  to produce both ozone and aerosols.
The question then arises, can natural  HC's be a significant source of ozone
and visibility reduction in rural  areas?   Also, does vegetation contribute
to photochemical air pollution problems that exist in most large metropolitan
areas?
     This paper is concerned with  natural  hydrocarbons and their possible
contribution to air.  The specific topics  covered  are:  (1) HC emission
measurements, (2) Reactivities of  the  natural HC's and (3) source-receptor
relationships.
NATURAL HYDROCARBON EMISSION MEASUREMENTS
     There are three methods that  have been  used to establish natural hydro-
carbon emissions; (1) environmental chamber  that encloses the entire plant, (2)
bag enclosure technique for part of the plant,  and (3) vertical gradient
measurement over the vegetation.
                                                           PROCEEDINGS-PAGE 45
                                                        First US-France Conference on
                                                    Photochemical Ozone/Oxidants  Pollution

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Environmental Chamber Technique
     The principal proponent of the environmental chamber technique is
Tingey(5),  With this chamber, many of the variables such as temperature,
light, dew point, and CO. could be controlled.  However, since  the chamber
is not very large, only tree saplings can be studied.  Tree saplings may
not have the same emissions as older more mature trees and therefore the
emissions may not be representative.  Also, in a closed system  the air
movements are not easily duplicated to those in the natural state.  Thus,
the leaf temperature may be different thus giving erroneous emission rates.
(Leaf temperature determines emission rates).
Bag Enclosure Method
     The most extensive work done on emission rates for vegetation has  been
by Zimmerman (6,7).  In his studies, Zimmerman not only measured  emissions
from various types of vegetation but also examined the different  plant  species
at different locations in the United States.  In the Zimmerman  method,  a
plastic bag (usually Teflon) is placed around the tree branch and then  the
build-up of hydrocarbon within the plastic container is measured. This
buildup of hydrocarbon can then be used to calculate emission rate.  The
reproducibility of this technique is poor since extreme  care must be taken
in not damaging the tree limb.  A damaged tree liberates much higher hydrocarbon
levels.  Also, there is a slight temperature increase within the  enclosure
that will result in excessive emissions.  Thus, many of the problems of the
environmental chamber technique are also problems with the bag  enclosure method.
Vertical Gradient Measurements
     The vertical flux technique has been employed by Arnts et  al.  (8). Alpha-
pinene emissions from loblolly pines have been measured at an International
Biological Program site in central Piedmont of North Carolina.  In this tech-
nique, a vertical profile of the terpene was measured above a pine forest.   By
employing an energy balance equation (i.e., by measuring temperature, water
vapor, carbon dioxide, and net solar radiation), they were able to calculate
alpha-pinene flux values.  Figure 2 shows a typical experiment  with the vertical
gradients.  With this method, vertical gradient measurements of the hydrocarbon
were difficult and subject to large errors.  The accuracy of this technique  depends
upon precise alpha-pinene measurements and meteorological component measurements.

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Assumptions of smooth  terrain  and  constant wind fetch dimensions are required
(forest must be sufficiently large and  regular to  allow the smooth flow of
air at the top of the  canopy).   Consequently errors  are very likely to occur
with this technique also  aside of  the difficulties mentioned above with the
three techniques there is the  added problem  in intercomparing the methods.
Both the chamber and bag  enclosure methods measure emissions from one sample
and then extrapolate to a large area.   Specifically,  a tree branch or sapling
is first tested for emissions,  clipped  and then dried to a constant weight.
The leaves are then removed and an emission  factor per weight of dry leaft
is obtained.  By using published dry leaf per tree values one can obtain emissions
from one tree.  Using  established  tree  densities the  emissions for an entire
area can be estimated.  The vertical gradient technique does not need the leaf
biomass assumption but does need the foliar  density  in order to calculate
national or worldwide  emissions.
SOURCE-RECEPTOR RELATIONSHIPS
     Source-receptor relationships are  extremely important when considering
oxidant production from natural HC's in the  atmosphere.   Rather high emissions
have been calculated for  the natural hydrocarbons.  Zimmerman (9)  has calculated
that approximately 68% of the  non  methane hydrocarbons in the greater Tampa-
St. Petersburg are due to vegetation.   Also,  in another report Zimmerman
                           o
calculates approximately  10  tons/year  of natural  emissions from the continental
United States.  This is 80% of  the total non-methane  hydrocarbons  liberated.
Clearly, the ambient data obtained in a number of  areas  as shown in Table 1
do not substantiate the high emission fro the natural hydrocarbons.   Even if the
emission rates are high,  there  is  an unfortunate tendency to assume one-to-one
relationships between  pollutants from various sources of emissions.   For
example, the experimental measurements  would  suggest  that nitric oxide emissions
from power plants will not significantly affect ozone production until the air
mass travels 25-30 km  downwind  (21,22).  In some cases,  no ozone increase is
observed at all.  The  reasons  for  these observations  is  that a very low HC/NO
                                                                              x
ratios do not favor ozone production.   Also,  very  low concentrations of low
reactivity hydrocarbons do not  produce  significant levels of ozone.   The case
is quite different with nitric  oxide emitted  by auto  exhaust.   In  this latter case,
the HC/NO  ratio is favorable and  ozone is produced after a short  solar
         X
irradiation time.

                                                            PROCEEDINGS—PAGE 47
                                                         First US-France Conference on
                                                    Photochemical Ozone/Oxldants Pollution

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      In order to assess the Importance of natural hydrocarbon emissions into
 a city, a box-type photochemical model was employed.   The conditions employed
 for this modeling effort were:
                            4   2                                 -
      (1)   Source area of 10  km
      (2)   Diurnal insolation (k, (max) - 0.52 min  )
                                      7                   2
      (3)   HC emission rate of 60jfcg/m  min;  NO  at 5)ftg/m min
                                               X
      (4)   Propylene as surrogate terpene
      (5)   0- initially of 40 ppb (V/V)
      (6)   5% dilution per hour  containing 40 ppb of 0,
      (7)   Mixing height of 1.8  km (the summer condition for North Carolina
           (23)).

      Propylene was  chosen as the surrogate terpene since a validated mechanism
 cannot,  at this  time,  be written for alpha-pinene. The use of propylene and
 a high  emission  rate is probably grossly overestimating the photochemical
 potential of terpenes since propylene has been shown  to produce more ozone
 on  a  parts-per-million-carbon equivalent then most terpenes (Figure 3) (24).
      The  photochemical model indicated that  after an  irradiation period of
 10  hours,  the total ozone in a  box 100 x 100 x 1.8 km  was 70 ppb.   The con-
 centration of ozone actually produced by the propylene was only 30  ppb since
 the initial 03 and  dlution air  0- was 40 ppb.  When the initial 0.  and dilution
 0»  was  zero,  and the HC/NO  ratio increased  to 200 (by decreasing NO  emissions)
 •J                         A                                         X
 the 0_  found after  10 hours is  only 12 ppb.   This latter modeling scenario is
 probably  the more reasonable one since clean dilution air usually does not
 contain very high 0, levels and in rural areas,  the HC/NO  ratio is quite
 high.
 CONCLUSION
     Although additional information is  needed in order to firmly establish
 the role  of  natural hydrocarbons in ozone formation,  the present data suggest
 emissions  from vegetation are not likely to  have signficant effects on air
 quality.   This appears  to be the case for both rural  and urban areas.  All
 gas-phase  HC analyses  (Table I)  and carbon aerosol studies (25,26)  suggest
 that natural  hydrocarbons do not exist at sufficiently high concentrations to
affect air quality.   Emissions  data do not agree with ambient air measurements.
                                                                         o
Those measurements  suggest  that the previously published value of 9 x 10  tons/yr
needs to be  lowered  by  at least one order of magnitude.

        PROCEEDINGS—PAGE 48
     First  US-France Conference on
 Photochemical Ozone/Oxidants  Pollution

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     Additional work  in  this  area should include:

(1)   Establish better  emission values
                                                   144fL2
(2)   Better collection and  analyses are needed.  C/t    ratio should be
     measured for aerosols  and for gases in both rural and  urban areas
(3)   Additional smog  chamber  data are needed in order to elucidate the
     mechanism of reaction  of terpenes.
(4)   Finally modeling  exercises are needed with various  emisison scenarios.
     These computations  would then be compared to observe air quality data
     in order to assess  the emission scenario most compatible with air
     quality data.
                                                             PROCEEDINGS—PAGE 49
                                                          First US-France Conference on
                                                      Photochemical Ozone/Oxidants Pollution

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 REFERENCES

 1,   Haagen-Smit, A.J., Fox, M.M. "Automobile Exhaust and Ozone Formation,"
      S.A.E. Trans., 63:575, 1955.

 2.   Schuck, E.A., Doyle G.J. Air Pollution Foundation Report No.~ 29, San
      Marino, CA, October 1959.

 3.   Leighton, P.A. "Physical Chemistry:  Vol. IX, Photochemistry of Air
      Pollution," Academic Press, New York, 1961.

 4.   Altshuller A.P. Bufalini, J.J., "Photochemical Aspects of Air Pollution-
      A review" Photochem. Photobiol., 4:97, 1965.

 5.   Tingey, D.T. Standley, C., Field, R.W., "Stress Ethylene Evolution:
      A Measurement Ozone Effects of Plants," Atmos. Environ., 10:969, 1976.

 6.   Zimmerman, P.R. "Testing of Hydrocarbon Emissions from Vegetation, Leaft
      Litter, and Aquatic Surfaces, and Development of a Methodology for
      Compiling Biogenic Emissions Inventories,"  Final Report, EPA-450/4-79-004,
      EPA, RTP, NC, March 1979.

 7.   Zimmerman, P.R. "Tampa Bay Area Photochemical Oxidant Study." Final Report,
      EPA-904/9-77-028, EPA, RTP, NC, February 1979.

 8.   Arnts, R.R., Seila, R.L., Kuntz, R.L., Mowry F.L., Knoerr K.R., Dudgeon,
      A.C. "Measurement of Alpha-Pinene Fluxes from Loblolly Pine Forest,"  In:
      Proceed,  rth Joint Confer, on Sensing of Environ. Pollut., RTP, NC,
      1978, 222 pp.

 9.   Zimmerman, p. R.  "Procedures for Conducting Hydrocarbon Emission Inventories
      of Biogenic Sources and Some Results of Recent Investigation."  Pre-
      sented at the EPA Emission Inventory/Factor Workshop, Raleigh, NC, Sept.
      1977.

 10.  Rasmussen, R.A.,  Went, F.W. Volatile Organic Material of Plant Origin
      in the Atmosphere," In:  Proceed. N.A.S., 53(1): 215, 1965.

 11.  Rasmussen, R.A.,  Chatfield, R.B. Holdren, M.W., Robisnon, E., "Hydro-
      carbon Levels in a Midwest Open-Forested Area."  Draft Report submitted
      to the Coordinating Research Council, October 1976.

 12.  Lonneman, W.A., Seila, R.L., Meeks, S.A. "Preliminary Results of Hydro-
      carbon and Other Pollutant Measurements Taken During the 1975 Northeast
      Oxidant Transport Study.  "In:  Proceedings of Symposium of 1975 Northeast
      Oxidant Transport Study, EPA-600/3-77-017, February 1977.

 13.  Whitby, R.A., Coffey, P.E. "Measurement of Terpenes and Other Organics
      in an Adirondack Mountain Pine Forest," Journal of Geophysical Research,
      82:5928, 1977.

 14.  Lonneman, W.A. Seila, R.L., Bufalini, J.J. "Ambient Air Hydrocarbon
      Concentrations in Florida," Environ. Sci. Technol., 12:459, 1978.


       PROCEEDINGS—PAGE 50
    First US-France Conference on
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15.  Schjoldager, J., Wathne, B.M. "Preliminary Study of Hydrocarbons  in
     Forests." Norsk Institute for Luftforskning, P. 1-26, 1978.

16.  Seila, R.L. "Non-Urban Hydrocarbon Concentrations in  the Ambient  Air
     North of Houston, Texas."  EPA-600/3-79-010, U.S. Environmental Pro-
     tection Agency, RTP, NC., February 1979.                     ^

17.  Holdren, M.W., Westberg H.H., Zimmerman, P.R. "Analysis of Monoterpene
     Hydrocarbons in Rural Atmospheres." J. Geophysical Research, 84:5083,
     1979.

18.  Arnts, R.R., Meeks, S,A. "Biogenic Hydrocarbon Contribution  to the
     Ambient Air of Selected Areas," U.S. EPA, RTP, NC, EPA-600/3-80-023,
     January 1980.

19.  California Air Resources Board. "Lake Tahoe Communities Hydrocarbon
     Analyses." Haagen-Smit Laboratory, El Monte, California, January  1979.

20.  Cronn D.R., Harsch D.E., "Smoky Mountain Ambient Halocarbon  and Hydro-
     carbon Monitoring, September 21-26, 1978, Draft Report, U.S. Environmental
     Protection Agency, Grant No. R-804033, (1979).

21.  Westberg, H., Sexton K., Holdren M. "Contribution of  the General  Motors
     Automotive Painting Facility at Janesville, Wisconsin to Ambient  Ozone
     Levels."  Report to GM by WSU, August 1978.

22.  Wilson, W.E. "Sulfates in the Atmosphere:  A Progress Report on Project
     MISTT."  Atm. Environ. _12, 537 (1977).

23.  Holzworth G.G. "Mixing Heights, Wind Speeds, and Potential for Urban
     Air Pollution Throughout the Contiguous United States."  EPA Publication
     101, U.S. Environmental Protection Agency, Research Triangle Park, NC
     (1972).

24.  Arnts, R.R. Gay, B.W. Jr. "Photochemistry of Naturally Emitted
     Hydrocarbons", EPA-600/3-79-081, Research Triangle Park, NC, September 1979.


25,  Grojean, D., Van Cauwenberghe, K., Schmid, J.P., Keley, P.E., Pitts
     J.N. Jr., "Identification of C^-C.Q Aliphatic Dicarboxylic Acids  in
     Airborne Particulate Matter." Environ. Sci. Technol.  12;313, 1978.

26.  Stevens, R.K. Concentrations and Organic Aerosols in  the Great Smoky
     Mountains and the Soviet Union." Presented at the EPA Symposium on
     Atmospheric Biogenic Hydrocarbons, Emission Rates, Concentrations and
     Fates, Research Triangle Park, NC, January 1980.
                                                             PROCEEDINGS-PAGE 51
                                                         First US-France Conference on
                                                      Photochemical Ozone/Oxidants Pollution

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                                                            First US-France Conference  on
                                                       Photochemical  Ozone/Oxldants  Pollution

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                                          First US-France Conference on
                                     Photochemical  Ozone/Oxidarts Pollution

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                                   AEROSOL RESEARCH BRANCH  PROGRAMS

                                   presented by  Leonard Stockburger




                                    Environmental  Protection  Agency

                                              United States
                                                                              PROCEEDINGS—PAGE 57
                                                                           First US-France Conference on
                                                                       Photochemical  Ozone/Oxidants Pollution

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      The Aerosol Research Branch performs  and  sponsors research of the chemical


and physical properties of atmospheric aerosols and the mechanisms and rates of their


formation and  removal.  The ultimate aim is to develop a model which will aid in the


planning and enforcement of air quality standards.   Figure  I shows the individual


compounds and the time schedule for each module to be include in the model.


      The major emphasis of  this branch is the development and validation of an urban


aerosol model.   In this context urban means the transport of an air mass for up to two


hours or 25 kms. The model chosen for development  is AROSOL which is an adaption


by Brock of the Shir and Shieh K-theory dispersion  model.  The  first version of this


model, AROSOL-1, was validated for primary area sources and transport in Phoenix,


Arizona.  The urban aerosol formation, transport and removal model  is being developed


simultaneously  with the investigation of input parameters such as  dry deposition rates


and gaseous and aqueous phase  oxidation of  SO , NO  and organics.  As the  modules


become available they are validated by field or  chamber studies.


      The relationship between anthropogenic emissions and the formation and effects


of organic aerosols  is presently incompletely understood.  Specific knowledge  and


understanding of the reaction chemistry and aerosol properties is required in order for


EPA to apply selective controls to improve visibility and lower fine aerosol mass.


      In a urban area the  oxygenated hydrocarbons (secondary organic  aerosols) can


account for 60% of the total secondary aerosol mass.  Typical  ranges of this aerosol


composition is as follows:

                                                     3
                sulfate                     2-25 ug/m


                nitrate                   .2-4  ug/m


                organic aerosol             2-40 pg/rrr


      In the past the major  emphasis  on  secondary aerosol  has been placed on  the


conversion of SQj to sulfate while  the gas phase studies have emphasized the effects


                                                                  PROCEEDINGS—PAGE 59
                                                               First US-France Conference on
                                                          Photochemical Ozone/Qxidants Pollution

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         PROCEEDINGS—PAGE  60
     First US-France  Conference on
Photochemical  Ozone/Oxidants Pollution

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of hydrocarbons and NO  on ozone formation.  Very little is known about the chemical


composition of the secondary organic aerosol.  This can be contrasted with the primary


organic aerosol where much information is available as to its physical and chemical


composition.


      About 70 compounds have been studied for their aerosol formation ability using


various experimental conditions and measuring methodologies such that only qualita-


tive intercomparisons can be made. The genera! conclusions of these studies are:


      I.    alkanes and Cr  alkenes  produce  aerosol  with the amount  increasing with  carbon


           number


      3.    cylic  alkenes  and -dienes  produce more aerosof  than the corresponding


           straight chain alkene


      4.    conflicting results are  reported for the aromatics, some  observers have


           reported  aerosol  being  formed while others  have reported little aerosol


           formation.


      The few organic  analysis  of ambient  aerosols and those produced in smog


chambers show that most  of  the aerosol  is  composed  of  difunctional  compounds


containing a mixture of alcohol, carboxy acid,  aldehyde and nitrate  groups.  It should


be noted that  most of these compounds are very polar and difficult to analyze.  The


development of new  techniques like HPLC and  ion chromatography, new liquid phases,


and derivates for gas chromatography make it possible to do a much  better job on the


analysis of the organic aerosol.


      Objective:  To develop a model  for predicting the chemical transformations  of


organic compounds to organic aerosols, emphasis will be on understanding the reaction


mechanisms and chemical composition of organic  aerosols using a smog chamber and


"model" organic compounds  to simulate  the urban environment.  The  outputs of this


task  will be used to develop the organic aerosol  module for AROSOL.


                                                            PROCEEDINGS—PAGE 61
                                                         First US-France Conference  on
                                                    Photochemical Ozone/Oxidants Pollution

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      Preliminary experiments with  cyclohexene  and  ozone  in  an outdoor  smog


 chamber show about 3 percent conversion to aerosol.  Of  the  mass collected on  the


 Teflon filter about 60 percent are the dicarboxylic acids, succinic, glutaric and adipic.


      The non-methane hydrocarbon composition of  urban air is  about 60 percent


 alkanes, 15 percent alkenes and 25 percent aromatics.  To simulate this mixture we


 will use butane, cyclohexene and toluene.  Exclusive of methane, butane is the major


 alkane species.  Cyclohexene is not normally measured in ambient air, but it is present


 in automobile exhaust and its  oxidation products have been measured in ambient air.


 in addition it is estimated that the cycloalkenes are responsible for  15 percent of  the


 removal of the alkenes by 'OH and 75 percent of the removal of the alkenes by ozone.


 Toluene is a  major aromatic constituent of urban ambient air at J*3  yg/m for each of


 the Cc, C^,  and C-, diacfds.   Toluene  is one of the most abundent  aromatic species


 measured in ambient air.


      In the ambient and smog chamber measurements of organic aerosols the aerosol


 formation parallels the ozone  formation.  Thus it is likely that the organic aerosol


 results from  the reactions of 0-, with the hydrocarbons.


      The first set of experiments will  involve reactions  of ozone with the individual


 model hydrocarbon  compounds in a smog chamber.  The  emphasis will  be on the


 physical  and chemical  characterization of  the aerosol and obtaining a  carbon  mass


 balance on the  organic  aerosol species.  Ozone will  then be reacted with the three


 hydrocarbons to determine if an synergistic effects exist.


      The next  set  of experiments will involve varying the  hydrocarbon and NO


 concentrations and ratios, then measuring the gaseous and particulate species will be


 studied and finally the complete mixture. The data set that will be produced will then


 be used to develop a model for  organic aerosol formation.


      Several literature articles have suggested that aqueous phase  reactions of SO*


 could be responsible for significant conversion of S05  to sulfate in the atmosphere.  To



       PROCEEDINGS—PAGE 62
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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examine this possibility, a contract was initiated with Aerospace to measure the rate




constants for aqueous oxidation of 50^ 'n the presence of metal ion catalysts, organic




inhibitors, dissolved (X and other oxidants (NC^, ^(X, and Oo).



      The significant findings to date are:




      I.    V02+, Pb2*, Cu2*, and Co2+ are not effective catalysts.


             *3         T

      2.    Fe   and Mn   are catalytic and synergistic.




      3.    ^0 is formed  in the reaction between nitrite and sulfite 2HONO + HLSCK



           -> N20 + H20.



      4.    organics did not significantly inhibit the catalyzed oxidation rate.




      The results to date indicate that  aqueous phase oxidation  of SC^ cannot compete




with  the  gas  phase reactions  of SO* with free radicals.  However, the  important




reactions of HUC^, 0^ and  0^ with SCX have not yet been studied.



      In addition to the aqueous inorganic reactions,  we are  looking  at the aqueous




reactions of O^ with Cc and Cr hydrocarbons.  The results to date indicate the rate of
             J       JO


aqueous  ozonation  in  aerosols  «  the rate of gas phase ozonation.   However,  the



aqueous phase ozonation may be important in the complete oxidation of c=c and phenyl




groups in aerosols.  The products observed in the aqueous  ozonation of pentene and



cyclohexene  are the same as those  observed in  the gas  phase, i.e.  acetaldehyde,




propionaldehyde, butyraldehyde, acetone, methy ethyl  ketone, butyric acid and valeric



acid.




      During  I960 and  81  the aqueous  ozonation of  hexene,  cyclohexene, aromatic



compounds and terpene will be studied.
                                                              PROCEEDINGS—PAGE 63

                                                          First US-France Conference on

                                                      Photochemical Ozone/Oxidants Pollution

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           VISIBILITY
presented by  Thomas G.  Ellestad




Environmental  Protection Agency

          Urn'ted States
                                        PROCEEDINGS-PAGE 65
                                     First US-France Conference on
                                Photochemical  Ozone/Oxidants  Pollution

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                             VISIBILITY
                        by Thomas G. Ellestad

      The  term visibility has a number of meanings, most of which are related
 either to human vision or to the theory of light propagation through the
 atmosphere.   The former meanings include the farthest distance a dark object
 can  be seen,  the clarity or contrast with which an object can be seen, or
 the  apparent  discoloration of an object.  Theoretical concepts include the
 light scattering, absorption, and extinction coefficients, and can be measured
 by such instruments  as a nephelometer.  Visibility 1s reduced by the scattering
 and  absorption of light by gases and by particles.  With the exception of
 nitrogen  dioxide, the contribution of gases is fixed and is usually considered
 negligible.   It is the suspended particles, or aerosols, which are responsible
 for  visibility problems.
      The  extent of visibility reduction in the U.S. can be seen on a map of
 median yearly visual  range for suburban and nonurban areas for 1974-1976
 (Fig.  1).  The range  is from 10-15 miles in the eastern U.S. to about 75
 miles  in  the  southwestern U.S.   By contrast, an atmosphere free of particulate
 contaminants  would have a visual range of about 125 miles.  Trend analyses
 have  shown that in the eastern U.S. from the mid-1950's to the early 1970's
 non-urban visual  range declined about 10-40%.   The decline was especially
 marked during the summer months with an average decrease of 45% in visual
 range.  The trend in  the western U.S.  has been similar with a 10-30% decrease
 in visual range.   Furthermore,  in the eastern  U.S.  visibility degradation is
 now a  regional  problem; rural  areas are no longer significantly better in
 visual  range  than urban areas  as they were in  the mid-1950's.
     Visibility has become an  important topic  in  air  pollution.   Its  possible
effects include citizen  dissatisfaction,  decrease of  tourist revenue  and
                                                          PROCEEDINGS—PAGE 67
                                                      First US-France Conference on
                                                  Photochemical Ozone/Oxidants Pollution

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          property values in scenic areas,  hazards to aviation,  reduction of solar
          radiation for photosynthesis  and  energy production, heating or cooling of
          the  atmosphere which may change the length of growing  seasons, and changing
          precipitation levels.
               One federal  law now exists to regulate visibility.   It mandates pro-
          tection  of visibility in such areas as  national  parks, including the reduc-
          tion of  any existing manmade  air  pollution which impairs visibility.  EPA is
          also considering  the promulgation of a  nationwide standard for visibility.
               Our knowledge of the causes  and characteristics of visibility-reducing
          aerosol  has increased greatly in  the past ten years.  One of the most signifi-
          cant realizations  has  been that aerosols between the sizes of 0.1 and 1.0 ym
          are  responsible for most visibility reduction (Fig. 2).   This results from a
          rapidly  decreasing number concentration at larger particle sizes and a
          rapidly  increasing scattering efficiency per particle  at about 0.1 urn; the
          scattering coefficient is the product of these curves  and the cross sectional
          area.  Thousands  of measurements  of atmospheric  aerosol  size distributions
          have shown that on a mass, volume, or surface basis the aerosol exists in up
          to three distinct  size modes:   nuclei  {<0.1 ym diameter), accumulation (0.1
          ym to 2.0 um),  and coarse particle (>2.0 urn) (Fig. 3).  The number of modes,
          mean diameter,  and the mass,  volume, or surface  in each mode depend upon the
          source and history of the aerosol.  Accumulation mode  aerosol is of most
          concern  in visibility  research because  (1) it occurs at the size range of
          maximum  scattering potential,  and (2) it persists in the atmosphere for
          relatively long periods, compared to the coarse  or nuclei modes.
               To  understand and ultimately to control visibility reduction we must
          know the composition of accumulation mode aerosol.  Currently we believe
          that sulfate,  elemental  carbon, nitrate, and in  some cases organic aerosol
          account  for most anthropogenic submicrometer mass.  Except for elemental
       PROCEEDINGS—PAGE 68
    First US-France Conference on
Photochemical Ozone/Oxidants  Pollution

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carbon, these species are believed to be mostly secondary  in  origin  (i.e.
formed in the atmosphere from gaseous precursors).   Numerous  studies  have
shown sulfate compounds to account for about 40* of  the  fine  particle mass.
The origin of fine anthropogenic sulfate is believed to  be emissions  of
sulfur oxides which have been converted by any of several  proposed atmospheric
reactions.
     Another accumulation mode constituent is elemental  carbon,  or soot,
which is especially important in urban areas.  It is an  excellent absorber
of light and a fairly good scatterer.  Its probable  source is  the combustion
of liquid fuels, particularly in diesel engines.  Studies  by  Weiss et al.
indicate that the absorption coefficient in urban areas  is typically  10-50
percent of the light extinction coefficient, which is an index of visibility.
Considering that elemental carbon aerosol also has a scattering  contribution,
it may be that elemental carbon aerosol is the dominant  material in deter-
mining urban visibilities.  Furthermore, with the projected increase  in
usage of diesel engines, visibility  reduction due to elemental carbon may
increase significantly in the near future.
     Two other possible constituents of submicrometer aerosol  are nitrate
compounds and organic compounds.  Unfortunately these aerosols are volatile
to varying degrees.  We have very little confidence  in previously used
sampling methods and feel that there may have been significant underestimates
of the atmospheric concentrations of these aerosols.  Assessment of the
effect of these compounds on visibility reduction must await  suitable sampling
methods and numerous atmospheric measurements.
     Researchers recognize that many major aerosols  species are  hygroscopic
and thus their visibility-reducing capability changes with relative humidity.
The light scattering of some sulfate species increases smoothly  with  increasing
relative humidity; other sulfate species exhibit sudden  particle size growth
                                                       PROCEEDINGS-PAGE  69
                                                     First US-France  Conference on
                                                Photochemical Ozone/Oxidants Pollution

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      at or above certain  humidities  and  a  subsequent 2-3 fold increase in light
      scattering.  To compound  the  effect of humidity on visibility reduction, the
      light scattering to  humidity  response of many atmospheric aerosols is highly
      dependent on size distribution  and  molecular composition.
           The visibility  research  objectives of the Aerosol  Research Branch are:
      (1) to determine accurately the composition of submicrometer aerosol at a
      number of eastern U.S.  sites; and  (2) to test proposed regulatory methods.
      These objectives are being pursued  by conducting and supporting field studies
      with concerted effort  to  measure volatile aerosol  accurately, and by supporting
      a chamber study of the  effects  of  volatile aerosol on visibility measurement
      methods.  The final  step  of relating  atmospheric aerosols to their sources
      will be handled by the  chemistry and  dispersion models being developed in
      other projects and by  statistical methods.
       PROCEEDINGS-PAGE 70
    First US-France Conference on
Photochemical Ozone/Oxidants  Pollution

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          PROCEEDINGS—PAGE  71
      First  US-France  Conference on
Photochemical  Ozone/Oxidants  Pollution

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     PROCEEDINGS—PAGE 72
   First US-France Conference on
Photochemical ^zone/Oxidants Pollution

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                                               PROCEEDINGS—PAGE 73
                                             First US-France Conference on
                                           Photochemical Czone/Oxidants Pollution

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ASSESSMENT OF SECONDARY AEROSOL  FORMATION POTENTIAL

               FROM  NEW ENERGY  SOURCES
          presented by  Ronald K. Patterson



           Environmental  Protection  Agency

                    United States
                                                   PROCEEDINGS—PAGE 75
                                                First US-France Conference on
                                            Photochemical Ozone/Oxldants Pollution

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r
                         ASSESSMENT OF  SECONDARY  AEROSOL  FORMATION POTENTIAL
                                        FROM  NEW ENERGY  SOURCES
                                          Ronald  K.  Patterson
                                       Aerosol Research  Branch
            Introduction
                 The United States has established  synfuel  priorities  aimed at reducing
            this Nation's dependence on  imported and  diminishing  domestic  oil  supplies.
            The major synfuel technologies under development  are  (1)  Indirect  lique-
            faction; (2) Oil Shale; (3)  Direct Coal Liquefaction;  and  (4)  Coal  Gasifi-
            cation.  Air Pollution related to these technologies  may cause the following
            adverse effects:  respiratory problems  due to inhalable toxic  and  carcinogenic
            vapors and particulates; acid rain; visibility  degradation;  and dry deposition
            in the biosphere of toxic and acidic chemicals.   Synfuel-related emission
            source identification and characterization, and the determination  of ambient
            air pollutant transport and  transformation products related  to synfuel  process
            emissions, may lead to regulatory strategies and  control devices which  could
            mitigate or alleviate these  effects.
                 Conventional ground-based and/or aircraft  sampling are  not suitable (or
            practical  in some cases) for assessing the ambient air emissions and chemical
            transformation products from synfuel processes.   Few,  if any,  of the processes
            of interest are or will be isolated from other  sources and/or  uncontrollable
            phenomena  such as power plants, urban centers,  industry, pollutant  incursions
            from other areas or regions,  meteorological uncertainties, etc.  Another
            important  consideration is the need to assess the biological effects of  these
            processes.   Few of our present sampling technologies  (especially airborne
            sampling systems) are capable of collecting sufficient quantities of material
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 for  biotesting.   The above mentioned problems, the unreliability of theore-
 tical  predictions on the nature and quantities of secondary pollutants from
 synfuel  processes,  and  the lack of any commerical scale synfuel  plants in
 the  United  States led to the development of an Aerosol  Research Branch
 program  which  includes  the construction of a mobile flow-through reactor
 (dynamic smog  chamber)  under a  contract to the Radian Corporation at
 Austin,  Texas.
     The objectives  of  this multi-year program are (1)  to develop a
 transportable  flow  reactor, effluent delivery, and clean air dilution system;
 (2)  to characterize  secondary aerosol  products formed through simulated atmos-
 pheric reactions  involving synfuel  and conventional  energy source effluents and
 end-use  synfuel combustion products; (3) to collect sufficient quantities of
 secondary aerosols  for  biological  assays;  and (4) to compile a data base for
 use  in ambient air model  development and testing.
     Most of the  smog chambers  used in previous secondary aerosol formation
 studies  were batch  reactors.  One  advantage of this design (batch) is that
 it allows changes in  pollutant  and  aerosol  concentrations with time to be
 monitored.  However,  batch designs  suffer  from the disadvantage of providing
 only a fixed amount  of  gas whose composition will be continually changing.
 Now, it  is  certainly  possible to design a  batch reactor which is large enough
 to supply the  amount  of sample  needed  for  organic aerosol characterization and
 biotesting.  However, one problem  with this approach is that a chamber this
 large would be very  difficult to transport from site to site for testing
 purposes.   Also,  if  the experiments were to be done under a constant, high-level
 [k,  [NOo] = 0.4 min   ]  irradiation, the costs of enclosing the chamber and providing
 the necessary  ultraviolet light source would be very high.  For all of these
 reasons  a flow reactor  (dynamic smog chamber) provides  an attractive alternative
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which reduces the required size of  the chamber  and  makes  it less expensive and
more portable.  The major disadvantage of  a  flow  reactor  is that it will
isolate only one point in time with  respect  to  gas-phase  products and secondary
aerosol formation reactions.
     Flow reactors have been used extensively to  investigate gas-phase photo-
chemistry to determine reaction rate constants  and  gas-phase behavior in  terms
of ozone formation.  Flow reactors  have  been utilized  less  frequently for
secondary aerosol formation studies.  Another factor which  limits the
applicability of previous flow reactor research to  this program is that it
has generally focused upon high concentrations  of initial  reactants (>50  ppm)»
short residence times (<5 minutes)  and high  light intensities {krf >1.0 min" ).
All these conditions are attempts to scale the  reaction time to short residence
times.  The Aerosol Research Branch  program  will  be much  more realtistic  in
terms of ambient concentrations, light intensities  and residence times.
     The dynamic flow reactor which  will be  constructed in  order to
accomplish the objectives of this program  will  consist of the following:
     -an 800 ft  (heat sealed FEP Teflon cylindrical bag)  flow-through
      reactor housed in a 40 ft  mobile  trailer with U.V.  irradiation
      [krf [NCL] ~ 0.4 min" ] and stirring  capability,
     -a clean air system,
     -an effluent delivery system,
     -an ozone generator,
     -a sampling manifold system,
     -a gas-phase analytical instrument  package,
     -aerosol sizing instrumentation, and
     -a data acquisition/logging system.
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  Approach
      It is currently anticipated  that  the  following advanced fossil fuel
 conversion processes will  be  addressed as  part of the EPA's overall secondary
 aerosol assessment program:
      (1)   Conventional Combustion  Modifications
      (2)   Atmospheric  Fluidized  Bed Combustion
      (3)   Low-Btu Coal Gasification
      (4)   Coal Liquefaction
      (5)   Oil Shale
      (6)   Chemically Active  Fluidized Bed Gasification
 The program which will  be  conducted to evaluate these emission sources will
 consist of a one-year base-phase, followed by two optional one-year test-
 phases.
 Test Plan
      During the Year 1  base-phase (FY-80), three distinct types of activities
 are planned.  First, detailed Flow  Reactor System design and operating
 specifications will be  developed.   Then, the test unit will be constructed
 and a series of preliminary break-in tests will be conducted.  Finally,
 toward the end of the base year,  the Flow  Reactor System will be transported
 to Research Triangle Park, North  Carolina, and tested using the following
 waste gas sources at Industrial Enviornmental  Research Laboratory test
 facilities:
      (1)   Combustion Modification  Test Facility (low NOV Burner/Package
                                                          P\
            Boiler)
      (2)   Sampling and Analytical  Test Rig (experimental FBC unit)
      (3)   Stationary Diesel  Engine Test Unit
      (4)   North Carolina  State University Fluid Bed Gasifier
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     Subsequent test work, which will  be  funded at EPA's option will involve
transporting the  Flow  Reactor  System to the following test sites:
     Option 1. Year 2  (FY-81):
     Location
     1.   Duluth, Minnesota

     2.   District of Columbia
     3.   Alliance, Ohio


     Option 2. Year 3  (FY-82):
     Location
     1.   Fort Lewis,  Washington
     2.   Catlettsburg, Kentucky

     3.   San Benito,  Texas
     4.   Grand Valley, Colorado
     Facility
Foster Wheeler/Stoic; Two-stage,  low
BTU gasifier.
Foster Wheeler Energy Corporation/Pope,
Evans and Rofabins/Georgetown University;
TOO MM Btu/hr industrial FBC boiler.
EPRI/Babcock and Mil cox; 6'x6' FBC
prototype unit.
     Facility
Gulf Mineral Resources; SRC-II pilot  unit.
Ashland Synthetic Fuels,  Inc./HRI;  H-Coal
Demonstration Plan.
Foster Wheeler Energy Corporation/Central
Power and Light; Chemically Active
Fluidized Bed Demonstration Unit.
TOSCO; In situ Oil Shale  Burn.
     Radian will supply instrumentation  and  personnel  to perform a two-week
series of experiments using  the  flow  reactor at each of the synfuel facilities
tested.
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      Operation of the flow reactor system will involve:
           -interfacing with the existing combustion sources  to  obtain  the
            effluent sample,
           -calibration of all monitoring instruments,
           -continuous monitoring of gaseous pollutants,  aerosols  and  reactor
            operating parameters,
           -daily zero/spans of instruments,
           -collection of grab samples for gaseous, and particulate  analysis,
           -data acquisition and processing.
      The EPA intends to fund these options on an  incremental  basis.   This
 will be done both to maximize program flexibility and to guarantee  contractor
 responsiveness.  For example, it may develop that the H-Coal  Demonstration
 Plant will not be operational within the time frame allotted to this  program.
 If this situation occurs, Radian will propose alternative sites for testing.
 Radian has a proven record of planning and executing successful environmental
 test programs at a variety of commercial test sites.  This includes several
 of the specific facilities which are proposed for testing as  part of  this
 overall program.   Therefore, obtaining access to  the proposed test  sites
 should not be a significant problem for Radian.

 Sample Collection Plan
      The process  gas will be sampled using a clean air aspiration system
 which will also accomplish the necessary dilution of the process  gas.   The
 clean air system will  provide clean, humidity controlled air at a rate of
 250 liters per minute.   A heat traced cyclone will be placed in the sample
 line prior to the aspiration system to remove particulate matter  greater
 than 3 urn in size from the process gas.  The temperature of  the diluted
 sample gas will  be controlled by an air or water cooling system prior  to
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the flow reactor Inlet sampling manifold.  The source effluent flow rate will
be measured by a standard pHot inserted 1n the sampling line downstream of
the cyclone and prior to the aspirator.  Pressure differentials across the
pi tot and the'source effluent temperature will be monitored and recorded by
the data acquisition system.
     Reactor inlet and outlet streams will be passed through a heat traced
manifold system constructed of glass pipe with a 25 mm inner diameter.
Samples collected prior to and after the flow reactor will be transported to
the analytical instrumentation through heat traced teflon lines.  An  ozone
generator with an output capacity of 4 grams per hour will be housed  in the
mobile lab to serve as an injected reactant in planned experiments.   Instru-
mentation will also be on board to sequentially monitor the inlet and outlet
streams of the reactor for:  ozone (03); sulfur dioxide (SOg); oxides of
nitrogen (NO ); particle diameters >.002 pm (Condensation Nuclei Counter,
            A
CNC); particle diameters between  .01 and 1.0 gm (Electrical Aerosol Analyzer,
EAA); particle diameters between  .3 and 10 pm (Optical Particle Counter, OPC);
and light scattering properties (Integrating Nephelometer).  The inlet and
outlet manifolds are also equipped with ports for filter sampling, grab
sampling, and organic vapor trap  sampling on absorbent polymer.
Data Acquisition, Processing and  Validation Plan
     The Radian Data Acquisition  System includes a DART II system, two
device controllers (for controlling solenoid valves), a Model 43 Type
Keyboard Printer, and a terminal  connection panel.  The Radian DART  II  (Data
Acquisition, Reduction, and Transmission) system is a third generation micro-
processor controlled data acquisition  system and will be used with a  device
control peripheral.  This subsystem allows the DART  II to control relay
closures (Solenoid valves) for the sampling flow systems.  This will  allow
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 the gas analyzers to switch from the inlet to the outlet of the flow reactor
 and will also purge zero concentration gases or calibration concentration
 gases through the separate analyzers.
      The DART'System will signal the gas analyzers to alternately sample
 the inlet and then the outlet of the flow reactor with a zero air purge
 in-between these sampling times.  The length of time associated with each
 of these steps  will be a keyboard selectable function for the DART II.
 Manual  key-ins  on the operator keyboard will place the system into a
 calibration mode which will independently or concurrently calibrate each gas
 analyzer.   The  DART II can be operated completely in the manual mode.  The
 sampling time and nested averages for the gas analyzers are a keyboard
 selectable variable.
      The aerosol analyzers will alternately monitor the inlet to the flow
 reactor and then the outlet with a zero air purge in-between.  The capability
 of external calibration will also exist.  The CNC and the nephelometer
 outputs will  be acquired exactly as the gas analyzers are sampled with five
 minute  averages being generated and converted to one hour summaries with
 instantaneous highs and lows and one hour averages.  The EAA and the OPC
 will  be routinely operated with a two minute and a five minute cycle time
 respectively, requiring data to be acquired after these cycle times.  The
 DART  II will  accept information from these two analyzers on an interrupt
 basis when they have completed their independent cycles.  This information
 will  be stored  and printed along with the gas analyzer data.
      Due to the fact that the DART II System is implemented with 32 analog
 inputs, other Flow Reactor System Status inputs will be acquired.  These
 other inputs  into the data acquisition system are:  gas temperatures, baro-
 metric  pressure, system static pressure, various flow rates, relative humidity,
 and fan motor amperage.
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     The  DART  II will  store permanently all  five minute averages along with
EM  and OPC  data and  one hour averages with  highs and lows in a summary
report.   This  information will  be stored on  a floppy disk system located
within the DART  II  system.   It  1s expected that the storage capability
within this  system  will  be  greater than one  day's worth of data for the flow
reactor system.  Radian  will  retrieve data disketts from the field and copy
them to 9-track magnetic tape back at Radian's facilities.  All raw data
signals will be processed to  engineering units by the DART II in real  time.
Gaseous pollutant data is routinely reported 1n ppb and is corrected to
the  daily zero/span off-set.  Particle size  distribution data are processed
to provide differential  number,  surface and/or volume densities.
Sample Analysis Plan
     The  results from  sampling  the inlet of  the reactor will be analyzed to
assess the impact of  the primary emissions of each source with respect to the
chemical  composition of  the gaseous components, the primary aerosol size
distribution,  loading, and  composition.   The differences between outlet and
inlet concentrations of  the reactor will  be  used to assess the Impact of the
tested sources upon the  ambient  atmosphere.   The irradiated test results
will be analyzed to determine the photochemical  potential of the diluted
effluent streams.   The non-irradiated tests  with ozone addition will be
analyzed  to assess  the potential  of these effluent streams to form
secondary aerosols.
     Analysis of the gaseous  constituents  will  yield an assessment of the
photochemical potential  with  respect to  hydrocarbon oxidation, NO oxidation,
S02 oxidation, and  possible ozone formation  (more important for hydrocarbon
rich sources).  Analysis  of _i£ sHu. aerosol  measurements will yield an
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 assessment of aerosol formation  and  growth  potential  under irradiated and
 dark-phase conditions.  Chemical analysis of  the  filter  collections will
 yield information on the composition and concentration of primary and
 secondary aerosols.  Biological  analysis of the filter collections will
 yield information on the carcenogenic  and mutagenic  nature of the primary
 and secondary aerosols; and  some microscopical analyses  will  be conducted
 in order to obtain information on  the  morphology  of  primary and secondary
 aerosols from each of the synfuel  processes studied.  The contractor will
 perform the following determinations on selected  samples collected from
 each synfuel process studied during  FY-81 and FY-82:
      -The determination of Organic Aerosols and Gases by GC/MS,
      -The determination of Fixed Gases, Sulfur Gases  and Gaseous
       Organic Compounds,
      -The determination of Inorganic Sulfate, Nitrate, and Trace
       Metal Aerosols, and
      -The determination of Aerosol Morphology
 Samples for biotesting will  be collected and  analyzed using protocols
 established by the EPA Health Effects  Research Laboratory, Genetic Bioassay
 Branch.
      Interpretation of these results will give quantitative and qualitative
 estimates on the potential production  of secondary gaseous products, and
 inorganic and organic aerosols;  as well as  the potential for forming toxic
 mutagens and carcinogens.  This  type of information  will provide useful
 inputs to the EPA's control  strategy development  studies since they will
 define what sources should be controlled and  indicate what levels of control
 are appropriate.
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Data Analysis Plan
     Since the primary emphasis  of  this  program  is  on  characterizing the
nature of the produced aerosols  and not  on  studying their formation kinetics,
problems associated with aerosol  deposition on internal  reactor surfaces will
not present serious limitations  to  data  analysis.   Generally,  the  limited
scope of the testing  which  will  be  conducted at  each test site will simplify
the data analysis problem substantially.  In most backmix reactor  systems,
computer reaction rates would  be correlated against measured  levels of
critical reactor variables  (reactant concentrations and  temperatures).  In
this program, however, a very  limited number of  these  types of experiments
will be conducted.  This means that the  primary  focus  of the  data  analysis
task will be on data  quality rather than data correlation.
     While the reactor is lining out (until  at least three  residence times
have elapsed), ozone  and NO  levels in the  reactor  outlet will  be  monitored
to confirm that a reasonable approach to steady-state  conditions has been
achieved.  Also, aerosol concentration and  size  distribution  measurements
will be used to confirm that conditions  favorable for  aerosol  formation
have indeed been established.  In cases where extremely  low aerosol formation
rates are observed, consideration will be given  to  modifying  the conditions
of the experiment.  Modifications which might be necessary  in  order to promote
reasonable aerosol formation rates  might include:   decreasing  the  dilution
ratio, increasing the ozone addition rate,  or increasing the  irradiation rate.
The type of corrective action  taken in a given situation would depend on the
relative concentrations of  reactive species  which were being  observed in the
reactor outlet gas.  Other available data from the  first year's testing will
be the baseline test data taken  to  characterize  the flow reactor.   These
tests will  examine such variables as  aerosol  deposition  in  the reactor and
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 natural (nonlrradiated) pollutant degradation due to wall effects.  The
 lineout tests will also include a flow reactor study with a hydrocarbon-rich
 sample source.  The procedure used for this study will be similar to that
 used in evaluating the three IERL sources.
      The emphasis of the first year's work will be to verify that the
 equipment is operating properly and that meaningful pollutant concentrations
 are  being obtained.   The use of data analysis in equipment validation will
 fall  into the following categories:
           (1)  analysis of the variability of pollutant concentration
                measurements in the reactor after steady-state conditions
                have  been established,
           (2)  mass  balance calculations, and
           (3)  Analysis of repeatability.
      The exact set of experiments to be run for each plant studied will be
 strongly influenced  by the results of the first year.  The replication
 variance,  for example, will be avaluated in the first year.  This will
 determine  whether replicate measurements in subsequent years' tests are needed.
 Quality  Assurance Plan
      The QA  effort for this project will be coordinated by Radian's Quality
 Assurance  Director,  who will  report to the Program Manager and Project
 Director.  He will review the test plans at each site, sampling and calibra-
 tion  procedures,  analytical quality control  procedures, and data validation
 procedures.   An  independent audit of all monitoring instrumentation will
 be performend by  Radian's Quality Assurance Group.  Software will be developed
 to test  for  outlying data points  and control  charts will be used to evaluate
 trends over  time.
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Conclusions
     The flow reactor system will  be applicable to all existing or planned  synfuel
and conventional energy  source  technologies.  Also under consideration  is the use
of this reactor in the evaluation  synfuel  end-use products.  For example, the com-
bustion products from a  test-boiler using  shale oil as a feedstock can  be tested in
the flow reactor, and the  potential  for secondary aerosol formation determined and
assessed for human exposure and atmospheric degradation effects prior to its  exten-
sive use by industry and the general public.  At the same time the petroleum  analog
of each synfuel product  can be  tested and  compared.  The overall program planned for
the Aerosol Research Branch Flow Reactor is expected to be a valuable tool  to the
Agency in its efforts to determine the secondary pollution potential from existing
energy sources and from  planned new energy producing complexes.
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KOSOVO  AMBIENT AIR MONITORING PROGRAM
  presented  by Ronald  K.  Patterson



   Environmental Protection Agency

             United States
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                      KOSOVO AMBIENT AIR MONITORING  PROGRAM

                               Ronald  K. Patterson
                             Aerosol Research  Branch
INTRODUCTION
     Coal gasification is emerging as one  alternative  to  the  energy crisis  in
the United States.  This process uses coal,  the  Nation's  primary energy resource,
to produce low, medium, and high BTU gas and  it  is  the first  step in many coal
liquefaction processes which  turn coal  into  gas  and then  into a variety of
liquid fuels. The Aerosol Research Branch  of  the Environmental  Sciences Research
Laboratory, Research Triangle Park, North  Carolina  (ESRL-RTP) conducted a 16-day
continuous ambient air study  in  the Kosovo Region of Yugoslavia in order to
gather data regarding the impact of a commercial  gasification facility on the
surrounding environment.

     Kosovo was chosen as the site for  the study because  (1)  it has a commercial
scale Lurgi design medium BTU coal gasification  facility  (a design likely to be
used by  U.S. builders),  (2) the  facility is  isolated from other major sources,
(3) Yugoslav interest in the  ambient air study guaranteed manpower support and
access to the plant, and (4)  large amounts of process  emission and engineering
data were available from the  Kosovo facility  through the  EPA  Industrial Environ-
mental Research Laboratory.   The Kosovo complex  houses six East German Lurgi
gasifiers and the typical support facilities:  coal mining, handling and storage;
by-product storage and handling; power  plant; air-separation  plant; fertilizer
plant; and ash handling and storage.

     The objectives of this study were  (1) to characterize ambient aerosol  and
volatile organic pollutants,  (2) to correlate specific pollutants to the gasifi-
cation plant, and (3) to evaluate the impact  of  the Kosovo Lurgi gasification
process  on the air quality.


APPROACH

     Five sampling sites were established  around and approximately 2 kilometers
outside  the fenceline of the  Kosovo industrial complex.   Samples were collected
from 0000-hrs May 14 through  2400-hrs May  29, 1979.

     Sampling and analytical  techniques were used to determine  organics in  total
particulate matter; total and  fine particle mass, inorganics, and elemental
species; trace metal in size  fractionated  particles; and  vapor  phase organics.
Physical and inorganic chemical analyses were carried  out on  the collected
particulate matter using gravimetric analysis, ion  chromatography,  and scanning
electron microscopy.  Elemental analysis was done using the inductively coupled
argon plasma emission technique, proton-induced  X-ray  emissions  and combustion
analysis.  Both particle catches and vapors trapped on Tenax  resins were subjected
to organic analysis using gas  chromatography.  Flame ionization  detection and
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and sulfur and nitrogen specific detectors were employed in addition to  the GC-
MS method in organic compound identification and quantification.  A comprehen-
sive program in quality assurance and quality control was  implemented  to ensure
the validity of the sample collected and analyzed.   Detailed  sampling  and analy-
sis strategies are contained in Reference 1, and a summary of all analysis
results is presented in Reference 2.


Conclusions

     The major results from this study  indicated that  (1)  aerosols  in  the form
of coal dust was a significant pollutant from the coal  handling  operation and
tended to overshadow any aerosol emissions from the  gasification process; (2)
ambient aerosol concentration levels exceeded National  (U.S.) Ambient  Air Quality
Standards and may be of concern in a large U.S. facility;  (3) aerosols appear to
be carriers of polynuclear aromatic hydrocarbons (PAH's);  (4) ambient  air concen-
trations of benzene and benzo (a) pyrene downwind of the gasifiers  exceeded  the
Ambient-Multimedia Environmental Goal  (AMEG) target  values (Reference  3) by  a
factor of 10-100 and 1000, respectively; (5) a broad range of organic  compound
classes were found in the ambient air downwind of the  gasifiers  and  included
aliphatic and aromatic hydrocarbons as  well as their sulfur-, nitrogen-, and
oxygen-containing derivatives (see Table 1); and (6) organic  pollutants  were
traced to the gasification process through comparisons  with gasifier by-products
(see Table 1).

     This study proved that pollutants  unique to the gasification process are
being carried beyond the fenceline of the industrial complex  and that  those
pollutants can be differentiated from other emission sources  in  the complex.
Even though the Kosovo complex is 10 years old and one-tenth  the size  of pro-
posed U.S. facilities, the results from this study produced a valuable data base
which should be consulted when making decisions on the  development, control,  and
placement of coal gasification facilities in the United States.   The major areas
of concern highlighted by this study are coal transport, handling, and storage;
ash handling and storage; gasifier by-product storage and  venting; and valve
leakage.   The results from this study also suggests  the need  for a comprehensive
health assessment study and a long-range (10-20 km)  transport study in Kosovo,
in order to develop risk assessment data.
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r
              REFERENCES

              (1)  Bombaugh,  K.J.,  G.C.  Page, C.H. Williams, L.O.  Edwards,  W.D.  Balfour, D.S.
                   Lewis,  and K.W.  Lee.   Aerosol Characterization  of Ambient Air Near a Commer-
                   cial Lurgi Coal  Gasification Plant:  Kosovo Region,  Yugoslavia.   EPA-600/7-
                   80-177.   U.S.  Environmental Protection Agency,  Research  Triangle Park, North
                   Carolina,  1980.

              (2)  Patterson, R.K.   Ambient Air Downwind of the Kosovo  Gasification Complex:  A
                   Compendium.   Presented at the Symposium on Environmental  Aspects of Fuel Con-
                   version Technology -  V, St. Louis, Mo., September 16-19,  1980.   To be published
                   in  proceedings.

              (3)  Kingsbury, G.L., R.C.  Sims, and J.8. White.  Multimedia  Environmental Goals
                   for Environmental  Assessment; Volume III and IV.  EPA-600/7-79-176a/b.  U.S.
                   Environmental  Protection Agency, Research Triangle Park,  North  Carolina, 1979.
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       TABLE 1    .   COMPARISON OF CHEMICAL  SPECIES PROFILES IN KOSOVO AMBIENT
                     AIR SAMPLES AND MIDDLE  OIL5
COMPOUND OR ISCMZE. GROUP
IDENTIFICATION

benzene
toluene
C2-alkyl benzenes
Cj-alkyl benzenes
C^-alkyl benzenes
naphthalene
aethyl naphthalenes
acenaphthene
fluorene
anthracene/phenanthrene
methylanthracene
fluoranthene
pyrene
chrysene
benzanthracene
triphenylene
benz(a and e)pyrenes
benz(b and k) fluoranthene
perylene
•
terphenyl

trimethylphenyl indane
MOL.
WT.

78
92
106
120
134
128
142
154
166
178
192
202
202

228


252


230

236
NO. ISCMERS
DETECTED
NORMALIZED CONCENTRATIONS
TENAX
HI VOL | MEDIUM OIL
HYDROCARBONS
1
1
>3
>6
>9
1
>2
1
1
>1
>2
1
1

>1


>3


>3

1
89
101
131
141
40
100%*
50
17
8
19

1.9
1.6

ND


ND


ND"

1.4
ND2
ND
ND
ND
ND
ND
6%
ND
5
100Z1

230
240

360


1100


300

ND
24%
23
20
17
15
100%
34
8
10
18
8
3.2
3.0

1.2


0.5


' 0.4

0.2
   :Absolute concentration of naphthalene * 3 yg/m3,  anthracene - 0.003 yg/m'

   2ND -  Not detected by GC-MS.
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r
               TABLE 1
(Continued)
COMPOUND OR ISOMER GROUP
IDENTIFICATION

phenol
methyl phenols
C 2 -alkyl phenols
'
acetophenone

dibenzofuran

diphenylquinone

phthalate ester @ 14.4 mln.
ph thai ate ester @ 17.5 mln.
. - - 	
""
methyl thiophene
C2- alkyl thiophenes
C3- alkyl thiophenes



MQL.
WT.
HO. ISCMERS
DETECTED
NORMALIZED CONCENTRATIONS
TENAX
HI VOL
MEDIUM OIL
C-H-0 COMPOUNDS
94
108
122

120

168

260




1
>2
>5

1

1

1

1
1

87
83
67

6

13

33

7.7
11.3

ND
ND
ND

ND

ND

ND

300
3000
18
44
43

3

9

ND

4.0
5.6

C-H-S COMPOUNDS
98
112
126



2
*4
S3



4
8
D3



ND
ND
ND



1.9
2.8
1.8



                  detected by HECD-N  analysis;  not detected (<1Z)  by GC-MS due to hydrocarbon
                  interference.
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    TABLE 1
(Continued)
COMPOUND OR ISOMER GROUP
IDENTIFICATION

pvridiae
nethyl pyridlnes
C2- alkyl pyridines
Cs- alkyl pyridines
•
quinoline
isoquinoline
methyl quinolines
Ca- alkyl quinolines











MOL.
WT.
NO. ISOMERS
DETECTED
NORMALIZED CONCENTRATTO\2
>4
>5

1
1
>5
no











DS
D
D
D

D
D
D
D











ND
ND
ND
ND

ND
ND
ND
ND











100%"
790"
830*
640*

600"
100*
320*
150*











   "Detected and  quantified in the  basic extract of  middle oil,
    normalized  to pyridine.

     From Reference 1.
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INORGANIC  POLLUTANT  ANALYSIS BRANCH

         RESEARCH PROGRAMS
 presented by  Robert K. Stevens



 Environmental  Protection Agency

           United  States
                                          PROCEEDINGS—PAGE  99
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                   ATMOSPHERIC CHEMISTRY AND PHYSICS DIVISION

                       Inorganic Pollutant Analysis Branch

                                Research Programs

                          Prepared By Robert K. Stevens
Introduction
     The  Inorganic  Pollutant  Analysis  Branch   (IPAB)  performs  research  to
develop  new and  improved analytical  procedures  to measure  and  characterize
gaseous  and particulate  pollutants.   Past programs of  the IPAB  include:  (1)
the development  of the  first  chemiluminscence  instruments to monitor ozone,
oxides  of  nitrogen and  sulfur containing  gaseous  pollutants (2) development
and validation of  long  path  laser  systems  to  measure  carbon  monoxide  and
ozone;  and  (3)  development  of aerosol sampling and analysis  procedures  to
measure  the mass,  chemical  and  elemental  composition  of size  fractionated
aerosols.

     In  fact,   a   long   term  objective  of  the   research  of  the  IPAB  is  to
determine the  chemical  or  at  least  the elemental  composition of atmospheric
aerosols.   Knowledge  of  the  elemental composition  of aerosols  can point  to
likely  compounds  that  may be present, guide  future chemical analysis and can
set upper limits  for the concentrations of any  possible compounds  containing
these elements.  Elemental data can, by use of receptor models, also lead  to a
remarkably  detailed   determination  of  pollutant  sources.   The   value  of
elemental   and  chemical  composition,  data   is   significantly  enhanced   when
accompanied by  aerosol  particle size  information,  since  the size affects  the
respirability  of   the  aerosol,  governs  its  impact on  visibility  reduction,
determines  its potential  for long  range  transport  and  indicates possible
sources.

     Over the past 4 years EPA, with the help of  Lawrence Berkeley Laboratory,
completed development  of an  integrated system for  the automatic collection of
aerosols  into  two  distinct  size   ranges   and  developed  improved  x-ray
fluorescence  and  f3-gauge  systems  to  measure  respectively  the   elemental
composition  and mass.  These  procedures  do  not  change  the  integrity  of  the
aerosol,  consequently  analysis by  x-ray   diffraction and  scanning electron
microscopy  (SEM)   are   also   performed on  the  sample to  provide  additional
information on chemical  character of the aerosol.   IPAB is  sponsoring research
to  advance  the state  of the art  in x-ray diffraction  and SEM so  that these
procedure can be quantitiative  and  less time  consuming.

     The  IPAB   is  also  involved in  some   specific programs  in  the gas  and
aerosol measurement area.  The  discussions  that follow highlights  research to:
(1) measure nitrates and nitric acid; (2)  application  of receptor  models  to
determine   sources  of   aerosol  pollution;  and,  (3)   procedures  to measure
visibility.
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                              CURRENT RESEARCH PROGRAMS

  A.    Nitric Acid and Nitrates

       Nitrates in the atmosphere  may occur as solids  (e.g.,  ammonium or metal
  nitrates in particles)  or  as gases (e.g., HNO  )  and  a difficulty has existed
  in  distinguishing between  them because  of possible nitrate artifact formation
  during  sampling.    The  problems  of  atmospheric  nitrate artifacts  are  now
  thought to be of two  kinds:  (1)   the  formation of particulate nitrates from
  gaseous nitrates on a  collection  filter (positive artifacts), and (2) the loss
  of  particulate nitrates as  gaseous nitrates due  to  chemical reactions on the
  filter  (e.g.  H  SO.  aerosol  and  particulate nitrates  reacting  to particulate
  sulfates and  gaseous HNO-) or  loss  due  to  evaporation.  The  occurrence  of
  positive nitrate artifacts has  been  reported  by Stevens et al.  (1978a)  and
  Spicer et al. (1978) and  the loss of  particulate nitrate by chemical reaction
  on  the collecting  filter  has been demonstrated in the laboratory by Marker et
  al.  .(1977).  Shaw,   et  al.  (1979)  developed  a  procedure called  the  Denuder
  Difference  Experiment (DDE)  which used  to is separately determine particulate
  nitrate and gaseous HNO  ,  without influence of either type of artifact.

  Instrumentation  and Methods:  The DDE requires two sampling assemblies.  Both
  assemblies  consist   of a Teflon particle filter  followed  by  a HNO  collection
  tube (Hare,  Wininger and Ross,  1979).   For one of the assemblies, however,  the
  particle filter  is  preceded by an acid gas diffusion denuder (Stevens, 1978b)
  coated  with  a  strong   base,  and  the  residence  time  of a  particle  in  the
  denuder, under  typical operating  conditions   is  approximately 0.4 seconds.
  This  denuder  will   remove  acid  gases,  in particular  HNO ,  and  pass  aerosol
  particles.  Thus  we see that the difference between  the amounts  of  nitrate
  collected by  the  two assemblies will  be  due  only to  the removal  of gaseous
  HNO,  in  one  assembly.  We  may   express the measured quantities  as follows:
  Quantities  of Interest
       N,,
        H
Total  atmospheric  nitrate  (particulate  nitrate
HNO ).
particulate nitrate
gaseous HNO
and  gaseous
  Observed Quantities
                 nitrate measured on filter behind denuder
                 nitrate measured on filter in assembly without denuder
                 nitrate measured on collection tube behind denuder
                 nitrate measured on collection tube in assembly without denuder
  Thus,
        H
       V11
        T
       •1
N  - N
F+ T P
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Therefore
               NH =  (F + T) -  (FD + TD)

     Notice  that the experiment  depends  on  the following  characteristics  of
the apparatus:

(1)  the diffusion  denuder removes all  gaseous  HNO_  and passes all particles.

(2)  the combination of  particle filter  and  HNO collection tube will collect
     all gaseous HNO and  particulate  nitrate.

(3)  the two assemblies sample  equal amounts  of  air.

Discussion:  The results  of the DDE are not  affected by artifacts due to loss
of particulate  nitrate  as HNO,, from the filter  or  gain of particulate nitrate
from  reactions  of   HNO   on  tne filter.  Alos nitrates are  not  significantly
dissociated  in  the  denuder since the  residence  time  in the denuder is no more
than 0.2 seconds. In fact, the  DDE  results may be used to determine the amount
of nitrate  loss or  gain due to artifacts.  From the  definitions above, we see
that T   is  equal to  the  amount of nitrate lost as HNO  from the filter since
the diffusion denuder prevents  gaseous HNO., from entering the filter-collector
assembly.  On  the  other hand,  particulate nitrate  gain  from HNO,, is given by
the  difference F -  F-y   Since nitrate  formation from HNO.,  is  negligible for
Teflon  filters,  (Spicer,  1978) any measurable gain would presumably be due to
gaseous conversion on the  collected aerosol.

     In  this  discussion  it has been assumed  that amounts of gaseous nitrates,
other  than  HNO,,, are negligible.   If amounts  of  other  gaseous  nitrates are
significant,  tfieir  effect on  the  DDE  can be  determined by  considering the
event matrix:
     Collector  Efficiency
     Denuder Efficiency

100%                   0%
           100%
                                    T = X
                    TD = X

                    T = X
   = T = 0
                                                        TD = T = 0
where X  is  the  amount  of gaseous nitrate (not HNO,.) which enters the system, T
and  T^  have  been previously  defined and,  for  simplicity, we  assume  that no
particulate  nitrates  are  present.   If  the diffusion  denuder  removes  the
gaseous  nitrate and  the  tubes  are capable of collecting it, then the amount of
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gaseous  HNO,,  determined  will  be  too  high  by  the  amount  X.
demonstrated by the relation:
                                                                       This  is
        = (F + T) - (F
                      D
                           TD)
and  in  this  case  (as  represented  by the  upper left matrix element):

      M  = T  - T   =  Y.
      •NH  i   ID    x

      In all  other  cases,  the values of NH  are  not affected.  If  the denuder
does  not  remove the  gaseous  nitrate and the tube  collects  it (as represented
by  the upper  right  matrix  element), the  value Np  will be  too  high by  the
amount  X.  For all  other  cases  the  values  of N   are not affected.
                                              P
      As mentioned above,  loss  of particulate nitrate may occur by evaporation
from  the  collecting filter.  Significant  losses of NH,NO« have been observed
in  the laboratory  in  an extreme  experiment  -- loading a  filter  with  pure
NH.NO  aerosol  and  subsequently passing  clean  air through it (Reutter, 1978).
Because of   their much lower vapor  pressures,  metal nitrates  are  expected to
show  much lower evaporative  losses  than  NH.NO .

      Losses  of  NH NO   by evaporation  from urban aerosols may be  supressed by:
1) presence  of  gaseous NH   and HNO,,  in  the  atmosphere in equilibrium with the
particles  and  2)  reduction  of  vapor  pressure  of the  particles  due to  the
presence  of  other  materials.  If,  however, evaporative loss  from  the filter
occurs, we expect the NH.NO.,  to decompose  according to:
As  explained  above,  in  the DDE,  HNCL  collection  tubes  follow  the  particle
filters  and so the DDE  results  will not be affected  by evaporative loss.  If
however, more  than  one  artifact  process  becomes significant,  interpretation of
the DDE  may become  complicated.

     To  summarize,  the DDE  provides  the  following  measures  of atmospheric
nitrates :
     N
     N
     N
     F  -
                    gaseous HNCL
                    particle nitrate
                    total atmospheric nitrate
                    artifact due to loss of particulate nitrate by  reaction  on
                    the filter
                    artifact  due  to gain of  particulate  by transformation  of
                    gaseous nitrate.
Nitrate-Nitric  Acid Intercomparison  Study:   During the period  from  27 August
to  3 September,  1979,  a group of  scientists  met  at  Harvey Mudd  College in
Claremont,  CA to compare measurement techniques for nitric  acid  and nitrates
in  the ambient  air.   ESRL is  currently  reviewing the results  of  this study.
Preliminary examination of  the results  of the study  revealed  the following:

1.   When  NASA  glass   fiber  filters  and  quartz  fiber  filters were  used to
     collect  simultaneous particulate samples,  significantly different amounts
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of nitrate  were observed.  JFor NASN  glas
nitrate values was_19.9 Mg/n>  to.,94.3  |Jg/m
range was 2.2 pg/rn  to 14.8 jJg/m  .
                                                  fiber  filters, the  range  of
                                                  for  quartz fiber  filters the
2.   HNO  concentrations  ranged from 0-20 ppb  during the course  of  the study
     as  measured  by  an  FTS-IR   system  and   a   chemi luminescence   monitor.
     Integrative  sampling  techniques  for  HNO   show approximately  the  same
     levels  and  follow  similar   trends.   The  high  nitrate  concentrations
     measured  on  glass  fiber  filters  correlated  with high  concentrations  of
     HNO ; however these glass  fiber  nitrate values significantly exceeded the
     sum of  HNO  measured by FTS-IR  and  the particle nitrates  as measured on
     the quartz fiber fitlers.  The high nitrates  found  on glass fiber filters
     may be  due  to  nitrate artifacts  caused by  their interaction  with  NO .

3.   The range  of nitrate values collected on both the  fine  and  coarse filters
     (Teflon)  of  an  LBL dichotomous  sampler  range from  1  Mg/m  to 23.5 Mg/n> -
     On  the  average,  coarse   particle nitrate  is  approximately twice  fine
     particle  nitrate.   Table  I  shows other values of interest  from  the LBL
     sampler.

4.   Based  on  preliminary  statistical  analysis   of the HNO.  measurements,
     Hi-vol  data  and  total nitrate measurements,  it appears  the  positive
     nitrate artifact produces  a significantly  larger error in aerosol nitrate
     measurements  than the  negative  artifact  that may occur on  inert filter
     samples .
     In  addition  to nitric acid  and  nitrate  concentrations,  a number of other
air quality  parameters were measured,  e.g.,  0_,  NO,  N0?,  SO^, b    , humidity
and CO.   A careful analysis of the convariance  of  these compounds and nitrate
is expected  to clarify the factors causing nitrate artifacts during sampling.
Table I.  Characterization of  Nitrate  Values  from a LBL Dichotomous Sampler
                             Fine
                                       Coarse
Total
Average ([Jg/m )
Range (pg/m )
Fraction of Total
Fraction of Fine Mass*
1.81
0-11.3
0.31
0.03
3.97
0.9-12.2
0.69
™ ~
5.78
1.0-23.5
1
~ ~
"'"Average fine mass was  42.7  |Jg/m  as  determined by beta gauge.   Fine nitrate/
 fine mass ranged from  0  --  0.12 pg/m  being highest during episodes of reduced
 air quality.

References

Harker,   A.,   L.  Richards,  and   W.   Clark,  "Effect  of  Atmospheric  SO
Photochemistry  Upon  Observed  Nitrate  Concentrations," Atmos.  Environ.  11,
87-91,  (1977).
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Spicer,  C.,  P.  Schumacher,  J.  Kouyoumjian  and  D.   Joseph,  Sampling  and
Analytical  Methodology  for  Atmospheric Particulate Nitrates, EPA-600/2-78-067
(1978).

Stevens,  R.,  T.  Dzubay,  R. Burton,  G.  Russwurm  and  E. Tew,  "Comparison of
Hi-Vol and Dichotomous Sampler Results on Nitrates and Sulfates, "Preprint for
the  the  Division  of  Environmental  Chemistry,   American   Chemical  Society,
September.  Paper No, 98, (I978a).

Stevens, R. ,  T.  Dzubay,  G.  Russwurm  and D.  Rickel,  "Sampling and Analysis of
Atmospheric Sulfates and Related Species," Atmos.  Environ. ^2, 55-68, (1978b).

Hare, R. , M.  Wininger,  and W. Ross,  "Selective Collection  and Measurement of
Gaseous  HNCL  in  Ambient Air,"  In  "Current Methods  to Measure  Atmospheric
Nitric Acid and Nitrate Artifacts,"  edited by R.K. Stevens, EPA-600/2-70-051,
U.S.  Environmental  Protection  Agency, Research  Triangle Park,  N.C.  (1979).

Shaw, R. ,  T.  Dzubay  and R. Stevens,  "The Denuder Difference Experiment," In
"Current Methods  to Measure  Atmospheric  Nitric  Acid  and Nitrate Artifacts,"
edited  by  R.K.  Stevens,  EPA-600/2-70-051,  U.S.  Environmental  Protection
Agency, Research Triangle Park, N.C.  (1979).

B.   Source Apportionment Studies

     Federal,  state and  local  agencies  generally  use  atmospheric dispersion
models  to  provide  guidelines  in the  control  of  particulate  loadings in the
atmosphere.   These   source-oriented  dispersion   models  based  on  emission
inventories  and  meteorological  parameters,  were  developed  to  predict  the
impact of a particulate emission source on a receptor site.

     An  alternative to  the  predictive  dispersion  models   to  assist  in  air
quality  management  is   the application  of  receptor  oriented  models.   The
Chemical Element  Balance (CEB)  Model is  one type of  receptor  model that has
been widely used  over the past ten years to measure the  impact of particulate
sources on air quality  (1-3).

     These  CEB  models  assume  that  the elemental  composition of  ambient
particles  collected  at  a   receptor  site  is  a  linear  combination  of  the
components  of  the  particulate matter originating from  various  sources.   In
theory,  knowledge of the  elemental  composition  of  the  ambient air  particles
and  the  emissions of all  important sources  permits the  solution  of a set of
simultaneous equations which will provide, quantitatively the contributions of
each source of the aerosol to a selected receptor.

     In practice, the information is  never as complete or reliable as desired,
so  the   assumptions  that go  into  the model must be  simplified.   Typically,
rather  than  use  all the emission  data  from  each  source, a  set  of marker
elements is used  to characterize a  few prominent  sources.  The marker elements
are  normally  those  that  are  strongly  associated  with  specified sources,
examples  are  lead  and  bromine with motor vehicles, sodium  with sea salt and
vanadium or nickel with combustion  of fuel oil.

     Kowalczyk,  et  al  (4),  Watson  (5) and  Dzubay  (6)  have reported  results
from CEB  analysis on filters  collected from  networks  of samples  in  the three

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cities, Washington, D.C., Portland, OR and St. Louis, MO respectively.  Watson
and  Dzubay analyzed  aerosol that  was fractionated  into  two  size  ranges  to
separate primary  from  secondary aerosols.  Figure 1 is a figure from the work
of Dzubay  (6) which shows  a comparison of the  average mass concentration  in
the  coarse fraction  (particles >2.5  pro) and  the  components  deduced  in the
chemical element balance.  The corresponding fine fraction was mainly composed
of sulfate.

     These previous applications of CEB to source apportionment studies suffer
from  the  following  shortcomings  (1)  all major sources contributing  to the
ambient  aerosols  at  the time of the study were not well characterized  (2) the
computational methods  used  had  not been verified nor  their sensitivities  to
variations in input  parameters  established and  (3) ambient and source aerosol
characterization was incomplete.

     Whereas  CEB  methods apply  knowledge about  source characterization to a
relatively small set of filters to derive a source contribution, multi-variate
analysis methods,  such as  factor analysis pattern recognition methods extract
information about  a source  contribution on  the basis of  the variability  of
elements measured  on  large  numbers of filters.  In  factor  analysis,  data  on
the  concentrations  of  each element  in  each  sample  of   the  data  set are
manipulated to  find  groupings of variables (common factors)  that best explain
the variations of elemental  composition from their average values.

     Factor  analysis  has  been  applied  by  Hopke et  al (7)  to  a  set  of  18
elements in 90  samples from  the Boston area. From this data  set, 77.5 percent
of  the  variance  could  be   accounted  for by  six common  factors.   From the
composition of  the factors  primary airborne particles  could be attributed  to
several  sources:   soil mixed with emissions from coal  fired  power plants, sea
salt,  combusion  of  fuel  oil, auto  emissions  and incineration of  refuse.  A
sixth  factor, with large loadings for only manganese and selenium could not  be
identified with a particular  source.

     Factor  analysis  has  several  advantages  over  CEB in   that no a priori
assumptions  need  to be made about  either the  number  or composition  of the
sources.   Thus,  secondary   particles  that  become   associated with  primary
particulates  between   release  and  collection  can  be  incorporated   in the
analyis. For example Gaarenstroom (8)  found that sulfate, ammonium and nitrate
ions in  the ambient aerosol  can be included in factor analysis.

     The major  weaknesses  in factor analysis is that  it  requires  a data set
where  there   are  large variation  in the  concentration of  the elements from
sample to  sample.   In  addition factor analysis can only provide information  on
the  number of  sources contributing to  a receptor  but not  the  magnitude  of
their  contribution.

     The source of aerosols  can also be determined by microscopic methods  (9).
These methods have high resolving capabilities for sources with characteristic
morphological features  such  as wood  fiber, pollen, quartz, mica and  tire  dust.
To be  quantitative,  however, one must estimate  the number of particles,  their
density  and volume and must  analyze enough  particles  to be  representative  of
the total  sample.
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      Microscopic  methods  can  be  divided  into  two  categories:  optical,  which is
 generally  limited  to  particles  greater  than   1  pro, and  scanning  electron
 microscopy  (SEM)  which  is  applicable  to  smaller particles.

      Recently  Lee et al.  (10) coupled  an SEM with an energy dispersive x-ray
 fluorescence  system and automated the  instrument to  scan and  analyze  a large
 number  of  particles.   The system  promises  to extend  the  general  applicability
 of microscopic methods.

      Davis  (11)  has applied  x-ray transmission  and diffraction  techniques to
 the analysis of hi-volume  filters  collected in Rapid  City,  S.D. These  analyses
 revealed that  a  majority  of  the aerosol pollution in  Rapid  City was  a result
 of emissions from quarrying activities  near the city.   These  x-ray diffraction
 techniques  show  promise of being  able  to quantitatively  measure  the source of
 aerosol  pollution  in  variety of  urban  locations where reentrained dust  is a
 major aerosol pollution problem.

 References

 1.    Miller,  M.S.,  Friedlander,  S.K.   and  Hidy,  G.M.,  "A  Chemical  Element
      Balance  for  Pasedena Aerosol,"  Journal  of Colloid and Interface  Science,
      39  (1), 165  (1972).

 2.    Friedlander, S.K.  (1973) Chemical  element balances  and  identification of
      air pollution  sources.   Environ. Sci.  and Technology 7:235-240.

 3.    Gatz,  D.F.   (1975)  Relative  contributions of different sources  of urban
      aerosols:   Application  of  new  estimation  method to  multiple sites in
      Chicago.  Atmos. Environ. 9:1-18.

 4.    Kowalczyk,  G.S.,  C.E. Choquette, and  G.E. Gordon (1978) Chemical element
      balances  and identification  of  air pollution sources  in Washington,  D.C.
      Atmos. Environ.  12:1143-1153.

 5.    Watson,  J.G.,  Jr.  (1979)  Chemical  Element  Balance Receptor Methodology
      for Assessing  the Sources  of Fine  and Total Suspended Particulate Matter
      in  Portland,  Oregon.  Ph.D.  Thesis, Dept.  of Chemistry,  Oregon  Graduate
      Center, Beaverton.

 6.    Dzubay,   T.G.    (1979)   Chemical   element   balance  method   applied  to
      dichotomous  sampler  data.   In Proceedings  of the Conference on  Aerosol:
      Anthropogenic  and  Natural   — Sources  and Transport.   New York:  New York
      Academy of Sciences.  (In press).

 7.    Hopke,  P.K.,  E.S. Gladney,  G.E.   Gordon,   W.H.  Zoller,  and  A.G.  Jones
      (1976) The  use of multivariate  analysis to  identify  sources of  selected
      elements  in  the  Boston urban  aerosol.  Atmos.  Environ.  10:1015-1025.

 8.    Gaarenstroom,  P.O.,   S.P.  Perone,   and J.L.  Moyers  (1977) Application of
      pattern   recognition and    factor  analysis   for  characterization  of
      atmospheric  particulate  composition in  the Southwest Desert atompshere.
      Environ. Sci.  STechnol. 11:795-800.
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9.   Graf,  J.,   R.H.  Snow,  and  R.G.  Draftz  (1977)  Aerosol  sampling  and
     analysis -  Phoenix, Arizona.   EPA-600/2-77-015:   Washington, B.C.,  U.S.
     Environmental Protection Agency.

10.  Lee, R.J.,  Fasiska, E.J.,  Jonocko,  P., McFarland,  D.  and Penicala,  S.,
     "Electron Beam  Particle  Analysis," Industrial Research/Development,  June
     1979, pp 105.

11.  Davis,   B.L.  Additional  Suggestions  for X-ray Quantitative  Analysis  of
     High Volume Filter Samples, Atmos. Environ, 12,, 1403-1406  (1978).

C.   Measurement of Visibility

     In  response  to  requirements of  the 1977  Clean  Air Act  Amendment,  the
Environmental Protection Agency is  considering  the  feasibility of a standard
for visibility  that is  based upon  the mass  concentration of fine particles.
In considering  such  a  standard, a measurement  method  for defining visibility
must  first  be  selected.   Several   methods  to  measure visibility exist,  but
there is  only a limited amount of data showing  how the methods compare.   IPAB
is  conducting  tests  in  Houston   to  determine  the  relationships  between
visibility data  determined by  a human  observer,  an integrating  nephelometer
and a telephotometer.   In addition,  these data  will be compared with mass  and
compositional data  obtained for aerosols collected  in a dichotomous sampler.

     Although human  observers and integrating  nephelometers have been widely
used  in  the   past,  the telephotometer  method is  fairly  unique.   This method
utilizes  a telephotometer  to  measure the relative brightnesses of the horizon
sky and  a black  object.   In  the  IPAB study, the black  object consists of  a
black box with  an aperture located  500  meters  from the  telephotometer.   From
the  known   distance  and  the  measured  contrast,  the  visibility  can   be
calculated.

     The  compositional  measurements  will  be   sufficiently  comprehensive  to
enable degradation  in  visibility to be apportioned  to chemical species.   The
measurements  will include determination of fine  and coarse mass, total carbon,
trace elements,  sulfate and related  cations.  In  addition,  the light absorption
coefficient of the aeorsol will be determined.
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CALIBRATION OF OZONE INSTRUMENTS IN THE U. S.
        presented by  Richard J.  Paur



       Environmental  Protection  Agency

                 United States
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              TECHNICAL NOTE — INORGANIC POLLUTANT ANALYSIS  BRANCH




                  CALIBRATION OF OZONE INSTRUMENTS IN THE U.S.




                                 Richard J. Paur


                   Environmental Sciences Research Laboratory


                      U.S. Environmental Protection Agency


                       Research Triangle Park, N.C. 27711




     From the inception of EPA's monitoring programs for ozone  until  early


1979 the 1% neutral buffered potassium iodide  (NBKI) method was used  to assay


ozone calibration atmospheres.  The NBKI method was widely criticized for its


inconsistent results and  in 1974 the EPA began examining other  methods for


assaying the calibration  atmospheres.




     Two forms of gas phase titration, a modified version of  the potassium


iodide method and ultraviolet absorption photometry were studied in detail.


In gas phase titration ozone is reacted quantitatively  with known


concentrations of nitric  oxide and  the ozone concentration  is calculated from


either the decrease in nitric oxide  (excess NO version) or  the  decrease in


ozone (excess ozone version).  The modified version of  the potassium iodide


method used boric acid as a buffering agent and  included pretreatment of the


solution with a small amount of hydrogen peroxide  to  consume  any reducing


agent present as impurities.  The ultraviolet  photometric method measures the


attenuation of 254 nm radiation by  ozone's  strong  absorption  band in the


200-300 nm region.
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     All of the above methods were run through  intensive  single-scientist


studies and were demonstrated to be precise, reliable,  and  in  excellent


agreement with a UV photometric procedure under research  lab conditions.


Tentative detailed method write-ups were completed  and  the  methods  were


subjected to a collaborative test procedure.  The collaborators  were chosen to


be representative of the user community.  During the  test all  measurements


were referenced to a battery of ozone analyzers which were  calibrated with a


UV photometer which had been demonstrated to give stable, precise results.




     Relative to study reference systems, the collaborators obtained results

biased approximately 7% high when using gas phase titration.   The standard


deviation of the slopes obtained from 20 comparisons  (two from each of 10


different systems) of the gas phase titration systems and the  house reference

system was 3.8%.




     The boric acid potassium iodide systems were biased  an average of 5% low

with a standard deviation of the slopes equal to 7.1%.




     The photometric systems yielded an average bias  of 0.4% and a standard


deviation of the slopes of  only  1.2%.




     The ultraviolet photometric technique was  chosen to  replace the NBKI


method as the Federal Reference  Method  for the  calibration of ozone monitors


due to its relatively high  precision and the  fact  that  it did not show any


significant bias when used  by the  collaborators.  The new method was put  into


effect in February  19791.
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     In addition to establishing  the  photometric  procrdure as the Federal

Reference Method for calibrating  ozone monitors the  EPA also established rules

for allowing the use of other calibration methods.   The rules were prescribed

in terms of the performance  specifications  that the  other methods, referred to

as transfer standards, had to meet  in order to adequately relate their results

to photometric assays.



                                                  2 3
     To support the new regulations two  documents '   were prepared.  The first

document, "Technical Assistance Document for the  Calibration of Ambient Ozone

Monitors," deals with  the theory  of photometric measurements, contains a

step-by-step discussion of the ultraviolet  photometric calibration procedure

and gives some information on sources of suitable photometers.




     The second document deals with the  concept of transfer standards, the

utility and scope of the standards, and  prescribes the specifications of the

standards.




     In continuing support of the new photometric calibration method EPA is

working with the National Bureau  of Standards to  establish a small national

network of ozone calibration photometers which will  be available to the user

community as a means of verifying that  the  users  calibration equipment is

giving accurate results.  The network,  consisting of some 10-15 instruments,

is scheduled to be available in  September 1982.
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REFERENCES




1.   Federal  Register, 44:8221, February  8,  1979.




2.   "Technical Assistance Document  for the  Calibration of Ambient Ozone

     Monitors,"  Richard J. Paur and Frank F.  McElroy, EPA/RTP,

     EPA-600/4-79-057, September 1979.




3.   ''Transfer Standards for Calibration  of  Air Monitoring Analyzers  for

     Ozone,"  Frank F. McElroy, EPA/RTP, EPA-600/4-79-056, September  1979.
       PROCEEDINGS—PAGE 116
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           THE COLLECTION AND ANALYSIS OF

HAZARDOUS ORGANIC  EMISSIONS FROM  INDUSTRIAL  SOURCES
            presented  by Kenneth  J.  Krost



           Environmental Protection  Agency

                     United States
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                           THE COLLECTION AND ANALYSIS
                         OF HAZARDOUS ORGANIC EMISSIONS
                             FROM INDUSTRIAL SOURCES
                                Kenneth J. Krost
                         Environmental Protection Agency
                     National Environmental Research Center
                        Research Triangle Park, NC  27711
                                Edo D. Pellizzari
                           Research Triangle Institute
                        Research Triangle Park, NC  27711
                             Stephen G. Wai burn and
                                Sarah A. Hubbard
                             Northrop Services, Inc.
                        Research Triangle Park, NC  27711
 Abstract
     Over the  past  five years,  the Environmental  Protection Agency has been

developing, under contract with the Research Triangle Institute, the analytical

capability to  collect,  characterize and quantitate volatile organic compounds

present in typical  ambient air  environments.


     This paper summarizes the  progress made on this development and the

results of some selected exploratory monitoring.   The analysis system described

encompasses the collection and  concentration of organic pollutants from

ambient air using tubes  packed  with polymeric beads.  The cartridges after

sampling are then thermally heated under He, the  compounds desorbed, trapped

and subsequently introduced into  a high resolution glass capillary (SCOT)

column.
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  Introduction


       Carcinogenic vapors  have been postulated  to occur in the atmosphere.


  Until  the  present program was initiated  no  serious  or thorough endeavor had


  been made  to collect and  determine these substances.




      The National  Academy of  Sciences  panel  in a study of the Biological


  effects of atmospheric  pollutants  has  concluded and recommended in their  report


  on Particulate  Polycylic  Organic Matter  "Research is  needed on the chemistry


  and biological  activity of air  pollutant cocarcinogens and tumor-promoting


  agents, such  as polyphenols and paraffin hydrocarbons, and on the  oxidation


  products of airborne  olefins  and aromatic hydrocarbons,  including  the  nature


 of the epoxides, hydroperoxides, peroxides,  and  lactones  formed and their


 biological properties".       Recently, Van  Duuren        summarized a review on


 the biological  properties  of  carcinogenic vapors with  the statement "in view


 of the obvious  importance  of  these aliphatic compounds (epoxides,  hydroperoxides


 and peroxides}, it is imperative that  studies  be undertaken on the analysis


 of volatile organic air pollutants".   Once  the identity of the physiologically


 active vapors present in polluted atmospheres  are known,  then investigators


 can ascertain which substances need to be routinely analyzed, studied  epide-


 miologically and eventually controlled.



      The primary mission of this research program has  been  to develop  methodology


 for the reliable and accurate collection and analysis  of  mutagenic and


 carcinogenic vapors present in the atmosphere  down  to  nanogram per cubic meter


 amounts.



 Experimental


      Apparatus.   Figure 1  schematically  illustrates the basic  collection and



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 analysis system.   A Varian MAT CH-7 glc/ns/comp system was used to perform


 the analyses.   Typically the mass spectrometer was first set to operate in


 the repetitive scan mode.   In this mode, the magnet was automatically scanned


 upward from a  preset low mass to a high mass value.  Although the scan range


 may vary depending on the particular sample, typically the range was from m/e


 23  to m/e 400.   The scan was completed in 1.5 sec.  The instrument then reset


 itself to the  low mass  position in preparation for the next scan.   The information


 was  accumulated  by an on-line 620/L computer and then was transferred to magnetic


 tapes.   The reset period required 1.5 sec.   Thus a continuous scan cycle of


 3 sec was maintained.



      Prior to  running known  samples,  the system was calibrated by  introducing


 a standard substance, such as perfluorok'ercsene into the instrument and


 determining the time  of appearance of known  standard peaks  in relation to


 the  scanning magnetic field.   The calibration curve which was generated was


 stored  in the  620/L computer memory.



      With the magnet  continuously scanning,  the sample was  injected and


 automatic data acquisition initiated.   As each  spectrum was  acquired  by the


 computer,  each peak which exceeded the  preset threshold was  recognized and


 reduced  to  centroid time and  peak intensity.   This  information was stored


 in the computer core while the  scan was  in progress.   Samples were analyzed


 using a  variety of capillary  columns  and analyses  conditions  as  summarized in


 Table  1.   A single stage glass  jet separation was  maintained  at  240CC and  used


 to interface with a SCOT capillary column to  the mass  spectrometer.



      Identification of  the constituents  in the  samples  was  established by


comparing  the mass cracking  pattern of  the unknown  mass  spectra  to an Eight


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   Peak index and  to  the Wiley Collection.   In many cases, the identification


   was confirmed by comparing the mass cracking pattern of an authentic compound


   run under identical conditions to that of the unknown.



        The elution temperatures were also compared based on the chrcmatography


   of the authentic compound under identical  conditions to the unknown.  In


   some cases,  the identification was achieved  using a computer based mass


   spectral  search system  and/or the  PSM/Stirs  system located at Cornell University.



       Utilizing  either the  total  ion current  monitor when  the constituents


  were adequately  resolved or the  use of  mass  fragmentogrsms when not, the


  concentration of each substance was determined.   In order  to eliminate the


  need to obtain complete calibration curves for each compound,  we used the


  method of relative molar response factor.
       A Nutech Model  221-A AC/OC sampler (Nutech Corp, Durham, NC} was  used


 as the sampling apparatus  for Tenax cartridge samples.   At  times the


 DuPont personal  samplers  (E.  I.  Dupont de Nemours, Wilmington, De.), were used


 for  long  term sampling  (8 hours  or  greater).   Capillary traps were constructed


 of Nr tubing,  0.02-0.04"  internal diameter, in lengths of from 0.25m to 1.5m.


 The  six port  high  temperature  low volume  valve (Valco Inc., Houston, Tx.),


 was  used  for  sample  introduction.



      Cartridges used to concentrate organic vapors consisted of a 1.5 x 6.0cm


 bed of Tenax GC (35/60).  All  sampling cartridges  were pre-conditioned by


 heating to 275°C fora period  of 20 minutes under  a helium purge  of 20-30 ml/~.in.


 After cooling in predefined Kimax  culture  tubes,  the  containers  were sealed to


 prevent contamination of the cartridges during transportation  and storage.



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ANALYSIS, RESULTS AND  DISCUSSION
Quant1tatiyjB and Qua!i tati ve Assessment of N-N Pi methyln i trosamine 1n
Ambient ATr '''


     The detection and  identification  of N-N  Dimethylnitrosamine in ambient


air has been reported in  Baltimore,  Md.  (Tables 2,3),  and  Belle, West Virginia.


The potency of N-N Dimethylnitrosamine (DMN)  as a  carcinogen has been


established in several  experimental  animals such as mice,  hamsters, guinea


pigs, rats, rabbits and several  species  of fish.   Using  the above mentioned


technology, unequivocal identification and confirmation  was achieved for DMN


in Baltimore, Md. and Belle, West  Va.   The highest DMN values seen were

                                     •3
in Baltimore and reached  32,000  ng/m  at the  FMC industrial site, Figure 2.


The values observed for Belle, West  Va.  were  on the average three orders of


magnitude less than those seen in  Baltimore,  Md.


Qualitative and Quantitative Assessment  of Volatile Pollutants Near a
Chemical Waste Disposal Site


     The objective of this  study was to  determine  the  composition and


concentration of organic  volatile  compounds occurring  in ambient air near


a chemical waste disposal operation.   Figure  3 illustrates schematically


the general area sampled.   Large quantities of chemical  wastes were known


to be dumped at this location over past  years.


     The sampling strategy was designed  in order to obtain information as to
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 whether  significant pollution of the ambient air in this geographical  area
 might  be occurring  as  a  result of the chemicals which were disposed of at this
 dump site,   The  sampling strategy surrounding the disposal site incorporated
 upwind,  downwind and crosswind sampling.   In addition, sampling on the top
 of the dump  mound itself was  done,  in an  effort to ascertain which organic
 compounds were emanating from the landfill  itself.   The ambient air samples
 were collected according to the previously  described procedures.   Collected
 samples  were submitted to a glc/ms/comp analysis for organic compound
 characterization.   The general  analytical protocol  for this analysis has been
 previously described,  Table 1.   Samples were analyzed on a 100 m glass SCOT
 capillary coated  with  OV-101  stationary phase and/or a 50 m glass SCOT coated
 with Carbowax 20M.   The  capillary column  was programmed from 20-240°C  at
 4°/min for the OV-101  and from 80-240°C at  4°/min for the Carbowax 20M.   Each
 sampling period  was  approximately 2  hours in duration with a volume of 100-
 150 liters collected.  The sampling  system  for the  collection of ambient air
 pollutants including vinyl chloride  consisted of a  Tenax cartridge and an
 SKC Carbon cartridge in  tandem.

      The identity  of  some representative compounds in the samples obtained
 from upwind  and  downwind  positions as  well  as on top of the chemical dump
 are listed in Table  4.   After comparing the results obtained for each  of the
 samples  surrounding  the  chemical  dump  site,  compounds were selected for
quantification based on  their presence only in samples obtained either on the
mound,  downwind  from the  chemical dump site,  or their extraordinary high
 concentration.
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      Very high concentrations of benzene, dichloromethane, toluene, vinyl


 methyl  ether,  vinyl  isopropyl ether and methyl chloroform were observed.   In


 addition to several  chlorinated hydrocarbons, methylene bromide was identified.


 It was  the only time we detected this compound in our atmospheric studies.



 Collection and Characterization of Ambient^AirPollutants from the Plaquemine
 Louisiana Area


      The Plaquemine, Geismar and Baton Rouge, Louisiana areas were chosen


 because  of the high  concentration of synthetic organic chemical  producers and


 petroleum refining operations located along  the Mississippi  River.  Also a


 high  incidence of cancer for this region has been reported.       This area


 provided  an  excellent opportunity for further methods development, identification


 of possible  toxic organic chemicals,  and characterization of pollution profiles.


 Figure 4 shows the general  area and  locations sampled.



      The  potential emissions  and plant locations  were examined and it was


 decided  that essentially four areas would be studied.   These  areas included


 clusters  of chemical  producers  just north of Baton  Rouge,  the downtown complex,


 and the  industrial areas  near Plaquemine and Geismar  which are down  river from


 Baton Rouge.



     All  ambient air  sampling was  done  off industrial  site properties.



     The organic pollutants were  concentrated  on  duplicate Tenax  GC  cartridges

                                                                            D
 in tandem with carbon cartridges.  Sampling  cartridges  were stored in  Kimax


cultured tubes before and after  loading  to protect  them from  contaminated vapors.


The preparation procedures  used were  as  previously  described.  Samples were taken


using either DuPont personnel samplers or  Nutech  samplers  at  approximately 1  1/min.


A Meteorological Research Incorporated weather station  was used to orovide continuous



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 readout of wind  direction,  speed,  humidity,  and  temperature  at the sampling  site,

       Because of the  sprawling  chemical  facilities,  it  was not possible to
 thoroughly sample all  sites,  but  instead selected  sampling was conducted.  Much
 of the chemical  activity  is associated with  the  production of  halogenated
 hydrocarbons and assorted fine  chemical  products.  The  availability of chemical
 emission data provided a good opportunity to apply the  collection  and analysis
 methods previously developed.

      The results for  Plaquemine  (Iberville  Parish),  are  shown in  Table 5.
 Twenty-two halogenated hydrocarbons were quantified  at  eleven  locations.   In
 addition, we quantified benzene at the same  locations.  Of particular interest
 was the large number and concentration of halogenated hydrocarbons observed.
 The highest level observed was  for 1,1,1-trichloroethane  at  8,760  ng/m .

      Furthermore, at  location  No. 7, we found the highest concentration of
                                     3
 bis-2-chloroisopropyl ether (363 ng/m  ).   The highest level  of benzene
 occurred at location 8 (16,077  ng/m  ),   In contrast,  an upwind sample (Location
 No. 11) from the  chemical industrial complex contained  421 ng/m of halocarbon
 pollutants.  Interest  in the analysis of ambient air  from Baton Rouge,  La. was
 again based on the magnitude of the chemical  industry located  there.   Much
 of the chemical  emission is again  associated with  the production of halogenated
 hydrocarbons.  In addition to the  chemical industry,  an incineration  facility
was sampled near Baton Rouge.   This facility destroys aliphatic hydrocarbons,
 aromatic hydrocarbons, alcohols, viscous  oils, polyglycols,  tars,  chlorinated
 aliphatics, chlorinated benzenes and other aromatics, waxes  and rubber.
 The waste materials treated are of a diverse origin.  The collection

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 of ambient  air samples near the facility provided useful  information as to the
 potential emissions associated with the incineration of chemical by-products,
 particularly  halogenated compounds.
     A  summary of the organic compounds identified indicates a total  of IS
 halogenated hydrocarbons and 25 oxygenated compounds were identified in these
 samples.  The predominant halogenated compound was chloroform which was found
 at considerably higher levels throughout all  sampling periods and at all
 locations,  relative to other halogenated compounds.   Table 6 presents the
 minimum halogenated hydrocarbon values seen for this area.  In some cases,
 the minimum exposure levels reached 10,000 ng/m .
     A  fourth major environmental  situation investigated  was the Love Canal
 area in Niagara  Falls,  NY.   Figure 5 schematically illustrates the area
 sampled.  The Love  Canal  was an old landfill  used  by several  companies back
 as  far  as the 192Q's as  a dumping  ground for  chemical  residues.   Subsequently
 this area was covered and suburban housing constructed over the  landfill.   In
 recent years  due  to the  corrosion  of the drums,  the  chemicals have come to
 the surface and  the residues began leaching into  the basement sumps of
 surrounding housing.   Two sampling and analysis  techniques were  used, one for
 volatile organic  compounds  and  the other for  the  semi-volatile compounds  such
 as polychlorinated  biphenyls.
     This protocol  was adopted  because of uncertainties as to exactly what
was dumped  in  this  area.  The general  analysis  parameters  for the volatile
compounds are  given  in Table 1.  A 100 m SE-30  glass  capillary column was  used
 for the chromatographic  separations.   The specific analysis parameters for
polychlorinated biphenyls and other semi-volatile  organic  compounds are given
in Table 7.
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       Ambient air samples were taken in 11 homes and 1  elementary school
  along the Old Love Canal area of Niagara Falls, NY and in 1 elementary school
  in a nearby neighborhood between February 7, 1978 and  Thursday February 9, 1978.
  Table 8   summarizes  the volatile organic vapors collected on Tenax GC cartridges
  which were detected in air from household basements and school rooms in
  Niagara,  NY.   A  total  of 42 halogenated compounds were identified.

       Eleven of these  represented halogenated hydrocarbons, some of which were"
  "site specific"  compounds.   These were pentachlorobutadiene, 1,3-hexachloro-
  butadiene,  1,2-dibromoethane and 1,2-dichloropropane.   The remaining halogenated
  hydrocarbons  were  present in only trace quantities and probably are representative
  of a  ubiquitous  background  normally observed during sampling of ambient air.

       A  total  of  31  halogenated  aromatics were present.   The majority of compounds
  were  primarily chlorinated  benzenes and toluenes.

       Other  compounds  identified  were esters,  ethers, aldehydes,  ketones,  alcohols,
  and acids.  At the  No.  1  location chloronaphthalene, pentachlorotoluene and
  dichloroaniline were detected on polyurethane foam.  At location 2, t\vo isomers
 of hexachlorocyclohexane were identified as  well  as pentachlorotoluene  isomers,
  hexachlorobenzene,  hexachlorotoluene,  dichlorobiphenyl  (tentative), chlorobenzo-
  fluorene  (tentative) and heptachlorotoluene.   In  addition  to chloronaphthalene,
 hexachlorocyclohexane,  pentachlorotoluene, we identified dichlorophenol,
 trichlorophenol and trichloroaniline  (tentative)  for the ambient air sample
 taken at location 4.  The sample obtained at  location  6 contained additional
 new compounds which were dichloronaphthalene  and  pentachlorobiphenyl  (tentative) •

      The levels of  benzene and halogenated organic  vapors  in air which  were
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 collected  on  Tenax GC cartridges from household basements were estimated.


 Significant concentrations  of the majority of the halogenated hydrocarbons were


 found.   The most serious  case occurred for the sample collected at location 6


 in which many of the halogenated compounds occurred in pg/m  amounts.  The


 level of benzene reached  522,697 ng/m .   Also shown is the estimated total


 halogenated organic material  for each of the locations.   The sum of the


 halogenated organics for  the  sample  taken at location 6  was 1,786,636 ng/m .


 The  total  level  of halogenated organics  in the ambient air samples taken at the


 elementary schools (L12A, 13A and 138] was 7,644 ng/m .



 Conclusions and  Discussion


     The reproducibility  of this method  has  been determined to range from +10


 to +30*  of the relative standard deviation for different substances when


 replicate  sampling cartridges were examined.   The inherent analytical  errors


 are  a function of  several factors:   (1)  the  ability to accurately determine


 the  breakthrough volume for each of  the  identified organic compounds, (2) the


 accurate measurement of the ambient  air  volume sampled,  (3} the percent recovery


 of the organic from the sampling cartridge after a period of storage, (4) the


 reproducibility of thermal  desorption for a  compound from the cartridge and its


 introduction  into  the analytical  system,  (5)  the accuracy of determining the


 relative molar response ratios  between the identified substance and the external


standard used for  calibrating the  analytical  system, (6)  the reproducibility  of


transmitting  the sample through  the  high  resolution gas  chromatographic column


and, (7) the  day-to-day reliability  of the ms/comp system.



     The accuracy  of analysis  is  generally +30*;  however, the accuracy of analysis


 is dependent  to some  extent on  the chemical  and  physical  nature of the compounds


analyzed.

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       The overall  system sensitivity attainable is shown in Table 9 and  is
  dependent to  a  large  degree  on the collection efficiency of a particular com-
  pound.
       This  research  program on  the  development of analytical  techniques  for
  measuring  carcinogenic  ambient atmospheric  vapors has  attempted to  furnish a
  comprehensive and systematic approach  to  this problem.   It has attempted to
  develop  and evaluate  the sampling  device, field  collection methodology, and
  the entire procedure  of the  data analysis of  carcinogenic vapors in  the atmosphere.
  Until this research program was initiated,  the ability to collect  from  the
  atmosphere and  analyze  a wide  variety  of chemical  classes which contained toxic
  and/or carcinogenic organic compounds  did not exist.   For this reason,  research
  programs to determine and evaluate  the health impact of carcinogenic compounds
  in the environment had  not been conducted.  Comprehensive studies on the levels
  of carcinogenic agents  in all media  in addition  to  air and the correlation of
  this exposure to body burden and health effects  on  man  could  also not be executed.
  Thus, a well-defined epidemiological approach which is  required in this type of
  study to establish whether an associational relationship  existed has in the past
  suffered from the lack of appropriate  technology in order to  achieve these goals.
      The main reasons for identifying and determining  environmental  carcinogenic
 organics even at low concentrations  are as  follows:
      (1)  A knowledge of the presence and concentrations  of mutagens and
           carcinogens in the air is mandatory for a better understanding of
           genetic diseases and future carcinogenic  and  mutagenic problems
           which  may arise after a long induction  period.
      (2)  If the incidence of cancer in the US is to be understood and
       PROCEEDINGS—PAGE 130
    First US-France Conference on
Photochemical Ozone/Oxidants Dollution

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          controlled,  it will  be  necessary to  determine the concentration
          of environmental  carcinogens.   It is necessary also to understand
          the complete organic composition of  the atmosphere since there are
          antagonistic and  synergistic  relationships,  i.e., anti- and co-
          carcinogenic factors which  may  occur and contribute to the observed
          incidence of cancer.
     (3}  It is known that  higher cancer  mortality rates have been shown to
          occur near various sources  of air pollution.   In statistical  studies,
          it has been demonstrated that cancer associated with the respiratory
          system is higher  where  high air pollution occurs.
     (4)  Recent estimates  indicate that  chemical  synthesis adds some quarter
          of a nillion new  chemical compounds  each year to the several  million
          already in existence.   These  new compounds can be a serious source
          of air pollution  and  may have a significant  effect on the health of
          the human populace.
     (5}  The development of an analytical  technique for measuring carcinogenic
          ambient vapors must  provide a thorough  analytical approach which will
          measure a wide number of potential environmental  carcinogens  and
          mutagens as well  as  their precursors  and various  cofactors and anti-
          factors.
     The development of analytical  techniques  for measuring carcinogenic ambient
atmospheric vapors has attempted  to provide  a  conceptual  approach which will
allow the answering of questions  cited  above in subsequent research programs.
                                                           PROCEEDINGS—PAGE 131
                                                        First US-France Conference on
                                                    Photochemical Ozone/Oxidants Pollution

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                        FLOW METER
                                                                 CARTRIDGE
    GLASS
    FIBER
    FILTER
                                                  PUMP


                                  VAPOR  COLLECTION  SYSTEM
                            CARRIER
                              GAS
                                                               HEATED BLOCKS
                                                           2-POSITION VALVE

                                                                     \      \

                                                                                 PURGE
                                                                                  GAS
                                                                                 THERMAL
                                                                               DESORPT10N
                                                                                CHAMBER
u
                                              CAPILLARY
                                                 GAS
                                            CHROMATOGRAPH
                                                      CARRIER
                                                        GAS
   EXHAUST
                                                                     CAPILLARY
                                                                       TRAP
      Figure 1.  Vapor collection and analytical systems for analysis of orqanic
                 vapors in ambient air
         PROCEEDINGS—PAGE 132
     First US-France Conference on
Photochemical nzone/Oxidants Pollution

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                             EAST BROOKLYN,
                         BALTIMORE, MARYLAND
                 GHESS1E
              COAL PIERS
                                         CURTIS  BAY
                                               SCALE: ONE INCH =0.5 miles
Figure 2-    >'ap of  sampling area  in East Brooklyn, Balrinora, Maryland
                                                 PROCEEDINGS—PAGE 133
                                              First US-France Conference on
                                          Photochemical Ozone/Cxidants Pollution

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         PROCEEDINGS—PAGE 134
     First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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Figure'*. */aps snowing locations  of ambient air sampling si:es in Louisiana, Upper
rr.ap is  an arsa near Baton Rouce, lower left is an area in Ibervii'.e Parish,  lower
right is 3 detail of  Industrial Co'mpiex  within 'eft map.

                                                                PROCEEDINGS—PAGE 135
                                                            First US-France Conference on
                                                        Photochemical Ozone/Qxidants Pollution

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 Figure 3.  .Vap  of  Buffalo •  Niagara Falls, NY, area with  inset showing placement  of
 sampling sites  near  Gld  Love Canal.
        PROCEEDINGS—PAGE 136
     First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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    "abie 1.  SENE3AL :F£?jVr:.v!G 3iSAMET-SS  "03  SLC/^S/CCfPUTES  SYSTEM
                                                             Se-tina
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OV-T01 glass  SCOT (1CCM)
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3£'3S glass  SCOT (55M)
          2 CM  glass  SCOT (3SM)
 20-225'C, 4'C/siin,  4
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single staca  glass  jet
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fi'ament curranz
   x  1C"0 torr
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scan rats,
scan ranee
 1  sec/decade
 .•n/e  20 - iOO
                                                             PROCEEDINGS—PAGE 137
                                                          First US-France Conference on
                                                      Photochemical Ozone/Qxidants  Pollution

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     First US-France Conference  on
Photochemical  Ozone/Oxidants  Pollution

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     First US-France Conference on
Photochemical  Ozone/Oxldants  Pollution

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     First US-Franci Conference on
Photochemical  Ozone/Oxidants  Pollgtion

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     First US-France Conference on
Photochemical  Ozone/Oxidants Pollution

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                                                                             First US-France  Conference on

                                                                        Photochemical  Ozone/Oxidants Pollution

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r
                         Table 6.  MINIMUM TOTAL HALCGENATED  HYDROCA33CN VAPOR  IN

                                       AMBIENT AIR OF SATCN P.OUGE.  LA
Location
LI 7
L18
LI 9
L20A- • •
L21
L22 ;
L20B
L23
L24
' ng/mJ
10,976
10,326
2,349
7S2
7,154
553
2,132
3,930
3,083
Location
L25A
L25A
L27
L23
L253
L253
L29
LE
L30
ng/m'3
11,797
- 1,925
1,455
5,517
9,407
2,559
709
10,003
1,387
                                                                              PROCEEDINGS—PAGE  US
                                                                          First US-France Conference on
                                                                      Photochemical Ozone/Oxldants Pollution

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     Table  7.   SAMPLING AND ANALYSIS  FOR POLYCHLORINA7ED  3IPHENYLS AND OTHER
                       SEMI-VOLATILE ORGAN!CS  IN AMBIENT AIR
  1.0   PROCEDURE FOR CLEANUP OF POLYURETKANE FOAM  PLUGS
  1.     Cut 5 cm diameter x 13 cm long plugs from sheet of  Olympic"2315
        polyurethane foam,
  2.     Mark each plug with an identification number  in the top  using  a
        hot wire.
  3.     Place four plugs in bottom of clean four liter beaker, add  EDO ml
        hot toluene (100°C).
  4.     Compress the plugs 10 times using a one liter Erlenmeyer flask.
  5.     Let sit five minutes  on steam bath.
  6.     Repeat Steps 4 and 5.
  7.     Compress the plugs and decant the toluene.
  8.     Add 250 ml  fresh,  hot toluene and repeat Steps 4 through 7.
  9.     Repeat Step 3 three times (total  of five extractions).
 10.     Using  clean tweezers,  transfer each plug into a foil-wrapped wide-
        mouth  jar and cover loosely with  a foil-lined cap.
 11.     Dry in vsc-jg at  50° for 12  hours.
 12.     Remove from oven,  tighten cap and store  eway from potential contaminants.
  2.0    PROCEDURE FOR EXTRACTION  OF POLYCHLCRINA7ED  3IPH-NYLS FRCM POLYURETHANE
        FOAM PLUGS  AND GLASS  FIBER  FILTERS
  1.     Using  cleaned tongs,  remove foam  plugs  and  filters frcm  storage
        jars and  place them in  400  ml  beakers.
  2.     Add  150  ml  of toluene  to  beakers  containing  foam plugs and 50 ml
        toluena  to  beakers  containing filters.
  3.     Compress  the  foam  plug  10 times to the bottom of the beakers with a
        125  ml  Erlen-eyer  flask,  soak for  five minutes and compress an additional
        10  times.
 4.     Squeeze  the  toluene out of  the plug and  decant into a flat bottom
        boiling  Task.   Similarly decant  the toluene frcm  the glass fiber
        filter  into  a separate  flask.
  5.     Repeat  Steps  2 through 4  two  rr.ore  titles.
 5.     Concentrate  in a flat bottcm  boiling flask topped  with a  Snyder
        column  to approximately 15  ml.

       PROCEEDINGS—PAGE U6
    first US-France Conference en
Photochemical Ozone/Oxidants Pollution

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                              Table 7.   (cant'd)
 7.     Transfer  concentrate to 1.5 x 120 mm culture tubes, assuring  quanti-
       tative  transfer  with small  portions of petroleum ether.  Slow down
       under N-  at  <25°C  just to dryness,
 8.     Dilute  to  approximately 1 ml  with hsxane and proceed with co'-jinn
       cleanup.
 9.     Concentrate  column eluant with a Kuderna-Danish (K-Q) apoaratus
       to  2.0  ml.
 3.0    COLUMN  CLEANUP PROCEDURE
 1.     Silica  gel (Davison  Chemical  Division, H. H. Grace, Baltimore, MD).
       Grade 923, 100-200 mesh is  washed with toluene, followed by hexane,
       dried at 130° for  16 hr and stored  in a sealed amber bottle.
 2.     Using a 1.0  x 30 en  glass column, pack with a plug of class wool,
       silica  gel in a hexane slurry to 10 cm height, and 1.0 C.TJ Na-SQ^.
 3.     Wash column  with 50  ml  hexane to settle the bed and clean any  residual
       contaminants.
 4.     Transfer sample to column in  1.0 ml  or less solvent (preferably
       hexane) with washing.
 5.     Elute the PCS's with  50  ml  hexane.
 6.     The foam background  and  pesticides  are eluted with toluene.
 7.     Concentrate  hexane eluate in  K-D apparatus, followed by nitrogen
       blew down if necessary to achieve a  detectable concentration.
3.    Analyze by GC/ECO  or  GC/MS  as  described elsewhere.
4.0    IAS C-.=CMATOGaA?HY/MSS  S?£C75GME7t3 ANALYTICAL C^DITION'S
       Instrument:  rinnigan  3200  Quadripole cas chrcr.atograph/T.ass
           spectrometer with  POP/12  computer
       Co 1umn:   130 cm x  2 xm i.d. g1 a s s
       Column Packing:   2% OV-101  on  Chrorncsorb  W HP
      Oven Ta-rperatjre:  150°,  3  min.  3°/min to 230°,  Hold
       Flew "ate:  30 cc/.irin,  helium
      MID Tons:   133,  222,  256, 230,  324,  358,  392, 125  (nominal)
      Full Scan:  110-500 m/e
       lonization Voltage:   70  eV  (ncminal)
      Detector Voltace:  1.8 - 2.2 kV
                                                            PROCEEDINGS—PAGE 147
                                                         First US-France Conference on
                                                     Photochemical Ozone/Oxldants Pollution

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           Table 8.   ESTIMATED LEVELS OF BENZENE  AND  HALOGENATED ORGANIC VAPORS  IN AIR OF

                         HOUSEHOLD BASEMENTS AND  SCHOOL  ROOM  IN NIAGARA, NYa
Sampling/Location
Chemical
benzene
d 1 ch 1 oroe thy 1 ene
methylene chloride
chloroform
1,1,1-trichl oroe thane
carbon tetrachloride
trichloroethylene
tetrach 1 oroethy 1 ene
pentachloroe thane
pentachl orobutadiene
1 ,3-hexachlorobutadiene
chlorobenzene
dichlorobenzene i saner
dichlorobenzene isomer
dichlorobenzene isomer
tri chlorobenzene t saner
tri chlorobenzene isomer
trichlorobenzene isomer
tetrachl orobenzene isomer
tetrachlorobenzene isomer
tetrachl orobenzene isomer
pentachl orobenzene isomer
chlorotoluene isomer
chlorotoluene isomer
dichlorotoluene isomer
dichlorotoluene isomer
dichlorotoluene isomer
trichlorotoluene isomer
trichlorotoluene isomer
trichlorotoluene isomer
trichlorotoluene isomer
trichlorotoluene isomer
tetrachl orotoluene isomer
tetrachl orotoluene isomer
chlorobenzaldehyde isomer
dichlorobenzaldehyde isomer
bromo toluene isomer
bromochl orotoluene isomer
chloronaphthalene isomer
1 ,2-dichloropropane
total halogenated organics
LI
13.896
<263
1,534
1,670
3,656
200
1,224
6,346
<19
<22
<22
1,940
2,044
260
<30
642
58
<22
16
12
<22
<22
2,562
3.820
8,836
3,956
<19
634
3,336
<19
42
19
148
58
. <26
<26
25
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59,489
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496
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114
4.232
4.400
2,442
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9,600
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1,810
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Photochemical  Ozone/Oxidants Pollution

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          PROCEEDINGS—PAGE  15E
      First US-France  Conference on
Photochemical  f>zone/0xidants  Pollution

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       ION CHROMATOGRAPHY
  presented by  James D.  Mulik



Environmental Protection Agency

          United  States
                                          PROCEEDINGS—PAGE 153
                                      First US-France Conference on
                                  Photochemical Ozone/Oxidants Pollution

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                             ION  CHROMATOGRAPHY
                               James  D.  Mulik

     Ion Chromatography  (1C)  is  a  relatively  new technique for the analysis
of anions and cations  in  solution  and  has  proven to  be a  significant addition
to the field of chromatographic  analysis.
     The originators,  Hamish  Small and  co-workers of Dow  Chemical  introduced
this newer form of analysis  in 1975.
     Ion Chromatography  has  given  the  analyst a  analytical  method  that has
sensitivity (ppb) and  selectivity, as  well  as the capability of doing direct
multi-ion analysis on  species  that previously required laborious sample
preparation.
     Since its introduction,  1C  has  seen phenomenal  growth in most areas of
analytical chemistry and  has  become  a  versatile  and  powerful  technique for
the analysis of a vast number of ions  present in the environment and in
biological tissues and fluids.   Table  I illustrates  the wide variety of mixtures
that have been analyzed with  1C.  This  list suggests the  potential  of 1C for
analysis of numerous other environmental and  biological samples.   Table 2
lists many inorganic and  organic chemicals  that  can  be analyzed with 1C.
     The U.S.  Environmental Protection  Agency (EPA)  became interested in
ion Chromatography in early 1976 because of the  many different techniques used
to assay various ionic pollutants.   For example,  there are over 200 available
methods to assay for sulfate and nitrate; most suffer from a  lack  of sensitivity
or selectivity or are difficult  and  cumbersome to use.
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      Many employ chemical  reagents  of various  types;  some of these reagents
 are  hazardous  to human  health.   Ion chromatography offers a single method
 with the  capability  to  analyze  not  only sulfate and nitrate but numerous
 other pollutants as  well.   Figure 1 {1C analysis of F~,  Cl", N02~, P04~, Br",
 N03~,  and SO,")  and  Figure 2  (1C analysis  of Na , NH^ ,  and K ) provide
 evidence  of  this.
      Ion  chromatography is a  combination of the successful methodologies of
 ion  exchange,  liquid chromatography and conductimetric detection made feasible
 with the  addition  of eluant suppression.   The process of ion exchange was known
 to provide excellent separation of  ions by  1850; chromatographic separation
 of ions by ion exchange evolved in  the early 1940's when ion-exchange resins
 became commercially  available.
      This is a powerful  method  of separation of inorganic and some organic
 ions through their relative affinities for  an  ion-exchange resin and enables
 the  separation of  many  ionic  species from  a large variety of complex mixtures.
 Primarily because  of the lack of a  universal  detector, however, ion exchange
 has  never reached  its full  potential  as an  analytical tool.
      Three of  the  most  common detection methods that have been attempted with
 ion-exchange chromatography are photometry, refractive index, and conductivity.
 Photometric  analysis is limited to  ions which  absorb light either individually
 or as  a complex  with another  compound.   The most common  disadvantage of
 photometric  methods, however, is that not  all  ionic species absorb light to
 a measureable  amount or can be  changed into or made to complex with molecules
 that do.
      Refractive  index methods are either not quite sensitive enough or do not
 show a sufficiently  large difference between the refractive index of the sample
 ions and  eluant  to be useful  in analysis.
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     Conductivity detection  is  the  most  widely preferred method because
conductivity is a simple function of  concentration  and  can be considered
nearly linear at low concentrations.   Because  of  the  method's sensitivity
and universal response  to  ionic species,  conductivity detection with ion
exchange was often attempted.   These  attempts  met with  limited success,
however, because of the large background conductance  produced by the eluant
used to elute ions of interest  from the  chromatographic column.   Successful
combination of ion-exchange  separation and conductivity detection required
a method to remove background ions.
     Introduction of the unique technique of eluant suppression  in 1975
enabled the coupling of conductivity  detection with the powerful  resolution
of ion-exchange chromatography.  "Eluant  suppression" is  the  removal  or
suppression of unwanted eluant  ions from  the eluant stream by means of a
second ion-exchange column ("suppressor  column")  downstream from the analytical
column.  The resins in  the second column  suppress the conductivity of the
eluant while leaving the ions of the  sample unaffected  for entry into the
conductivity cell.
     The principles of  both  anion and cation analysis are  shown  schematically
in Figure 1A.  In each  case, the instrumentation  involve a  sample inject
valve, a pumping system for  both eluant and suppressor  column  regeneration, an
ion-exchange separator  column,  and a  conductivity detector.
     To better illustrate the suppression of background  ions  in  the eluant
consider the ion chromatographic analysis of the anions  sulfate  and nitrate
in an aqueous eluant of sodium  bicarbonate.  If there were  no  suppressor column,
the conductance of the  sodium bicarbonate would be  so high  that  it would mask
the smaller concentration of individual nitrate and sulfate ions  during  entry
into the conductivity cell.
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     As the aqueous sodium bicarbonate solution passes through the suppressor
column, the sodium ions of the eluant are exchanged with H   ions of  the  suppressor
resin converting the bicarbonate ions to carbonic acid.  Carbonic acid is  a
very weak acid with a much lower conductivity than the original aqueous  sodium
bicarbonate eluant - hence the term "eluant suppression".
     Following separation in the analytical column, sulfate  and nitrate  are  also
converted to their respective acids.  The ions of sulfate and nitrate enter  the
conductivity detector as sulfuric acid and nitric acid in a  weak solution  of
carbonic acid, making it possible to assay for these  ions.   Before the advent
of eluant suppression, these types of assays would have been difficult to
accomplish.
     Since the suppressor column accumulates the ions that it removes from the
eluant stream, it must be regenerated periodically for reuse.  The suppressor
column capacity allows a large number of samples to be separated and analyzed
before regeneration is necessary.  Regeneration for anion analyses simply  involves
the pumping of dilute acid through the suppressor column followed by a water
rinse in the opposite direction of the normal flow.
     For anion analyses, the analytical or separator column  contains a strong
anion exchange resin, while the suppressor column contains a strong  cation
exchange resin in the hydrogen form, Dowex 50W X 8 H  .  For  cation analyses,
the analytical column contains a strong cation exchange resin; the suppressor
column contains a strong anion exchange resin in the hydroxide form  (for example,
Dowex 1 X 8 OH"}.
     Depending on the separation desired, column dimensions  range from 3 mm  X 100 mm
to 3 mm X 1000 mm.   Columns with the inside diameters of up  to 9 mm  have also been
used.
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     Baseline resolution can be achieved practically  for  all  anions  shown in
Figure 1 by judicious adjustment of flow, eluant  strength,  and  column  length.
For example, better resolution can be obtained  by lowering  flow and/or eluant
strength; in so doing, analysis time will increase, however.  In many  analyses,
a low concentration of one  ion can be measured  in preponderance of another.
     In some cases, the assay of certain components in a  mixture may be
sacrified to achieve the required speed or resolution of  other  components.
Species identification is accomplished by comparison of retention times with
standards and since the detector is nondestructive the component can be collected
for further identification  by another analytical  technique.   Quantisation is
achieved by comparison of peak heights or peak  areas to those of standard
solutions.
     Depending on the dissociation of the species, 1C linear  response  ranges
from 0.01 yg/mL to 100 ug/mL.  Strong acids and bases that  are  highly  dissociated
or ionized (pK, and pK,  values of less than 7)  are easily assayed ion  chromato-
              ck       D
graphically.  Weak acids and bases (pK  and pK.  values of more  than  7}  lack
sufficient ionic character  to be measured with  the conductivity detector.
     However, 1C researchers have demonstrated  that a simple  modification of
a standard ion chromatograph permits analysis of  some weak  acid anions.   The
minimum detectable level can now be extended still lower  by means of a
concentrator column.  The concentrator column is  3 mm X 50 mm in length,  packed
with the same resin as the  analytical column, and installed in  place of the
sample loop.  Because large sample volumes can  be pumped  through the concentrator
column, it allows the accumulation to detectable  levels of  extremely low  concen-
trations of ions (for example, as found in rainwater and  drinking water).
     Samples varying from 1 to 100 mL can be injected into  the  concentrator
column by hand or by syringe pump.  Samples also  can be loaded  into  concentrator
                                                          PROCEEDINGS—PAGE 159
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columns  in  the  field  and  analyzed  several  days  later without  sample  degradation.
     Most ionic pollutants  currently  assayed  in ambient  air are  associated
with parti culates.  In  the  Federal  Register Reference Method  for the Collection
of Atmospheric  Particulates,  air is pulled through  a glass fiber filter
                                                    3
(8 in. X 10 in.) for  24 hours at approximately  1.7  m /min; at this flow rate,
approximately 2400 m  of  air  are samples  per  day with the Hi-Vol  apparatus.
There is more than enough sample collected on the Hi-Vol glass fiber filter
to perform  1C analysis  for  the various  ions,  even if they were present in
                               3
concentrations as low as  1
     Health effects researchers  have  become more  concerned  with the  smaller
suspended particulates capable of entering the  respiratory  system.   The inhaled
particulate (IP) range has been  defined as 0-15 um.   As  a result, much of the
recent research effort has centered on a dichotomous  sampler  that collects IP
in two fractions: <2.5 pm and 2.5-15  um.  A recent  EPA sponsored aerosol  sampler
comparison study showed that there is no ideal  particulate  sampler for all
sampling and analytical requirements.
     Since the dichotomous sampler collects small amounts of  parti culates
M mg/24h; 1/100 of the Hi-Vol) and  is a popular method for  the collection
of fine particles, it is important to note here that  ion chromatography has
sufficient sensitivity to assay for sulfate and  nitrate and  other ions  in  the
sample collected.  Extensive research is ongoing  both within  EPA and the  private
sector to determine whether or not sufficient sample  for the  assay of  some
organic pollutants can be collected with the dichotomous sampler.
     A method for collection and 1C analysis of sulfur dioxide  has been developed
by EPA.  The ion chromatographic method for S02 is  currently  under evaluation
as a candidate equivalent method.  Methods standardization  testing will establish
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the  best  technical  description  to  assure that users of the method will produce
comparable  high  quality  data.   This  method  consists of the collection of ambient
sulfur dioxide in a dilute  solution  of hydrogen peroxide that converts the
sulfur dioxide to sulfate ion,  which is then assayed by ion chromatography
(Figure 3).   Sulfur dioxide is  absorbed from air in a solution of 0.6% hydrogen
peroxide, using  the gaseous pollutant sampling train.
     Samples  are collected  at field  locations and taken to a central  laboratory
for  storage and  eventual analysis  by 1C.  This method is generally applicable
to 24-hour measurements  at  sampling  rates of from 200 to 500 cm/min.   Concen-
trations  of sulfur  dioxide  in the  range of  25 ug/m  to 1000 yg/m  (0.01  to 0.40
ppm) can  be measured  if  the sample flow rate is 200 cm/min and sampling time
is 24 hours.  Lower or higher concentrations can be measured by changing the
sampling  rate or time of sampling.
     Hydrogen peroxide collection  and ion chromatographic analysis were developed
as an improved alternate time-integrated  method to measure sulfur dioxide in
ambient air.  Initial evaluation of  the method indicated several  advantages in
comparison to the EPA reference method described in Appendix A of Title 40 of the
Code of Federal  Regulations  (40CFR),  Part 50:  the Pararosaniline Method.   Recent
evaluations of the  pararosaniline  method  have indicated a serious problem with
collection of sulfur dioxide using the specified absorbing reagent (0.04 M
potassium tetrachloromercurate  (TCM)).
     The dichlorosulfite mercurate complex  formed when sulfur dioxide  is
absorbed from the air into  the TCM solution,  decays at unacceptable rates if
the absorbing solution is exposed  to  temperatures above 25°C both during and
after sampling.  This necessitates the need  for a temperature-controlled gas
sampler as well  as  temperature control  during  both shipment and storage  of
collected samples.
                                                            PROCEEDINGS—PAGE 161
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     The ion chromatographic method  has no temperature stability  problems  and
eliminates use of the toxic chemical potassium tetrachloromercurate.   Furthermore,
samples can be collected in the same samplers now used by  state and  local  air
pollution agencies to collect sulfur dioxide data by the EPA reference method.
The hydrogen peroxide absorbing reagent is a very efficient collector  of  sulfur
dioxide; when a prefilter is used in the sampling train to remove aerosol  sulfates,
there are no apparent interferences.  In addition, the sulfate formed  in  the
sampling procedure is stable over a  long period of time.
     Ion chromatography's primary success obviously has been in the  analysis
of inorganic anions and cations, however, there are certain organic  ions  that
can also be assayed with the Ion Chromatograph.  Since 1C  had simplified  the
analysis of many inorganic ions we believed that its use should be expanded
to the analysis of organic pollutants wherever possible.   As a result, we  are
currently developing a method for the collection and ion chromatographic  analysis
of formaldehyde in ambient air.
     Formaldehyde is an important chemical species in photochemical  pollution.
It it one of the most abundant aldehyde's found in the atmosphere and  has  been
shown to be a carcinogen.
     There are several formaldehyde  methods currently available such as the
chromatropic acid-colorimetric method; derivatization followed by gas  chromato-
graphy; GC-MS; FTIR; and a relatively new chemiluminescent method.   All of
these techniques suffer from lack of sensitivity, or selectivity, or are  too
expensive, complex and cumbersome to use.
     Ion chromatography offers a simple reliable selective and sensitive method
for the analysis of formaldehyde in  ambient air as formate ion.
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     After testing several  solutions  for the collection of formaldehyde it
was found that a dilute  solution  of hydrogen peroxide-water was the most
effective.  Standard gas  sampling bubbler trains similar to the bubblers used
to collect sulfur dioxide and  nitrogen  dioxide were used to collect known
dynamically generated concentrations  of formaldehyde.
     Essentially 100% collection  efficiency was obtained at concentrations of
0.5 ppm.  However, the concentration  of formaldehyde  in ambient air usually
is a factor of 10 lower.
     Formaldehyde standards have  been generated using  permeation tubes which
we have found to be erratic, therefore  we have switched to diffusion tubes
for a more constant output  of  formaldehyde.
     At this writing we  have not  resolved the possible interference from formic
acid vapor.  Research is  continuing on  this problem along with the determination
of collection efficiencies  at  low parts per billion levels.
     I am convinced that  ion chromatography will  be a  reliable accurate means
of measuring formaldehyde with an ease  and simplicity  heretofore unattainable
with other methods.
                                                            PROCEEDINGS—PAGE  163
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                                   TABLE 1
                   Mixtures Analyzed by Ion Chromatography
    Aircraft exhaust emissions
    Atmospheric aerosols
    Atmospheric gases
    Auto exhaust emissions
    Boiler compensates
    Boiler feed condensates
    Brine solutions
    Caustic solutions
    Cerebrospinal  fluid
    Coal combustion products
    Coal-fired utility emissions
    Coal gasification by-products
    Coal liquefaction by-products
    Combustion products
    Commercial amines
    Cosmetics
    Cutting fluids
    Diesel  exhaust emissions
    Drug additives
    Electronic device process water
    Engine coolants
    Fertilizers
    Flue gas desulfurization effluents
    Food additives
    Foods
    Fuel cell effluents
    Fuels
    Geothermal waters
    Groundwater
High altitute air samples
High purity water
Human serum
Industrial atmospheres
Kraft black liquors
Marine cores
Milk
Nuclear fuel reprocessing
  streams
Ocean water
Oil shale water effluents
Paper mill effluents
Petrochemical effluents
Plating baths
Polymer combustion products
Pond water
Rainwater
Scrubber liquors
Smelter aerosols
Soil extracts
Spent sulfuric acid
Stack gases
Steam generator condensates
Surfactants
Turbine condensates
Uranium refining liquid
Urine
Waste effluents
       PROCEEDINGS—PAGE 164
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                                      TABLE 2
                     Chemicals  Analyzed by Ion Chromatography
                                   INORGANIC IONS
Ammonia
Ammonia salts
Arsenate
Azide
Barium
Borate
Bromate
Bromide
Calcium
Carbonate
Cesium
Chlorate
Chloride
Chromate
Cyanide
Disulfide
Dithionate
Fluoride
Hydrobromic acid
Hydrochloric acid
Hypochlorite
lodate
Iodide
Lithium
Magnesium
Nitrate
Nitrite
Orthophosphate
Potassium
Rhenate
Rubidium
Selenate
Silicate
Acetate
Adi pate
Aerylate
Analine
Aromatic amines
Ascorbate
Benzoate
Butyrate
Butyl phosphate
Butyphosphonic acid
Citrate
Chloroacetate
Cyclohexylamine
Dibutyl phosphate
Dichloroacetate
Diethanolamine
Diisopropanolamine
Dimethylamine
Ethylmethylphosphonic
  acid
              ORGANIC  IONS
             Formaldehyde
             Formate
             Formic acid
             Fumarate
             Gluconate
             Glycolate
             Hydroxycitrate
             Hippuric acid
             Isopropy1 methylphos-
               phonic acid
             Itaconate
             Lactate
             Maleate
             Malonate
             Methacrylate
             Methyl phosphonate
             Monoethylamine
             Monomethylamine
             Monisopropanolamine
             N-butylamine
Sodium
Strontium
Sulfate
Sulfide
Sulfite
Sulfur dioxide
Sulfuric acid
Tetrafluoroborate
Thiocyanate
Thiosulfate
                    Oxalate
                    Propionate
                    Phthalate
                    Pyruvate
                    Sarcosine
                    Succinic acid
                    Tartaric acid
                    Tetraethyl ammonium
                      bromi de
                    Tetramethyl ammonium
                      bromi de
                    Trichloroacetate
                    Triethanolamine
                    Triethyl amine
                    Trifluoromethane
                      sulfonate
                    Tri i sopropanolami ne
                    Trimethyl amine
                    Tri-n-butylamine
                                                                  PROCEEDINGS-PAGE 165
                                                               First US-France Conference on
                                                           Photochemical Ozone/Oxidants Pollution

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                                   MINUTES

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        PROCEEDINGS—PAGE 166
    First US-France  Conference on
Photochemical Ozone/Oxidants  Pollution


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                                                                                         PROCEEDINGS—PAGE  167
                                                                                    First US-France Conference on
                                                                              Photochemical Ozone/Oxidants  Pollution

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                          Ion chromatogram of cations (positive ions)
                                                                 Eluant flow - 2.6 ml,'mm.
                                                                 Eiuant      -C.C02NHC!
                                                                 Cclumn length - 250 mm
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                                  inject
        PROCEEDINGS—PAGE  168
     First US-France Conference on
Photochemical Ozone/Oxidartts Pollution
                                                   'T
                                                        Efuant flow    -3.8 mL'min.
                                                        ctjanl        -C.CC3 t.' \'aHCO3
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                                                        Aitenualion    -x 0.3
                                                          SO4 Peak -0."2 ug/ml
                                                     5                10
                                                        Time, minutes
                                                                                      15

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OVERVIEW  OF THE ENVIRONMENTAL PROTECTION AGENCY  (EPA)

    GROUND-BASED REMOTE  SENSING OF AIR POLLUTION
           presented by William  F.  Heroet



           Environmental Protection Agency

                     United States
                                                    PROCEEDINGS—PAGE 169
                                                 First US-France Conference on
                                             Photochemical Ozone/Oxidants Pollution

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                         Overview of the Environmental Protection Agency (EPA) programs for
                                    ground-based remote sensing of air pollution
.-Tcr'~er>:ai Scenes
        V'C-c
                                                 William F. Herget
                                                                        -cte-io<- -ge^c;
                                                    Abstract

     Demote  sensing methods offer  various advantages  over contact measurement methods both for characterizing
 the  gaseous and  particulate air pollutants emitted  by different types of  sources and for verifying  that
 established emission standards are being met by  regulated  industries.  Two such instrumentation systems are in
 routine use for  characterization  studies:  a mobile  pulsed ruby lidar system measures stack plume opacity with
 an accuracy comperable to an  in-stack transmissometer; and a mobile high  resolution (0.1 cm"') infrared
 spectrometer system measures  multiple gaseous species concentrations in a longpath absorption mode  or in a
 single-ended emission mode with near- laboratory  accuracy.  A laser-poppler velocimeter system for measuring
 the  velocity of  stack plumes  and  winds aloft has recently  been obtained.  Several systems particularly aimed
 at -neeting  tne measurement needs  of enforcement  personnel  are under evaluation.  Tuneable laser systems for
 use  in the  longpath absorption mode and in tne differential absorption lidar mode are in various stages of
 development.  Research programs are underway to  determine  the feasibility of remotely measuring particulate
 size distributions and pollutant  (gases and particles) mass emission rates.  This paper presents results
 ootained with the instruments currently in use and  summarizes the current state of development of the various
 other systems.

                                                 Introduction

     Remote  sensing of air pollution actually began  in the early 1900's with the use of "trained observers,"
 wno  n'sually compared black stack plumes to a series of cnarts of graduated blackness (Ringelmann method).
 This concept was extenaed in  the  1940's to plumes of different snades of  greyness by training observers to
 determine the degree to which a plume obscured background light (opacity method).  Although potentially sub-
 ject to considerable error (on the low side) due to  sky color and lighting conditions, the observer-opacity
 method has been  used to establish opacity standards  for particulate emissions.  However, steps have recently
 been initiated to officially  establish the lidar concept as an alternate method for determining pluse opacity
 for  aoth enforcement and standard-setting needs.  Although not available as an off-the-shelf item,  lidar
 systems for opacity measurements now consist of  standard components ana should be considered as a well-
 establish remote measurement method.

     The first commercially available remote sensor  for gaseous pollutants was developed by Sarringer Research
 of Canada over ten years ago.  This instrument uses  the matched-filter correlation concept and measures SO?/
 NOj optical depth in absorption with scattered ultraviolet/visible sunlight serving as a light source.  Infra-
 red  techniques have been used on a research basis to measure atmospheric pollution for over twenty yearsj
 There are no standard commercially available infrared remote sensors for air pollution measurements although
 tne EPA is using routinely an especially equipped standard Fourier transform interferometer system  (FTIS) for
 a variety of gaseous air pollutant measurements.  Also, the gas-filter correlation (GFC) concept is well-
 established as an accurate method for measuring specific gas concentrations in the absorption mode and offers
 considerable promise for use  in the single-ended mode (sensors utilizing this principal  for in-situ measure-
 ment of auto exnaust and stack gas concentrations are commercially available).

     In addition  to measuring pollutant concentrations, it is also necessary to measure pollutant flow rates,
 since Tiany of the EPA emission standards are based on a mass emission rate.  The CO? laser-Doppler velocimeter
 ;LOV! provides the necessary remote velocity measurement, although infrared and ultraviolet television (IRTV
 and I'VTV)  systems can provide similar data at the stack exit in certain cases.   The IRTV can provide velocity
 aata day or night but probably cannot provide concentration data.   The UVTV system is limited to daytime use
 out can provide S02 concentration and opacity data,  in addition to velocity.   The LOV systems can provide wind
 or stack exit velocity measurements.   The wind measurement is particularly applicable in measuring emission
 rates from extended area sources.   This is of considerable importance, since the EPA has established the
 "bubble conceot" wnereby a industry such as an oil  refinery would have to meet a total  emission standara
 e.g., *or hydrocarbons)  rather than a  standard for  individual  sources within the refinery.   Only remote
 sensing tecnnicues can adequately determine the emissions from such extended area sources.   (3y measuring the
 2o""-jtant ODtical aepth in a vertical  column surrounding a source and the wind velocity, the pollutant nass
 emission rite can be determined.;

    Laser systems offer considerable promise in the area of remote sensing of gases  in that they can provide
 range-resolved and three dimensional  concentration data.  Two-ended systems utilizing CO? and diode lasers
 nave been  developed for EPA,  and low level  funding of research an the differential  absorption lidar concept
 "as occurred over tne sast ten years  or so.  Principal difficulties of the laser systems, as compared with
conventional spectroscopic systems,  are lack of frequency ana intensity stability and lack  of ability to reacn
ail desired wavelengths.   The development  of these systems  and the solving of such  problems  nas proven time
consuming  and  relatively  expensive.   Fortunately other government agencies have interest in  the development
                                                                                 PROCEEDINGS—PAGE 171
                                                                             First  US-France  Conference  on
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 of laser systems for remote measurement of gas concentrations, and much of the work in this area has been sup-
 ported  by Air Force, NSF, NOAA, and NASA funds (and recently, funds from the OOE and the EPRI).  The various
 laser systems being developed under the NASA Environmental Quality programs have been discussed in the pre-
 vious paper, along with some of airborne remote sensing work that is being conducted at the EPA Las Vegas
 laboratory.'

     The remainder of this paper will disucss recent results and current activities within the EPA intramural
 and extramural ground-based remote sensing programs.  For a complete discussion of essentially all remote
 sensing techniques applicable to measurement of source emissions the reader is referred to the work of Ludwig
 and Griggs.'

                                            Instrumentation

     Li'dar for opacity measurements.  The lidar technique for remote measurement of plume opacity was first
 demonstrated by Evans,* who used lidar equipment designed for atmospheric studies.  He showed that the opacity
 and transmittance of a plume could be determined by aiming the laser beam through the plume and comparing the
 relative backscatter intensity of the beam by the atmosphere in front of and behind the plume.  In 1972, a
 van-mounted lidar designed for plume opacity measurements was developed for EPA by General Electric Company.
 The operating characteristics of the system are given in Table 1.

                             Table 1.  Mobile Lidar System Characteristics
Component
Characteristic
Transmitter
Laser Rotating prism, Q-switched
ruby
Wavelength 594.3 nm
?ulse width \FWHH) <30 nanoseconds
Maximum output 1.0 joule
Repetition rate 3 pulses per minute
Cooling Oeionized water
Objective lens 12.7 cm, f/5
Beam divergence --0.5 mi li radian full angle
Comconent
Receiver
Objective lens
Field-of-view
Bandpass (FWKH)
Photomultiplier
Off-gating
Response
Characteristic
15.25 cm, f/5
4 mi li radian full angle
1 .2 nm
IT4T F4QS4 (modified
S-20)
:60 dB
-.100 nanoseconds

     The accuracy of the lidar system was determined by using neutral  density screen targets of known opacity.
 The opacity of 1-m diameter screens was determined by laboratory transmissometers,  which were in turn cali-
 brated by using Kodak Wratten neutral density filters.  The lidar opacity measurements of the calibrated
 targets were made at a distance of 200 m.  The results indicated that the lidar is  accurate to within 3%
 opacity for opacities less than 50%.   At higher opacities the results showed maximum error of about -15".
 opacity for a targeted opacity of 100*.  This decline in accuracy for high opacities is of little concern since
 no opacity standards for emission sources are above 50% opacity.  Agreement between lidar and in-stack trans-
 arissometer measurements of opacity are excellent;  correlation coefficients of 0.996 are typical.
                                                                                                 5 6 "*
      The EPA lidar system and associated measurements are described in detail  in the literature. '°''
 Specific ongoing work in this area includes development of a low-cost lidar system, determining relation-
 ships between opacity and mass density, and development of a system for remote determination of particulate
 size distributions.   (The lidar work at EPA/RTP is directed by William 0.  Conner.)   Recently, the EPA
 National Enforcement Investigation Center in Denver has obtained a similar lidar system.  The data obtained
 with these two systems is being used to establish  the lidar method as an  alternate  Reference Method for
 opacity measurements.

     Fourier transform interferometer system.  About three years ago a Nicolet Model 7199 was configured to
 fit into an existing van.  The FT IS replaced a grating monochromator system and is  matched to a Dall-
 Kirkham telescope (30 cm diameter primary mirror}  to collect infrared energy either from a remotely
 located light source (with identical  telescope) or from warm gases exiting industrial  stacks.  A flat
 tracking mirror is used to assist in sighting on stack exits (or :o obtain solar spectra).   Measurements
 of gas pollutant concentrations have been made at  a variety of pollutant  sources, e.g., water treatment
 ponds at phosphate fertilizer plants, jet engines, coal-burning power plants,  and waste gas flares.8.'  On
 a recent -neasurements program the system line of signt was across the top of a brick kiln (30 x 17 x 7
 Deters, 1.2 million bricks).   The bricks are gas-fired over a period of three days  until the entire kiln
 reacnes a temperature of approximately 1500°K.  Typical spectra obtained  are shown  in  Figure 1.  Spectra
 obtained at other sources are shown in Figure 2.  The FTIS, which has the acronym ROSE (Remote Optical  Sensing
 of Emissions) system, has proven a highly useful and versatile instrument for characterizing source emissions.

     Lastr.J-pPPler '-/elocimetry.  Since emission standards for stationary sources are generally based on a
 •nass-emission rate,  it is necessary to measure effluent velocity as well  as concentration by remote methods
 to take full advantage of remote-sensing techniques.   The LDV tecnnique has been in use for about 10 years
 to make non-contact velocity measurements in experiments concerning wind  tunnels, clear-air turbulence,
 wake vortices and atmospheric winds.   In this method a COj laser Deam is  propagated through the atmosphere and
 brought to focus at the desired range.  Aerosols in the atmosphere or in  a plume scatter a fraction of the
 laser energy back toward a receiving telescope.  Since the aerosol  particles are in motion, backscattered
 energy will be shifted in frequency from the outgoing laser beam because  of the Qoppler effect.  The shift in

         PROCEEDINGS—PAGE 172
     First US-France Conference on
Photochemical "zone/flxidants Pollution

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 "CLERN RTMOSPHERE"   560 METER PflTH   RESOLUTION = 0.125 CM -I
 BRICK KILN   35 METER PflTH

           .H2S01       C02
              C02
    302
800     850    900    950   1000    1050

   "CLEflN flTMOSPHERE"  560 METER PflTH

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                  1100    1150   1200

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                                                       ,v*r\
                                 HF
                              HF
 2770    2775   2780   1170   1175   1180   1170   1175   1180

                           MRVENUMBERS
       rigure 1. Absorption spectra of bricn 
-------
  SOLRR SPECTRUM   05/17/79  07!37tl«i  RESOLUTION * 0.06 CM -1
             HN03  fP BRfiNCH)
863     865    867    869     871

 CORL-BURNING POWER PLRNT  PLUME
            C02
                   C02
    873     875    877     878

     RESOLUTION  =  0.25  CM  -1

           302                 HCL
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                                                   :as a^l
      PROCEEDINGS-PAGE 174
   First US-France Conference on
Photochemical Ozone/Oxldants Pollution

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 frequency depends on the  laser wavelength and  the  velocity component along  the  laser  beam.  The  backscattered
 energy and a fraction of  the outgoing  laser beam fall on  the same detector, and  the difference in  frequency  is
 aetected by conventional  heterodyne  techniques.
     In order to determine the feasibility of remotely measuring stack effluent velocity oy IDV, a program was
uncertaken using an existing LDV system at a coal-burning power plant.  Measurements were conducted in Auayst
"    and January 1975, and the results have been describee in detail by Miller and SonnenscheinJ°  Although
                                                                                                       a
                                                                                                      tered
                                                                                                       was
snown that a reasonably linear relationship exists between plume attenuation coefficient and mass density for
a given type of particulate source.  Thus, the LDV measurement, utilizing a single instrument, has the potential
to give a mass-emission rate for particulates.
.»/•» ana January i*/s, ana trie results nave been describee in detail  by Miller and Sonnenschein.IU  Altr
the primary aim of the program was to demonstrate the feasibility of the remote velocity measurements, a
secondary aim was to determine what, if any, relationship exists between the intensity of the backscatte
signal  and tne attenuation coefficient of the plume (as determined from the opacity of the olumej.  It w
    Analysis of the velocity measurements found the LDV values within 14i, of the in-stack values obtained
by using EPA Reference Method 2.  Since Reference Method 2 is considered accurate to ±2(h, the agreement is
aoout as good as might be expected.  Although only two sets of data relating backscatter signal strength to
plume attenuation coefficient were obtained, there is certainly good indication that a linear relationship
exists.  This relationship, if verified by additional measurements on a variety of sources, would allow a
single LDV instrument to Se used to measure a particle mass-emission rate when calibratea empirically for each
tyce of source.  Otner measurements have shown that the jse of an LDV system (as opposes: to pilot balloons or
otrier conventional wind measuring methods) can significantly enhance the accuracy of remote TOSS emission rate
measurements for SQ?.1^  (In this "uplooking" perimeter mode the SO? optical depth is measured in a vertical
column surrounding the source in question.  By also .Treasuring the local wind velocity, the SOj mass emission
rate *rom the source may be calculated.)  Raytheon Corporation has recently designed and fabricated a mobile
IZV system for the EPA.  After an intensive evaluation of tne system by NOAA's Wave Propagation Laboratory,
tne system will be jsed. for further studies on gaseous and particulate mass emission rate measurements.

    Gas-Fi 1 ter Correlation Instruments.  The EPA has had a number of GFC instruments built under contract for
-easwirement of auto exhaust emissions and for in-situ smoke stack measurements. c  These instruments, along
with a longpath version (for SO? and CO at pathlength up to a kilometer) nave worked very well.  The longpath
instrument can be converted to a passive instrument for stack exit measurements.  Another 3FC instrument also
operates in the passive mode but is used in an uplooking configuration to sense ambient temperature pollutants
against the "cold" sky background.  Preliminary measurements show that the two passive instruments, which have
applications in the enforcement area, do work, but time has not allowed a thorough evaluation of tnese instru-
ments.  These evaluations should be completed by mid 1980.   It is planned to sensitize the longpath rode! for
HF and evaluate the instrument at an aluminum refinery for measurement of pot room HF emissions in early 1980.

    UV and IR television.   A UVTV system for monitoring SO? ITBSS emission rates has been developed by Dr.
Peggie Exton of MSA/Lang ley Research Center and is now commercially available.  The SO? concentration data
are obtained by 'iltering tne TV camera first at 340 rim, where particulate opacity is measured, and then at
31D nm, where particulate opacity plus SOj opacity are measured.  From these two measurements, t.ie SO? attenu-
ation can be determined and the concentrations calculated.   Calibration is obtained by signting the TV camera
througn cells that contain known amounts of S02-   Effluent velocity is determined by tracking fluctuations in
the SO? concentration as they move downstream.  These fluctuations are actually large sca'e eddies which are
sroauced at the stack lip as the flow mixes with the ambient air.  The system electronics T«asures the average
distance novea by tne fluctuations in a given time interval.   The resulting velocity is -eferrad tc as the
ecdy convection velocity.   Measurements in the field on a variety of stacks have establishes a linear relation-
snip oetween the eday convection velocity ana the mean velocity determined from in-stack measurements (EPA
method 2}.   The system has the potential for measuring pluire particulate opacity, but this nas not yet been
•demonstrated.

    "he IRTV system, whicn is a dual channel  commercial system covering the 3-5 and 3-14 xicron regions is
used for plume visualization at the present time.   It is planned to couple the IRTV output to the UVTV system
electronics for velocity measurement studies.  (The IRTV has the advantage over the UVTV of night time opera-
tion.)  It is not expected that the IRTV will be able to measure pollutant concentrations.

                                               Summary

    A mobile lidar system for olume opacity measurements and a mobile Fourier transform interferometer syste-r
•"or ^ultiole gas concentration measurements are in routine -ise in the EPA remote sensing program.   Laser-
Icooier velocimetry, which is a well-proved concept,  will  saon join our fleet of Decile Demote sensing systems
arc .•»'."!  oe usec in studies related to the remote determination of pollutant "nass emission rates.   The gas-
filter correlation ana television systems have excellent potential for routine surveillance or enforcement
activities, but further evaluations are needed.
                                           Acknowledgment
    Sc:re of the
Seisinc of Stationary
                general  concepts  presented  here  were  first  described  by  Herget  ana  Conner  in  "Instrumental
               ionarv Source Missions"  Environmental  Science  i  Technology,  .'o: .  11,  962-967  (1977).
                                                                                  PROCEEDINGS—PAGE  175
                                                                              First US-France Conference on
                                                                         Photochemical Ozone/Oxidants Pollution

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                                            References

     1.  Hanst,  P. "Spectroscopic Methods for Air Pollution Measurement," in Advances in Environmental Science
 ana Technology, J. N. Pitts ana R. .. Metcalf,  eds., John Wiley and Sons, Inc., New York, 1971.
     T.  AT la Ho, F., W,  Ayers, and J. M. Hoell, "An Overview of the NASA Tropospheric Environmental Quality
 Remote Sensing  Program^'  Paper -195-37, 23rd SPIE Symposium, San Diego, 1979.
     3.  Ludwig, C. 8., and M.  Griggs, "Application of Remote Monitoring Techniques in Air Enforcement," EPA
 Reoort No.  650/2-75-062, 1975.
     4.  Evens,  W. t.,  "Development of a Udar  Stack Effluent Opacity Measuring Syste," NTIS PB  223-135/AS,
 Soringfield,  Virginia, 1967.
     5.  Cook, C. S., G.  W.  Sethke, and W.  0.  Conner, "Remote Measurement of Smoke Plume Transmittance Using
 Lfdar," Applied Optics,  Vol.  II, 1742-1748, 1972.
     6.  Conner, V. D., "Measurement of the Opacity and Mass Concentration of Particulate Emissions by Trans-
 missometry,"  NTIS PB 241-251/AS, Springfield, Virginia, 1974.
     7.  Conner, W. 0., K.  T.  Knapp, and J. S, Nader, "Applicability of Transmissometers to Opacity Measurement
 of Emissions" EPA Report No.  600/2-79-188, Sept. 1979,
     8.  Herget, H. F., "Air Pollution:  Ground-Based Sensing of Source Emissions" in Fourier Transform
 Infrared Spectroscopy, Vol.  II, J. R. Ferraro and L. J. Basile eds.. Academic Press, Inc., New York,1979.
     T.Herget, W. F. and J.  D. Brasher, "Remote Measurement of Gaseous Pollutant Concentrations  using a
 Mcoile Fourier Transform Interferometer System," Applied.. Optics, October 1979.
    10.  Miller, C,  R. ana C.  M. Sonnenschein, "Remote Measurement of Power Plant Stack Effluent  Velocity," £PA
 Report Ho.  650/2-75-062, 1975.
    '!.  Sperling, R.  B., M.  A. Peache, and W. «. Vaughn, "Accuracy of Remotely Sensed SO? Mass Emission
 Rates," EPA Report No. 600/2-79-094,  1979.
    12.  Herget, W.  F., J.  A.  Jahnke,  0.  S. Burch, and 3. A. Gryvnak, "Infrared Gas-Filter Correlation Instru-
 ment for In-situ Measurement of Gaseous  Pollutant Concentrations,"  Applied Optics. Vol. 15, 1222-122S, 1976.
   JET  ENGINE  PLUMES

       H20                CO
 COS
         RESOLUTION  =  0.125  CM  -1
                                                                       IDLE  POWER
           H20
COS
                                                                       RFTERBURNER  POWER
                                                                              26002700
                                            WflVENUMBERS
              Figure 2b.  Typical  ROSE  system spectra (emission from jet  engine plumes).
        PROCEEDINGS—PAGE  175
     First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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           INSTALLATIONS REGISTERED FOR

       PURPOSES  OF ENVIRONMENTAL PROTECTION
            presented by J. C.  Oppeneau



Ministere de ]' Environnement  et  du Cadre de  Vie

                       France
                                                 PROCEEDINGS—PAGE 179
                                             First US-France Conference on
                                         Photochemical Qzone/Oxidants Pollution

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MINI5TERE DE L'ENVIRONNEMENT ET DU CADRE DE VIE
Direction  de la Prevention des Pollutions.
                          INSTALLATIONS
                              REGISTERED
                          FOR  PURPOSES
                     OF ENVIRONMENTAL
                              PROTECTION
                    Act n- 76-663 of July 19, 1976
             decree n-77-1133 of September 21,1977
  SERVICE  DE L ENVIRONNEMENT  INDUSTRIE!.
                                 PROCEEDINGS—PAGE 181
                                First US-France Conference on
                              Photochemical Ozone/Oxidants Pollution

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        The  original french  texts of the following  law and decree,

as well as  subsequent regulations,  are published under the title



        " Brochure 10O1 - Tomes  I,  II et III -

          Installations classics pour la protection de 1'Environnement  "
                             by
          Imprinterie des Journaux Officiels,

          26,  rue Eugene Desaix

          75732 PARIS CEDEX 15.
                                                  PROCEEDINGS—PAGE 183
                                               First US-France Conference on
                                           Photochemical Ozone/Oxidants Pollution

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Installations Registered for  Purposes

     of  Environmental Protection
    Act No. 76-663  of July 19,  1976
 Decree No. 77-1133  of September  21, 1977
                                            PROCEEDINGS-PAGE  185
                                         First US-France Conference on
                                     Photochemical Qzone/Oxidants Pollution

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                 ACT N° 76-663 of JULY 19, 1976
                on Installations Registered for
           Purposes of Environmental Protection'*'
(Journal Officiel de la Republique Franchise - July 20, 1976)
         The National Assembly and the Senate have adopted,
         The President of the Republic promulgates the following Act
                            TITLE  I
                       GENERAL PROVISIONS
               Section 1,  The provisions of this Act shall apply  to  factories,
     workshops, depots, buildings and other sites, quarries and  in general
     installations operated or owned by any natural or  legal person,  public
     or private, which may threaten any danger or nuisance, whether in  regard
     to neighbourhood amenity; public health, safety or sanitation; agriculture;
     protection of nature and environment; or conservation of  sites and monu-
     ments.
               Section 2.  The installations referred to  in  Section  1  shall  be
     defined with reference to the Register of Registered Installations  esta-
     blished by a decree referred for the review to the Council  of State,  based
     on a report by the Minister responsible for Registered  installations  and
     the opinion of the Higher Council for Registered Installations. Such  decree
     shall subject installations either to authorisation  or  declaration  depen-
     ding on the gravity of any danger or nuisance threatened by their operation!
                                                       PROCEEDINGS—PAGE 187
                                                    First US-France Conference on
                                                Photochemical Ozone/Oxidants Pollution
(1)  See following page.

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           Footnote from page 1.
           (1)  IKEPARATORY DISCUSSIONS
           Senate  :
           Bill No.  295  (1974-1975);
           Report  by Mr.  Jean Legaret on behalf of the Cultural Affairs Cotanittee,
                                   No.  364 (1974-1975);
           Opinion of  the Finance Conmittee No. 363 (1974-1975);
           Discussion  and adoption  on June  11,  1975.

          National  Assembly  :
           Bill adopted by the  Senate (No.  1753);
          Non-government bill  (No. 392);
          Report  by Mr.  Charles Bignon,  on behalf of  the Law Conmittee (No. 2143);
          Discussion and adoption  on April 15, 1976.

          Senate  :
          Bill as amended by the National Assembly No. 261  (1975-1976);
          Report by Mr.  Pierre Vallon on behalf of the Cultural Affairs Committee,
                                    No. 274 (1975-1976);
          Discussion and adoption on May 5, 1976.

          National Assembly  :
          Bill, adopted  as amended by the Senate  (No. 2271);
          Report by Mr.  Charles Bignon, on behalf of the Law Commission (No. 2420);
          Discussion and adoption on June 25,  1976.

          Senate :
          Bill, as amended by the National Assembly No. 384 (1975-1976);
          Report by Mr.  Pierre Vallon on behalf of the Cultural Affairs Committee,
                                     No. 394 (1975-1976);
          Discussion and adoption on June 29,  1976.
          National Assembly :
          Bill,  adopted as amended by the Senate (No. 2439);
          Report by Mr. Charles Bignon on behalf of the Law Committee (No. 2469);
          Discussion and adoption on June 30, 1976.

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           Section 3. Installations which may  threaten the interests referred
   to in Section 1 with any grave  danger or  nuisance  shall be subject to
   authorisation by the Prefect.

           Authorisation  shall  only be  granted provided such danger or
   nuisance may be prevented by measures specified  in  the Prefectoral Order.

           The authorisation for such installations may,  inter alia,
   require that they be located away from residential  accommodation,  from
   buildings normally occupied  by  third parties,  establishments open to the
   public, watercourses,  roads, reservoirs,  or areas scheduled for  residen-
   tial use by town-planning documents  binding on third parties.

           Shall be subject to  declaration installations which, while
   unlikely to cause such dangers  or nuisances, must nevertheless comply
   with the general regulations issued  by the  Prefect  for the purpose of
   protecting, within the department, those  interests  referred to in Section  1.

           Section 4. The operator shall submit his application for autho-
   risation or his declaration  at  the same time as  his application  for a
   building licence.

           He shall renew his application for  authorisation or his  declaration
   in the event of any transfer, extension or  transformation of his installa-
   tions, or any change of manufacturing processes  giving rise to a danger or
   nuisance as defined in Section  1.

                          TITLE II
PROVISIONS APPLICABLE TO  INSTALLATIONS  SUBJECT TO AUTHORISATION
           Section 5. The authorisation referred  to  in  Section  3  shall  be
   issued by the Prefect, following a public  enquiry concerning any  possible
   effects of the project with regard to  the  interests  specified  in  Section 1
   and referred for review to the Municipal Councils concerned  and the  Health
   Council of the department. Authorisation shall be issued by  the Minister
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    responsible  for  Registered installations  after referral to the Higher
    Council  for  Registered  Installations  in cases where the dangers involved
    threaten to  affect  several departements or regions.

             A  decree  referred to the  Council of State shall lay down the
    conditions for implementation  of the  preceding paragraph* That decree
    shall also specify  the  circumstances  in which the Departmental or Regional
    Councils must be consulted and the  forms  of such consultation.

             Section 6.  The  installation and operating conditions deemed
    essential for protecting  the interests specified in Section 1 of this Act,
    the methods  of analysis and measurement and the action to be taken in the
    event of accident,  shall  be laid down by  the authorising Order and, where
    appropriate, by  supplementary  Orders  issued subsequent to the authorisation.

             Section 7.  For  the protection of the interests specified in
    Section  1 above, the  Minister  responsible for Registered installations
   may by Order, after consultation with the Ministers concerned and with
    the Higher Council  for  Registered Installations, lay down technical rules
   applicable to certain categories of installations covered by this Act. Such
   Orders shall be made  ipso jure in the case of new installations and shall
    specify, following  referral to professional bodies concerned, the time
    limits and the conditions under which they shall apply to existing ins-
    tallations.

             Such orders shall also specify  the conditions in which some of
    these rules may be  adapted to  local circumstances by the authorising
    Prefectoral Order.

             Section 8.  Authorisations shall be issued subject to the rights
    of third parties.
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          Section 9. In communes which  include  an "appellation d'origine"
wine-producing area, the opinion of  the Minister of Agriculture shall be
requested for the purposes of  the authorisation referred to in the first
paragraph of Section 4 above*  Such opinion  shall be given after consulta-
tion, where appropriate, with  the Institut  National des Appellations
d'Origine.

          The Minister of Agriculture shall also be consulted, at his
request, were an establishment subject  to the authorisation mentioned
above is to be set up in a commune adjacent to  a commune containing an
"appellation d'origine" wine-producing  area.

          The Minister of Agriculture shall have three months in which
to give his opinion. Such period shall  begin to run from the date on
which the file is referred to  the Minister  by the Prefect together with
his attached opinion.
                            TITLE  III
         PROVISIONS APPLICABLE TO INSTALLATIONS  SUBJECT TO
                           DECLARATION
          Section 10.  The general  regulations  referred to in the last
paragraph of Section 3 shall be  issued  by  Prefectoral  Order after obtaining
the opinion of the Health Council of  the department.  They shall apply
automatically to any new installation or installation  subject to a fresh
declaration.

          Subsequent amendments  to  these general  regulations may be made
applicable to existing installations  in accordance with the procedures
and time limits contained in the Prefectoral  Order, which shall also
specify the conditions in which  the general regulations may be adapted
to local circumstances.
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            Establishments subject to declaration under the provisions
  of the Act of December 19, 1917 and which have, under Section 19,
  paragraphs 1 ou 4 of the Act, been granted total or partial exemption
  from on or more regulations introduced by Prefectoral Orders, shall
  retain the benefit of such exemptions. The exemptions may however be
  terminated by Prefectoral Order, issued after obtaining  the opinion
  of the Health Council of the departement in accordance with the proce-
  dures and within the time limit laid down in the Order referred to.

            Section 11. Where the interests specified in Section 1 of this
  Act are not adequately protected by compliance with the  general regulations
  against nuisances inherent to the operation of an installation subject
  to declaration, the Prefect may, where appropriate on the request of
  interested third parties and after obtaining the opinion of the Health
  Council of the departement, impose by Order any necessary special regu-
  lations.

            Section 12. Installations which, although subject to declaration
  under this Act, were in possession of a regular authorisation before  the
  entry into force of the Act of December 19, 1917 are dispensed from any
  declaration; they shall be subject to the provisions of  Sections 10 and 11.
                           TITLE  IV
   HUJVISIONS APPLICABLE TO ALL REGISTERED INSTALLATIONS
            Section 13. Persons responsible for the inspection of Registered
  installations or for expert appraisal shall be bound under oath to respect
  professional secrecy on the terms and subject to the penalties laid down
  in Section 378 of the Criminal Code and, as the case may be, in Sections  70
  et seq. of that Code.

            They may visit the installations under their  control at any time.
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          Section  14. Decisions made in application of Sections 3, 6, 11,
12, 16, 23, 24 and 26 of  this  Act may be referred to the administrative
court  :

          1* By applicants  or  operators within a period of two months
             from  the date  on  which such decisions were notified to them;

          2* By third parties, natural or legal persons, or communes
             or groups  of communes  affected,  owing to any nuisances or
             dangers that the  operation of the installation threatens in
             regard to  the  interests specified in Section 1, within a period
             of four years  from the publication or public display of the
             decisions, such period being extended, where appropriate,
             until the  end  of  a period of two years following the instal-
             lation's entry into operation.

          Third parties who acquire or take a lease on immovable property
or erect buildings in the vicinity  of a classified installation after the
public display or  publication  of the Order authorising the opening of the
installation or easing  the  original regulations may not challenge such
authorisation before the administrative courts.

          The building  licence and  the deed of sale to third parties
of land or immovable property  shall expressly mention any servitudes
attached thereto in application of  the new Section L.421-8 of the Town
Planning Code.

          Section  15. A decree referred for review to the Council of
State and for an opinion to the Higher Council for Registered Installations
may order the dismantlement of any  installation,  whether or not covered
by the Register, which  threatens the interests specified in Section 1 with
any kind of danger  or nuisance that cannot be abated by measures available
under this Act.
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            Section 16.  Existing installations which are subject to the
 provisions of  this Act which,  before its entry into force,  did not fall
 within the scope  of  the  amended Act of December 19, 1917 on dangerous,
 insanitary, noisy or noxious establishments may continue to operate
 without  the authorisation  or declaration referred to in Section 4 above.
 However, before a date fixed by decree and within a period which shall
 not exceed two years from  the  entry into force of this Act, the operator
 shall make himself known to the defect, who may subject him to measures
 for the  safeguard of the interests specified in Section 1 above.
                            TITLE   V
                      FINANCIAL 1ROVTSICNS


           Section 17. I* Industrial and commercial establishments and
 public establishments of industrial or commercial character, some of
 whose installations are registered, shall be subject to a non-recurring
 tax payable at the time of any authorisation or declaration under this Act.

           Furthermore, an annual  charge shall be payable by those among
 the said establishments which, by virtue of the nature or volume of their
 activities involve special risks  for the environment and which, for that
 reason, require detailed, regular inspection.

           II. The rates of the non-recurring tax shall be as follows;

           Frs. 3,000 for establishments where at least one installation
           is subject to authorisation;

           Frs. 1,000 for establishments where at least one .installation
           is subject to declaration.
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          However, these rates shall be reduced to Frs.  750 and Frs.  250
in the case of small businessmen who do not employ more  than  two workers
and to Frs. 1,950 and Frs. 650 for other undertakings entered in the
Repertoire des Metiers.

          A penalty of double the amount of the tax  shall be  payable
by an operator who, for the purposes of assessment and recovery of  the
tax, fails to give the information requested or provides incorrect  infor-
mation.

          The amount of the tax shall be increased by 10 per  cent when
the amount due is not paid within the prescribed  time limits.

          III. The establishments referred to  in  the second paragraph of
sub-section 1 above shall be those engaging in one or more of the activities
included in a list established by decree referred for review  to the Council
of State and for an opinion to the Higher Council for Registered Installations

          The basic rate of the said charge shall be Frs. 500.

          The decree referred to above  shall specify, for each of the said
activities, as determined by its nature and importance,  a multiplier  from
1 to 6. The amount of the charge actually payable by the establishment  for
each of these activities shall be equal to the product of the basic rate and
the multiplier.

          Undertakings appearing in the Repertoire des Metiers shall  be
exempt from the said charge.

          The increases and penalties referred to in the fourth and fifth
paragraphs of sub-section II above shall also  apply  to the charge.

          IV. The non-recurring tax and the charge shall be recovered
in the same way as a direct tax.
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                          TITLE  VI
                     CRIMINAL  PENALTIES
             Section  18• Any person who  operates  an  installation without
   the necessary authorisation  shall be  liable  to a  fine  of Frs. 2,000 to
   Frs. 20,000.

             Should the cffence be repeated, he shall  be  liable  to a  term
   of emprisonment of two to six months  or  a fine of Frs. 20,OOO to
   Frs. 500,000 or to both penalties*

             Section  19. In the event of the imposition of a minor penalty
   (peine de police)  for breach of the Prefectoral or  Ministerial Orders
   issued under this Act or its implementing regulations, the  judgment
   shall, where necessary, specify and,  if  appropriate, make  subject  to daily
   penalties, the period within which the provisions which have  been  infringed
   are to be complied with. In  case of non-compliance  within  the prescribed
   period, a fine of Frs. 5,000 to Frs.  500,000 may  be imposed.

             The court may forbid use of the installations until the  work
   has been completed. It may also direct that  the work be carried out
   forthwith at the expense of  the person convicted.

             Section 20. Any person who  operates  an  installation following
   an order of closure or suspension of  operations under  this  Act, or when
   its use has been prohibited  under the preceding Section, shall be  liable
   to a term of imprisonment of two to six  months or a fine of Frs. 5,OO  to
   Frs. 5OO,OOO or to both penalties.

             Section 21.  Any person who obstructs those  responsible  for  the
   inspection or appraisal of Registered installations in the  performance
   of their duties shall be liable to a  term of imprisonment of  ten days
   to three months or a fine of Frs. 2,000  to Frs 50,000  or to both penalties.
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          Section 22.  Offences  shall  be  reported  officially in statements
by police officers of the criminal  investigation department and inspectors
of registered installations.  Such official  statements  shall be prepared in
two copies, one of which shall be forwarded to  the Prefect and the other
to the Director of Public Prosecutions. They shall be  deemed conclusive
evidence until the contrary is proved.
                      TITLE  VII
               ADMINISTRATIVE PENALTIES
          Section 23.  Independently  of  any  criminal  proceedings which
may be instituted, whenever an inspector of  registered  installations
or an expert appointed by  the Minister responsible  for  registered instal-
lations finds that requirements  imposed  on the  operator of a registered
installation are not being complied with, the Prefect shall serve notice
on the latter to comply with such  requirements  within a specified period.

          If, on the expiry of the period specified,  the operator has
not complied with the notice, the  Prefect may  :

          - proceed to enforce the prescribed measures  at the operators
            expense, or

          - require the operator to deposit  with  a  public accountant
            a sum covering the cost of work  to  be carried out, this sum
            being returned to the  operator as the work  progresses; in
            appropriate cases this sum may be recovered in the same way
            as debts unconnected with taxation  and  public property, or

          - suspend the operation  of  the installation by Order,  after
            obtaining the  opinion  of  the Health Council of the departement,
            until requirements have been complied with.

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              Section 24.  'When a registered installation is operated without
      having been the subject of the declaration or authorisation required by
      this Act, the Prefect shall serve notice on the operator to regularise his
      situation within a specified period by lodging a declaration or application
      for authorisation, as the case may be. The Prefect may, by justified Order
      suspend the operation of the installation pending the submission of the
      declaration or pending a decision on the application for authorisation.

              If the operator does not comply with the notice to regularise
      his situation or if his application for authorisation is rejected, the
      Prefect may, in case of necessity, order the closure or dismantling of
      the installation. If the operator does not comply within the specified
      period, the Prefect may give effect to the procedures referred  to  in
      Section 23 (third and fourth paragraphs).

              The Prefect may order seals to be placed by a police officer
      on an installation which continues to operate following an order of
      dismantling, closure, or suspension of operations under Section 15,
      Section 23 or the first two paragraphs of this Section, or in  spite of
      a decision refusing authorisation.

              Section 25.  Throughout the period of suspension of operations
      as directed under Section 23 or Section 24 above, the operator  shall pay
      his employees wages, allowances and other remuneration of any  kind to
      which they were hitherto entitled.
                             TITLE  VTII
                      MISCELLANEOUS PROVISIONS


              Section 26.  When the operation of an  installation not included
      in the Register of Registered Installations  threatens the interests
      specified in Section 1 of this Act with any  grave danger  or nuisance,
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the Prefect, after obtaining  the opinion  -  save  in urgent cases * of the
Mayor and the Health Council  of the  department,  shall serve notice on
the operator to take the necessary steps  to eliminate any danger or
nuisance duly found to exist. Should the  operator fail to comply with
this notice within the period specified,  effect may be given to the
measures referred to in Section 23 above*

          Section 27.  With regard to  installations belonging to services
and bodies of the State, and which shall  be included in a list established
by a decree, the powers granted to the Prefect under this Act shall be
exercised either by the Minister responsible for  registered establishments,
or by the Minister responsible for defence  matters in the case of instal-
lations under the control of his department.

          The penalties referred to  in Title VI  shall be applicable to
those coming under the juridiction of  military courts or tribunals of the
armed forces, in accordance with the Code of Military Justice and notably
Sections 2, 56 and 100 thereof.

          Section 28.  The procedure giving effect to this Act shall be
determined by decrees referred to the  Council of  State.

          These decrees shall also specify:

          1. In the case of the installations mentioned in Section 27
             above, the enquiry and  authorisation procedures and the con-
             ditions of supervision  and control;

          2. In the case of other State services,  and in the case of
             local authorities and public bodies  (etablissements publics)
             of an administrative character:
          (a) the conditions of application of  the measures  referred
              to in Sections 19, 23, 24, 25 and 26;

          (b) the persons who shall be deemed to be  criminally liable
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               Section 29.  The  provisions of this Act shall come into force
     on January 1, 1977. Thenceforward the following measures shall be repealed:
     the Act of December 19,  1917  as  amended on dangerous, insanitary, noisy or
     noxious establishments,  the ratified Decree-law of April 1, 1939 introducing
     an emergency procedure for  the preliminary investigation of applications
     to construct storage depots for  hydrocarbons, and provisions applicable
     to installations covered by this Act which are at variance with the Act.

               Reference to this Act  shall replace all references to the Act
     of December 19, 1917 in  all relevant instruments.

               This Act shall take effect as an Act of the State.

               Issued at Paris July 19,  1976.
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              DECREE No. 77-1133 of September 21, 1977
           implementing Act No. 76-663 of July  19,  1976
on Installations Registered for Purposes of Environmental  Protection
  (Journal Officiel de la Republique Franqaise  - October 8,  1977)
              THE PRIME MINISTER,

               On reports  by  the  Keeper  of the Seals,  Minister of Justice,
     the Minister of  the Interior,  the Minister of Defence, the Minister of
     Culture and the  Environment,  the Minister Delegate for the Economy and
     Finance, the Minister for Equipment and Land-Use Planning, the Minister
     of Agriculture,  the Minister of Industry, Commerce and Craft Trades, the
     Minister of Labour and the Minister of Health and Social Security.

               Having regard to Act No.  76-663 of July 19, 1976 on installations
     registered  for purposes of environmental protection;

               Having regard to Act No.  61-842 of August 2, 1961 on the
     control  of  atmospheric pollution and odours;

               Having regard to Act No.  64-1245 of December 16,  1964  on  the
     regime governing waterways and water distribution and control of their
     pollution notably Sections 2 and 6 thereof;

                Having regard to Act No. 75-633 of July 15, 1975  on waste
      disposal and the recovery of materials;

                Having regard  to Act No. 76-629 of July 10, 1976  on nature
      protection, notably  Section 2  thereof;
                Having regard  to  the  Penal  Code  and notably Article R.25
      thereof)
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                Having regard to the Act of March 30, 1928 as amended on the
       regime governing oil imports;

                 Having regard to the Decree of February 1, 1925 setting up
       the  interministerial committee on hydrocarbon storage depots;

                 Having regard to Decree Ho. 53-578 of May 20, 1953 as amended
       adopting public administration regulations for the application of
       Sections 5 and 7 of the Act of December 19, 1917 as amended on dangerous,
       insanitary,noisy or noxious establishments;

                 Having regard to Decree No. 72-1240 of December 29, 1972
       specifying the procedure for the recovery of the annual charge appli-
       cable  to certain establishments classified as dangerous, insanitary,
       noisy  or noxious and Decree No. 75-1370 of December 31, 1975 establishing
       the  list of activities liable to the annual charge payable by certain
       establishments classified as dangerous, insanitary, noisy or noxious;

                 Having regard to Decree No. 73-361 of March 23, 1973 specifying
       the  procedures for the recovery of the non-recurring tax applicable to
       establishments classified as dangerous, insanitary, noisy or noxious;

                 Having heard the Council of State (Public Works Section),

                 Decrees;

                 Section 1.  This decree shall apply to installations covered
       by the Act of  July 19, 1976, subject to the special provisions contained
       in Sections 27 and 28 of that Act.
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                        TITLE  I
        IROVTSIONS APPLICABLES TO INSTALLATIONS
               REQUIRING AUTHORISATION
          Section 2.  Any person proposing to operate an  installation
requiring authorisation shall submit an application to  the  Prefect of
the departement in which the installation is to be situated.

          The application, to be submitted in seven copies, shall  state:

1.        In the case of a natural person, his name, first  names and
habitual residence, and in the case of a. legal person,  its  trade name
or company name, its legal form, the address of its registered office
and the capacity of the signatory of the application;

2.        The site on which the installation is to be located;

3.        The nature and volume of the activities which the applicant
proposes to undertake and the section or sections of the  Register  in
which the installation should be recorded;

4.        The manufacturing processes which the applicant will employ,
the materials which be will use and the products which  he will manufac-
ture, so that any impending danger or nuisance can be assessed. Where
appropriate, the applicant may submit a single copy under separate cover
of any information whose dissemination he feels might cause manufacturing
secrets to be divulged.

          Where a building licence is needed for the establishment of an
installation, the application for authorisation shall be  accompanied or
supplemented within the 10 days following its submission  by proof  that
a building licence has been applied for. Grant of the building licence
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    shall not amount to authorisation under the Act of July 19, 1976.

              Section 3.  Each copy of the application for authorisation
    shall be accompanied by the following documents:

    1.         A map to scale 1/25,000 or alternatively to scale 1/50,000
    on which shall be indicated the site of the proposed installation;

    2.         A plan at least to scale 1/2,500 showing the surroundings
    of the installation up to a distance which shall be at least equal
    to one-tenth of the distance specified for the public display of
    notices in the Register of Registered Installations for the category
    of installation concerned, but which shall in no case be less than
    1OO metres* The plan shall indicate all buildings and their use,
    railway lines, public highways, water outlets, canals and watercourses;

    3.         A general plan at least to scale 1/200 indicating the
    projected layout of the installation and, up to at least 35 metres
    from  it, the use of neighbouring buildings and land together with
    the routes of existing drains. A smaller scale down to 1/1,000 may
    be accepted by the authorities at the request of the applicant;

    4.         The impact study referred to in Section 2 of the Act of
    July  10, 1976.

              That study shall set out facts relevant to the existing
    position of the interests referred to in Section 1 of the Act of
    July  19, 1976 and shall describe any foreseeable effects of the
    installation on its environment from the standpoint of such interests.

              The study shall also specify the origin, nature and scale
    of any nuisance likely to result from the operation of the installation
    in question. For this purpose, it shall in particular specify to the
    extent necessary the noise level of equipment to be used, the mode and
    conditions of water supply and water use, measures proposed for the
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protection of ground water,  the  purification and disposal of waste
water and gaseous emanations,  the  removal  of wastes and residues from
the installations,  the  conditions  of  transport  to the installation of
materials to be processed  therein  and of the finished products therefrom.

          The measures  envisaged by the applicant to eliminate,  limit
or compensate any nuisance caused  by  the installation shall be the
subject of specifications  describing  the proposed layout and operating
arrangements, details thereof  and  anticipated performance.

5.        A study setting  out  any  danger threatened by the  installation
in the event of accident and proving  the existence of measures to
reduce the likelihood and  possible effects thereof, as determined under
the applicant's responsibility,  this  study shall specify in particular,
having regard to the public  emergency services  known to exist, the
reliability and organisation of  private emergency services  at the
disposal of the applicant  which  he has arranged to call upon for the
purpose of combatting the  effects  of  any accident;

6.        A notice  regarding the conformity  of  the proposed installation
with current legislation and regulations on  the health and  safety of
employees.

          The studies and  documents referred to in this Section  shall
relate to all the installations  or equipment operated or proposed by
the applicant and which, due to  their  proximity or connection to the
installation subject to authorisation, are liable to alter  any danger
or nuisance connected therewith.

          Section 4.  One  copy of  the  documentation supplied by  the
applicant, including information supplied  under separate cover,  shall
be forwarded by the Prefect  to the Inspection Service for Registered
Installations.
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            When the Prefect considers that the proposed installation
    is not covered by the Register of Registered Installations, he shall
    notify the person concerned accordingly. When he considers that the
    application or attached documents are irregular or incomplete or that
    the installation is subject to declaration) the Prefect shall request
    the applicant either to regularise the application or replace the
    application by a declaration.

            Section 5. When he considers that the application is complete,
    the Prefect shall by Order direct the opening of the public inquiry*   Such
    Order shall specify :

    1.      The subject and date of the inquiry, the duration of which
    shall be one month ;

    2.      The times and place at which the public may inspect the
    application and documents and record their observations in a register
    provided for that purpose ;

    3.      The name of the Commissioner holding the inquiry  ; he should
    be present at the place where the documents may be consulted for at
    least three hours per week throughout the duration of the inquiry  ;

    4.      The area within which the notice to the public referred to
    in Section 6 will be displayed. Such areas shall be at least equivalent
    to that required for the display of notices to the public as specified
    in the Register for the category within which the installation is  to
    be included.

            When communes whose territory comes within the area defined
    above are situated in another departement, the Prefect shall arrange
    with the Prefect of that departement for the publication  of the notice
    therein.
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         At the request of the applicant,  the Prefect may  remove  from
the documentation submitted to the inquiry and  consultations referred
to below any items liable to  involve,  inter alia,  the disclosure  of
manufacturing secrets.

         Section 6.  A notice to the public shall  be displayed at the
expense of the applicant by the Mayor  of  every  commune  part of whose
territory comes within the area referred  to in  the preceding Section.
The notice shall be displayed at the Town Hall  at  least 8  days before
the opening of the public inquiry and  in  the vicinity of the proposed
installation so as to ensure  that the  public is adequately informed.
The Mayor of each commune concerned  shall certify  that  such notices
have been displayed.

         The notice, which shall be  printed in  conspicuous characters,
shall specify the nature of the proposed  installation,  the site on
which it is to be exerced and the dates of the  opening  and closure of
the public inquiry; the notice shall specify the name of the Commissioner
conducting* the inquiry and give the  dates and times at  which he will be
available to receive the comments of those concerned and the place where
the application and documents may be inspected.

         The inquiry shall also be announced by the Prefect at the
expense of the applicant in the eight  days following its opening in two
local or regional newspapers  circulating  throughout the departeraent  or
departements concerned and, where the  Prefect shall see fit, by any other
means in cases where the nature and  scale of the danger or nuisance
threatened by the project so  warrant.

         Section7.  The register of the  inquiry,  containing non-removable
sheets, shall be closed and signed by  the Commissioner.
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                  After  closure  of  the  inquiry,  the  Commissioner shall  summon
          the applicant within one week  and shall thereupon communicate  to him
          the written  and oral observations made, the latter being in the form
          of an  official  record,  and shall  request him to  submit a written reply
          within a period of  22 days*

                  Hie Commissioner  shall forward the inquiry papers to  the
          Prefect, with his reasoned conclusions, within eight days from
          receiving  the applicant's  reply or from the expiry of the time allowed
          for submitting  such reply*

                  Any natural or legal  person concerned may inspect the appli-
          cant's reply and the reasoned  conclusions of the Commissioner  at the
          Prefecture*

                  Section 8.  The Municipal Council  of the commune where the
          proposed installation is to  be erected  and  the Municipal Councils of
          each of the  communes whose territory comes  within the area of  notice
          display shall be asked  to  state their opinion regarding the application
          for authorisation on the opening  of the enquiry* Consideration may
          only be given to those  opinions expressed at the latest within the
          15 days following closure  of the  inquiry register.

                  Section 9.  "When  the  inquiry is opened, the Prefect shall
          forward a  copy  of the application for authorisation for review to the
          services of  the departeraent  dealing with equipment, agriculture, health
          and social matters,  emergency  services  and, where appropriate, to the
          labour inspection services,  water inspection services, the government
          architect  responsible for  historic buildings, and all other services.
          For this purpose further copies of the  application and supporting
          documents  may be required  from the applicant. The services consulted
          shall  give their opinion within a period of 45 days, failing which
          they shall lose their right  to be heard.
                  Section  10.  Having regard  to the inquiry papers and the
         opinions referred to  in  the  preceding Sections which shall be forwarded

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to it by the Prefect, the Inspection Service for Registered  Installations
shall prepare a report on the application for authorisation  and on  the
results of the inquiry; this report shall be submitted  to  the  Health
Council of the departement by the Prefect.

         The Inspection Service for Registered Installations shall  also
submit to the Health Council of the department its proposals  concerning
either the refusal of the application or the proposed regulations.

         The applicant shall be entitled to be heard by the  Council or
to appoint an agent for this purpose* He shall be  informed by  the
Prefect at least eight days in advance of the date and  place of the
meeting of the Council and shall at the same time  be  sent  a  copy of
the proposals of the Inspection Service for Registered  Installations.

         Section 11.  The draft Order containing the  decision  on the
application shall be brought to the attention of the  applicant by the
Prefect, and the applicant shall be granted 15 days in  which to submit
any written observations to the Prefect, either directly or  through
his agent.

         The Prefect shall take his decision within three  months from
the date of reception by the Prefecture of the inquiry  file  from the
Commissioner or, in the case referred to in Section 15, within three
months following receipt of an opinion from the Departmental Council
(Conseil General) or from the expiry of the period specified in that
Section. Should it be impossible to reach a decision  within  such a
period, the Prefect shall, by Order stating the reasons therefore,  fix
a new time period*

         Section 12.  Where several registered installations are to
be operated by the same operator on a same site, a single  application
for authorisation may be submitted covering all such  installations.
A single inquiry shall be made and a single Order  may be issued and
lay down the regulations referred to in Section 17.
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                    Section 13.  Operation of the installation before the Order
           of the Prefect has been issued shall automatically result in rejection
           of the application for authorisation in the event an unfavourable opinion
           is received from the Health Council of the departement.

                    Section 14,  With regard to oil installations, the nature and
           size of which shall be defined by Joint Order of the Minister responsi-
           ble for hydrocarbons and the Minister responsible for registered instal-
           lations, authorisation under the legislation on registered installations
           shall only be issued after the opinion of the Minister responsible for
           hydrocarbons has been obtained concerning the application of the provi-
           sions of the Act of March 30, 1928 on the regime governing oil imports
           and the Decrees relating to the interministerial committee on hydrocarbon
           depots.
L
                    To this end, when the enquiry is opened the Prefect shall
           forward to the Minister responsible for hydrocarbons supporting documents
           which will enable him to reach a conclusion* The Minister responsible
           for hydrocarbons shall have three months in which to express his opinion.

                    Section 15.  A Decree referred to the Council of State and
           issued on the proposal of the Minister responsible for registered ins-
           tallations shall, after the opinions of the Ministers concerned have
           been obtained, determine the categories of installations in the Register
           of  Registered Installations which, due to scale of impending nuisance or
           danger, may only be authorised after the opinion of the Departmental
           Council (Conseil General) has been obtained.
                    In the case of such installations, the Prefect shall lay the
          matter before the Departmental Council on the opening of the enquiry.
          The  opinion of the Departmental Council shall only be taken into consi-
          deration if it is expressed within a period of six months.

                    Section 16.  Without prejudice to the application of Section 15,
          where  due to their location, installations in the categories referred
          to in  that Section threaten any nuisances or danger to several departe-
          raents, the opinion of the Regional Council or Councils concerned shall
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be requested and the authorisation shall be granted by  the Minister
responsible for registered installations*

         To this end, the Prefect of the departement  in which  the
installation is to be located shall lay the matter before the  Minister
responsible for registered installations before  the enquiry  is opened.
Within a period of two months after the public enquiry  is opened the
Minister shall notify the Regional Prefect or Prefects  that  they are
to lay the matter before the Regional Council or Councils concerned
within a period of one month. Consideration shall only  be given to
opinions expressed within a period of eight months.

         The results of the enquiry and consultations shall  be
forwarded within eight days to  the Minister responsible for  registered
installations by the Prefects concerned.

         Within a period of three months from their receipt  the
Minister, after consulting the  Higher Council for Registered Instal-
lations, shall state his decision by Order and  shall  determine the
regulations referred to in Section 17. In the event no  ruling  is
possible within such a period,  the Minister shall fix a new  time
period by Order giving his reasons therefore.

         Supplementary orders subsequent to such authorisation shall
be issued by the Prefect of the departement where the installation is
located under the conditions specified in Sections 18 and 20.

         Section 17.  Layout and operating conditions shall  comply
with the regulations contained  in the Order of authorisation and,
where appropriate, in the supplementary Orders*

         Such regulations shall have particular  regard  to the  effi-
ciency and economy of available techniques as well as the quality,
function and use of the surrounding environment.
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                  In the case of installations subject to technical rules
         contained in a Ministerial Order under Section 7 of the Act of
         July 19, 1976, the authorising Order may lay down special arrangements
         for the application of such rules.

                  The authorising Order shall lay down the analysis and measurement
         procedures necessary for inspecting the installation and monitoring its
         effects on the environment, as well as the conditions in which the
         results of such analyses and measurements shall be brought to the
         attention of the Inspection Service for Registered Installations.

                  Section 18.  Supplementary Orders may be issued on the proposal
         of  the  Inspection Service for Registered Installations and after obtai-
         ning the opinion of the Health Council of the departement. They may
         prescribe any further regulations needed for protecting the interests
         specified in Section 1 of the Act of July 19, 1976, or may ease ori-
         ginal regulations whose continuation is no longer justified.

                  The operator shall be entitled to be heard and submit his
         observations under the conditions described in paragraph 3 of Section 10
         and in  the first paragraph of Section 11.

                  Section 19.  The regulations referred to in Sections 17 and
         18  shall also apply to other installations or equipment operated by
         the applicant which, whether or not mentioned in the Register, are
         liable  due to their proximity or connection to an installation subject
         to  authorisation to alter any danger or nuisance threatened by such
         installation.

                  Section 20*  Any change made by the applicant to the instal-
         lation,  to its mode of operation or surroundings, which may signifi-
         cantly  alter the facts reported in the application for authorisation
         shall be brought to the attention of the Prefect, together with any
         relevant Justification, before being carried out.
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         The Prefect shall where necessary  issue  further regulations
in the forms referred to in Section  18.

         Where he considers, after obtaining  the  opinion of  the
Inspection Service for Registered Installations,  that  the alterations
threaten any danger or nuisance mentioned in  Section 1 of the  Act  of
July 19, 1976, the Prefect shall invite  the operator to submit a  fresh
application for authorisation.

         The applications referred to  in the  two  preceding paragraphs
are subject to the same formalities  as initial  applications  for autho-
risation.

         Section 21.  For the information of  third  parties:

1.       Copy of the authorising Order and, as  the  case may  be, of
supplementary Orders shall be lodged at  the Town  Hall  (in Paris at
Police Headquarters) and shall be available for consultation;

2.       Extracts from the Orders, setting  out  in particular the
regulations to which the installation  is subject, shall be displayed
at the Town Hall (in Paris at Police Headquarters)  for a period of
at least one month; the official record  of  the  completion of these
formalities shall be prepared by the Mayor  (in  Paris by the  Police
Superintendent).

         The same extracts shall be  permanently displayed in a visible
fashion within the installation by the recipient  of the authorisation.

         A certified copy of the Order shall  be sent to every  Municipal,
Departmental or Regional Council consulted.

3.       A notice shall be inserted  by the  Prefect  at  the operator's
expense in two local or regional newspapers circulating throughout the
department or departements concerned.
                                                       «*•
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               At  the request  of  the  operator  certain provisions of  the
      Order way be excluded  from  the  publicity referred to in this Section
      whenever manufacturing secrets  might  thus be  divulged.

               Section 22.   The Prefect may, by Order made in the forms  and
      subject to the publicity arrangements specified above,  grant,  at the
      request of the operator, an authorisation for a limited period:

               'Where new processes are to be introduced in the installation;

               Or  where, in  the vicinity of the site on which the installation
      is to be located, changes are proposed in conditions of residence  or
      type of land use.

               The recipient of an authorisation of limited duration who
      wishes to obtain its renewal shall submit a fresh application  which
      shall be subject to the  same formalities as the initial application.

               Section 23.   When  the  installation is to operate for  less
      than one year, starting  within  a period  incompatible with the  normal
      course of the investigation procedure, the Prefect may, at the request
      of the operator and following a report made by the Inspection  Service
      for Registered Installations, grant an authorisation for a period  of
      six months renewable once,  without public enquiry and without  undertaking
      the consultations referred  to in Sections 8,  9 and 14 to 16.

               The temporary Order of authorisation by the Prefect shall
      specify the  regulations  referred to in Section 17. It shall be subject
      to the publicity arrangements set out in Section 21  above.

               Section 24.   The Order of authorisation shall  cease to  have
      effect when  the registered  installation  does  not begin  operations  within
      a period of  three years, or is  not operated for two  consecutive  years,
      save in cases of force majeure.
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                      TITLE  n
  PROVISIONS APPLICABLE TO INSTALLATIONS SUBJECT TO
                     DECLARATION
         Section 25 >  The declaration concerning an  installation shall
be submitted, before the installation begins  operations,  to  the  Prefect
of the departement in which the installation  is to be  located*

         The declaration shall state:

1.       In the case of a natural person, his name,  first names  and
habitual residence, and in the case of a  legal person,  its trade name
or company name, its legal form, the address  of its  registered office
and the capacity of the signatory of the  declaration.

2*       The site on which the installation is to be located.

3.       The nature and volume of the activities that  the applicant
proposes to undertake and the section or  sections of the  Register in
which the installation should be recorded.

         The applicant shall submit a land registry  plan  of  100  metres
radius and an overall plan at least to scale  1/200,  accompanied  by a key
and if necessary descriptions sufficient  to explain  the material layout
of the installation and indicating the use made up to  at  least 35 metres
from the installation, of neighbouring buildings and land, and showing
water outlets, canals, water courses and  drains. The mode and conditions
of use, purification and disposal of waste water and emanations  of all
kinds, as well as regarding the removal of wastes and  residues from the
installation shall be stated. The declaration shall  also  mention measures
proposed to be taken in the event of accident. The scale  may, with the
agreement of the Prefect, be reduced to 1/1,OOO.
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               The declaration  and  the  documents  set  out  above  shall be
      submitted  in triplicate.

               "With regard  to certain oil  establishments, the nature and
      size of which shall be defined by Joint Orders  of the Minister respon-
      sible for  registered  installations and the  Minister responsible for
      hydrocarbons, the declaration documents shall only  be admissible if
      they include a favourable opinion from the  Minister responsible for
      hydrocarbons concerning application  of the  Act  of March 30,  1928
      on the regime governing oil imports  and the Decrees relating to the
      interministerial committee on hydrocarbon depots.

               Section 26»  Should the Prefect consider that the proposed
      installation is not covered by the Register of  Registered Installations
      or that it comes under the system of authorisation, he shall notify
      the person concerned  accordingly.

               Should he consider that  the declaration is in form  irregular
      or incomplete, the Prefect shall  request the person making the decla-
      ration to regularise  or complete  it.

               Section 27.  The Prefect shall acknowledge receipt  of the
      declaration and shall send the person making it a copy of the general
      regulations applicable to the installation.

               The Mayor of the commune where the installation  is  to be
      operated (in Paris the Police Superintendent) shall be sent  a copy
      of the declaration and the text of the general  regulations.  A copy
      of the receipt shall  be displayed for a period  of at least one month
      at the Town Hall (in  Paris at Police Headquarters)  mentioning the
      possibility for third parties of  consulting the text of the  general
      regulation on the spot. The official record of  compliance with this
      formality shall be prepared by the Mayor (in Paris  by the Police
      Superintendent).
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         At the request of the operator, certain provisions may be
excluded from such publicity whenever manufacturing  secrets might
thus be divulged.

         Section 28.  Layout and operating conditions  shall comply
with the general regulations referred to in Section  3  of  the Act of
July 19, 1976 and, where appropriate, with any  special provisions
introduced under Section 30 below.

         Section 29.  The general regulations applicable  to installa-
tions subject to declaration shall be the subject of Prefectoral Orders
made under the authority of the Minister responsible for  registered
installations, after obtaining the opinion of the Health  Council of
the department. Amendments and adaptations referred to in Section  10
(2nd paragraph) of the Act of July 19,  1976 shall be effected by
Prefectoral Orders based on reports from the Inspection Service for
Registered Installations and advice received from the  Health Council
of the department.

         Certified copies of the Orders referred to  in the preceding
paragraph shall be sent to all mayors of the departement  and extracts
therefrom shall be published in two local or regional  newspapers cir-
culating throughout the departement.

         Section 30.  Should the person making  the declaration wish
to have any of the regulations applicable to the installation amended,
he shall submit an application to the Prefect,  who shall  give his
decision by Order.

         Orders made under the preceding paragraph and those referred
to in Sections 10 (third paragraph) and 11 of the Act  of  the July  19,
1976 shall be based on reports from the Inspection Service for Regis-
tered Installations and on advice received from the  Health Council of
the departement. They shall be subject  to the publicity arrangements
referred to in Section 27.
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             The applicant shall be entitled to be heard by the Council
    or to appoint an agent for that purpose. He shall be notified at least
    eight days  in advance  of  the date and place of the meeting of the
    Council and shall at the  same time be supplied with a copy of proposals
    by the Inspection Service for Registered Installations.

             The draft Order  shall be notified by the Prefect to the
    applicant and the latter  shall have 15 days in which to forward any
    written observations to the Prefect,  either directly or through his
    agent.

             Section  31.   Any change by the applicant to the installation,
    to its mode  of operation  or surroundings,  which may significantly alter
    the facts reported in  the initial declaration, shall be brought to the
    attention of  the  Prefect  before being carried out, and the Prefect may
    then require  a fresh declaration to be submitted.

             Any  transfer  to  another site of an installation subject to
    declaration  shall  require a fresh declaration.

             The  declarations referred to in the two preceding paragraphs
    shall be subject  to the same formalities as initial declarations.

             Section 32.   The declaration shall cease to have effect when
    the installation  does  not begin operations within a period of three
    years, or is not operated for more than two consecutive years, save in
    cases of force majeure.
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                     TITLE  HI
  PROVISIONS CCMMCN TO ALL REGISTERED INSTALLATIONS
         Section 33.  The Head of the Interdepartmental  Service  for
Industry and Mines  shall be responsible, under  the authority  of the
Prefect, for organising the inspection of registered  installations.

         Inspectors of registered installations shall be  engineers or
technicians appointed by the Prefect on the proposal  of the Head  of the
Interdepartmental Service for Industry and Mines. However, the appoint-
ment of inspectors  responsible for the inspection of  installations
comprised in an agricultural holding, and of  stock farms, abattoirs
and knacker's yards shall be made on the proposal of  the  Director of
Agriculture for the departement.

         The appointment of civil servants shall be subject to
authorisation by their superior officer.

         The Departmental Council may create  posts in the departement
for the inspection  of registered installations. Under Sections 89 and  90
of the Act of August 10, 1871, two or more departements may jointly
determine how the expenditure resulting from  the creating of  such posts
should be shared between them, where inspectors are appointed to  carry
out their functions in the departements in question.

         The salaries and allowances of inspectors occupying  the
posts referred to in the preceding paragraph  and, where appropriate,
allowances paid to  civil servants responsible for inspection  shall be
fixed by the Departmental Council, on the proposal of the Prefect and
shall be charged to the budget of the departement.
         Section 34.  When the operator of an authorised or  declared
installation changes, the new operator or his representative shall  so
inform the Prefect by declaration within the month  following the  take-
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      over of operation.  Such  declaration shall mention,  in the case of a
      natural person,  the name,  first  names  and permanent residence of the
      new operator and, in the case  of a  legal  person,  its trade name or
      company name,  its legal  form,  the address of  its  registered office
      and the capacity of the  signatory of the  declaration* A receipt for
      such declaration shall be  issued without  charge.

              When an  installation ceases to be operated for the activities
      which had required  the authorisation or declaration, the operator shall
      restore the site of the  installation in such  a way as to remove the
      threat of any  danger or  nuisance referred to  in Section 1 of the Act
      of July 19, 1976. In default,  effect may  be given to the procedures
      referred to in  Section  23 of  that  Act.

              Section  35.  In  the case of existing  installations subject
      to the provisions of Section 16  of  the Act of July 19, 1976, the
      operator shall,  before December  31, 1978  supply the Jrefect with the
      following informations*

      1.      In the case of a natural person,  his  name,  first names and
      habitual residence; in the case  of  a legal person,  its trade name or
      company name,  its legal  form,  the address of  its  registered office and
      the capacity of  the signatory  of the declaration;
      2.
The site of the installation;
      3.      The nature  and volume of the activities undertaken and the
      section or sections of the Register in which the installation should
      be recorded.

              Section 36.  Installations which, after having regularly
      begun operations, are made subject, by virtue of a decree relating
      to the Register of  Registered Installations, to authorisation or
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declaration may continue to operate without  such authorisation or
declaration, subject to the provisions  set out below,  on the sole
condition that the operator has  supplied  to  the Prefect  or supplies
him within the six months following the publication  of the decree,
with the information specified in  the preceding section.

         Section 37.  In the cases referred  to in  Sections 35 and 36,
the Prefect may require production of the documents  referred to in
Sections 3 or 25 of this Decree.

         The Prefect may, in the circumstances referred  to in Sections
18 and 30 above, prescribe appropriate measures for  safeguarding the
interests specified in Section 1 of the Act  of July  19,  1976.

         Such measures shall involve no large  scale  alterations to the
structure of the installation, nor major  changes in  its  mode of
operation.

         The provisions of the preceding  paragraph shall cease to
have effect when operations have been interrupted  for  two consecutive
years, save in case of force majeure or when the installation is
covered by Sections 20, 31 or 39 of this  Decree.

         Section 38.  The operator of an  installation  subject to
authorisation or declaration shall promptly  notify the Inspection
Service for Registered Installations of any  accident or  incident
occurring as a result of operating such installation such as to
threaten the interests specified in Section  1  of the Act of
July 19, 1976.

         Section 39.  The Prefect  may decide that  the  renewed
operation of an installation temporarily  out of use  as a result of
fire, explosion or any other accident resulting from its operation
shall be subject, as the case may  be, to  fresh authorisation or
declaration.
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             Section 40.  By order issued after consulting the Higher Council
     for Registered Installations, the Minister responsible for registered
     installations may give his official approval to laboratories or other
     bodies for the purpose of any analyses or inspections which may be
     prescribed under this Decree and charged to the operators.

             Section 41.  When an installation has been the subject of a
     direction for its dismantling, closure or suspension, the operator shall
     take all necessary steps for the supervision of the installation, the
     safeguarding of supplies, and the removal of any dangerous, perishable
     or obnoxious materials, and any animals within the installation.
             If the operator fails to take the necessary steps effect may
     be given to the procedures under Section 23 of the Act of July 19, 1976.

             Section 42.  When an installation is to be established on the
     territory of several departments, the application or declaration
     required by this Decree shall be submitted to the Prefects of all the
     departements, who shall proceed with their preliminary investigations
     in accordance with this Decree; decisions shall be made by Joint Order
     of such Prefect, save in the case specified in Section 16.

             Section43.  The following shall be liable to a fine of
     Frs.600 to Frs.2,000:

     1.      Any person who operates an installation subject to declaration
     without having made the declaration referred to in Section 3 of the Act
     of July 19, 1976;

     2.      Any person who fails to take the measures required of him
     under Section 26 of the Act of July 19, 1976;

     3.      Any person who operates an installation subject to authorisation
     whithout complying with the regulations referred to in Sections 17 and
     18 of this Decree;
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4.      Any person who operates an  installation subject to declaration
without complying with the general  or  special  regulations referred to
in Sections 28, 29 and 30 of this Decree;

5.      Any person who fails to give the notifications referred to in
Sections 20 (first paragraph) and 31 (first  paragraph) of this Decree;

6.      .Any person who fails to make the declaration or give the
notification referred to in Section 34 of  this Decree;

7.      Any person who, after being served notice so to do, fails
to comply with the regulations applied to  him under Section 34 (third
paragraph) of this Decree;

8.      Any person who fails to supply the information specified in
Sections 35 and 36 of this Decree;

9.      Any person who fails to submit the declaration referred to
in Section 38 of  this Decree.
                       TITLE  TV
               TRANSITIONAL IROVISICNS
         Section 44.   For the time being, the Register of Dangerous,
Insanitary, Noisy or Noxious Establishments under the Decree of
May 20,  1953  as amended shall constitute the Register of Installations
Registered  for  the Protection of the Environment referred to in Section 2
of the Act  of July 19,  1976.

         For the application of the preceding paragraph dangerous,
insanitary, noisy or noxious establishments of categories 1 and 2 shall
                                                 PROCEEDINGS—PAGE 223
                                              First US-France Conference on
                                          Photochemical Ozone/Oxldants Pollution

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    be  installations  subject  to  authorisation and dangerous, insanitary,
    noisy or noxious  establishments  of  category 3 shall be installations
    subject to declaration*

            The radius  for the display  of notices to the public referred
    to  in Section 3,  6  and 8  of  this Decree  shall be that appearing in the
    Register of Dangerous, Insanitary,  Noisy or Noxious establishments;
    failing that it shall be  500 metres.

            Section 45.  The  provisions of this Decree shall not apply
    to  requests for authorisation in respect of which an enquiry has been
    opened prior to the date  of  entry into force of this Decree.
                            TITLE  V
                    MISCELLANEOUS PROVISIONS
            Section 46.  A Joint  Order  of the Minister responsible for
    registered installations,  the Minister of the Interior and the Minister
    of Finance shall  lay down  the terms of compensation for the Commissioner
    conducting the enquiry*

            Section 47.  The powers conferred on the Prefect by the Act
    of July 19, 1976  and by this  Decree shall be exercised in Paris by the
    Prefect of Police.

            Section 48•  Section  2 of the Decree of March 23, 1973 shall
    be amended as follows:

            •'Section  2. The benefit of  reductions in rates for small
    businessmen and for other  undertakings (the remainder unchanged)*"
       PROCEEDINGS—PAGE 224
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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        Section 49.  All  provisions contrary to those of this Decree
shall be repealed, notably Decree No.  64.303 of April 1, 1964.

        Section 50.  The  Keeper  of  the Seals, Minister of Justice,
the Minister of the Interior,  the Minister of Defence, the Minister
of Culture and the Environment,  the Minister delegate for the Economy
and Finance, the Minister of Equipment and Town Planning, the Minister
of Agriculture, the Minister of  Industry, Conmerce and Craft Trades,
the Minister of Labour  and the Minister of Health and Social Security
shall be responsible, so  far as  each of them is concerned, for the
execution of this Decree, which  shall  be published in the Official
Journal of the French Republic.
        Issued at Taris  September 21, 1977.
                                               PROCEEDINGS—PAGE 225
                                            First US-France Conference on
                                        Photochemical  Ozone/Oxidants Pollution

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         REGLEMENTATION DE  LA POLLUTION

               DE  L'AIR EN  FRANCE
           presented by Daniel  Duvoid




Hinistere de 1'Environnement et du Cadre de Vie

                      France
                                                 PROCEEDINGS-PAGE 227
                                              First US-France Conference on
                                         Photochemical Ozone/Oxidants Pollution

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        REGLEMENTATION DE LA POLLUTION DE

                 L'AIR EN FRANCE


                        par


                  Daniel DUVOID
           lere reunion FRANCE - U.S.A.

             sur la pollution par les

             oxydants photochimiques
              Research  Triangle Park

                      27 - 28
MINISTERS DE L'ENVIRONNEMENT ET DU CADRE DE VIE
   Direction de la Prevention des Pollutions

14, Bd  du General Leclerc - 92521 Neuilly/Seine
              Telephone  :  758.12.12
                                           PROCEEDINGS—PAGE 229
                                        First US-France Conference on
                                     Photochemical Ozone/Oxidants Pollution

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            REGLEMENTATION DE LA  POLLUTION
                  DE L'AIR EN FRANCE
           Le  probleme de la pollution de I1air par les  oxydants
photochimiques  n'a ete souleve  en  France que tres recemment.
Cela explique que nous ne possedions  pas encore de reglementation
specifique a  cette forme de pollution.
          Aussi,  nous nous proposons  d'examiner les grandes
lignes de notre reglementation  et  voir comment elle peut  etre
applicable  a  1'avenir au probleme  des oxydants. Enfin, nous
presenterons  les  moyens de mesure  qui sont actuellement  en
place pour  la surveillance de la pollution atmospherique  dans
1'ambiance  et a 1'emission.
                                              PROCEEDINGS—PAGE 231
                                           First US-France Conference on
                                        Photochemical Ozone/Oxidants Pollution

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I - LA REGLEMENTATION DBS SOURCES FIXES

    1. Le fonctionnement du mecanisme  reglementaire

                 II est base  essentiellement  sur  la loi  du 19 Juillet
    1976 qui vise 1'ensemble  des installations  polluantes.

              La loi s'applique systematiquement  a  toutes les instal-
    lations nouvelles ou qui  subissent des  transformations impor-
    tantes. Pour le cas des installations existantes,  les prescrip-
    tions sont laissees a 1'appreciation des  autorites locales en
    fonction des problemes particuliers qu'elles  posent.

              Cette loi accompagnee de ses  textes d'application
    fonctionne suivant le mecanisme ci-apres  :
    - Les activates industrielles qui presentent  des  dangers graves
      pour 1'environnement sont repertoriees  dans une  liste dite
      "Nomenclature des Installations Classees".  Cette liste peut
      etre modifiee sur proposition du Ministere  de 1'Environnement
      chaque fois que necessaire. Aujourd'hui,  cette  liste comporte
      environ 300 rubriques qui correspondent a 50  000 installations.

    - Lorsqu'un industriel souhaite construire  une  installation dont
      1'activite correspond a une des rubriques de  cette  liste,  il
      doit, avant de commencer la construction, demander  une autori-
      sation a 1'Administration locale. II  doit attendre  d'avoir recu
      cette autorisation, avant de commencer  1'exploitation de
      1'installation.

    - Le  dossier de demande d'autorisation  doit comporter principa-
      lement :
      • les resultats d'une etude d'impact  chargee  d'evaluer les
        consequences qu'aura  sur 1'environnement  le fonctionnement
        de 1'installation ;
                                                  PROCEEDINGS—PAGE 233
                                                First US-France Conference on
                                             Photochemical Ozone/Oxidants Pollution

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     • la description de 1'installation et des precedes de
       fabrication ;
     « la description des moyens de prevention qu'il se propose  de
       mettre en place ;
     • les performances des  moyens de prevention.

  Lorsque le dossier est juge complet,  il est soumis a 1'avis
  des  populations pendant 1 mois.

  L'Administration locale examine ensuite les avis recus et
  1*ensemble du dossier. Si 1'autorisation est accordee, on
  mentionne  dans ce  document les prescriptions que devra respec-
  ter  1'industriel :  normes d1emission, mise en place de moyens
  de mesure  automatique  a I1emission et autour de 1'installation,
  analyses periodiques,  etc...

  On remarquera que  pendant le  deroulement de la procedure
  d'autorisation,  surtout pour  les dossiers importants, de
  nombreuses discussions ont lieu entre 1'Administration et
  1'industriel  pour  determiner  les meilleurs moyens de prevention
  a  mettre en place  et la valeur des normes d'emission.
2« Les textes reglementaires nationaux qui visent lesbranches
   indus trielies  import ant es

          Nous  avons  vu  que le dossier de chaque installation est
traite par 1'Administration locale.  Pour que les decisions prises
soient suffisamment hotnogenes sur 1* ensemble du Pays, nous dis-
posons de 10 textes reglementaires (instructions ou arretes), qui
precisent en detail les  prescriptions minimales qui doivent etre
exigees dans toutes les  installations nouvelles qui appartiennent
a 10 categories d'activites industrielles (branches industriel-
les). Ces branches industrielles sont les suivantes (voir tableau
n° 3).
      PROCEEDINGS—PAGE 234
   First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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          Les  prescriptions indiquees dans ces textes  sont  mini-
males, c'est-a-dire  que 1'Administration locale peut les  rendre
plus severes ou  en ajouter de nouvelles si les conditions locales
le justifient.

          Pour les installations qui n'appartiennent pas  a  ces
branches industrielles  mais dont 1'activite figure a la nomencla-
ture des installations  classees, les prescriptions sont determi-
nees sur la base de  ce  qui a ete demande sur d'autres  instal-
lations du meme  type en France ou en fonction d'experiences a
1'Etranger.
3. Principales  prescriptions  pour reduire la pollution o^e 1,'air

          Nous  allons  examiner les deux plus importantes  : les
normes maximales  d1emission et les moyens de mesure.


     a. Normes  maximales  d1emission

          L'originalite de  notre reglementation consiste dans le
fait qu'elle ne prevoit pas de normes limites pour les differents
polluants dans  1'air ambiant.  En revanche, nous fixons chaque
fois que possible  des normes  limites d'emission, ou des perfor-
mances minimales  pour les dispositifs d'epuration.

          Si nous  reprenons la liste des branches industrielles
importantes, les normes d'emission sont les suivantes (voir
tableau n° 3).

          Comme nous le voyons,  les normes nationales limites
portent surtout sur les poussieres exprimees en concentration
massique et tres peu sur  les  gaz (seulement les oxydes d'azote
et les odeurs).
                                              PROCEEDINGS—PAGE 235
                                            First US-France Conference on
                                        Photochemical Ozone/Oxidants Pollution

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            On doit toutefois faire une triple remarque  :

    Des  normes particulieres sur les poussieres sont fixees pour
    certaines  installations qui emettent des poussieres  toxiques  :
    cas  du  plomb et de 1'amiante par exemple ou les normes attei-
    gnent respectivement 10 mg/m3 et 0,5 rag/m3 (en poussiere
    totale).

    Des  normes sont fixees au coup par coup pour certains gaz
    dangereux  dans 1'industrie chimique (monochlorure de vinyle,
    polychlorure de biphenyl, chlore, etc...). En outre, des quotas
    d'emission en HC sont fixes aux raffineries.

    Notre reglementation comporte le principe fondamental suivant  :
    la valeur  des normes a I1emission est revisable dans le sens
    d'une plus grande severite en fonction de 1'apparition de
    nouvelles  techniques d'epuration plus performantes ou de la
    decouverte de dangers pour 1'environnement.
      b. Mo^ens^de mesure

            Le  tableau n° 3 donne les branches industrielles  pour
 lesquelles la mesure en continu a la source est obligatoire.
 Remarquons qu'il s'agit de la mesure en continu de la  concentra-
 tion massique des poussieres et non de 1'opacite. Ces  mesures  en
 continu sont  completees par des mesures manuelles. Sur les  unites
 d'acide nitrique, on effectue la mesure en continu des NOx.

            Parmi  les  prescriptions qui sont fixees a 1'occasion
 de 1'autorisation pour une installation, la reglementation  permet
 d'imposer  a 1'industriel la mise en place d'un reseau  de mesure
 au voisinage  de  1'installation. Nous presenterons la constitution
 de ces reseaux a la  fin de 1'expose.
      PROCEEDINGS—PAGE 236
   First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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II - LA REGLEMENTATION  DBS  SOURCES MOBILES

               Nous  appliquons en France depuis 1971 la  reglementation
     des Communautes Europeennes.


     1. Vehicules a moteur  a  essence

               La reglementation consiste a mesurer les  quantites  de
     CO, HC et de NOx emises  pendant un cycle parcouru par  le  vehicule
     a homolojruer sur un  bane a rouleaux. Le cycle utilise  est le
     cycle europeen  et  correspond environ a 4 km.

               Les emissions  limites autorisees sont fonction  de la
     masse du vehicule. Par exemple, pour un vehicule de  1  250 kg,  les
     limites d1emission exprimees en g/essai sont de 8?  g CO,  7,1  g HC
     et 10,2 g NOx.

               Les vehicules  en service sont controles de maniere
     inopinee sur la route.  Us doivent respecter une emission maxi-
     male de 4,5 9» CO au  regime de ralenti .


     2 . V e hi c uAe s a mot eur  di e s e 1

               La reglementation europeenne qui date de  1975 (alors
     que la reglementation  francaise existait des 1964) consiste
     seulement a limiter  les  emissions de fumee.

               Au niveau  de  1'homologation, on effectue deux types
     d'essais : des essais  a  differents regimes stabilises  sur bane
     a rouleaux et des essais en acceleration libre. Dans chaque cas,
     on mesure 1'opacite  des  fumees  (non 1'emission massique).

               Sur les vehiculjj en  service, on n1effectue  que
     1'essai en acceleration  libre.               PROCEEDINGS-PAGE 237
                                                First US-France Conference on
                                             Photochemical Ozone/Oxidants  Pollution

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  3.  Evolution de la reglementation des sources mobiles

            Depuis 1971, toutes  les limites d1emission ont  ete
  revisees plusieurs fois  dans le  sens d'une plus grande  severite.

            Les prochaines modifications prevues sont les
  suivantes :

  - Une  reglementation communautaire devrait etre prochainement
   adoptee pour CO et HC, concernant les  vehicules a deux  roues.

  - En  198l -  83, reglement  communautaire  concernant les  emissions
   de  CO,  HC  et NOx des vehicules diesels.

  - En  1983 -  85, proposition de nouvelles normes plus severes pour
   CO,  HC et  NOx, concernant les  vehicules a moteur a essence.
      PROCEEDINGS—PAGE 238
   First US-Trance Conference on
Photochemical Ozone/Oxidants Pollution

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- LES MOYENS DE MESURE ACTUELLEMENT UTILISES EN FRANCE

  1. Les mesures a 1'emission

            Un tres gros  effort  a ete fait en France pour develop-
  per les appareils de roesure  de concentration massique de poussiere
  a 1'emission. Pour  verifier  le respect des normes, on s'oriente
  vers 1'utilisation  d'appareils automatiques utilisant le principe
  de la jauge ^3. Au cours  de 1981-82,  la moitie des centrales ther-
  miques de production d'electricite seront equipees de ces
  appareils.

            Nous disposons  par ailleurs d'appareils optiques pour
  le controle des installations  plus petites et pour la detection
  de la deterioration des  filtres a manche.
  2. Les reseaux de mesure  dans  1'environnement
            La surveillance  de  la  pollution atmospherique est
  assuree aujourd'hui par  :
  • 60 reseaux de surveillance
  •  9 reseaux d'alerte
  • 12 stations multipolluant informatisees.
(en service ou en
 cours d'installatior
            Les reseaux de  surveillance  ou d'alerte sont constitues
  principalement d'appareils  de  mesure  automatiques du S02. Une
  dizaine de ces reseaux comporte  des  appareils de mesure automa-
  tiques de HC, NOx, CO et des poussieres en suspension par jauge p.

            Les stations "multipolluant" mesurent S02,  CO, NOx, HC,
  03 et les poussieres en suspension. Dans ces stations les donnees
  sont archivees sur "flopy disque"  et  centralisees au niveau
  national pour le traitement et la  constitution d'une banque de
  donnees.
                                               PROCEEDINGS—PAGE 239
                                             First US-France Conference on
                                         Photochemical Ozone/Oxidants Pollution

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IV - REFLEXION SUR LA REGLEMENTATION7 FRANCAISE EN REGARD DU PROBLEME

     DES OXYDANTS PHOTOCHIMIQUES
               Bien que notre  reglementation ne comporte pas de  dispo-
     sitions specifiques  aux oxydants,  nous devons retenir que  :

     * Pour les sources fixes,  la loi  de juillet 1976 permet a  tout
       moment d'elaborer  de nouvelles  prescriptions pour un polluant
       donne sur 1'ensemble d'une branche industrielle.

     • Pour les sources mobiles,  nous  sommes lies aux directives  de
       la Communaute Europeenne pour les normes d'homologation  des
       vehicules.
     0 L'ensemble des reglements  evoluent dans le sens d'une plus
       grande severite.

               Nous nous  trouvons actuellement dans une phase d'obser-
     vation et de recherche en  ce qui  concerne le probleme des  oxy-
     dants .

               Si ces recherches  nous  montrent que cette forme  de
     pollution risque de  poser  un probleme sur certaines zones  de
     notre territoire, de nouvelles prescriptions,  eventuellement
     limitees a certaines regions, pourront etre fixees sur la  base
     du cadre reglementaire existant.
        PROCEEDINGS—PAGE 240
     First US-France Conference on
  Photochemical Ozone/Oxidants Pollution

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r
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                                                                                               PROCEEDINGS—PAGE  241
                                                                                          First  US-France  Conference  on
                                                                                      Photochemical  Ozone/Oxidants  Pollution

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         PROCEEDINGS--PAGE 242
     First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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         PROCEEDINGS—PAGE  244
     First US-France Conference  on
Photochemical  Ozone/Oxidants  Pollution

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                                                PROCEEDINGS—PAGE  245
                                            First US-France Conference on
                                      Photochemical  Ozone/Oxidants  Pollution

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                                                                           TABLEAU n°  4
                EUROPEAN TEST  FOR HOMOLOGATION OF GASOLINE ENGINE VEHICLES
            V km/h
                                                         125
150       175      200
             EMISSION STANDARDS FOR  HOMOLOGATION  OF GASOLINE  ENGINE VEHICLES
Mass of the Vehicle
kg
M ^ 750
750 < M $ 85°
850 < M $ 1 020
1 020 < M ^ 1 250
1 250 < M ^ 1 470
1 470 < M ^ 1 700
1 700 < M 4 1 930
1 930 < M ^ 2 150
2 150 < M
4
Carbon Monoxyde
a/test
65
71
76
87
99
no
121
132
143
Hydrocarbon
9/test
6.0
6.3
6.5
7.1
7.6
8.1
8.6
9.1
9.6
NOx
g/test
8.5
8.5
8.5
10.2
11.9
12.3
12.8
13.2
13.6
       PROCEEDINGS—PAGE  246
    First US-France Conference on
Photochemical  Ozone/Oxidants Pollution

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PRE-ALARM AND PREVISION AID  SYSTEM


FOR AMBIANT AIR  MONITORING NETWORKS
   presented  by Jean Michel  Faqe




       Societe  Bertin &  Cie

              France
                                         PROCEEDINGS—PASE 247
                                      First US-France Conference on
                                  Photochemical Ozone/Oxidants Pollution

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r
              BERTIN & Cie
       Pre  -  alarm   and    Prevision    Aid    System
       for     Ambiant     Air    Monitoring    Networks
                                              by Jacques HOUSSAFIR,  engineer
                                              9ERTIN 4 CO.,  F-78370  Plaisir
                                              Tel. (1) 056 25 00 Telex 696231 I
          . L »  r;--j  .r
                               O*  rOS  MICSO-METEOHGLOGY
c-..tf-«rj;0iy  4r,d' mecnanics  of  turoulence have       causes, e.g.
^  -I'-ir.n,  :r.e*e   !a»t  years  a  new  field  of       it.
..c^'.icn: forecasting ana control  of  aliuospherical
                                                                           to the physical  mechanise-.* that
        3 * ,.-«t:er ol Ijc:,

         tr.« **;*r:ence of pollution  networks has shown that
         c provoite important harmful effects. This
         .s  t.-e proo»«oi of peaks of pollution  (in particular
         usoci«iea    *»:n   strong   temperature  inversions
         :.js* to  tr.e jrcund and tc situations of low wind),

         xvere .iccident*  can occur  in some industrial  iite»
          ieve»o,   lu.y.  Harritburg.  USA);  they  draw  the
         attention ci governments on the necessity  of  being
         .»:..< to  -ir,eteorolQi'.c4t  data.
             «vs,  a.r ?o..yf.jn  :;,cnj:onn4  networn*  produce
            , *re i..r. cf wmcn  is 'c reduce  the  amount  ot
            .cnk  *r.en  concentration  -)f  pollutant  i.tJiurcd
             ;o  '.nc  Arcana  sy  a  tc'ljin nun.ber Jl »«niort
            ^ j  .criain  t;:.,f jvcrnue^  4  urctet  ttire»hu!J.
             ,ev«L  >j  .JetineJ   bv   rr^ulationk,  wn>ch  arc
            i." c>   tci.-i:orjed  or   t.i,graved  bv  .i.eieorolo^ icji
        -•jr.;-r;'js  •jf-jr.gna: puj      .

        .i^j'...,  reauc:.on  01 err. -.ii.cm .T.uxe^  it  acssiCie  to
        avcij :\.rtr:«r -.orsenin^  of  the  situation,  but Joes not
        re:.. eve '1* «L:k>jJ< of pea« of  ^oLiuticn:  -.041 cf th«ri>
        ire ci-iea ay tn« iia-^jut of pol.uied layers  prswiou*-
        .v itjrec  in  lU-.'.uJe M'IJ. 1). It it  thus obvious to
        ur.cer4i.inc: :ij:  ;:ie  apparition  of a pea.< ;f po.lution
        is ;5nr.ec;ea  :o  all  the  ni»tory of  the  itinospn-ric ji
                               .ibcu! 1C1  'icurs before  :ne
                            to '!ie r.rvsTice or tr.e jO*
a function of oieasurements  realizea  by one o°:.oc.<  .n
me  night,  for instance. Such modehzjuon,  '..-.ce^-n-
Oently of used ii>atheinatical tool (statistical  .i.-.4i.s.i
or numerical model)  is made more difficult as*  t^e
phenomena   themselves  ( three-dimensional   tartj:«*.t
t'.ow)  and  by  the  large   aa.ount   of  para>r.< :«r»  :;
consider. To solve  expltcitelv the equations ci  sui-i j
problem  is  really  impossuie,   either in :.-.<\?ry   or
practically  for  a routine  prediction on a mor itcr-.n^
nctvorx.  Consequently,  the models  us«d  in  j*..-
4pproach will be  iiwtyt   drtsttcallv  si;;.p.i: .ed
order  nevertheless to  obtain  from   them  *n  >r('<
prevision,   the  sunpUest  lolution   is   to  f«cu
uiouels  wuh  the  largest  possible amount  cf  rcu  '-.-••'
.•Tiejiuremenis,  suftkcienily  preprocesscd  to  ->j .«  :-.«•
highest content in in/ormation. In particuUr, ;4ris.«-
ters {t.±.  values roujhly eitinated  frcu  othe- c^.^vi-
Ljted  values) will be replaced in  the proc»>ir.j   oy
real measurements nude  in »itu.
                                                    '.n other  words,  reliability ot a  noael can  ^e  -..-;-.
                                                    :ncre   in.proved  in  supplying  it  with  real i.ti:-.j.
                                                    conditions  (!i>easurenients  in  altil'ik^c) anJ.an:.'.
                                                      -.eei.  jctin^ »ocn en sources will  efficient./ re^_oy-,;er.
                                                      .-r!.i .j  prc-oesin." n reu-.v 4 sreventicn '.o;;,
                                                                                  PROCEEDINGS—PAGE 2^9
                                                                              First US-France Conference on
                                                                         Photochemical  Ozone/Oxidints Pollution
                                                                                                  ..>
                                                                                                   In

-------
 Extreib«!y  simplifying,  if  one admit*  that  the  amount
 of  pollution  stored  in  a  temperature  Invernon  11
 proportional 10  the  duration of emu«ion  "under" the
 inversion,   a   limitation  of  enussions  ordered  seven
 hours  in  advance  can  be  up  to  three times  mare ef-
 ficient  tnan  a  limitation   of  emissions  when  peak
 arrives (because such a peak  viU result from £ hours
 storage on 12  instead of 12 on  12).
 A systen. to predict pearcs  of  pollution
 A real  tne alarm  and prevision support  system that
 3ESTIS  is  actually  proposing  for atmospherical pollu-
 tion  ir.enitsring  networks   is  a   direct consequence of
 tnis approach. It consists  i't the following  package:

 II Twc powerful micro-meteorological  instruments:

   . the  ALCYON  EQUIPMENT  fluxraeter  for  real  time
     evaluation   of  all  turbulent  atmosphere-ground
     exchanges (heat,  quantity of movement,  humidity)
     as  we:, as all  parameters usually delivered by  a
     classical  xicro-meteoro logical station.
                                                                 the   BERTlN   Doppler  three-dimensional  Sodar,
                                                                 delivering  real  time vertical  profiles  of  wine
                                                                 modulus and  direction (range up to 300 to 1000m.'
                                                                 and giving an image of the thermal stratification
                                                                 within the planetary  boundary layer.
                                                            2) A  processing centre organized  around a mini-compu-
                                                               ter, the task of  which is:

                                                               .  to store  data (files for further  studies)
                                                               .  to deliver  visual  display (prevision  support'
                                                               .  to run  real  tine  modelling techniques (pre-aiar~.
                                                                  and  alarm)

                                                               Before  to give detailed  description of  the  characte-
                                                               ristics  of this  package,  it is useful  10 define:

                                                               .  what  are the meteorological situations considered
                                                                  a* hazardous from the air quality  point  of  vie*

                                                               .  what  are the  pre-atarm and alarm  procedures to
                                                                  be actually considered.
 ;.i..:--s^,':   VETICSCLCOICA;.  SITUATIONS  FROM THE AIR
 :.A:::Y ?:INT OF VIEW AND new TO PREDICT THEM
 •:  i  j-.v*n  s;:e.  pollution  levels  measured  at  ground
 .eve. ceper.c  ;n:

 - :*,t  nature  of  sources,  wmcn can  be concentrated  or
  oisirisutec'

 - :r.e  p.-.y«:cs  cf  transport:   advection  and  diffusion.
  Acvecucn corresponds  to  a mean movement, diffusion  is
  csnneciec  ic  turouient  movements at  different  scales
  »:tr.ir.   t-.e   planetary  Boundary   layer.   These  two
  p.-.er.cs.er.d  always  exist  »nd  their importance  depends
  en  trie  cvna.-.ic  cnaract-;r'.stics   of  the  flow  (relief,
  r*{esi:vi ar.c  -i' ;ts  sr-.ei.f.il  characteristics (ttmpara-
  :ure ,nv*rsigni.  •«« breeze,  heal  island).
 • -•:.?:• -.c a .  cr  stj'.>;icai  n.cae s

Tc  sres.ct  po..ution  levels  riose  to the ground  in  fact
 -ea.-.s  :c  irecict tfi« benav.our  of the planetary  boundary
.aver.

":   :r,.s  prev.s:or.  is reaii.'.e-J  with  a  numerical  model,
even very s:;r.p .::iea, mis  :ne  must  taxe into considera-
:.cn:
                                                            A rather  complex phenomenon

                                                            In  the  absence  of  important  orographic  effects  ar.c  c:
                                                            strong  thermal  stratification   (temperature  inversions-,
                                                            when  horizontal  movements  are much  larger than vert.^i.
                                                            ones,   gaussiens  models  or   box models   using  a  Tic^
                                                            equation  of  diffusion  deliver good  estimators of  T.e*r.
                                                            values and  fluctuations.

                                                            When  orographic  effects  are  Important   (vallevs;.  a-
                                                            approximated solution  to  full  equations ai  Savter-rcN*;
                                                            must  be  found,  taking into account  the relief, vr..c.-i  ..~
                                                            still rather badly  solved.  Nevertheless,  in  practice, ver-
                                                            short  term  alarm   procedures,  bas«d  en   po.lui un-«..- _
                                                            measurements, can  be implemented.

                                                            When  transfer  phenomena  are  essentially  U.ike:  "c  -£
                                                            vertical  structure  of  the  atmosphere,  situation  rec--.-
                                                            more  complex  in  most  of  the  cases.  X:anvm.e,  ::
                                                            situation  of  stagnation  (low wind, strong  :r:ernui.  s'.rj.'.-
                                                            fication)  where  pollution   levels  observec  cics«  u- •-
                                                            ground  can  reach  IS  to  20  times   the  average  .?%<•.
                                                            (generalized  peaks  of pollution)  simple mcaeis  ;$:j'.^-..-
                                                            cal  or  numerical)  are  satisfactory  provioc  a  c:r-j;.-
                                                            number of real time data is acquired.
  .  conservation ;f  ciass
  .  car.servif.cn of  quantity  ;( movement
  .  conservation of  energy

  ir.xt.j. ;cr. jif.cns  si  tne : .c1. :
  .  inii.i. cis'.r. Oution sf wine
  .  ir.::;!. ai«:r: 3u;;on if ie:;.perature
            ;cn-::;ans  s! flew:
           jjL   situation   'parameters  above   planeiarv
            v  .oyerl
           .cs   .irri   in*   ;r ;nc   (lurouient   fluxes  of
           t .it  ..... Vcil.e:.!, -I  :.rj], OI tlu.iilrtuy, r
                                     v.ir:able*
::,e*n  jraj-.en-.. of  w
•.fteir  #v.-u!icn  in  the II.T.C
evc.^ncn  ,-;  r.ej! fluxes c.c»
..:,?cr-.a:;cr jl ir.c:;on :c me
dso<           PROCEEDINGS— PAGE  250
           First US-France  Conference  on
      Photochemical Ozone/Oxidants  Pollution
                          in  J.ffcrent 4i:ilud«  layers  And

                                :c ;he
                                                            As a summary,  dangerous  situations from cne air :>...
                                                            point  of view  are  characterized  by the  presence  ::
                                                            major  phenomenon  which  opposes  the pollution  u./i^
                                                            (temperature inversion  -  low  wind, sea  Breeze -  .
                                                            breeze  system).

                                                            a) As  far   as   radiative  temperature   inversions
                                                            concerned,    (understand:   caused   by   coo  •. r. ;   ;c--
                                                            ground  during  the  night  preceeding the  polluf.jn  •>
                                                            sode),  BERTIN  has  a large experience.  Different s'--:
                                                            were conducted  since several  years with tne  SU?:.--T:
                                                            Secretariat General  du Haul Canute de l'En\ .ran,-.,?- •.•..:
                                                            CEE  and   Electricity  of  France   - D.E.x.   -  .  ...
                                                            M.A.f.A, auU leaJ  to jircv* the follow my «.r,c:..e
                                                                 .i^* of [nil
                                                                  (Figure ;)
                                                                                    wllhln  th«  Irivusioii
- dynamic  and  [henna!  break-up  of  inversion
  morning   producing   before   its   compie't
  pollutant   fall-out   and  consequently,   '.r.e
  pollution  peak (figure 3).

-------
 The  measurement  systems  Actually  proposed  (fluxmeter
 and three-dimensional Doppler Sodar)  have been designed
 fcr   supplying  all   physical  parameters   necessary  to
 ac-deltze  this processing.  It i*  usually  compatible  wuh
 existing monitoring networks  (figure 4).

 The mechanism of radiative  inversion, associated  to low
 winds, is recognized a*  responsible  for 70 to 90 % of ge-
 neralized  pollution peaks,  included at sea shore.

 b)  Other  mechanisms  e«n  be  responsible  for  pollution
 peaks,  if  they  contain  stable   thermal  gradients  and
 important  vertical movements.  This  Ls  the  case  for »«a
 breeze - Und breeze systems. The knowledge of three-di-
 mensional wind  in altitude and  of the  thermal  structure
 as  delivered  by  the  Sodar  Is  an essential  tool  for the
 understanding and modelization of these phenomenon.
 In particular,  it  is  classical  in  such  a  situation  that
 winds measured close  (c  the  ground  ind in  altitude Hav*
 an  opposite  direction   (typical  problem  cf  heigh:  of
 chimneys).  Particular mechanisms tinned to tne site also
 can appear. For  them,   tne  experience  of the  monuerir-.j
 network operators and cf the local  meteorologists  tan  b<
 helpful.
 In spite of all these difficulties,  described  measuresien:
 systems deliv«r- sufficient  information  ic  allow  SERTIN's
 engineers  tc r:i$age themselves  on a  prevision  rate  fcr
 dangerous  situations, under conditions to  be  defined from
 case  to case. Such  a rate  is Uke.v :s  grow n '.he :ir:;e.
 PSE-ALARM AND  ALARM PROC^URES
 Taxing  into account  the amount  of  information  delivered
 3v ;he  Soclar  and  the  fluxmeter on  a  certain  number  of
 soserved  dangerous  situations  and   the  behaviour   of
 BEXTIN's models on each site, it  can be foreseen that the
 efficiency  of the  prevision*  will grow in  the future. That
 11  why  it appears  sensible  to  define  two  procedures:
 pre-alarm  and alarm.

 Pre-a'.arn  procedure

 T'-.e processing centre:

 ai  - receives on-line information delivered by  the Sodar
     and the fluxmeterd)
   - executes  routine processing  (Integration,  variation
     rate)
   - stores  all data
   - produces and stores on  file  a  colour image for each
     sodar  parameters  (echo,  modulus  and  direction  of
     wind,  dispersion of vertical  speed!
   - displays  at   any   time   the   value  of   measured
     parameters, the  history of past sodar parameters  on
     fern  of   colour  facsimile.  (All  these   tasks  are
     ccntinuously executed  and  system  behaves  like  an
     acquisition centre).

 b> - runs  real  time  modelling techniques which corres-
     pond  .o numerical models  more or less simplified
   - produces the  pr*>alarm:  either  as a YES/NO signal
     or  as  a numerical value corresponding  to  a  risk
     level,  to be compared to a programmable  threshold.
As  soon as  this threshold  is  overridden, pre-alarm is
given:  the central computer  decides as a  function of the
established  diagnosis  and  of  the other  network  data,
and warns an operator.

On  the  spot,  the operator car. take benefit  of:

1)  - a  full  colour  image  of micro-meteorological  situ-
      ation.  He  can thus resume:
     . the  evolution  of  the  inversion  layer  during  the
       hcurs  proceeding pre-alarm
     . the  evolution of  wind in altitude (modulus, direc-
       tion!
     . the  history of turbulence level  as a  function of al-
       titude  (flux  - an image of large scale meteorological situation  (me-
     teorological facstmlK of the network).
 The operator must  then validate or invalidate pre-alarm
 diagnosis.   For  this,   he  has   several  means  at   his
 disposal  (tests  to  be  conducted  constitute  a  necessary
 Step for a safe alarm prscsdure):

 1.  Extra  data  coming  fcr  instance  from  network  sensors
    are  supplied to  the  rum-computer on  the  conversatio-
    nal  mode


 2.  Execution  of extra rout.ne tests.

 3.  Comparison of observed colour facsimile with previous-
    ly   recorded  ones   (they  are  conserved  as  files  of
    pictures, or stored  in the mini-computer).

 Pre-alarm procedure  requires  a  duly  trained operator.
 Human  intervention  pa.hates  the  probably  tso  severe
 character of  first previsiois.
Alarm procedure

After several months  of pre-alarm  procedure exploitation.
data  stored  will  be  sufficient  to  consider  a systetr, that
will  warn  the  operator  less  often,  without losing  any
efficiency.  Such  a  result  will  be  obtained  in committing
to  the  minicomputer  the  most  of  checks  previously
devolved  upon  the  operator  and  in  implementing  more
sophisticated numerical ncdels  (that will  be tested on se-
rious situations already observed by the system).

Distinction  between  alarm  and  ore-alarm  makes  appear
two levels of fineness in  the processing of data delivered
by  the SODAR and the flux-meter:

- in  the  pre-alarm   phase,  warnings  are   jtven  in  an
  eventual  redundant  way:  it  means two or three tiir.es
  too  often.  Such  a practice will be considered as a sue
  study from the point of  view of pollution peaks

- in  the  alarm  phase,  systetr.  is  fully operational and
  one  endeavours  to  minimize  its  failure  rate,  e.i.  tc
  improve prevision rate  of  dangerous episode* (9C ;» fcr
  instance)

More, system offers  simulation capabilities:

- prevision   of  ground  leve'.   concentrations  (precision
  warranted: ^ 20 *,  for 90 =i cf the  cases)

- prevision  of ground level concentrations  In the hypo-
  thesis  of   sector intervention  iitcp  of  certain  sources
  only)
                                                                                 PROCEEDINGS-PAGE 251
                                                                             First US-France Conference  on
                                                                        Photochemical Ozone/Oxidants  Pollution

-------
FlgxiMtvr

>,
W i
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AOAM 11
Microcomputer

!SL^
N /
AOAM 11
Mkrocomputvr

                               I
                 Block   diagram
                 of  instrumentation
                                              .•-«'^7Vt"-Jfc&g#
                                               ^•-Jii^SB^i

                                                                                     ^f^W^vr-*''11: •••••:-  .
        PROCEEDINGS—PAGE 252
    First US-France Conference on
Photochemical nzone/Oxidants Pollution

Polluted Uycr Jicred :n :ht invcrtion Uyer. Spot tjken
on D«e. 12. 1977.  j; K  i.,u..  bctve«n 2nd and 3rd fleer
of liffcl Tower in  Parts.

-------
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         First US-France Conference on
     Photochemical Ozone/Oxidants PoHution

-------
                     Height

                                                                                         ( Very stable
                                                                                             layer
                                                           Flux at inversion base
                                               adiabatic layer
                                       Flux close to
                                       the ground
                                 n
                                                                           Flmmeter
or?
          Sodcr
                              potential
                              temperature
                   Prcposea  n.easurenieru  system  which is  compatible with
                   -se rn  .i.orv.tcr n; and ilarm network.
               Pollution
                 level
               1600-
                                                                          Peak 2
                                                              18
                                                             12
T.V.CJ.  «vclu(:;r.  of SO, concentraticn  riur-.
c:  DJ..U:.,-. .Doservec ir, ^ins ^n j.inuary  1
                                                              two peaks
        PROCEEDINGS—PAGE  254
     First US-France Conference on
Photochemical  Ozone/Oxldants Pollution

-------

         ATMOSPHERIC CHEMICAL  KINETICS
         presented  by Georges  LeBras



Centre  National  de la Recherche Scientifique

                     France
                                              PROCEEDINGS—PAGE 255
                                           First US-France Conference on
                                       Photochemical Ozone/0x1 dants Pollution

-------

-------
             ATMOSPHERIC  CHEMICAL  KINETICS
                    Georges  LE  BRAS
    (CNES - Centre de Recherches  sur  la Chimie de la
         Combustion et  des  Hautes  Temperatures

             450^5 - ORLEANS  CEDEX FRANCE)


                         --oOo—
            Up to now, it  appears  that  th-e french activity in
  CHEMICAL KINETICS has not  been too  much directly involved in
  the study of the lower tropospheric chemistry,  and especially
  the photochemical ozone-oxidants  chemistry.  However several
  researches carried OUT in  France  have some relation to this
  problem or raise some potential  interest in it,  through either
  the techniques used or the topics investigated.  These researches
  mainly concern the kinetic studies  of elementary reactions of
  stratospheric interest,  and  also  in some extent  the chemical
  kinetics of combustion processes.
- KINESTICS STUDIES OF ELEMENTARY REACTIONS  OF  STRATOSPHERIC

  INTEREST

            The kinetics of  elementary  reactions  of free radicals
  has been studied for more  than 10 years  at the  CNRS-CRCCHT in
  Orleans. The reactions first  considered  were  related to flame
  propagation of flame inhibition. These  studies  have been extended
  some years ago to reactions of stratospheric  interest. They are
  related to the problem of  ozone depletion  by  halocarbons in the
  ozone layer. The following reactions  have  been  investigated :

  - reactions of Cl and CIO  with hydrogenated species of the
    stratosphere :  CH4, C2H2, HNO3, H2O2,  H02,  H2CO.  These reac-
    tions have been considered  as possible sinks  of stratospheric
    Cl, CIO which can slower the catalytical cycle of 03 consump-
    tion by Cl and CIO :
            Cl
CIO
                   CIO
Cl
                                                    PROCEEDINGS—PAGE 257
                                                 First US-France Conference on
                                              Photochemical Ozone/Oxidants Pollution

-------
    Cl being produced by photolysis of "Freons" in the stratos-
    phere (Fig. l).

    In a similar way the Br + H2CO reaction has been studied
    (potential depletion by BrO  compounds).
                               J\
                    o
  - reactions of 0 ( P)  and Cl with hydrogenated halocarbons
    (CHFC12,  CHF2C1, CHF3,  CH2, FC1,  CH3CF2C1, CHF3, CH2C1). This
    study was connected  with the possible industrial use of these
    compounds in replacement of "Freons" 11 and 12.

            Reactions of sulfur compounds have been also investi-
  gated recently (reactions of S and  SO with OH), in relation with
  flames containing  sulfur  compounds  and also with H2S04 cloud
  formation in the atmosphere of Venus.

            The work on  stratospheric reactions is a part of a
  french program on  Physical-Chemistry of the stratosphere, coor-
  dinated by the DGRST.


       I.I.  Experimental

            The technique used is the discharge flow with mass
  spectrometry or E.P.R. for the analysis of fore radicals in the
  gas  phase.  Two quadrupole mass spectrometers have been successi-
  vely used  with sampling by one stage effusion in the first one
  (Fig.  2)  and by a  modulated molecular beam in the second one
  (Fig.  3)•  Both have been  adapted to the detection of free radi-
  cals.  The  detection is made by electron impact ionisation at low
  energy (15-20 eV). The following free radicals have been kineti-
  cally studied in our Laboratory (the source of the free radical
  is indicated in brackets) :  H, 0 (3P),  N,  Cl, Br (microwave
  discharge  in the molecular gas), CIO (Cl + C120 or C1O2), CH3,
  CH2C1  (H,  Cl + CH2N2), NCI,  NC12, N3 (Cl + N3C1), H02 (Cl + H2
  02).  Figures k and 5 show examples  of mass spectrometic kinetic
  analysis  of CIO gas phase recombination (Fig. k) and CH3 gas
  phase  recombination and reaction with C12  (Fig. 5)« It can be
  expected  that mass spectrometry will be developped in the next
  years  for  kinetic  measurements of large free radicals involved
  for  instance in the chemistry of the polluted troposphere.

            In the E.P.R. system,  the flow reactor crosses the
  large  access E.P.R.  cavity (Fig. 6). This  technique has been
  used  in our laboratory to study some reactions of H,  0 (3P), F,
  Cl,  Br, S,  SO,  OH  and  CIO.

           The typical  experimental  conditions in the flow reactor
  are  the following  :  pressure : 1 torr,  flow velocity :  5-50 m/s,
  concentration of reactants : 101Q - 10*° cm-3.
      PROCEEDINGS—PAGE 258
   First US-France Conference on
Photochemical Ozone/Oxidants Pollution

-------
Generally  the  pseudo  first order conditions are used. And then
for  a reaction between a molecule A and a radical X used in great
excess over A_the  rate constant k is obtained from the expres-
sion : k s - v d In {£xj /dx/ (/)„) . v is the mean flow velocity, x
the  reaction distance  which is varied by moving the central probe
in the reactor.
      1.2. Results
           Some  examples  of the results obtained, generally at
298 K, are illustrated  in the following figures :

Figure 7   :  absolute  determination of the rate constant of the
                                      HC1 + HO,
                                             '2-
Figure 8   : relative  determination of the rate constant of the
            reaction  Cl  +  H202 where the reaction Cl + CHk is
            taken  as  the reference.
Figure 9   : temperature  dependence of the rate constant of the
            reaction  Cl  +  CH.  	^ CH_ + HC1.

            This reaction  has  been intensively studied since not
            less than 12 determinations of the rate constant have
            been issued  from different laboratories these last
            years.

Figure 10  : kinetics  of  the  Cl +  H02 reaction studied as the
            secondary step of  the Cl + H202 reaction. Under the
            specific  conditions used,  the rate constant of the
            Cl + HO2  reaction  could be deduced from the ratio
            concentrations (H202J / JH02J  and from the rate constant
            of the Cl +  H202 reaction previously measured.

Figure 11  : absolute  determination of the rate constant of the
            reaction  Cl  +  H2CO 	^ HC1 + HCO studied by E.P.R.

Figure 12  : comparative  reactivity of CHF3, CHF2C1 and CH F C12
            with Cl atoms.

Figure Ij  : absolute  determination of the rate constant of the
            reaction  SO  +  OH 	^  S02 + H. The following chemical
            system had to  be considered :
H + H2£
H + SH
S + 02
0 + OH
                                          H
         SH

         S
                                           2
                                          SO  +  0

                                          °  *  H
                         OH
                              wall
products.
                                                 PROCEEDINGS—PAGE 259
                                              First US-France Conference on
                                           Photochemical Ozone/Oxidants Pollution

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        1.3-  Atmospheric implication of the results
             The results obtained have contributed to show that the
   reaction of Cl atoms with CH4, H02 and H2CO have some importance
   in  trapping Cl atoms in the stratosphere and then reducing the
   ozone  depletion by halocarbons. Against the reactions of Cl with
   C2H2,  HN03 and H202 appear to be negligible.

             For CIO,  the results obtained have indicated that the
   reactions of CIO with CH4,  C2H2, H202 and H2CO are negligible in
   trapping the CIO + H02 	> HO Cl + 02 reaction can have some
   importance.  Howevever this  importance will depend on the rate of
   photodissociation of HO Cl  and of the nature of the products
   which  both remain to be precised.

             We have also studied recently the reaction of Br atoms
   with H2  CO in relation with the possible depletion of ozone by
   bromine  compounds following the similar cycle as for Cl atoms :

                                     BrO + 02

                                     Br  + 0^
                                  — 12             — 1—1
            A  rate  constant of 10    cm3 molecule   s   has been
  measured  at  298 K for the reaction Br + H2CO - >  HBr + HCO. Then
  this reaction  could  be an efficient sink for Br atoms because
  the other reactions  of Br atoms with hydrogenated species, except
  H02, are  slow  at  the stratospheric temperatures.
            The  results  obtained have shown that if these "freons"
  were used instead  of freons  11 and 12,  most of them would react
  mainly with  OH.  On the troposphere, although for some of them,
  reaction with  Cl atoms could be not totally negligible.


       I.d. Future work

            The  studies  on  reactions of stratospheric-interest
  will be continued,  but some  work on trophospheric reactions
  already initiated,  will be developed,  mass spectrometry being a
  suitable method  for analysis of large radicals of tropospheric
  interest .
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II - CHEMICAL KINETICS IN COMBUSTION PROCESSES

           Among the topics which can be related  to the ozone-
oxidants  pollution chemistry, the following  are  developed in
several Laboratories in France :

           -  Combustion of hydrocarbons at  low temperatures (slow
             oxidation,  cool flames).

           -  Pyrolysis of hydrocarbons.

           -  NO  chemistry in flames and post-combustion processes.

           -  Soot  and polyaromatic hydrocarbon formation in flames.

           Some of the elementary steps in  chemical mechanisms of
both polluted  troposphere and combustion processes such as low
temperature  oxydation of hydrocarbons can  be considered similar.
Therefore  some of the kinetic data obtained  from these combustion
processes  may  be  of interest to the chemistry of the  polluted
troposphere.
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                         REFERENCES
"Detection du radical  CIO par spectrometrie de masse et etude de
 sa reactivite"
 C.R. Acad. Sc. Paris  -  Serie C (1973)  2?6 - 463 - 66 (G. POULET,
 G. LE BRAS, J. COMBOURIEU)

"Etude par spectrometrie de  masse de la reactivite du radical methy-
 le, recombinaison  et  reaction avec le  chlore et des especes chlorees
 Communication presentee au  2erne Symposium Europeen sur la Combustion
 (Orleans - Sept. 1975)  p.  19-24 (G. LE BRAS, G. POULET, J.L. JOURDAI^
 J. COMBOURIEU)
"Elementary gas phase reactions  studied by molecular beam mass
 spectrometry"
 Communication presentee  a  la  7    international Mass Spectrometry
 Conference. Florence,  Sept.  1976 - publie dans "Adyances in Mass
 Spectrometry vol. 7" (G. LE  BRAS,  G.  POULET, G. LAVERDET, J.L.
 JOURDAIN, J. COMBOURIEU)
"Mecanismes chimiques de  la  pollution atmospherique par les composes
 halogenes : etude cinetique de  reactions elementaires possibles"
 Communication presentee  au  IVe  Congres International sur 1'air pur
 Tokyo - Mai 1977 - Publie dans  la  Revue "Pollution atmospherique"
 (1977) N" 75, P- 256 (J.L.  JOURDAIN,  G. POULET,  J. BARASSIN, G. LE
 BRAS, J. COMBOURIEU)

"Kinetics of the Cl + C2H2 reaction - Stratospheric implication"
 Journal of Physical Chemistry  (1977),  8l.  23O3.  (G. POULET, G. LE
 BRAS, J. COMBOURIEU)
"Etude cinetique des reactions  du  1,  1,  1  trifluoro 2 chloroethane
 avec les atomes de chlore  et d'oxygene"
 J. Chimie Physique (1978)  75. (3),  3l8.  (J.L.  JOURDAIN, G. LE BRAS,
 J. COMBOURIEU)
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"Kinetic study of the  reactions  of Cl atoms with HNO., H2°2  et H02"
 Journal of Chemical Physics.  (1978)  _§£ (2) ?6?. (G. POULET, G. LE
 BRAS, J.COMBOURIEU)

"E.P.R. Kinetic study  of  the  reactions of CF_ Br with H atoms and
 OH radicals"
 Int. J. Chem. Kinetics  (1978),  X,  I20p (G. LE BRAS, J. COMBOURIEU)

"Kinetic study of some elementary reactions of sulfur compounds
 including reactions of  S and  SO with OH radicals"
 Int. J. Chem. Kinetics  (1979),  XI,  569 (J-L. JOURDAIN, G. LE BRAS,
 J. COMBOtJRIEU)

"Etude cinetique par resonance paramagnetique electronique de la
 reaction des atomes de  chlore avec  le formaldehyde"
 C.R. Acad. Sc. Paris. Serie  C (1979),  288, 2k\ (R. FOON, G. LE BRAS,
 J. COMBOURIEU)

"Elementary reactions  of  Cl and  CIO  radicals with hydrogenated
 species of stratosphere  Interest" World Metoerological Organization
 Symposium on the Geophysical  Aspects and consequences of changes in
 the composition of the  Stratosphere. Toronto 26-3O Juin 1979
 (G. POULET, G. LE BRAS,  J. COMBOURIEU)

"A Kinetic study of the reactions of  F atoms with HCHO and CH2FC1 by
 EPR". IXeme Symposium International  sur la Chimie du Fluor Avignon -
 Septembre 1979 (R. FOON,  G. LE  BRAS, J. COMBOURIEU)

"EPR Kinetic study of the  reactions  of H-CO with F, Cl and Br atoms
                      o
 and CIO radical" NATO  Advanced Study Institute :  "Atmospheric
 Ozone : its variations and human Influences". Aldeio das Acoterias
 Portugal 2-13 Octobre  1979  -  Proceedrings F.A.A. (U.S. Dpt of
 Transport) - (G. LE BRAS, R.  FOON, G.  POULET, J.  COMBOURIEU)
                                                 PROCEEDINGS—PAGE 263
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\ a o rts
                                                 —cio.o2

                                            CIO.O —.Cl
             Jauge Mac Leod
   1

     :  -r•
         Pompe
 //™

  CH2N2


2450 MHz
                       t_
                                         2450MHz
                                         W///1///1
                                                 >He
 J  [cioj
  xl01srad./cm3
 .1
 .0,5
                              10   temps (x10-3s)
                  >Q.
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                                                                                       ts
                                                                                                t (mi)

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         '•    M°2  _T
         ;  u o2)  -»
IP« cavity
H.HaUw^
                                 dftcherg*
                  ^
 FIG. ?•  H?O, decay as a {unction of Cl concentration at 298 K.
 (The values are taken from Table U.)
         FIG. g  Plot of relative rates of
         reactions Cl- H,O: and CKCHj.
         The slope is the rate constant ratio
         *(/*T at 298 K.
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                                                                                             FlG.'tO  Plot of relative rates of
                                                                                             reactions Cl - HiO, and Cl - C H4.
                                                                                             The slope is the rate constant ratio
                                                                                             V*r at 298 K-
                                UOOl
                                 aoo
                                 4OO
                                                                      20      25
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Fig.

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                       20           40           60

                           TEMPS OE REACTION  (10'3 »c )
              (. dlo«iOHi/di -»«,'o;,.iiw  I
             -600
             -400
Figure JJ Least-squares plots for the reaction SO + OH — 3OS .+ H (2)
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       REACTION KINETICS OF NH2  RADICALS

    AND  FATE OF AMMONIA IN THE  ATMOSPHERE
         presented  by Robert Lesclaux



Centre  National de la Recherche  Scientifique

                     France
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           REACTION  KINETICS  OF NH2 RADICALS
         AND FATE OF AMMONIA  IN THE ATMOSPHERE.
           Robert  LESCLAUX - Laboratoire de Chimie Physique A
                              Universite de Bordeaux  I
                                   33405 TALENCE-FRANCE
                         ABSTRACT
        In this  paper is presented the measurement  of  the absolute
rates constants  of  NH^ with NOo and 03, using a  flash  photolysis-laser
resonance fluorescence technique. From the reaction rate constants of
NHp with Op, 0^,  NO and NO,,, the possibility of  formation or elimination
of nitrogen oxides  by radical degradation of ammonia in the atmosphere
is examined.
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   INTRODUCTION
        Ammonia is released in the atmosphere in large amounts from soils
   [l]  and oceans [2]  but its contribution to chemical processed in the
   atmosphere remains  unclear. Heterogenous reactions and dissolution  in
   rainwater are certainly important removal processes of this compound.
   However,  as emphasised by Me CONNELL [3], reactions of NH3 in the gas
   phase by  radical  processes, might represent a potentially large source
   or sink of nitrogen oxides.
        The  decomposition of ammonia proceedsessentially through two reactions
   the  direct photolysis by sun light in the stratosphere and the attack by
   OH radicals in the  troposphere :
                    NH.
                            hv
                         A < 220 nm
                              H
                 NH3 + OH
                                              (1)
                                                            (2)
  The  subsequent  steps  of the ammonia oxidation depend therefore, only on
  the  reactions of the  NH« radical.
       According  to the relative concentrations of atmospheric constituants,
  and  the  rate constants of NH2 reactions, there are four possible reactions
  for  this  radical  :
        NH,
        NH,
        NH,
        NH,
         NO
°3
NO
NO
 , + H20
 ,0 + H20
                                                                        (3)
                                                                        (4)
                                                                        (5)
                                                                        (6)
         Reactions (5) et (6) correspond to the elimination  of nitrogen oxides.
   Reaction (5} is very fast
= 2.0 x 10
          "11
                           cm3  . molecule   . s   at  room  temperature[4] . This  is
   the order of magnitude of the rate constants for NH2  recombination  with  other
   radicals [5] and it is unlikely that faster reactions for  this  radical will
   be found. Therefore, any reaction with a  constituent  of the  atmosphere whose
   concentration is smaller than those of NO can be neglected.
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       Reaction (3) and (4) are potential sources of nitrogen  oxides.
Reaction (3) has been shown to be very slow  [6]  :
k  < 2 x 10"18 cm3, molecule"1, s"1 either at  room  temperature  or  at  500  K.
However, this reaction is efficient at high  temperature,  in  the  combustion
of ammonia for exemple, the products being in  this  case HNO  and  OH  [7j.  It
is therefore likely that the  low rate constant found between _300 and 500 K
is due to a high activation energy and that  the  actual value of  k^  at  room
temperature is much smaller than the upper limit determined  at 500  K.
Assuming a minimum of 10 kcal. mole"  for the  activation  energy, it  will
be shown further on that reaction  (3) cannot compete with reactions (4),
(5) and (6) in atmospheric conditions. It is therefore much  important  to
measure the rate constant of  reaction (4) and  (6) in order to  decide wether
the NH2 reactions are a source or a sink of  nitrogen oxides.

       We have measured these rate constants in  the temperature  range  295-500 K,
 using a flash photolysis-laser resonance fluorescence and absorption  technique.
 Great care has been taken to eliminate the  dark reaction between NH.,  and  0-,
 or NQ2 and to avoid perturbations of the kinetics  by NH2 radicals  formed  in
 chains reactions initiated by the flash. The  magnitude of the rate constant
 of reaction (4) and (6) are discussed in term of atmospheric  chemistry  of
 ammonia.

   EXPERIMENTAL
             The NH2 radicals are produced by  flashing ammonia at wavelengths
   longer  than  180  nm.  The  flash photolysis apparatus equipped with a  laser
   resonance absorption  detection has  been described in details  in  preceeding
   papers  [8, 9j .

            A  new  flash  photolysis set  up with the  detection of NH? by laser
   resonance fluorescence,  has been constructed for  the kinetic study of
   reaction  4 and 6.                                    The high  sensitivity
   of fluorescence measurements  allows to  photolyse  NH3 with  a  flash of very
   low energy,  thereby limiting  to  a negligeable fraction  the photodecomposition
   of N02 (or 03). Moreover, the volume of the  fluorescence cell  can be reasona-
   bly small (< 200 cm ), which gives the possibility of producing the  reactions
   in a slow gas flow, to renew continously the reactants. The  signals  from
   several  hundreds flashes can therefore be  accumulated without  the problem
  of secondary reactions.
            The excitation laser is a CW, single mode dye laser  (Spectra Physics
  580), tuned on a  strong NH2 absorption line  at 597.73 nm in  the 0,9,0  «-  0,0,0
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         vibrationnal band. The flash is generated by discharging a capacitor
         (0.5 yF charged at 2 to 6 kV), between two tungsten electrodes, in nitrogen
         at atmosphere pressure. A quartz lens is used to form a nearly parallel
         beam which is directed into the cell. In a few experiment the lens has been
         removed in order to lower the photolytic intensity. The discharge can be
         triggered at frequencies wich are varied from 0.5 to Sflashes per second.
                   The fluorescence intensity is measured by photon counting, using
         a cooled photomultiplier RCA C31034, and the signals are accumulated in a
         multiscaler (SEIN, Interzoom 1024). A filter eliminates the  light of wave-
         lengths shorter than 580 nm.
                   The fluorescence cell is a hollow blackened aluminium cube
         (12 cm of side) having six openings. The windows are fitted with viton
         0-rings. The flash, the laser, and the fluorescence beams are directed
         along the three perpendicular axes of the cube.
                   A system of diaphragms and baffles reduced the scattered lights
         from the flash and from the laser to a negligeable  level.
                    For  measurements  of the  temperature dependence of rate constants,
         the  cell  can be heated  up  to 200°C.
                    The  carrier  gas  is  helium which is  used to control the total
         pressure  and the  flow  rate.  N02  (1%  in  He)  or  pure ozone is injected in
         the  stream  of helium  through a needle valve,  so that it reaches the cell
         homogeneously diluted  in  the carrier gas.  On  the contrary,  NH., is injected
        directly  in  the  reaction  zone,  at the center of the cell, in order to
        prevent any  dark reaction  between NH., and  N02  (or 03).  The total  pressure
        (3  to  10 Torr) is  measured with a capacitance manometer.  The pressures of
        N02 (1 to  6  mTorr),  03  (0.2  to  1.5 Torr),  and  NH3 (0.02 to 0.5 Torr)  are
        determined by  measuring  the  increase  of  the total  pressure when these gases
        are injected.  The  flow  rate  (1  to 4  cm.  s    at 760 Torr) is determined so
        that  the  irradiated  gases  are renewed between  two flashes.
                    The  concentration of  NH~  radicals  is very small  and cannot be
        measured directly.  However, we  have  roughly determined the spectral  distri-
        bution of  the  flash  emission  and  estimated  that the initial  NH, concentration
                    g      Q                o                            t-
        is  around  10  -  10   molecules,  cm  .
                    As a test, the well known rate constant  of reaction 2 was
       measured, using this new arrangement of our flash photolysis apparatus.  The
       value obtained :  k., = 1.9 (± 0.2) x 10   cm  . molecule   . s    is in exellent

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 with  the previous determinations.
            Gases are from L'AIR LIQUIDE ; NCL{99.0%} is degassed and
 distilled at low temperature. Helium (99,995';} and NH3 (99,96%) are taken
 directly from the cylinder. Traces of oxygen in these gases should not  be
 important since NH2 does not react with this compound [4].
            Ozone is prepared by flowing oxygen through a  high voltage
 discharge, trapped at 77 K and carefully degassed.


RESULTS AND DISCUSSION
           The photolysis of ammonia
    NH      hv       >    NH  (2B,) + H                     (3)
      J    X > 180 nm       *     i
produces NhL radicals mostly in their ground electronic and vibrational
state      . No emission could be detected after the flash  in the fluorescence
cell, in the absence of laser excitation.
                                                     2
           The fluorescence is emitted from the NH- ( A,)  excited state.
  This state undergoes          a very fast collisional quenching      and,
as a consequence, the pressure in the fluorescence cell was limited to about
10 Torr.

I - Measurement of ks in the flash ohotolysis-laser resonance absorption
    apparatu?
           Due to the large volume of the absorption cell, measurements
were performed in a static gas mixture and therefore, the  rate constant  was
determined from a single decay. The flash energy had to be large enough  to
                                                             12             -3
produce a concentration of NH2 sufficiently high (2 to 5 x 10   molecules, cm  ),
corresponding to an initial absorption of about 10 to 20%. In these conditions
the photodecomposition of N02 and 03 had  to be  considered.
           The concentration of N02 in the reaction cell was measured  before
and after the flash by absorption spectrometry, using the argon laser line at
514.5 nm and a multipass system.  In the absence of ammonia, no significant
decomposition could be detected.  However, in the conditions of measurements
of k , i.e. NH, = 0.2 - 0.5 Torr  ; H09 * 0.01 - 0.03 Torr, 5 to SOS of NQ?
    Q         J                      L.                                    C.
disappeared after each flash. This is much larger  than the decomposition
produced without   NH3 (< 2%} and about 20 to 100  times the amount of  NH2
and H atoms obtained in the direct photolysis of ammonia.  Obviously the  flash

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      light initiates some chain reactions which have not been elucidated.
                 In spite of this complication due to NCL photolysis, the NH?
      decays were pseudo first order and a value of k, could be determined. However,
                                                     o
      measurements were not reproducible since the values obtained^for k, varied
      from 0.8 to 2.8 x 10"11 cm3,  molecule"1, s"1.
                 Obviously, this determination of kg is not reliable, due to the
      decomposition of N02,but it shows that reaction 1 is rapid .
      Moreover, these experiments allow the evaluation of the amount of N02 and 0, that
      may be decomposed in the next experiments, using the fluorescence detection.

      I!  - Measurements  of  k.  and kg  in the flash  photolysis-laser resonance
          fluorescence  apparatus
                 The  disappearance  of  NH^  radicals  in  the fluorescence cell, in
      the absence of any reactant,  is essentially  due to the diffusion of the
      radicals  out  of  the photolized  volume and to  the  recombinations on the walls.
      The initial decay  rate  varied  from 100 to 300 s   according to the pressure.

                 In the  presence of  N02, the  overall decay  kinetics of NH2  can be
      expressed as :
                 d[NH2]  /dt = kg [NH2][N02] + kQ   [NHg]            (1)
      kQ is the rate of  the NH2 decay  in the  absence of N02 and  is measured before
      each experiment.  [N02] being much larger than  [NHL],  the expression of the
      pseudo first order decay is  :
                            o =  IF/IoF = exp  [(kfi  [N02]  +  kQ)  (tQ  -  t)J       (2)
      [NH2]Q  and [NH2] are the concentrations at  the  time tQ  and  t.  I  p and lf
      are the corresponding fluorescence intensities.  The  pseudo first  order decay
      rate  varied from about  800 to 5000 s~l.
                 The  very  high  sensitivity of fluorescence measurements and the
      possibility of  accumulating up to  a  thousand decays, allow to run the expe-
      riments with  very low initial  concentrations of NH?, about four orders of
      magnitude  lower than the  minimum concentration detectable in the resonance
      absorption system. A simple extrapolation  indicates  that the photodecomposi-
      tion  of N02 and 0-, in the fluorescence cell  should be negligible, even though
      this  decomposition arises from a chain reaction and  is therefore
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proportional to the square root of  the flash  intensity. Moreover,  the
pressures of NH, and NCU can be ten times  smaller  than  those  used  in  the
absorption cell, which necessarily  reduces  the efficiency  of  any reaction
between these two compounds.
           The results and the experimental conditions  of  a few experiments
at room temperature are given in table I and  II. The different experimental
parameters were varied in the following way :
                - total pressure :   3     to     10.5 Torr
                - flow rate  :       1.5     to     4  cm3,  s"1 at 760  Torr
                - flash energy :  0.15     to     10 joules
                - NH3 pressure :  0.03     to   0.6 Torr
                - N02 pressure :     1     to   6.5 mTorr
                - 0^ pressure :     0.2     to   1.5 Torr
thus illustrating one of the advantage of  the flash photolysis-laser
resonance fluorescence technique which allows to change the experimental
conditions in fairly large ranges.
           The values of !<4 and kg  obtained at room temperature are  :
                k4 = 6.3 (± 1.0) x  10"14cm3. molecule"1, s"1
                kg = 2.30 (± 0.2) x 10"Ucm3. molecule'1,  s"1
           The possibility of a systematic error in the measurements  may
principally be due to the photodecomposition of  NO^ or  0^  by  a chain
reaction which may produce NhL radicals after the  flash. This would result
in perturbations of the decay kinetics, even  though the fraction of the
reactant decomposed is very small.  However, these  perturbations should be
strongly dependent on the experimental conditions, particularly on the
pressures of NO-, 0^ and NH- and the flash  intensity. These parameters
were varied by a factor of 6.5, 6.2, 20 and 66 respectively and no significant
change in experimental  results could be observed  as shown in table I and  II.
It can therefore be concluded that  no systematic error  can arise from
secondary reactions and that uncertainties are only due to the scattering
of the results.
           The temperature dependence of reaction  6 was studied between
298 and 505 K. The results, obtained in similar  experimental  conditions  as
room temperature measurements, are  presented  in  fig. 1. Although the  varia-
tions of kg are fairly small, there is significant decrease of the rate

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 constant with  increasing  temperature  (about  a  factor 2  in the range of
 temperature examined).  Such  a  negative  temperature  effect generally
 means  that the  reaction occurs without  any activation energy, the effect
 being  only due  to  the variation  of  the  preexponential factor. -The tempera-
 ture dependence of  kg can  be expressed  as  :

            kg  = 3.8 x  10"8  T"L3°  cm3,  molecule"1,  s"1

            In  the  Arrhenius expression form,  this  is equivalent to a
 negative activation energy  : E =  -1.0 = 0.2  kcal. mole    which is the
 value  generally found for  this type of  fast  reaction. A very similar
 temperature dependence  was found  for reaction  5  [4].
            The temperature  dependence  of k,  was  studied between 298 and 380 K.
A chemiluminescence appeared when  ozone was  introduced in the cell, with
an increasing intensity  as the  temperature was  raised.  This introduced
a background of luminescence and  the  temperature  had to be limited to
about 380 K. Nevertheless, a significant  activation  energy was observed
as shown by the Arrhenius plot  in  figure  2.  The Arrhenius expression
deduced from this plot is :
            k4 = 4.2 x 10~12exp (-2.5 ± 0.5/RT)
k. in cm .  molecules   .  s   , E  in  kcal. mole
              The rate constants  of  the  possible  reactions  of NH~ in the
atmosphere being known, it  is now possible  to  determine the fate of NH~
radicals and therefore of ammonia, in  the same way  first suggested by STUHL
[10~!. There subsists, however,  the problem  of  the NhL  + 07  reaction, since
                             -183              -1
only a higher limit of 2 x  10     cm  .  molecules,  s    has been determined
for the rate constant, either at  room  temperature or  at 500 K.  As emphasised
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previously { ;" >-1'1
                                pfrl  it is likely that this reaction has an
  activation  energy larger than 10 kcal.  mole  .  From the higher limit at
  500  K,  this would yield  a higher limit  of 2.5 x 10    cm .  molecule " . s"
  at 300 K and 6 x 10"24 cm3, molecules"1, s"1 at 220 K.
           Assuming that reactions (3)and (4 'create nitrogen oxides and that
  reactions (5)and (6 Eliminate them,  the ratio :
                   R = (k3[02j  + k4ro3])/(k5[NO]  + k6[N02j)
is larger than one if there is a production of nitrogen oxides and smaller
  than one in the other case. This ratio  has been calculated  in four typical
  cases :  at  the sea level for the continental and marine tropospheres ;  at
  8 km of altitude which,  according  to CRUTZEN [ll]  corresponds to a deep
  minimum of  the nitrogen  oxides concentration ;  at 20 km in  the stratosphere
  where the ozone concentration is close  to its maximum and ammonia begins to
  undergo photodissociation.  The results  are shown in Table 3  in which are
  included the concentrations and rate constants  used. The concentrations are
  typical  day time values. At 8 and  20 km NO and  N02 are considered together
  since their reaction rate constants with NH- are not much different. The
                                                          O  ^ i or
  rate expression  used for  k   is          : k  = 2.4 x 10  j"      [4]
           In both continental  and marine troposphere the rate of NH2
  reaction with molecular oxygen is, at the maximum, of the same order of
  magnitude as that with ozone, but always much smaller than the rate of
  reaction with nitrogen oxides. This results in both cases, in R values much
  smaller than one. It seems therefore that the elimination of nitrogen
  oxides is predominant in the low troposphere.
           The situation is different at the altitude of 8 km. Due to the
  very low concentration of nitrogen oxides, calculated by CRUTZEN [ill,
  reactions (5)and(6)are very slow and the principal reaction of NrL is the
  one with ozone, resulting in a valued significantly higher than one. The
  reaction with oxygen is now completely negligeable, due to the low
  temperature.
           The R value of 1.2 found at 20 km shows the difficulty of reaching
  a  definitive conclusion about the situation in the stratosphere. Indeed,
 small  variations of the concentrations of ozone and nitrogen oxides, or
 uncertainties on their values, would result either in the formation or in
                                                         PROCEEDINGS—PAGE 279
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                                                  Photochemical Ozone/Oxidants Pollution

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   the elimination of nitrogen oxides.

   Conclusion                       vi .
            This work brings some of^Mnformations  necessary for determining
   the fate of ammonia in the atmospheric  gas  phase.  However, it was not
   our purpose to give a total budjet of the formation or elimination of
   nitrogen oxides from the radical reactions  of ammonia. Some typical
   situations are envisaged and tentative  conclusions presented, which should
   be discussed taking into account the uncertainties on the concentrations of
   the atmospheric constituants involved.  More definitive conclusions will only
   be obtained by integrating the present  results  in  a complete modeling system
   of the atmosphere. Furthermore these results cannot be applied to the possible
   oxidation reactions of ammonia, taking  place in the liquid or solid phase
   of the atmospheric particulate matter.
       PROCEEDINGS—PAGE 280
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                            REFERENCES


{1}  - G.A. OAWSON, J. Geophys. Res.  82  (1977)  3125.

(2)  - T.E. GRAEDEL, J. Geophys.  Res. 84 (1979)  273.

(3)  - J.C. Me CONNELL, J. Geophys.  Res.  78  (1973)  7812.

(4)  - R. LESCLAUX, P.V. KHE, P.  DEZAUZIER and  J.C.  SOULIGNAC, Chem. Phys. Letters
       35 (1975) 493, and references  cited therein.

(5)  - R. LESCLAUX and M. DEMISSY, J. Photochem.  9  (1978) 110.

(6)  - R. LESCLAUX and M. DEMISSY, Nouv.  J.  Chimie  1  (1977) 443.

(7)  - D. HUSAIN and R.G.W. NORRISH,  Proc. Roy.  Soc.  1 273 (1963) 145.

(8)  - R. LESCLAUX, J.C. SOULIGNAC,  P.V.  KHE, Chem.  Phys. Letters 43 (1976) 520.

(9)  - P.V. KHE and R. LESCLAUX,  J.  Phys. Chem.  83  (1979) 1119.

(10) - F. STUHL, J. Chem. Phys. 59 (1973) 635.

(11) - P.J. CRUTZEN, I.S.A. ISAKSEN  and  J.R. Me AFEE, J.  Geophys. Res.
       83 (1978) 345.

(12) - E. ROBINSON and R. ROBBINS, J. Air Pollut. Contr.  Ass. 20 (1970) 303.
                                                            PROCEEDINGS—PAGE 281
                                                         First US-France Conference on
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|N02|
(niTorr)
1.0
1.5
1.9
1.9
2.5
3.0
3.3
4.2
4.7
4.9
6.4
1.5
1.8
2.5
1.3
1.7
2.0
JNH3|
(Torr)
0.4
0.2
0.13
0.4
0.2
0.2
0.3
0.2
0.4
0.3
0.4
0.10
0.09
0.6
0.03
0.05
0,05
Flash energy
(Joules)
0.95
4.9
6.5
1.4
10.3
4.9
1.6
2.8
1.9
1.6
1.9
0.14
0.24
0.24
2.8
2.6
1.3
10* Decay rate
(s-1)
0.73
1.20
1.35
1.61
1.95
2.31
2.67
3.55
3.43
3.72
4.05
1.12
1.35
1.72
1.06
1.24
1.52
10». kj
(cm3, molecule"1, s"1}
2.21
2.43
2.15
2.57
2.37
2.33
2.45
2.56
2.22
2.30
2.20
2.26
2.26
2.37
2.47
2.22
2.30
                                    TABLE I  Measurements of the reaction rate constant of NH2 with
                                             NO- with the principals experimental  parameters.
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[o3]
(Torr)
0.44
0.33
0.24
0.42
1.48
0.80
0.72
0.25
1.29
0.24
O.fO
0.57
1.05
1.28
0.80
0.92
0.28
0.96

(Torr)
0-02
0.03
0.02
0-04
0.6
0.03
0.03
0.03
0.03
0.05
0.5
0.03
0.70
0.70
0.70
0.70
Flash energy
(artn'tr. units)
6.25
6.25
6.25
3.0
0.18
0.18
0.18
0.18
0.06
0.06
0.06
0.06
0.12
0.12
0.12
0.12
i
10"3 decay
rate (s"1)
1.16
0.81
0.58
0.97
2.93
1.84
1.50
0.39
2.55
0.42
1.18
1.02
2.20
2.75
1.88
2.10
10'4 k4
(cm . molecule"*. s"*)
7.9
7.4
7.3
7.0
6.0
7.0
6.3
5.4
6.3
5.3
6.0
5.4
6.3
6.5
7.1
6.9
0.02 j 0.22 0.53 5.7
0.60

0.22
1.77 5.6
1
TABLE II Measurements of the reaction  rate  constant of NhU with 03>

         with the principals experimental  parameters.
                                                       PROCEEDINGS—PAGE 283
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                                              Photochemical  Ozone/Oxidants Pollution

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0 kr 0 kn
Continental Marine
C2 5.25 x 1018 5.25 x 1018
03 6 x 1011 4 x 1011
NO 5 x 1010 2.5 x 108 )
N02 1 x 1011 2.5 X 1010 ^
^17j ! 2_:
concentrations
R 0.016 0.06
TA8L£ III Values of the ratio R and
8 km 20 kn
2 x 1018 3.6 x 1017
6 x 1011 4 x 1012
1 x 108 1,7 x 109
5.3 1.2
concentrations of the atmospheric
                                        constituants  used.
         PROCEEDINGS—PAGE  284
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                             K-
                             o
                             41
                             u
                             c
                            3
                            e>
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                -29.5
                -30.0
                -30.5
                       Ln
                                                                       1000/T(K)
                     2.6
2.8
3.0
3.2
                                  Figure 2 - Temperature dependance of
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     RECHERCHE DANS  LE  DOMAINE DE

LA PHYSIQUE DES AEROSOLS ATMOSPHERIQUES
      presented by Guy MadeUine



   Commissariat a 1'Energie  Atomique

                 France
                                          PROCEEDINGS-PAGE 287
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      Reunion Environmental  Protection Agency USA
Hinistere  de  I'Environnement et du Cadre^de  Vig (France)

             Research Triangle Park, May  1980
              Recherche dans  le  domains de
        la Physique des Aerosols Atmosph£riques
                   par G.J. Madelaine
         Laboratoire de Physique de 1'Atmosphere
                                                    PROCEEDINGS-PAGE 289
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          La majeure  partie  en nombre des particules coraposant 1' aerosol
 atmospherique  provient de  reactions en phase  gazeuse. Ces particules sont
 contenues presque  exclusivement dans les modes "Nucleation" et "Agglomeration"
 et  sont  done en premiere approximation de dimension submicronique . Elles
 deviennent  particulierement nombreuses dans les Episodes aigus de pollution
 par "smog"  acide et  photochimique .  A notre avis, 1'etude de la formation et
 de  la dynamique et cet aerosol fin  revet une  importance capitale en physique
 de  I1 atmosphere et en  pollution atmospherique.
         Nos efforts ont  done porte  ces  dernieres annees sur l'e"tude des
parametres  re"gissant 1' apparition  par nucleation homogene et he"teorogene des
noyaux primaires 6voluant ensuite  par coagulation et condensation pour donner
la composante  fine de  1' ae'rosol  troposphe"rique  et stratospherique. Ces etudes
ont ete roenees en laboratoire  (smog  chamber)  et in situ.
I. Etudes en laboratoire
         Elles ont portes plus specialement sur l'e"tude des reactions en phase
gazeuse des composes soufre"s  : SO  , H.S,  DMS en air reconstitue et en air at-
mospherique exempt ou non d' ae'rosol.
   I.I. Etude de la transformation  du
                                         «
                                       —2
         Ces experiences ont e'te ef features  dans  une enceinte de simulation
de 1 m  en acier inoxydable permettant  le  controle  et la mesure de 1' irra-
diation et des impure t^s gazeuses mises en jeu.

         Les simulations avaient pour object! f non  d'Studier les reactions
rigissant la transformation SO. - ^ H2&04 — ^  aerosols mais de mettre en evidence
les processus susceptibles de jouer  un  role  non nggligeable dans la formation
de particules primaires dans 1 ' atmosphere .
         Les impuretSs gazeuses sont mes urges  i  1'aide  de methodes specifiques
permettant la detection de concentrations  inferieures a 0,1 ppm (SO.-NO-NO -
°3 ~ H2°^ ' Les a6rosois s°nt d^tectSs et mesure's  a  1'aide de compteurs de
noyaux de condensation associe"s ou non & des batteries  de diffusion et de 1'a-
nalyseur e"lectrique d1 aerosol.
        PROCEEDINGS—PAGE 290
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r
                    Les principaux risultats  obtenus peuvent se re'sumer comme ci-dessous.
Gaz porteur
Azote
Air reconstitue
Air re cons ti tu£
Air reconstitug
n
Air atmosph. sans
ae'rosol
Air atmosph.avec
ae'rosol
Impurete's gaze uses
S02 (0,2 ppm)
so2
SO (0 , 2ppm) +03 (0 , 3ppm)
S02 (0 , 2ppm) +N02 (0-lppm
SO- (0 , 2ppm) +N0_+H_0
S02 (0,2 ppm)
S02 (0,2 ppm)
Consommation SO-
non mesurable
non mesurable
non mesurable
de 0% a 7,5% h"1
de 0% a 7,5% h"1
2,1 % h'1
2,2 % h"1
Particules (CNC)
non mesurable
non mesurable
Cone. Max. < 5000 pern
Cone. Max. < 1C5 pern"
Cone. Max > 10 par."3
Cone. Max < 10 pcm
formation de nou-
veaux noyaux

                    Si 1'on conside're que  la mesure de reference est constitute par la
           consommation du SO2 en  air atraosphe rique non depoussiere on obtient un taux
           de conversion de 2,2  %  h~l [5,25  % h~l  pour un angle solaire au zenith de
           60°]. II re'sulte de nos experiences  que la seule contribution importante est
           celle du melange SO2  -  NO. elle est  voisine de 50 %.

                    L'e'tude expe'rimentale , nous a  permis de re Jeter un certain nombre
           d'oxydants tels que 1 'ozone,  les  oxydes supe"rieurs de lazote (NO-, N205' et
           de sugggrer les oxydants qui  apparaissent les plus reactifs a savoir : les
           radicaux hydroxyl   (OH), 1 'hydroperoxyl (HQ2)  et les radicaux organiques Ro
           et
                    La vapeur d'eau ne modifie pas  les  vitesses d'oxydation du SO2 mais
           augments de facon importante  la production de  nouvelles particules (HR de 0,5
           4 50 % - concentration particules  x  100  environ)  fig.l.
                    L'ae'rosoi "bruit de  fond" n'a aucune  influence notable sur le taux
           de transformation du SO,.

                    - Des analyses par diff ractionselectroniques de la nature chimique
           des particules forme'es nous ont montre la presence  conjointe de H_SO. , sul-
           fates d'ammonoium et calcium  et sulfate  acide  de  nit rosy le.

                    - Des experiences consacrees  a  1' etude de  la nucleation du systeme
           binaire eau-acide sulfurique  nous  ont  permis,  compte tenu d'une part des in-
           certitudes experimentales et  d'autre part des  lacunes concernant les calculs
           th^oriques, de montrer qu'il  existe un accord  "semi quantitatif" entre nos re-
           sultats experimentaux et les  resultats theoriques de Mirabel et Katz et ceux
           de Kaing et Staffer si 1'on adopte pour  la pression de vapeur saturante de
           H SO  la valeur de 3,4 10~4 torr.  De plus, pour la  meme valeur de la frequence
           de nucliation et pour une humidite relative  de 50 % cet accord existe encore
           lorsque Shugard et al. tiennent compte de la prisence d 'hydrates dans le sys-
           teme (fig. 2) .                                                 PROCEEDINGS— PAGE 291
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                                                                   Photochemical Ozone/Oxldants Pollution

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                  7
                  i
                     PARTICULES .cm"3
                                                               1OO
Fig. "I  :  Variation  de la concentration maximum des  particules  njesurSes  au  cours
          du temps en fonction  de  1'humidice  relative  (SO, =  20
          20 < K02 < 25 pphm ;  60  < C    < 70 pphm).
                              y
        PROCEEDINGS—PAGE 292
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r~
            t
          12
         10
          10
         10
         10"
         1C?
         10'
molecules  cm~3)
        1=1  CM"3S"1
                        ,KIANG &STAUFFER (ps:3,5 ID"4* torr)
                                  RESULTATS  EXPERIMENTAL^'
                                         SHUGARD & COLLAB/
                             MIR ABEL &KATZ
                                     & STAUFFER( ps.- 10~6torr
                           HUMIDITE  RELATIVE(%)
                                      50
                                            100
       Fig.Jl :  Variations de la concentration totale de molecules d'acide sulfurique
               en fonction de 1'humidite relative dans le cas d'une frequence"de

               nucleacion de I cni""^s""'.

                                      ' ' •  •  • • " •    .        PROCEEDINGS—PAGE 293
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           - Pour nous permettre de mode"liser d'une  fagon qualitative  voire serai -
  quantitative la prodction et 1'evolution de ces particules produites par
  reactions en phase gazeuse nous nous sorames ensuite  attaches a  1'itude de"tail-
  le"e des differents processus regissant 1'evolution des particules  au cours
  du temps.

           - Nucle"ation homog^ne heteromoleculaire des vapeurs produites con-
             duisant i la formation de particules ;

           - Coagulation des particules formees  -,

           - Condensation des vapeurs sur les particules produites.


     1.2. Etude de l^aerosol ultrafin produitjpar reaction en phase  gazeuse

           Notre demarche experiment ale a ete la suivante :

           - Etude de Involution d'un aerosol monodisperse produit  instan-
             tanSment ;

           - Etude de Involution d'un nuage de particulaire produit de fagon
             continue ;

           - Etude de la formation et de 1'evolution d'un nuage particulaire
             en presence de I1aerosol atmospherique preexistant.
          1.2.1.  Evolution d'un aerosol monodisperse ultrafin

           Get aerosol est produit par reaction radiolytique  (production de  par
  ticules par disintegration Q de 1'Actinon) ? son  Evolution est  regit unique-
  ment par les lois de la coagulation brownienne. La monodispersion  subsiste   _
  pendant un temps tres long  %  1 h) apres sa production  (t =  10  mn,  r = 4,410  urn.
      1,13 ;  t - 90 mn, r = 5,610~4
                                    um,
1,22)  {fig. 3). Si apres avoir  laisse
  se de"velopper cet aerosol on produit une seconde fois un aerosol  monodisperse
  identique au premier on peut etudier Involution au cours  du  temps  de ces deux
  aerosols representes au depart par une distribution bi-modale qui se re'sorbe
  tres rapidement pour redonner un aerosol monodisperse (fig. 3) . L'expe'rience
  est en bon accord qualitatif avec la the"orie, cet accord est  quantitatif a un
  facteur 2 pres si on tient compte que la valeur th^orique  du  coefficient de
  coagulation est connu avec une approximation qui ne tient  pas compte par ex-
  emple des forces intermol^culaire non n^gligeables dans le cas des  aerosols
  ultrafins.
          I.2.2.  Production continue en presence ou non d1aerosol prSexistant

           L" aerosol est cre'e' de facon permanente par irradiation UV.  La cham-
  bre de simulation est prealablement rempli d'air atmosph^rique filtrS  ou
  contenant 1'aerosol nature 1.  Cette deuxieme 6tape simule de  facon  plus rea-
  liste  le cas  de 1'atmosphere. Les principaux resultats obtenus permettent de
  formuler les  conclusions suivantes.
       PROCEEDINGS—PAGE 291
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                                                          t1=20  mn

                                                          t  B 90  mn
                                                          tgs  ,5  mn

                                                          t-js 120 mn
                                                          t=  25 mn
fig..3 .'evolution au cours du temps  dc la granulomctrieexpcrimentale
                     J experience
                                                      PROCEEDINGS—PAGE 295
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         Dans tous les cas et quel que  soit  le  taux  de  nucleation ou de la
 concentration de 1'aerosol preexistant,  la  formation de  nouvelles particules
 subsiste et 1"aerosol evolue sous 1'effet de la  nucleation,  la condensation
 et la coagulation, le role des particules ultrafines inferieures~a 10"^ ym
 n'etant pas negligeable  (fig. 4). La theorie de  Friedlander  - MazHurry
 (zero activation energy  scavenging) semble  assez bien  representer 1'evolution
 des aerosols produits par nucleation en  presence d'un  aerosol preexistant
 (cas de la troposphere et stratosphere}.

          Nos travaux montrent qua la verification experimentale de la theorie
 de MacMurry ne peut s'effectuer dans des conditions satisfaisantes que si
 1'on mesure les particules inferieures a 0,01  um (mode nucleation). A partir
 de ces experiences on peut egalement determiner  le  taux  d'apparition de nou-
 velles particules dans le mode nucleation et caracteriser  ainsi, en enceinte
 de simulation, des situations typiques susceptibles d'etre  rencontrees dans
 1'atmosphere (continentale, maritime, pollution).
 II. Etudes in situ

         La granulometrie et la dynamique de  I1aerosol  atmospherique ont
 etudides dans deux situations typiques.

         - Atmosphere urbaine moyennement polluee  (10 km  sud
         - Atmosphere marine (cote de la Bretagne).
    II.1. Atmospjhere _urbaine

          Les distributions en dimension de 1'aerosol  mesure  montrent la presence
 d'un mode ayant un diametre moyen gemetrique de  3,5  10~2  ^m,  la nuit ce dia-
 metre se situe aux alentours de 0,07 um. On detects egalement une  composante
 importante dans le mode nucleation dependant des conditions  meteorologiques
 et physico-chimique (direction des vents, pollution,  ensolelllement).  Les taux
 de nucleation (apparition de particules dans le  mode  nucleation sont situes
 entre 3 10~2 et 90 particules par seconde). La fig. 5 represente un exemple
 de distribution granulometrique obtenue.

          Toutes ces mesures sont effectuees & 1'aide  de la me"tnode utilisant
 les batteries de diffusion coupiees au CMC et avec 1'Electrical Aerosol Analyser.


    II.2. Atmosphere marine

          Ces memes experiences re"petees en bordure de mer montrent une situa-
 tion differente dans 1'evolution de 1'aersol atmospherique et on a pu mettre
 en Evidence une source importante de particules nature lies sans aucun  doute
 due 4 la transformation des composes soufres organiques emis  par la couche
 superficielle oceanique et par les organismes vivants (presence de DMS mesuree).
       PROCEEDINGS—PAGE 296
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                                                     30 mn
fig- "i.  : evolution de la granulometrie
                                                PROCEEDINGS—PAGE 297
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               dN
             dlogDl
[cm-3]
               101
               104
               103
               10'
              101
                                      10-2             10'1

                    fig  5  : Aerosol atmospherique orbain
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          Les  taux de  nucle"ation peuvent atteindre des valeurs de 1'ordre  de
plusieurs centaines par cm3.s~l,  toutefois une tres grande variation est  cons-
tatSe  (2.10~4 -400 cm"3.s~l  dependant des conditions meteorologiques et des
marges  (fig.  6).

          Toutes  ces experiences ont pour but de mieux comprendre par des  expe-
riences  conjointes en laboratoire et in situ, les differents parametres qui
re"gissent la  dynamique physico-chimique des particules comprises dans les rcodes
nucleations et agglomeration et a modeliser leur comportement dans diff§rentes
situations de pollution.
 III. Mesure  des  aerosols  fins

         Toutes  ces Etudes  ne peuvent s'effectuer avec une certaine precision
que si la detection et  la mesure  des  particules dans les domaines submicroni-
ques et particulierement  dans le  mode "nucle'ation" sont possible. Les seuls
dispositifs  disponibles a 1'heure actuelle sont pour la detection des parti-
cules  : les  compteurs de  noyaux de condensation (CNC)  et pour la roesure des
dimensions,  1'analyseur £lectrique de mobilite (TSI St Paul, Minnesota) et
les batteries de diffusion  associees  avec des  CNC.

         Les CNC existant jusqu'a ce  jour sur  le marche (G.E. Environment
One) ne permettant pas  la mesure  de faible concentration (C < 50 p cra~^) en
ont un regime pulse ce qui  re"duit leur utilisation et la precision des mesures
effectuees avec des batteries de  diffusion.  Nous avons done mis au point un
CNC a  flux continu permettant la  detection des particules une par une  (sen-
sibilite 0,1 p cm~3) . La  licence  a e"te cedee a Thermo. System Inc. qui en
assure maintenant la commercialisation aux USA et dans le reste du monde.

         Une me"thode de mesure de la  distribution en dimension des particules
par batterie de diffusion (honneycomb structure)  + CNC a flux continu a ete
mise au point apres un etalonnage a 1'aide d'aerosol monodisperse du CNC
(fig. 7) , elle nous a permis :

        - de pouvoir appreliender  la mesure des particules infe"rieures a 0,01 urn

        - de comparer les rfisultats obtenus  avec ceux dell'analyseur electrique
          TSI et de montrer que celui-ci  ne  permet pas notamment d'obtenir des
          re's ul tats en des sous de 0,01  um (fig.  8), les deux methodes etant
          comparables pour des dimensions supe'rieures.

         Cetce derniSre e"tude a fait  1'objet d'un contrat avec 1'Environmental
Protection Agency (M. Sllestad)  qui a contribue pour moitig au financement de
cette etude, le Commissariat a 1'Energie  Atomique (France)  financant la seconde
partie.
                                                          PROCEEDINGS—PAGE 299
                                                       First US-France Conference on
                                                   Photochemical Ozone/Oxidarts Pollution

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                    106
                    10
                    10'
                         [cm-3]
   9h30
 •  12
 A  13h30
_ 15h30
                        fig-  6  J granulometrie  mesuree  en bord  de mer
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                 dN
               dlogD
                                                   AME
                   104
                  /02
                  701
[crrr3
                                •  MBD

                                .  AME
                                     102              JO'1         Dl>m]

                       fig •  8   comparaison sur I 'aerosd  atmospherique
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ETUDE DE  LA POLLUTION  OXYDANTE SUR  LA FACADE MEDITERRANEENNE
                    presented  by Yves Barbry



     Ecole Nationale Superieure des Mines de  Saint-Etienne

                             France
                                                       PROCEEDINGS—PAGE 303
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ECOLE NATIONALS Sl'PERIEL'RE
DES  MINKS I)K  SVINT-KTIENNE
Departement Sciences des Materiaux

        YB/MCM/936

          4/05/80
               ETUDE DE LA POLLUTION  OXYDANTE SUR LA FACADE MEDITERRANEENNE
                            C0WTRAT  n"  77-31  -  RAPPORT FI.MAL
                                                        SO'JST^LLE - DI B£'iEDI"~C - BARBED

                                                        f'lAHCHAND -
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                                                                           Ffrjrisp  15SC

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                                 RESUME
           En  1979,  la  mise  en place totale du reseau "pollution oxydante" du litto-
 ral me'dite'rraneen a  ete  terminee.  Toutefois,  les conditions severes de fonctionne-
 ment et  les contraintes  inherentes a la localisation ggographique de stations "zero"
 nous ont oblige S en arrSter  momentan&ment le fonctionnement.

           Les mesures  faites  sur les stations les plus anciennes ont confirme la
 necessite  d'une inter-calibration frequente, d'un suivi et d'une maintenance rigou-
 reuse des  appareils  sur  site.  La premiere mallette prototype nous a permis d'une
 part de  rgaliser cette intercalibration pendant un an et d'autre part de "tester"
 le prototype.

           Pendant 1'annee 1979,  les mesures faites sur les differents sites ont
 §te stockees en vue  d'un traitement statistique ulterieur. Toutefois, nous pouvons
 d§s a present dggager  de grandes tendances, tant au point de vue de la quantite
 que de la  qualite de ces mesures.  Certains cas  particuliers ont pu etre ainsi
 degages.

           Enfin, avec  les donnees  transmises  3  1'Ecole des Mines, il a ete entrepris
 une analyse statistique visant S la prevision des mesures en ozone et ceci site
 par site.
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                                 SOMMAIRE
I  -  INTRODUCTION
II -  MISE EN PLACE  -  GESTION - FQNCTIONNEMENT DES  STATIONS DE MESURE
      7)  Foncttonnement et gea-ticw de-i  t4.qu.e. nu^e. en ceau^e
      2)  ktgofLithm
      3)  In^g-tet cf'un
VI -  CONCLUSIONS
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     I -  INTRODUCTION
              L'Stude des precurseurs de  la  pollution  oxydante  sur le  littoral
     mediterranean, s.i el le repr§sente un  programme original  en  France  a  §t§  pr§cedee
     d'importants travaux realises  sur ce  sujet aux Etats-Unis et  notamment a Los  Angeles.
     Plusieurs laboratoires en Studient encore les differents aspects trSs varies  et tr§s
     complexes.

              Le r£seau de mesure  de Tetude franchise prevu au depart comportait six
     sites de mesures repartis le long du  littoral mediterraneen et qui devaient fournir
     d§s 1978 les donnees quart-horaires des  polluants  (NO,  NO*, 0,, hydrocarbures, SO*}
    et des parametres meteorologiques {temperature,  pression, hygrometrie, rayonnement
     solaire total, part ultra violette, visible, infra-rouge, vitesse  et direction du
     vent).

              La mise en place et  la gestion de ce rSseau a Ste confine  aux  Services
    de 1'Industrie et des Mines de Marseille et Montpellier, et au MinistSre de la
     Sante pour le site de Nice.

              L'intercalibration des analyseurs a ete  confiie au  laboratoire d'analyses
    de TEcole des Mines de Saint-Etienne.

              Les r§sultats des mesures devaient subir un traitement statistique  confie I
     la sociSt§ ARLAB et seraient ensuite  transmis a  1'Ecole des Mines  de Saint-Etienne
    pour 6tre analyses et interpretfes.

              Les resultats des mesures devaient Sgalement  etre corrfiles avec ceux
    obtenus par 1'I.N.R.A. au cours de l'§tude de phytotoxicite des brouillards oxydants.
    II - MISE EN PLACE - GESTION - FONCTIONNEMENT DES STATIONS  DE  MESURE •
              La mise en place total e de toutes les  stations  s'est terminge courant
    1978.
              a) Les appare-ils de rnesures

              De fac.on general e les appareils sur site travaillent  dans  des  conditions
    souvent trSs sSvSres, il ne faut done pas s'etonner de certaines  faiblesses.  De  ce
    point de vue il semblerait nfecessaire de renforcer la maintenance des  appareils
    install es. Bien que la Socifetfe ENVIRONNEMENT S.A. fournisse en  ce domaine  un  gros
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effort, les temps d'intervention restent beaucoup  trop  longs  et  a"  1'avenir une
solution devra etre trouvle pour raccourcir  les dglais  d1intervention  sur site.
Notons que les tournges de maintenance ne permettent  :
          - que Tentretien courant des appareils
          -  que rarement la reparation d'un  appareil  sur site, il y a retour en
            usine  done pas d'appareil  sur site pendant des pc-riodes assez longues.
          - que la detection de pannes franches.

          Les  tourne'es d1 intercalibration quant a  elles  permettent :
          - La detection  de certaines dgfaillances non  franches  des  appareils
            (derive electronique, encrassement de  circuit hydraulique,  vieillissement
            d'organes  ...).
          - et evidemment  la calibration de  tous les  sites.
          b) Les appareils d'aacuisiticn des donnees
          D'apres les enregistrements des mesures que  nous a  fournis  la  Societe
ARLA3 a ce jour (3 savoir du 1/01/79 au 30/09/79 pour  les sites  de  NICE/SETE/
PQRQUERQLLES et LUBERON) on peut evaluer le pourcentage de donnees  disponibles.

          Pour les sites de NICE et SETE sont pris en  compte  environ  50  %  des
donnees. (Ce chiffre ne donnant pas d1 indication sur la validite de ces  donnees)
on doit toutefois faire remarquer que si on manque de  donnees  eel a  est surtout du
a des problemes d'acquisitions informatiques plus qu'a des pannes d'appareils de
mesures. On decele des "trous" complets de donnees pendant 3  semaines de suite
(en particulier a SETE).

          Ce probUme a ete souleve au cours d'une reunion technique  a" MARSEILLE
en Novembre 1979. Une solution que nous esperons satisfaisante sera nrise en  place
en 1980, cette solution consistera en la signature d'un contrat  de  maintenance
informatique avec la Societe SODETEC d'une part et d'autre part  en  la liaison
systematique des stations a un poste de contrQle permanent.
     2)
          Les premiers resultats ont montr§ que les sites  "zero" semblaient  bien
choi sis du point de vue pollution, malheureusement certaines difficulte's  rencontrees
au cours de la premiere annee de travail ont amen§ le service de I1 Industrie et des
Mines de MARSEILLE a en abandonner provisoirement 1 'implantation et 1'exploitation.
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              a.)  Le  site  "z&ro" du  Lub£ron
              Les principaux  problfcmes  rencontres  sont  :
              - Coups  de  foudre frequents amenant  la  disjonction  de  la  station  et  eel a
   malgre"  (ou peut-etre  a  cause) le  paratonnerre  tout  proche.
              - La station  e"tant placge  en bout de rfeseau  EOF,  elle  se  trouvait
   sujette a  de  fortes variations de la  tension electrique  du  reseau  d1alimentation,
   ceci Stant tres  n€faste pour le mateYiel  scientifique.

              - Difficultes d'acc§s du  vghicule le"ger transportant le matSriel  d1inter-
   calibration,  Thiver  cet acc§s  est meme parfois impossible.

             b) Le site  "z£rc" de  PORQUESOLLES
             C'est surtout 1'environnement marin  qui s'avere trop severe  pour  1'appareil
   lage. D'autre  part, Vacc§s a la  station  est quelquefois  al£atoire  pour la  barge
   de transbordement done  pour le  vShicule d'intercalibration.

             On notera que pour ces  deux stations, la  non surveillance en continu reste
   le probUme majeur.

             Pour toutes ces raisons, le service  de  Vindustrie  et  des Mines de
   MARSEILLE a proposi 1'abandon de  ces deux stations  pour tout  concentrer sur un
   seul  site ze>o futur qui sera fiquipe de materiel  neuf. Cette  nouvelle  station  sera
   mise en place en 1980 et sera reliee en permanence  au  poste de controle du  Service
   de 1'Industrie et des Mines de  MARSEILLE. Pour notre part,  nous  souhaiterions  que
   cette station soit Sventuellement deplagable (installee dans  une caravane ou une
   cabane mobile de chantier), cela  permettrait une  plus  grande  souplesse d'utilisation
   (site zfcro, doublement  d'un site  pour une campagne  de mesures, e"tude du transport
   I  longue et moyenne distance ...)•

             o)  Stations de NICE,  MARSEILLE, PORT de BOUC
             En  dehors des probl&nes propres a 1'apparel11 age, ces stations sont
   de loin les plus  fiables.  Leur  surveillance Stant continue pour MARSEILLE et
   PORT  de BOUC  et discontinue mais  importante pour celle de NICE.
L
             d) Sta.ti.on de SETE

             C'est sur cette station que le problfime de non surveillance continue
   s'est traduit de la fa$on Ta plus nette (voir acquisition des donnees).
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          En conclusion, nous  insisterons  sur  la  ngcessitS  de  relier les  diverses
stations a un centre de contr81e  continu.  Suite a" la  dernigre  reunion de  coordina-
tion,  il a ete adopts  le principe de  relier  la station  de NICE au  Laboratoire
d1Hygiene Municipal, la station de  SETE  au Service de I1Industrie  et des  Mines  de
MONTPELUER et la future station  zero  a  celui  de  MARSEILLE.  En 1980  toutes  les
stations oxydantes du  littoral seront  ainsi  sous  surveillance  continue. Cette
surveillance permettant de detecter rapidement les anomalies franches de  fonction-
nement, le probleme d1intervention  pour  reparation rapide restant  encore  en  suspend,
1'Ecole des Mines quant a" elle interviendra  pour  1'intercalibration  suivant  le
meme rythme.
Ill -  INTERCALIBRATION DES APPAREILS DE MESURE
          L'installation de reseaux de mesure de la pollution atmospherique
necessite 1 'intercalibration des appareils de mesure si  Ton veut pouvoir comparer
et traiter  les resultats de ces mesures.

          Pour Stre serieuse, cette intercalibration doit etre faite avec les  pol-
luants et autour de leur teneur habituelle dans 1 'environnement. La technique  de  la
permeation en phase liquide ou la dilution dynamique sont bien adaptees et couram-
ment utilisees au laboratoire, leur emploi est cependant delicat (surtout sur  sites)
(fragilite, sensibilite aux variations de temperature  ..,)• Aussi , nous avons  propo-
se  la solution suivante. II s'agit d'un systeme portable et autonome pendant  le
transport permettant la generation de melanges gazeux de concentration constante
et faible.

          Les polluants § doser sont : S02, NO, NOZ , CH,, et 03 (03 est obtenu  par
lampe UV}, obtenus en melange avec de Tair "zero" (de 1'azote pour NO).

          Le precede utilise la diffusion d'un polluant S 1 'etat gazeux i travers
un tube en teflon ou en silicone (fluore ou non) et ceci contrairement aux proced§s
actuels ou le polluant est liquSfie dans un tube.

          Le principe de la permeation est bienconnu, il consiste 5 faire diffuser
le polluant i travers la paroi d'un tube ou d'une membrane de polymere en mainte-
nant de part et d'autre de cette paroi un gradient de concentration de ce polluant.
                                                            PROCEEDINGS— PAGE 311
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                Si  ce  gradient  reste  constant,  le  taux  de  diffusion  (ou  de permeation)
     est  constant.

                En  balayant une des parois  du tube avec  de  1'air  zero  (air pur)  a  debit
     constant,  et  en  maintenant sur  1'autre paroi une pression constante  en  polluant,
     on obtient un melange air +  polluant  de concentration constante  et faible  en pol-
     luant.
               La figure ( 1) montre les deux sch§mas coraparatifs  des  syst§mes  :  permea-
     tion avec polluant liquefie (a) et permeation avec polluant  gazeux  (b).
     (a) Dans le cas de la permeation avec polluant  liqudfie  :
               - L'air purifie balaye 1 'exterieur du tube  thermostate
               - Toute modification de  la temperature de 1 'enceinte modifie  le gradient
                 des pressions partielles, or ce gradient  n'est stable qu'au bout de plu-
                 sieurs dizaines d'heures pour un tube teflon.
               - On joue sur le rapport des debits d'air pour obtenir diverses concentra-
                 tions en polluant.
               - Les tubes teflon commerciaux (teflon FEP)  sont difficiles a remplir au
                 laboratoire.
               - Le melangeur homogeneisateur grace  a sa sortie exces permet a 1'appareil
                 de mesure de prelever  1'echantillon dans  les memes conditions que 1'en-
                 vironnement (Pmglangeur - Patm. locale)-
     (b) Dans notre systeme de permeation avec polluant gazeux :
               - Le circuit fluide est le meme que pour (a) mais  le polluant gazeux
                 est stocke dans une cellule qui entoure le tube  teflon  (de  memes  carac-
                 teristiques que pour (a)) et c'est  1'air  pur qui passe  S 1 'interiejjr.
               Les phenomenes de permeation sont les m^mes dans les deux cas mais  si
     la meme Equation gouverne le taux de permeation dans les deux cas la variation de
     ce taux de permeation avec la temperature est differente (voir figure 2), en  effet  :
               Le taux de permeation q est donne par la meme equation  :
                    Q = A (pi - pQ) exp (- |r)

     q  en masse par unite de temps
        ou en volume (conditions normales) par unite de temps
     A  caracterise le couple tube/polluant

     P.J pression partielle du polluant d'un cot§ de la paroi du tube
       PROCEEDINGS—PAGE 312
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       'POLLUANT   L'lQUEF'iE
  airL_
purifie
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                                 utilisation
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                                 exces
                     ^'•x^jair  dilution
                                         Po=0
         POLLUANT   GAZEUX
           1
           u.
                               *
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Pi
                       Rg.1
                                        PROCEEDINGS-PAGE 313
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                                  Photochemical Pzone/Oxidants Pollution

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p   pression partielle du polluant  sur  la  paroi  balayee par lair pur
    (on admet que p  * 0)
E  gnergie d'activation de diffusion  du polluant a"  travers  le materiau du tube
R  constante des gaz parfaits
T  temp&rature en °K
          Mais les variations du  taux  de  permeation  avec  la  temperature (equations
            sont diffeYentes dans  les  deux  syst§mes  car dans le  cas  du polluant
liquefie (a) la variation de p.. avec T obe"it a  la  loi  de  Clapeyron,  alors  que pour
le polluant gazeux (b) (gaz parfait) elle obeit a  la  loi  de  Mariotte.

          Dans les equations -^ ~  f(y— ) AHe represente la valeur moyenne de la
chaleur de vaporisation dans 1'intervalle AT autour de T.

          Le tableau comparatif, relatif au SO*  (fig.  3)  montre  que  les  gains de
stabilite du taux de permeation sont de 4 (tube si li cone)  et 2  (tube teflon)
pour T = 300° K et AT = 1° en faveur du systeme  a polluant gazeux.

          Si le gain de stabilite  du taux de permeation est  important avec le
materiau silicone cela est du aux  faibles energies d'activation  de diffusion  des
polluants 3 travers celui-ci.

          Malheureusement, le silicone ne presente pas que des avantages,  en  effet :
          - On connait raal sa tenue dans le temps en  presence de S02,  NO,  N02
          - Les polluants ont une  grande solubility dans  ce  mat§riau,  si  bien qu'il
            est difficile de les obtenir a des  teneurs faibles
          - Sa grande Slasticit£ le rend deformable sous  contrainte  mecanique.
CONCLUSION :
          On peut resumer comme suit les avantages d'un  tel  systSme  a  polluant
gazeux
          - II accepte des hearts de temperature de - 0,5°C
          - II permet la diffusion de tous les gaz  : CO, CHi,, NO,  F2  ...
          - La pression partielle du polluant peut §tre choisie  par 1'utilisateur
                                                            PROCEEDINGS-PAGE 315
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                    o
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          - Une seule  thermostat! on  pour plusieurs  polluants
          - Remplissage  facile
          - Plusieurs  polluants  par  mallette,  ou  une cellule sur chaque appareil
            de inesure
          - Etalonnage en  trois  points  avec  trois debits  (par exemple)
          La figure (4 )repr£sente  la  cellule  utilisee  pour  1 'etude preliminaire rea
      au laboratoire.
          Les essais des cellules  ont  ete  effectues  avec  les  methodes  de references
 (chimiques) puis par comparaison avec  des  banes  de permeations  commerciaux et les
 appareils physiques install es  dans les stations  (sauf  ozone et  methane).
          Les bons resultats obtenus  ont  conduit  a  la  realisation  d'une mallette
portable et autonome. (schema  fluide  de cette mallette en  figure  5).

          Ce schema s'explique par  la necessite de  maintenir constant le gradient de
concentration du polluant dans la paroi du  tube et  de  maintenir §galement constante
la temperature des cellules. Un debit "d'entretien" en air (ou  azote) est assure
par une pompe 12 V = (batterie rechargeable d'autonomie 1  h  30, ou batterie du
vehicule pendant le transport).

          Une pompe 220 V = (en station)  sert d1alimentation "travail"  sur site
et grace aux derivations nous  delivre 3 debits, done nous  fournit  3 concentrations
differentes en polluant.

          La longueur du tube  de permeation dans  notre mallette est de  1'ordre de
30 mm. Pour le polluant NO, il faut un balayage par 1'azote  afin d'eviter 1'oxyda-
tion de ce gaz en N02. De plus, la cellule  NO contient de  1'azote  a pression
atmospherique pour eviter toute diffusion d'oxygene qui  aurait  le  meme  effet.

          Pour le methane on utilise une  bouteille  air + methane qui  est stable
dans le temps, le probleme d'un air zero  en methane reste  difficile a obtenir  car
en fait il  serait necessaire d'utiliser un four catalytique.
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       3 )
            Dans sa forme primitive  notre mallette  nous  a  permis  de  d§celer  des
  anomalies qu'il aurait St§  impossible de voir  par des  etalonnages  Slectroniques.

            1) On a ainsi detecte un decalage systematique du  zero des  appareils  de
               mesure du S02  : cela  provenait de  la facon  d'injecter Vechantillon
               dans Tappareil. Ce probl erne  "pneumatique"  a fete" r§solu  apres discus-
               sion avec les  ingenieurs de la maison  SERES et  il  s'est  aveYe que  notre
               methode Stait  la bonne, a savoir  : il  est necessaire  que Tappareil
               pr§16ve 1 'Schantillon dans les memes conditions que pour une  mesure.
               Cette correction etant faite, nous avons  pu detecter  par la suite  une
               derive "negative" systematique du  zero de tous  les appareils  de mesure
               S02 regies prealablement entre 0 et  5  ppb,  ce point est  actuellement
               souleve et semble du a une mise en equilibre assez Tongue aprgs retou-
               che des reglages.

            2) On a pu egalement d^tecter un defaut de linearite  de  la  reponse sur un
               appareil S02 grace a 1' injection de  deux  concentrations  differentes en
               S02  fournies  par la mallette, ceci  etant du sur cet  appareil  i un
               dSfaut dans la carte glectronique.

            3) Les problSmes  gventuels de conversion  du  four des appareils a oxydes
               d' azote ont pu etre decouverts grace 5 la possibility d'injecter NO
               et N02.

            4) Les appareils  de mesure des hydrocarbures peuvent presenter des phgno-
               mgnes de retention qui apparaissent  quand on injecte  du  methane
               et que Ton laisse se derouler le cycle : HT/methane/non methaniques.
               Une comparaison entre des bouteilles etalon nous a conduit 3  proscrire
               le melange methane dans N2 au profit de methane dans  air (d'ailleurs
               plus proche des conditions de 1 'environnement) .
            5) Les appareils ce mesure d1ozone nous laissent entrapercevoir d'even-
               tuels problernes de vieillissement des lampes UV utilisees pour  leur
               calibration . De fagon generale ces "visites" periodiques nous  permet-
               tent de dfeceler ou de connaitre tous les probl§mes qui apparaissent
               au niveau de la mesure. Ces renseignements nous seront precieux au
               niveau de 1'analyse des r§sultats.
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           Avec  les  6 + 1  stations "lourdes" visitees nous avons "essuye les platres"
 inherants  a  toute  nouvelle technique et exploitation, mais nous restons. persuades,
 et  chaque  intervention nous le prouve, qu'une mgtrologie fiable est 1 'Stape preli-
 minaire  indispensable § toute exploitation aussi  raffine"e soit-elle.
           Pour  ameliorer Vetalonnage des  appareils de mesure, nous avons congu
 un  autre modele de  mallette  plus  simple pour r§soudre les problSmes de therraosta-
 tation, d'encombrement et de poids  rencontres sur la premiere mallette prototype.
 Cette mallette  de deuxigme generation sera rSalisee en 1980 par le laboratoire
 d'analyse  de  1'Ecole  des Mines  de Saint-Etienne.

           Dans  cette  mallette la  permeation se produira dans une seule cellule
 facile a thermostater,  une seule  capacite  contenant 3 polluants dans 1 'azote
 (S02, NO,  hydrocarbure)  sera utilisee.  On  utilisera une dilution et la titration en
 phase gazeuse (dejS testee au laboratoire), ce qui  nous permettra d'obtenir en
 plus N02 et 03.
 IV -  INTERPRETATION DES  RE5ULTATS
          Les difficultgs et  retards apportes  dans  1 'implantation  des  stations
ne nous permettent qu'une interpretation  partielle  des  donnees  regues  actuellement.

          La Societe ARLAB nous a actuellement fait parvenir les donnies  suivantes
PORQUEROLLES

LUBERON
NICE
SETE
MARSEILLE

PORT de BOUC
1 Janvier 1979

1 Janvier 1979
1 Janvier 1979
1 Janvier 1979
1 Janvier 1979
arret de la station  avec enregistrement
                     graphique
arrSt de la station          "
30 Septembre 1979
30 Septembre 1979
Fin 1979             sans enregistrement
                                           graphique
1 Janvier 1979	Fin 1979
          Actuellement nous avons pu commencer a travailler  sur  les  rgsultats  des
stations de NICE et SETE.

                                                             PROCEEDINGS—PAGE 321
                                                          First US-France Conference  on
                                                      Photochemical  Ozone/Oxidants Pollution

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                Pour ces stations on peut  considgrer que  50 %  (SETE) et  70 %  (NICE)  des
      donnees sont disponibles. On a vu que  ce manque  de  donn£es  provenait essentiallement
      de probleme d'acqulsitlon et peu de  problSme d'appareillage de mesure.
                De par ses Studes sur des donnees relativement  restreintes  POINTEAU
      avait fair apparattre la notion de plage de vatidite  des  mesures.

                Les caracteYistiques de ces diffeYentes  plages  §taient  :
                - Des translations d'origine  (toutes  les valeurs  semblaient alors majorfces
                  ou minorSes d'une valeur 6gale)
                - Des affinit6s (toutes les valeurs paraissaient  corrigees  par un facteur
                  multiplicatif constant).

                POINTEAU avait tenter de corriger ces dgfauts,  ne pouvant y parvenir
      de faijon satisfaisante il avait alors pr&conise' la correction  de  Tanalyseur par
      intercalifarations frSquentes.

                D'aprSs les enregistrements 1979 pour les stations de NICE, SETE,
      PORQUEROLLES et LUBERON, cette notion de plages de mesures  n'apparatt plus, aussi,
      en attendant de pouvoir conclure dSfinitivement sur cette notion  avec les enre-
      gistrements futurs de MARSEILLE et PORT de BOUC on peut supposer  que  Tintercali-
      bration, raise en place dgbut 1979, a joue" le role  important que POINTEAU preconisait
L
                a) PORQUEROLLZS
                Une etude des moyennes, maxima, minima, fecarts entre maxima et  minima
      etc ... avait St6 faite par POINTEAU. Les rfesultats en sont confirmes par les
      mesures faites en 1979.
                Les concentrations moyennes suivantes sont de Tordre des concentrations
      en "sites nature!s".
      methane * 480 ug/m3
      hydrocarbures non me'thaniques * 70 ug/m3
      oxyde d'azote = 5 yg/m3
      ozone de 35 a 100 ug/m3 suivant la saison.
       PROCEEDINGS—PAGE 322
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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          b) NICE
          Plusieurs sites ont §t§ successivement ou  simultanement utilises  par le
laboratoire d'hygigne de la ville de NICE.

          POINTEAU concluait en une bonne representatives  des  sites  urbains  de
NICE centre. NICE port et Promenade des Anglais, a savoir  :  circulation  importante
avec emissions importantes bien correlees aux heures  de  fort trafic,  ainsi  que
pointes Slevees en ozone. Ces conclusions restent valables  pour les mesures reali-
sSes en 1979 sur le site de NICE Centre (seules donn^es  disponibles).

          D'aprgs POINTEAU, le site de Beausoleil situ€  § quelques kilometres  de
NICE prSsente les caracteristiques d'un "site de banlieue",! savoir concentrations
e'leve'es en ozone et pr§curseurs pratiquement inexistants (les donnees  de ce site
ne sont pas directement reliees au r§seau mais pourraient servir a 1'Stude  du
transport sur courtes distances).

          e) POET de 30UC/MARSEILLE
          Nous ne sommes pas actuellement en mesure de verifier 1'analyse qu'avait
faite POINTEAU en 1978 pour le site de PORT de BOUC,  a savoir frequent depassement
de seuil a 160 ug/m3 en ozone avec allure nettement pho.tolytique, mais si les
hydrocarbures etaient en presence significative, les  oxydes  d'azote etaient
anormalement faibles.
          a) Approche m6t6orologi,crue d grande £chelle - origine stratosp
             de 1 'ozone
          L1ozone semble avoir deux origines :
          - anthropog^nique
          - naturelle.
          Cette origine naturelle pouvant elle-meme se diviser en deux  :
          - mouvements verticaux sur quelques centaines de metres, § proximite
            de la surface du sol, lie's I des variations de gradients thermiques.
          - mouvements verticaux a plus grande echelle, contribuant a introduire
            dans la troposphere de 1'air stratosphSrique, tres charge en ozone.
                                                           PROCEEDINGS—PAGE 323
                                                        First US-France Conference on
                                                    Photochemical Ozone/Oxldants Pollution

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                II est important de dissocier tous ces mScanismes et de chercher des
      traceurs de ces diffirentes origines.

                La temperature au sol peut donner des renseignements sur  la stabilite
      des couches comprises dans les premieres centaines de metres d'altitude. Au cours
      de la journee, 1'augmentation de temperature augmente par mouvement de convection
      les ^changes entre 1e sol et les couches basses, cela se traduisant par un apport
      d1ozone au niveau du sol.

                Notons tout de suite que les variations de temperature au sol sont
      etroitement corrglees au rayonnement solaire et en parti culler au rayonnement U.V.
      qui joue un role important dans la formation photolytique de 1'ozone.

                L1assistance de la MSteorologie Nationale nous sera precieuse pour
      1'analyse de ces masses d'air.

                Par centre, POINTEAU  a pu mettre en evidence deux cas d'introduction
      d'air stratospherique dans la tropophere.  En effet, en octobre 76 et avril 77, il
      a  montre qu'il  existait une bonne correlation entre les mesures au sol des pous-
      sieres radioactivite B I vie Tongue (mesures faites a 1'Echelon du Sud-Est) et des
      teneurs elevees en  ozone 3 la meme epoque sur le site de PORQUEROLLES.

                Des etudes futures vont etre entreprises avec la collaboration du
      C.N.R.S., elles nous perrnettront la mesure du profil  vertical de 1'ozone et des
      temperatures  (mesures par Lidar).  Ces deux donnSes etant importantes pour 1'analyse
      de 1'origine  naturelle et anthropogenique de 1'ozone.


                b)  Episodes d forte concentration en ozone
                Ces episodes sont a classer en deux types :
                -  L'ozone depasse la  cencentration de 160 ug/m3 pendant quelques heures
                  au  cours d'une journee isolee.
                -  L'ozone depasse rggulierement  100 ug/m3 toute la journSe et ce, durant
                  plusieurs jours (la  concentration en debut d'apres-midi  atteignant
                  lierement 200 9u 250 ug/m3)/

                Les  facteurs  pr§pond§rants  a la  presence d'ozone en quantite importante
      sont  d'ordre  me'te'orologique (insolation, temperature  §lev§e, vent faible).
      PROCEEDIHGS—PAGE 324
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           Des  facteurs  semblent jouer un role secondaire (pression, precurseurs).
 En  effet,  11 est possible d1avoir des episodes a forte concentration en ozone sans
 que Ton soit  en presence de precurseurs en quantit§ importante (en particulier
 d'hydrocarbures).  Ces remarques faites par POINTEAU soulevent le probleme de 1'ori-
 gine de 1'ozone  d'une part et d'autre part ne sont pas en accord avec les modeles
 g§nera!ement admis.
 IV  - MODEL ISATION  DE  LA  FORMATION  DE L' OZONE
          La  formation photolytique  de  1 'ozone  a"  partir de precurseurs correspond
 a" un mecanisme  extremement  complexe  (une  centaine d'equations chimiques a peu pres
 simultanees sont a"  prendre  en  compte).

          Les divers  modules proposes font  appel  a un  jeu d1 equation trgs complet
 dont la mise  en oeuvre necessite des moyens lourds et  les verifications sont faites
 par simulation  en chambre a smog.

          Ces difficultes nous ont oriente  vers une model isation statistique dont
 1'interet principal est  de  prevoir 1'evolution  des concentrations dans le temps.
          L1 analyse des donnees  par agregation  autour  de  centres  variables  vise  a
regrouper en n classes N individus statistiques  definis dans  9? par  leurs p coordon-
nes, c'est-a-dire dans notre cas par  les  valeurs  prises § un  instant donne  sur un
meme site par p grandeurs appelees "caracteres".
     2]
          A 1'etape 0, on tire aleatoirement n  individus dans  le  nuage   dont  on
dispose : ils constitueront les "centres" de 1'etape  1.

          Cette etape 1 consiste 3 considerer successivement et de  fagon exhaustive
chacun  des N individus qui seront ainsi affectis  S  1'une  des  n classes  correspon-
dant aux n centres de V etape 1.
          A la fin de 1 'etape 1, on dispose de  n classes qui foment une partition
du nuage initial. On en calcule alors leurs n centres de gravite. On definit
ainsi les centres de 1'etape 2 et on reitere la procedure  jusqu'au  moment ou  1'on
constate que les classes de fin dj etape ne changent pas pour une  nouvelle etape.

                                                            PROCEEDINGS-PAGE 325
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                                                      Photochemical Ozone/Oxldants Pollution

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            Si 1'on definit chacun des individus statistiques par les valeurs prises
  i Tinstant t par les p grandeurs mesurges (concentration polluant, parametre
  me'te'orologique ...) on conceit qu'il sera facile de rechercher pour chacun d'entre
  eux la teneur en ozone mesuree S Tinstant t + 12 heures par exemple.

            Chacune des n classes §tant composed d'un nombre fini d'individus statis-
  tiques pour chaque classe on pourra done calculer une moyenne de ces teneurs
  ultSrieures en ozone et leur variance.  On fera alors la prevision comme suit :
  A  un  instant t sur le site envisage les p parame'tres mesures prennent p valeurs
  formant un vecteur individu.  On regarde a" quelle classe il  convient de rattacher
  cet individu.  La  prevision se fera  alors par reference a la moyenne et a la variance
  de teneurs en  ozone 12_h aprgs, associees a  cette classe.

  REMARQUE
            II convient dans le regroupement par classe de ne pas privilegier tel
  ou  tel  caractere.  Si  bien  que dans  1'ideal on sera peut-etre amene § construire
  5  partir des parametres  mesures un  systfime a  p caracteres  non corral§s deux 3 deux.
 VI - CONCLUSION
           Des etudes partielles  entreprises  jusqu'a  present,  il  decoule que si
 1'on veut entreprendre  une  §tude statistique correcte des  resultats,  il importe
 tout d'abord d'obtenir  un maximum de  resultats  fiables d'une  part et  comptabilisables
 d'autre part.

           Pour eel a, Tintercalibration  systematique ne peut  qu'augmenter la vali-
 dite des mesures 5  prendre  en  compte,  et elle permet en plus  de  mieux connaitre
 les problgmes affectant les appareils  sur sites.  L'amelioration  de la maintenance
 de ces appareils, ainsi  que la surveillance  en  continu des sites ne pourront que
 favoriser 1'acquisition d'un volume de plus  en  plus  important de donne"es utilisables
 a des fins  statistiques.

           Notons d§s 5  present que 1'Ecole des  Mines consciente  des problernes de
 gestion des stations de mesure se propose d§s 5 present d'organiser des cycles de
 formation a 1'intercalibration et a la mesure pour les gestionnaires  des r§seaux
 de mesure.

       PROCEEDINGS—PAGE  326
    First US-France Conference  on
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          !_' evolution  future  de  cette  §tude,  en parti culler la collaboration avec
le C.N.R.S. pourra,  nous  l'espe"rons» apporter une r^ponse § la question soulevee
par POINTEAU  : Peut-on assimiler brouillard oxydant et ozone ?

          En  effet,  les conclusions provisoires et partielles de 1'INRA que nous
avons en notre possession  semblent remettre en question les effets  imputables
sur la vegetation de la presence de forte  concentration en ozone (du meme ordre de
grandeur que  eelles  enregistrees aux U.S.A. dans des sites ou la presence de
brouillard oxydant est visible et se traduit  par des effets sur la  vegetation ou
la population).

          Les resultats prochains concernant  une etude statistique  nous permettront
une approche  sur la  possibility  de prevoir les concentrations en polluant I 12 ou
24 heures. II sera alors  interessant de  comparer ce module previsionnel avec son
application I un cas tres  recent d1episode de pollution oxydante sur la region
de FOS-MARSEILLE et d'en  tirer les conclusions necessaires.

          Les differents aspects et conclusions de cette etude seront prochainement
confrontes aux etudes  menees  aux U.S.A.  au cours d'un  voyage organise par le
Ministgre de  1'Environnement  et  du Cadre de Vie.
          Nous voulons remercier ici tous les participants  a  cette  etude et en
particulier Monsieur POINTEAU.
                                                           PROCEEDINGS-PAGE 327
                                                        First US-France Conference on
                                                    Photochemical Ozone/Oxidants Pollution

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                          THE MAIN CHARACTERISTICS OF  THE OXIDANT

                       POLLUTION PROBLEM  ON THE MEDITERRANEAN FRONT
                                  presented  by Yves Barbry



                   Ecole Nationale Suoerieure des Mines de  Saint-Etienne

                                           France
       PROCEEDINGS—PAGE  328
    First US-France Conference on
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                I would like to point out now the main characteristics of  the  oxidant
      pollution problem as it comes up on the Mediterranean front.     -

                Climatic conditions and high values in ozone concentrations  recorded
      several  times in large cities such as MARSEILLE have alarmed the authorities who
      ordered,  some years ago, a general study of the oxidant pollution.

                Six measurement stations have been equiped and located along the  coast
      line  (picture 1).
                -  Two  are situated in NICE and MARSEILLE, sites we will refer to  as  urban
      sites.
                -  Two  stand! in PORT de BOUC and SETE, that is to say industrial  sites.

                -  And  two standi in PORQUEROLLES and LUBERON that is to say natural  sites.

                The  stations are provided with  :
           1)    -  Sulfur dioxide analysers
                -  ozone  analysers
                -  Nitrogen dioxide and nitric oxide analysers
                -  Total  hydrocarbon, methane and non-methane analysers.

           2)  With the following meteorigical equipments in order to measure  :

                -  infra  red/ultra violet and visible
                -  hygrometrie
                -  Atmospheric pressure
                -  Wind speed
                -  Wind direction

           3)  And  with a computer for the data treatment, recording or sending.

       PROCEEDINGS—PAGE  330
    First US-France Conference on
Photochemical Qzone/Oxidants Pollution

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          That six stations, did  not work without trouble,  but Mr NADAL will  tell
you all about it.
          So we will only show you  the great  tendancies  observed.

          First at PORQUEROLLES  :
          As we can see on this  slide the yearly  average concentrations are :
          420 ug methane per cubic  meter
          1 to 10 ug nitrogen oxides per cubic meter
          35 to 80 ug ozone per  cubic meter.

          At the LUBERON station these averages are comparable.  If we compare  these
values with those considered as  normal for a  natural  site,  that  enables us to  say
that our referency station choice was a good  one.

          At the other stations  :
          - Generally for hydrocarbon we recorded  rather important values.
          - Sulfur dioxide values are rather  more  important on the FOS BERRE area
            (that is to say at PORT de BOUC)  than  at  the other stations.
          - Nitrogen dioxide and nitric oxide recorded measures  are generally  low.
          As example, on the next pictures  (2 and  3) you  can  see  the recorded
values at SETE and NICE stations.

          On the picture 2 (which shows us  the  recorded values  at SETE),  take notice
of the low values of the different pollutants but  total hydrocarbons.

          On the picture 3 (which show us the recorded values at  NICE)  we can note
that sulfur dioxide and ozone concentrations are  rather low, which is not  the
case for total hydrocarbons, and that nitrogen  dioxide concentrations  are rather
high but not very high, as it has always been registered  on urban sites.
                                                            PROCEEDINGS—PAGE 331
                                                          First US-France Conference on
                                                     Photochemical Ozone/Oxidants  Pollution

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                 Now let us speak of the ozone concentrations. Generally the curves look
       photolytic at all the stations. You can see on this slide  the PORT de BOUC hourly
       average.  Specially in summer, ozone concentrations are frequently overstepping  the
       160 ug/m3 limit, but when this occurs, whereas hydrocarbon concentrations are high,
       nitrogen  oxides concentrations are, as I said before, generally low.

                 In some cases, strastopheric air infusion into troposphere, down to the
       ground, can explain that.

                 At PORT de BOUC such an explanation has been justified twice :
                 in October 76
                 in April 77.

                 The falling down 8 particle measurements give an idea of that stratosphe-
       ric air infusion.

                 You can see on this picture that ozone concentrations and & particle
       measures  are correlated.
                 So it would be interesting to have contineous measurements of these
       particles,  in order,  to get further information on the ozone partition into its
       two sources  :
the natural source
and the anthropogenic source.
                 To sum up we may say that the mediterranean front can be characterised
      by the following conditions.
                 - it is sunshiny
                 - the temperature  is generally high
                 - sulfur dioxide concentrations are generally low but more significant
                   on FOS BERRE area
                 - Hydrocarbon are  generally high
                 - Nitrogen oxides  are generally low but more significant on urban area
                 - Ozone concentrations are note very important, the curves look photolytic
                   but specially in summer overstepping of the 160 ug/m3 limit occur.
       PROCEEDINGS-PAGE 332
    First US-France Conference on
Photochemical Cfcone/Oxldants Pollution

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           Now, if we  have measured  ozone without  nitrogen oxides  precursor, we  also

measured  the contrary,  and that, during a pollution  episod as  the following presen-

tation will  show us.
                                                              PROCEEDINGS—PAGE 333
                                                           First US-France Conference on
                                                       Photochemical Ozone/Qxidants Pollution

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         PROCEEDINGS—PAGE 334
     First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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                                                      PROCEEDINGS—PAGE 335
                                                  First US-France Conference on
                                              Photochemical Ozone/Cbddants Pollution

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                   540
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        PROCEEDINGS—PAGE 336
    First US-France Conference on
Photochemical  Ozone/OxIdants Pollution

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 A pollution  incident  on FOS BERRE area

for the period  79-12-02  through  79-12-06
                                         PROCEEDINGS—PAGE 337
                                      First US-France Conference on
                                  Photochemical  Ozone/Oxidants Pollution

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                  On early days of December 1979 a lasting anticyclone developed on  South
        Europe.

                  This situation was accompanied with reversal temperature phenomena and
        with a sudden and severe pollution incident.

                  This incident which concerned a great part of South East Europe, was
        particularly important in Spain where the highest ever recorded pollutant concentra-
        tions were reached in large cities such as MADRID.

                  The FQS-BERRE industrial area was affected by this incident  ; which
        alarmed  the authorities into putting on the pollution alert on the district and
        required reduction measures provided against such an incident (picture 2).

                  We are going to show you here the data as recorded in PORT de BOUC and
        MARTIGUES.

                   Neither we have gotthe measurements taken at that time in MARSEILLE
        where reports have been made of the phenomenon nor the ones taken in NICE where
        the  impact of the pollution has not been so heavy.

                  On the FOS-BERRE area, a large industrial area the two stations on work
        were PORT de BOUC and MARTIGUES, the BERRE station was infortunately out of work
        during the considered period.

                  The distance between the two stations is about five kilometers.

                  The PORT de BOUC station is part of the "Oxidant Pollution System". It
        is  located at the top of a small hill  back from the city and surrounded by vegeta-
        tion.

                  The MARTIGUES station is located in the city center, so, it can be
        considered as an urban station.
       PROCEEDINGS—PAGE  338
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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          It Is level with the sea and it is no part of  "the oxidant  Pollution
System" so that it is not provided with an ozone analyser.

          Let us examine the general meteorological conditions during this  period.

          - The wind speed was low, less than 0.3 meter  per second  direction  South
            West - North East in the day time with an  inversion  tendency  during the
            night.

          - The days were sunshiny.

          - The Atmospheric pressure was stab!Q/it ranged  from 1021 to 1026 mbar.
          - The temperatures were       j 14 to 17° centigrade for a maximum
                                        I  8 to 11° centigrade for the daily average.

          - In BORDEAUX and LACQ, the respective values  for the  temperature inversion
            were 20 degrees centigrade and 15 degrees  centigrade.

          The correspondant height of inversion layer  was  approximatively 300 meters.

          These two values give you an idea of the significance  of  the phenomena.

          Let us examine at once the values recorded in  PORT de  BOUC  during the
last five days of the incident (picture 3).

          You can see that the ozone values are not  very  important,  they are
comparable with those recorded in PORQUEROLLES which is  the site we refere to as
a natural site. The curve looks photolytic.

          The 300 ug per cubic meter peak is not significant, indeed  it does  not
last more than an hour, and it occurs one time.

          As for the precursors, unfortunately we had  no hydrocarbon  analysers  on
the sites during this episode.
                                                             PROCEEDINGS—PAGE 339
                                                          First US-France Conference on
                                                      Photochemical Ozone/Oxidants Pollution

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              On this curve you can see that the nitrogen dioxide and nitric oxide
    values  are low too  and  that none  exceeds 50 ug/n3  during the whole period.

              On the contrary you can see that the sulfur dioxide values are rather
    important with a 1883 ug/m3 peak  and that curiously enough this peak and the ozone
    peak  occur quite at the same time.

              Let us try to explain such peaks.

              If we assume  that it comes from the mi sanctioning of two analysers
    we must take into account that two  breakdowns are  not likely to occur simultaneously,
    So that  explanation does not fit.

              Now if we assume that a short and local  Meteorological  phenomenon occured,
    the explanation does not fit either because we have not got any nitrogen dioxide or
    nitric  oxide  peak.

              Now let us examine the  values recorded  in MARTIGUES during the same period.
              (picture  4)
              I  recall  you  that this  station is not a  part of "the oxidant pollution
    system",  so  that it is  neither provided with an ozone analyseur nor a sulfur
    dioxide analyser  but a high  acidity one.

              We  notice that in this  station the  nitric   oxide and nitrogen dioxide
    concentrations  are  rather important.

              The maximum occurs between  midday  and 4 pm for the nitrogen dioxide and
    later for  the  nitric   oxide (between 6 pm  and 8   pm).

              You can see that the high  acidity concentrations  are relatively high.

              On  the  next picture  we  have plotted the  daily averages  in PORT de BOUC
    and MARTIGUES  (picture  5).

              If we compare these  daily  averages  we can notice  the important difference
    for the nitric oxide  concentrations  between MARTIGUES  and  PORT de  BOUC.
       PROCEEDINGS—PAGE 340
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Photochemical Ozone/OxIdants Pollution

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           The  highest  concentrations registred in MARTIGUES are explained by the
 fact  that  MARTIGUES  is an urban site and also by its geographical situation : the
 city  lies  in a hollow  which aids to the accumulations of pollutants.

           As for  the sulfur dioxide and high acidity concentrations, the two u
 stations are comparable.  If we  consider the large industrial environment and short
 distance between  the two  stations,  these values are logical.

           One  also observes the pollutants  concentrations increase during the
 first 3 days,  we  can explain this by the reversal wind direction between day and
 night.

           At last, the more important fact  is the low ozone concentration registered
 during this episode.

           The  daily  averages are already below 60 yg/m3, that is to say comparable
with natural site values.

           We can conclude  that  if the FOS BERRE area was affected by a severe
 pollution  incident,  showed  by :

           - high sulfur dioxide concentrations,
           - high nitric oxide concentrations only in urban area,
           - reduction  of  the visibility,
           - many complaints.

We may ask however : Is this  incident an oxidant pollution one ?
                     Is it  photochemical  smog ?
                                                             PROCEEDINGS—PAGE 341
                                                          First US-France Conference on
                                                      Photochemical Ozone/Oxidants Pollution

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                                                                                       ___
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                                                                      PROCEEDINGS—PAGE  345
                                                                  First  US-France  Conference on
                                                             Photochemical  Ozone/Qxidants Pollution

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                         A PORTABLE SYSTEM FOR THE CALIBRATION  OF

                   ATMOSPHERIC POLLUTION ANALYSERS INSTALLED  IN STATIONS
                            presented  by Dominique DiBenedetto



                  Ecole  Nationale Superieure des Mines  de Saint-Etienne

                                           France
       PROCEEDINGS—PAGE 346
    Ffrst US-France Conference on
Photochemical Ozone/0x1dants Pollution

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     A PORTABLE SYSTEM FOR THE CALIBRATION OF ATMOSPHERIC  POLLUTION
                    ANALYSERS INSTALLED  IN STATIONS
  SUMMARY
           The first aim in the study of atmospheric pollution  is  the  quality of
  results given by the analysers* which have to be carefully calibrated with  "real"
  Standard; nisde with mixtures of pollutants in air.

           For analysers installed in stations, intercalibration must  be  made to
  ensure that these analysers give the same result when they sample  a mixture of
  pollutant in air of known and reproducible  concentration.

           This paper describes the development and testing of  a portable and self-
  contained calibrator providing mixtures of pollutants in air.

           Our calibrator gives known and reproducible  concentrations of pollutants
  in air at atmospheric pressure, with a total  flow enabling us  to calibrate  several
  analysers at the same time. With this calibrator, we have begun intercalibration  of
  ambiant air analysers installed in stations.  The pollutants we measure are  sulfur
  dioxide, nitrogen oxides, hydrocarbons and ozone.

           The operation of this calibrator is based on gas permeation, associated
 with gas phase titration (in our new calibrator).

           The permeation principle is used differently as for  classic permeation
  tubes where some selected pollutants are liquefied in a FEP teflon tube  ; our
  permeation cell  (in which permeation takes place through FEP or fluorinated silicone
  tubes} contains  the pollutants in the gas phase : consequently the cell  can be
  filled with all  gases,  CO,CHu, NO, F2 ...

           Larger limits in temperature variations can be admitted by  the  gas phase
 permeation, a favorable factor in portable systems.
           The first  results  v/e  have obtained are described :  they show that interca-
 libration has to be  made  before any data handling and computing.

       PROCEEDINGS-PAGE 348
    First US-France Conference on
Photochemical Ozone/Qxidants Pollution

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           There  is  a  need for intercalibration of ambiant air analysers installed
 in  stations.  These  stations  are  installed with automatic analysers"without permanent
 technical  supervision.

           Technicians  have therefore to visit these stations periodically to ensure
 that  the analysers  give accurate  results.

           Moreover,   when  one  has  to  compare results given by several stations,
 intercalibration  is a  fundamental  need.

           Ideally this intercalibration should be done with the pollutants, at
 concentrations around  their  usual  value,  and  in the same "pneumatic" conditions
 encountered by analysers  sampling  ambiant air.

          The permeation  and gas  phase  titration techniques are well suited for
 this problem and we propose  the  following solution.

          We shall describe  a  portable  and self-contained system,  which can generate
 span gases with low and constant concentrations of pollutants in air.

          The pollutants  of  interest are  sulfur dioxide,nitrogen monoxide, nitrogen
dioxide, hydrocarbons and  ozone  (ozone  is  obtained by  photolysis with a UV lamp).

          Our system can  be  extended to any other gas  (CO,  C02,  F2  ...).  The desired
concentrations are obtained  by diffusion  of the pollutant in the gas phase through
a polymer tube made of FEP teflon  or silicone  (fluorinated  or not).  We point out
that in commercial permeation  tubes,  the  pollutant is  liquefied in  the tube.

          The permeation  principle is well  known  :  the pollutant permeates through
a polymer tube wall  or membrane when  a concentration gradient exists on the two
sides of the wall or membrane.
                                                             PROCEEDINGS—PAGE 349
                                                          First US-France Conference on
                                                      Photochemical Ozone/Oxidants Pollution

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              If this gradient is held constant, the diffusion  rate, or  the  amount
    of pollutant (weight or volume) crossing the wall per time  unit is constant.

              When one side of the tube is swept by "zero" air  or another appropriate
    carrier (N2) at constant flow, and when the pollutant pressure ishield constant
    on the other side, a low and constant concentration of pollutant in  the  carrier
    gas is obtained.

              Fig. 1 shows the setting diagram :  when pollutant is liquefied in the
    tube (a),  zero air flows outside the tube placed in a controlled temperature
    chamber.  The desired final concentrations are obtained with a bypass on  the zero
    air flow.

              The Manifold  is necessary for correct mixing of  the gases, and the  "over-
    flow"  exit ensures that the analyser will pick up the mixture in the same conditions
    as in  the  environment, the pressure in the manifold being practically at atmosphere.

              In our first system (b) where the pollutant is in the gas  phase the
    pneumatic  diagram is the same, but zero air sweeps inside the tube,  and  the pollutan>
    is contained in a cell surrounding the tube.

              In our last configuration, the FEP  tube crosses through a  stainless  tee
    (1/4"  Swagelok), and the cell containing the  pollutant is connected with the third
    port.

              In the two cases, the same equation governs the permeation rate, but the
    variation  of this rate with temperature is different as shown by fig. (2).

              The permeation rate  q  is :

              q  • A (p.  - PO)  exp (  ^)

    where
              q   is expressed  in mass flow or volume flow per time unit.

              A  includes terms such  as geometry of the tube,  diffusivity and solubility
    of the  pollutant into the  polymer (..  solubility which may vary strongly with
    temperature, as shown by the SOZ - silicone system).

       PROCEEDINGS—PAGE 350
    Ffrst US-France Conference on
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 p.  Is  the  partial  pressure  of the  pollutant on  one side of the tube wall
 p   is  the  partial  pressure  of the  pollutant on  the other side swept by zero air
    or  carrier  :  p   =  0
 E   is   the activation energy  of diffusion  of the  pollutant
 R   is  the  gas  constant
 T   the temperature in  °K

           p. varies exponentially  with  T (Clapeyron -  Clausius law) for the lique-
 fied pollutant,  but only  linearly  with  T (Boyle Mariotte law) for the gaseous one.

           Changes  of  permeation rate  with  T are therefore quite different in the
 two cases,  as  shown by  the  equations  giving -3-  as a function of ^-.

           In these  equations,  AHe  is  the mean latent heat of vaporization of the
 pollutant  in an  interval! AT,  around  T.

           For  S02  and FEP teflon at 300°K  and for a AT of 1° :
          The permeation rate change  is 8  %  for  the  liquefied pollutant and
          only 4 % for the gaseous one.
          The table relative to S02  (fig.  3)  shows  that  for polymers  like silicones
(fluorinated or not) this variation  is four times lower.

          The very low activation energies"of SOZ and  the  great solubility of
this pollutant in silicones (solubility which  decreases  when T increases, lowering
the activation effect) explains this  interesting gain  in stability in spite of
temperature fluctuations, difficult  to overcome in  portable systems.

          The results for S02 permeation through silicone  tubes are promising :
around 60°C, the permeation rate variation with T is very  small,  confirming
Felder's results (1).
                                                            PROCEEDINGS—PAGE  351
                                                         First US-France Conference on
                                                     Photochemical Ozone/Qxidants Pollution

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             We were interested in mixing  several  pollutants  in  the same cell, but
   NO and S02 mixtures destroyed the tube  after a  certain  time   as  indicated by
   erratic changes in the permeation rate.

             Fluorinated silicones (Silastic LS 63U or  fluorilic inTrance)  offer
   the same advantages as silastic LS 63   (versilic in  France) for  S02  and  appear
   to be more resistant when NO is added.

             Owing to the low solubility of NO in  silicones, the measured activation
   eaergy is  higher,as shown by the Arrhenius plots of  fig. (4), the weak variation
   of solubility with T (around ambiant T) of NO can account  for this behavior.
   However certain problems can arise when using silicone  tubes.

             The higher solubility of gases in this material  and its deformation  under
   mechanical stress means that the permeation surface  must be reduced  and  the tube
   supported mechanically.

             We have placed the tube around a stainless steel tube  drilled with small
   holes (0.5 mm diameter) through which permeation takes  place.

             We ensure that no leaks occur between the  tubes  by  a proper choice of
   their relative diameters.
             The advantages of the gaseous permeation are summarized  in  the  following
   table.
             1) It withstands • 0.5° changes (FEP) or - 1°  (silastic)  for  -  2  %
   concentration variations.
             2) All gases can be employed : CO, CHU, NO, F2, C02  ...
             3) Partial pressure of the pollutant in the cell can be selected  between
   zero and a value slightly under the vapor pressure.
             4) Only one temperature regulation is required for several pollutants.
             5) Easy filling  and use
             6) Several pollutants can be used in one module, or an individual cell
   placed in the analyser.
       PROCEEDINGS-PAGE 352
    First US-France Conference on
Photochemical nzone/0xidants Pollution

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          7) Three-point  calibration.
          8) Multipollutant generation for smog chamber studies.

N.B  : The pressure  drop with time in the cell is :
          pi *pi(t=o)  exp (*at)
where
          a =
                 qoRT
q   is the initial  permeation rate in g mn"

M   the molecular weight of the pollutant
P-/«—   tne partial  pressure  of the  pollutant  at  time  t = o

V   the cell volume

The time t  for which  the  pressure drop has been 5 " (and  the concentration drop
too)is  :
t
- 6.7
M days
          for    at   *   0.05
Pi =0-95Pi(t=o)
             if  q    =   2  10"7  g.mn"1
                 p    =   0  5  Atm
                 T    =  310°:<
                 V    =   2  liters

          The pneumatic  diagram of the first system that we developed  can be seen
in fig. (5).
          The cylindrical  cell,  pressure gauge and stop valve  are  made  of stainless
steel.
          The FEP  tube  {1/4"  outer diameter, a 7 mm thickness,  100-200 mm length)
is held in the cell  axis  and  tightened by gas chromatographic ferrules (teflon,
swagelok) fig. (6).
                                                             PROCEEDINGS—PAGE 353
                                                          First US-France Conference on
                                                      Photochemical Ozone/Oxidants Pollution

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               Dry air is first  introduced  in  the  cell  (or nitrogen for NO) at atmosphe-
     ric pressure, the pollutant is  then  introduced  up  to  the  desired pressure (always
     below its vapor pressure) so  the manometer  indicates  the  partial pressure P-/t_ v
     of the pollutant in the cell.

               Air or nitrogen is  continuously swept inside  the  tubes,  satisfying the
     p  = 0 condition and the constancy of  the pressure  gradient.

               The temperature must  remain  constant  in the permeation cell  since  a small
     temperature change leads to a large  change  in the pollutant concentration.

               The continuous permanent air flow is  delivered  by a  12 DCV  pump powered
     by rechargeable batteries (with a life of 1 h 30).

               During transport, power is ensured by  the car-battery.

               The working and diluting pump is  powered by the 220 AC from  the station.

               Different gas concentrations are obtained using a set  of capillaries  and
     shut-off valves.

               For NO permeation, the carrier gas is  nitrogen since air leads  to  rapid
     and complete oxidation of NO to N02.

               A  careful   calibration is then made from liquid permeation tubes realized
     in our laboratory following the 0'Keefe(2) method either from commenral  FEP  tubing
     or tubes  machined in  FEP rods (8 mm over diameter,  1 mm thickness).

               The filled  tubes  are set in a controlled temperature oven and swept with
     zero  air.  They are weighed  at regular time intervals,  allowing a determination  of
     their diffusion  rate,  and  thus the concentrations obtained in a calibrated carrier
     gas  flow.

               We also use  span  gases in compressed gas  cylinders (100 ppm NO  in
     nitrogen), gas  phase  titration and chemical  reference  methods (Saltzman, West-Gaeke,
     buffered  KI  ...)  to ensure  the best results  for our calibration.
       PROCEEDINGS—PAGE 354
    First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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          Hydrocarbon analysers  are  calibrated from methane  in compressed  gas
 cylinders (5. 10 ppm of methane in air). The permeation of methane  is  possible,
 but zero air  for methane is very difficult to obtain, the only method being
 catalytic oxidation, which is difficult to install in a portable calibrator.

          Our first calibrator enabled us to detect certain  defects which  would
 have been impossible to find with only electronic or pneumatic controls  :

          1}  The "zero" problem  of S02 analysers (Flame photometric.  Seres)  :
 a systematic  offset {= 20 ppb) of the zeros has been observed during  our visit
 of stations.  These offsets were caused by a different pressure-drop on introducing
 zero air in the analyser : in our method, the analysers sample zero air in the
 same way as they do in the environment, with the same pressure drop (located  in
 the sampling  tubing), contrary to the manufacturer's first method, where zero air
was introduced slightly above the atmospheric pressure.

          2)  Linearity of response : with the two concentrations of SQz  available
 in the calibrator, we found non-linear response for one analyser.

          A transistor failure caused this defect and only a very  careful  testing
of the electronics would have enabled us to find the trouble.

          3)  Conversion yields of NO into N02 in the furnace of NO  analysers have
 to be measured with NO in air and NOz in air. A conversion factor  different
 from 1 could  be due either to a difference in flow between the NO  path and the
 furnace path, a wrong furnace temperature, or an ageing of the furnace tubing.

          4) Unwanted  retentions of hydrocarbons arose in the active charcoal
scrubber of the hydrocarbon analysers (the charcoal adsorbing all  the gaseous
hydrocarbons over the methane),  leading to "memory" effects owing  to  competitive
adsorptions  of different hydrocarbons.

          Methane in nitrogen gives different results in FID analysers when used in
place of methane in air. We think methane in air is the correct blend to use,
hydrocarbons being sampled in air and not in nitrogen !
          Though our experience is still relatively short, we can conclude that
intercalibration has proved an important factor in improving the quality of the
results.
                                                          PROCEEDINGS—PAGE 355
                                                       First US-France Conference on
                                                   Photochemical Ozone/Oxidants Pollution

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              Our first calibrator suffered from certain defects, mainly  in the
    complexity of the flow diagram, leading to heavy weight and difficulties  in  tempe-
    rature control.  Due to the encouraging results obtained with silastic LS  63  U, we
    developed a simpler system.

              Fig.  (7)  shows the flow diagram.

              The cell  is enlarged (two liters) to decrease the pollutant pressure drop
   with  time.  The temperature control  is restricted to the swagelok tee and the  tempe-
    rature set at 60°C.

              Chemical  compatible pollutants can be mixed in the cell like S02,  NO,
    C3H8  ...  with different partial pressures owing to their different permeation rates.

              The flow diagram complies with the gas phase titration  requirements using
   a splitting in the dilution air flow (splitting ratio 1 to 3), 03  being generated
   by UV photolysis in the low flow side.

              Like  CH.,, NO is not well  adsorbed on charcoal and we shall try  to  pass
    sampled air around the UV lamp, leading to almost complete oxidation of NO to N02
    (readily  adsorbed with 03 on the charcoal). We hope to obtain zero air for all
    pollutants except methane.

              The p  = 0 condition is satisfiedas soon as a small flow of carrier is
                  ro
    established inside the tube, so the permeation rate is approximately independent
    of this flow, an advantage over commercial calibrators working with tank  sources
    (in  these instruments, all the flows must be accurately established to obtain
    accurate  concentrations).

              We have not yet tried propane permeation, but if it works well, we shall
    be able to calibrate S02, NO , hydrocarbons and ozone analysers with a very  simple
                                A
    calibrator.

              This  calibrator will be developed with a french manufacturer.
       PROCEEDINGS—PAGE 356
    First US-France Conference on
Photochemical Qzone/Oxidants Pollution

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                              BIBLIOGRAPHY
(!) R.M.  FELDER, R.D.  SPENCE, and  O.K.  FERRELL  :  J.  of Chem.  and'Engin.  Date,
    20, 3,  235, 1975.

(2) A.O'KEEFE : An. Chem., 49, 8,  1278, 1977.
                                                              PROCEEDINGS—PAGE 357
                                                           First US-France Conference on
                                                       Photochemical Ozone/Cbddants Pollution

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                     LIQUEFIED  POLLUTANT

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      PROCEEDINGS—PAGE 358
   First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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         PROCEEDINGS—PAGE 360
     First US-France Conference on
Photochemical Ozone/Oxidants Pollution

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    ilnCNO
 5.1
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 4.5
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                                     Arrhenius   plote

                                     For NO-silasHc LS 63U
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   2.8    Z9     3     3.1    3.2    3.3    3.4    3.5
                              FIG. 4
                                                 PROCEEDINGS—PAGE 361
                                              First US-France Conference on
                                          Photochemical Ozone/Oxidants Pollution

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         PROCEEDINGS—PAGE 362
     First US-France Conference  on
Photochemical  Ozone/Oxidants  Pollution

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         PROCEEDINGS--PAGE 363
     First US-France Conference on
Photochemical Ozone/Ox1dants Pollution

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            Air inlet
                                    SO2 + NO
       Controlled
       temperature
         Oven
Carrier
    -0
         Ozone
       Generator
  to analysers
                                           V
                           Reaction
                          chamber
                                 I  0-9Q *
                                           J_
  manifold
   over now
                 Flo
0
              Pump
                                 Charcoal  Scrubber
                              FIG:7
      PROCEEDINGS—PAGE 364
   First US-France Conference on
Photochemical Ozone/Oxldants Pollution

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