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
-------
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
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PROCEEDINGS—PAGE 7
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
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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.
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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.
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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.
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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
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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.
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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
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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.
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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.
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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
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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
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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
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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
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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
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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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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.
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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
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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).
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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.
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r
PHOTOCHEMICAL KINETICS MODELING PROGRAM
presented by Mareia C. Dodge
Environmental Protection Agency
United States
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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
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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
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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
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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
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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
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Figure 2. Ring Cleavage in the Toluene-OH Reaction
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Figure 3. Predicted and Observed Profiles Obtained
in the UCR Smog Chamber Study of the
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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
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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.
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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.
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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.
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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.
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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.
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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
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PROCEEDINGS—PAGE 55
First US-France Conference on
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r
AEROSOL RESEARCH BRANCH PROGRAMS
presented by Leonard Stockburger
Environmental Protection Agency
United States
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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
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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.
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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
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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.
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VISIBILITY
presented by Thomas G. Ellestad
Environmental Protection Agency
Urn'ted States
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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
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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
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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
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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.
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V% *rt I*
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us
oo
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o s.
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c r-
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SCATTERING
EFFICIENCY
0.1
DIAMETER
Figure 2.
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r
COARSE
FINE OR
ACCUMULATION
NUCLEI
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Figure 3
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ASSESSMENT OF SECONDARY AEROSOL FORMATION POTENTIAL
FROM NEW ENERGY SOURCES
presented by Ronald K. Patterson
Environmental Protection Agency
United States
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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
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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.
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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
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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.
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FLOW METER
CARTRIDGE
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VAPOR COLLECTION SYSTEM
CARRIER
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Figure 1. Vapor collection and analytical systems for analysis of orqanic
vapors in ambient air
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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
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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.
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Figure 3. .Vap of Buffalo • Niagara Falls, NY, area with inset showing placement of
sampling sites near Gld Love Canal.
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Photochemical Ozone/Oxldants Pollution
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PROCEEDINGS—PAGE 143
First US-France Conference on
Photochemical Ozone/Oxidants Pollution
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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
-------
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
-------
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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78
1,406
59,489
L2
73,785
<334
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834
506
496
2.920
10.652
<53
<63
114
4.232
4.400
2,442
<63
10,084
1,010
<63
1,832
9,600
<63
494
14,990
<53
20.926
6.316
<53
206
3,790
1,810
342
<53
168
<26
180
<63
T(53)
<53
84
<53
172,713
L3
4,194
<294
1,300
464
412
TC83)
270
3,342
<19
<23
<23
1,000
154
76
418
72
T(23)
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<23
62
<23
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1,754
<19
<19
86
48
46
62
T{19)
T(19)
<19
<27
<27
<19
<23
<19
<19
<31
<19
13,760
L4
6,286
<263
1,334
684
400
5,038
5,344
5,386
<17
<20
26
3,674
2,940
2,106
3,654
56
1,306
1,066
280
360
<20
18
4.586
<17
5,240
5,320
314
134
1,786
•07
594
60
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16
746
<20
134
80
<27
<17
58,968
L5
T(39)
T(79)
•11,556
13,484
3,890
562
1,374
51 ,992
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T(10)
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2,778
8,914
6,024
2.294
26
3,424
580
214
406
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30
3,022
<8
7.428
2,318
<8
1,644
4,908
466
160
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56
<8
34
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66
28
<13
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1 27, 778
L6
522,698
T(334)
9,428
8,584
1,000
704
15,880
37,442
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414
<107
100,476
51 ,600
34,686
27,228
2,370
3,686
2,400
17,142
<43
250
266,514
223 ,042
158.628
98,428
109,872
6,886
42,286
43,700
25,986
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<18
970
4,058
950
4,372
1,542
3,414
<36
1,786,636
L12A
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T(334)
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2,668
<334
<95
T(116)
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<116
<140
<140
<348
<186
<186
<186
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PROCEEDINGS—PAGE 150
First US-Franct Conference on
Photochemi'cil Ozone/Oxidants "Dilution
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PROCEEDINGS—PAGE 1ST
First US-France Conference on
Photochemical Ozone/Oxidants Pollution
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PROCEEDINGS—PAGE 15E
First US-France Conference on
Photochemical f>zone/0xidants Pollution
-------
ION CHROMATOGRAPHY
presented by James D. Mulik
Environmental Protection Agency
United States
PROCEEDINGS—PAGE 153
First US-France Conference on
Photochemical Ozone/Oxidants Pollution
-------
-------
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
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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.
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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.
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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
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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
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Ion chromatogram of cations (positive ions)
Eluant flow - 2.6 ml,'mm.
Eiuant -C.C02NHC!
Cclumn length - 250 mm
Attenuation ~x 1
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Ion chromatogram of SO2 collected as sulfate
inject
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'T
Efuant flow -3.8 mL'min.
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5 10
Time, minutes
15
-------
OVERVIEW OF THE ENVIRONMENTAL PROTECTION AGENCY (EPA)
GROUND-BASED REMOTE SENSING OF AIR POLLUTION
presented by William F. Heroet
Environmental Protection Agency
United States
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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
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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
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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
VINYL CHLORIDE FLflflE fSOOTYl
H20
CO
C02
RESOLUTION = 0.25 CM -1
HCL
19
in 5>oho 2ihn ?2hn 23on 2«*hn ?snn 2ehn 27hn
WRVENUMBERS
-;CSE systern
:as a^l
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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
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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).
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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
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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!.
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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.
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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
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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!
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(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
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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)*"
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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.
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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
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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
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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.
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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 ;
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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).
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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).
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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.
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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
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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.
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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.
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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.
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PROCEEDINGS—PAGE 245
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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
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PRE-ALARM AND PREVISION AID SYSTEM
FOR AMBIANT AIR MONITORING NETWORKS
presented by Jean Michel Faqe
Societe Bertin & Cie
France
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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
-------
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 .
PROCEEDINGS--PAGE 260
First US-France Conference an
Photochemical Ozone/Qxidants Pollution
-------
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.
PROCEEDINGS—PAGE 261
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Photochemical Ozone/Oxidants Pollution
-------
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)
PROCEEDINGS—PAGE 262
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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)
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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)
-------
'• 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.
-------
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
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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.
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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.
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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.
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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.
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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
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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
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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.
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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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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
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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.
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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
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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).
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30 mn
fig- "i. : evolution de la granulometrie
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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.
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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 -
PROCEEDINGS—PAGE 305
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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.
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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
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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
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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.
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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.
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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.
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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).
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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.
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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.
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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.
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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
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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.
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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
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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
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Photochemical Ozone/Qxidants Pollution
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PROCEEDINGS—PAGE 334
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PROCEEDINGS—PAGE 335
First US-France Conference on
Photochemical Ozone/Cbddants Pollution
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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
First US-France Conference on
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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___
PROCEEDINGS—PAGE 344
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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
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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
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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
Photochemical Ozone/Oxidants Pollution
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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
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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
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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
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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
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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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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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First US-France Conference on
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Air inlet
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FIG:7
PROCEEDINGS—PAGE 364
First US-France Conference on
Photochemical Ozone/Oxldants Pollution
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