United States Office of
Environmental Protection Research and
Agency Development
Environmental Sciences Research EPA-600/7-77-076
Laboratory
Research Triangle Park, North Carolina 27711 August 1977
AEROSOL RESEARCH BRANCH,
ANNUAL REPORT FY 1976/76A
Federal Interagency
Energy/Environment
Research and Development
Program
Interagency
Energy-Environment
Research and Development
Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/7-77-076
August 1977
AEROSOL RESEARCH BRANCH
ANNUAL REPORT FY 1976/76A
Federal Interagency Energy/Environment
Research and Development Program
Edited by
William E. Wilson and Christine Danskin
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
-------
DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
ii
-------
ABSTRACT
The research program of the Aerosol Research Branch includes research
grants and contracts at institutions in many parts of the United States, in
addition to an intramural program. The purpose of these projects is to
study the chemical and physical properties of aerosols, identify the mecha-
nisms of aerosol formation and removal, and conduct experiments to measure
these rates.
The results of the research are being used . (1) to establish the contri-
bution of the various sources to the ambient atmospheric aerosol loading,
(2) to characterize urban, natural, and primary and secondary aerosols, (3)
to develop quantitative descriptions of the generation and removal rates
associated with each major aerosol source and sink, (4) to quantify the
effects of aerosol on atmospheric chemical reactions, and (5) as a scientific
basis for recommending regulatory actions concerned with air quality
improvements.
In addition to base funding through EPA's Office of Research and Develop-
ment, the Aerosol Research Branch (ARB) also receives funds from the Federal
Interagency Energy/Environment Research and Development Program. This pro-
gram is coordinated by the Office of Energy, Minerals, and Industry, Dr.
Steven Gage, Deputy Assistant Administrator. The tasks conducted by ARB
under this program relate to the transport and fate of pollutants associated
with energy sources.
Tasks funded by the base program are not described in this report but
are listed by title and principal investigator. The FY 1976/76A annual
report of the base program is found in EPA Report 600/3-77-080.
iii
-------
CONTENTS
Abstract ill
Abbreviated Functional Statements .' vii
Acknowledgements viii
1. Introduction 1
2. Summary of Aerosol Research Branch Fiscal Year 1976
Program by Project 2
3. PROJECT MISTT Project Reports
Direction of MISTT Field Studies, by W.E. Wilson ... 4
Management of MISTT, by W.E. Wilson 6
Aircraft Monitoring and Analysis for an Aerosol
Characterization Study in St. Louis, by
D.L. Blumenthal 11
Project MISTT Field Program, by R.B. Husar 13
Formation of Atmospheric Aerosols—Aerosol
Characteristics Measured at Glasgow, MO and in
the St. Louis Urban Plume during the Summer 1975,
by K.T. Whitby 17
Formation of Atmospheric Aerosols—Coal Fired Power
Plant Plume Studies in St. Louis, Summer 1976,
by K.T. Whitby : 20
Project MISTT - Synoptic Scale Haziness and Air
Pollution, by R.B. Husar 22
Processing and Analysis of Project MISTT Data, by
R.B. Husar 27
St. Louis Plume Study - Halocarbon and Hydrocarbon
Measurements, by R.A. Rasmussen 32
Application of Statistical and Mathematical Methods
to Air Pollution Problems, by J.H. Over ton 34
Atmospheric Boundary Layer Measurements in Project
MISTT; MISTT-II, by B. Hicks 38
Field Sampling and Analysis of Airborne Particulate
Material in Conjunction with MISTT, by
P.T. Cunningham 40
-------
Formation of Atmospheric Aerosols—Aerosols Produced
by Combustion, by K.T. Whitby 43
Aerosol Formation and Removal in Plumes, by
J.R. Brock . . . 47
Mobile Laboratory Operations in Support of Project
MISTT, July-August 1975, by T.G. Ellestad 51
Gas Calibration Support for 1976 MISTT Summer Field
Program, July 1976, by T.G. Ellestad 52
Data Processing Support for 1976 Summer Field Program,
July 1976, by K. Fuchs 53
Relationships among Ground-level Sulfate Concentrations,
Visibility Reduction, and Meteorological Conditions,
by D. Fondario 54
Mesoscale Sulfate Concentration Study, by
R.K. Patterson 55
Appendices
A. List of ARE Projects funded by ORD base funds (Titles
and Principal Investigators) 56
-vi
-------
ABBREVIATED FUNCTIONAL STATEMENTS
The Environmental Sciences Research Laboratory (ESRL) conducts -research
programs in the physical sciences to detect, define, and quantify the effects
of air pollution on urban, regional, and global atmospheres, and the sub-
sequent impact on air and water quality and land use. ESRL is responsible
for the planning, implementation, and management of research and development
programs designed to quantitate the relationships between emissions of
pollutants, from all types of sources, air quality, and atmospheric effects.
ESRL also plans, implements, and manages a research and development program
to provide needed techniques and instrumentation for the measurement and
characterization of pollutants in the ambient air and in the emissions from
all types of sources. ESRL's research and development program consists of
grants, contracts, and in-house work.
The Atmospheric Chemistry and Physics Division (ACPD) conducts research
programs (1) to characterize the chemical and physical properties of ambient
air pollutants and (2) to relate quantitatively the chemical and physical
properties of emissions from mobile, stationary, and natural sources to the
effects on air and water quality and land use. ACPD also develops techniques
and instrumentation for the measurement and characterization of gaseous and
aerosol pollutants.
The Aerosol Research Branch (ARB) studies the chemical and physical
properties of aerosols, identifies the mechanisms of aerosol formation and
removal, and conducts experiments to measure these rates. The properties-
of atmospheric aerosols are related to health and welfare effects for the
purpose of selective control of pollutant sources.
vii
-------
ACKNOWLEDGEMENTS
The program of the Aerosol Research Branch is under the scientific
direction of A.P. Altshuller, Director, Environmental Sciences Research
Laboratory. EPA funds are provided through OALWU, Thomas Murphy, DAA
(Transport and Transformation Program) and OHEE, Delbert Barth, DAA
(Catalyst Program). Federal Interagency Energy/Environment Research and
Development Program funds (Project MISTT) are provided through OEMI, Steven
Gage, DAA. We also thank Robert Papetti and Deran Pashayan, OALWU, and
Greg D'Alessio, OEMI, for management support.
viii
-------
INTRODUCTION
The Aerosol Research Branch (ARE), as part of the Environmental
Sciences Research Laboratory of the U.S. Environmental Protection Agency,
administers an extramural research program consisting of grants and contracts
at institutions in many parts of the United States. In addition to the
extramural program, ARB conducts a modest in-house program. Since the major
responsibility of ARB is to conduct an extramural research program, the
in-house program is designed to support the extramural program. It has three
major functions: 1) to provide rapid-response capability to respond to
agency needs, 2) to test out concepts prior to establishing extramural pro-
grams, and 3) to maintain the scientific competence of the EPA project
officers. It is considered extremely important that the scientific competence
and reputation of ARB's project officers be such that grant and contract
principal investigators consider them as scientific peers rather than funding
clerks.
This progress report presents results of tasks which were active during
fiscal years 1976 and 1976A and funded through the Federal Interagency
Energy/Environment Research and Development Program. This work represents
a portion of ARB's program as shown in the Summary of Aerosol Research
Branch Fiscal 1976 Program by Project. ARB tasks funded through the base
program are listed by Title and Principal Investigator in the Appendix.
-------
SUMMARY OF AEROSOL RESEARCH BRANCH
FISCAL YEAR 1976 PROGRAM BY PROJECT
Project MISTT (Midwest Interstate Sulfur Transformation and Transport)
A study of pollutant transformations and removal during atmospheric
transport over various scale lengths.
Urban scale (50 km): Tracer and portable chamber studies.
Power plant plumes (250 km): Aircraft measurements.
Urban plumes (500 km): Aircraft and ground measurements.
Blobs (2000 km) : Weather Service visibility reports and a ground
network of 14 stations extending from eastern Kansas to
New England.
Model Development and Data Analysis.
Funded by the Federal Interagency Energy/Environment Research and
Development Program through USEPA, ORD, OEMI. Program Element 1NE625.
Auto-Exhaust Catalyst Program
Determination of chemical and physical properties of sulfuric acid
aerosol produced by automobile catalysts.
Funded by USEPA, ORD, OHEE. Program Element 1AA601.
Atmospheric Processes and Effects
Aerosol Formation, Growth and Removal. Identification of physical and
chemical mechanisms for aerosols processes in the atmosphere, measurement
of important rate constants, and development of models for formation, growth
and removal of atmospheric aerosols.
Aerosol Characterization and Sources. The utilization of physical
properties, elemental and chemical analyses, and microscopy for the charac-
terization of atmospheric aerosols and the use of this information to
determine the primary and secondary source contributions to urban pollution.
Visibility and Radiation Effects. Measurement of pertinent aerosol
properties and determination of relationships between concentration, com-
position, size and effects.
Heterogeneous Reactions. Measurement of the rates and mechanisms of
reactions involving gases with surfaces or condensed phases.
Technique Development. Development of new instruments or techniques
required for the aerosol research program.
Funded by USEPA, ORD, OALWU. Program Element 1AA603 and 1AD712.
-------
PROJECT MISTT
(Midwest Interstate Sulfur Transformation and Transport)
A study of pollutant transformations and removal during atmospheric
transport over various scale lengths.
Urban scale (50 km): Tracer and portable chamber studies.
Power plant plumes (250 km): Aircraft measurements.
Urban plumes (500 km): Aircraft and ground measurements.
Blobs (2000 km): Weather Service visibility reports and a
ground network of 14 stations extending from eastern
Kansas to New England.
Model Development and Data Analysis.
Funded by the Federal Interagency Energy/Environment Research and
Development Program through USEPA,_ORD, OEMI. Program Element 1NE625,
-------
1. Task Title: Direction of MISTT Field Studies
2. Objective:
To provide on site EPA technical direction to insure integration
of the ten groups involved in the field study phase of MISTT: Washington
University, St. Louis - field director, data manager, communications air-
craft, instrumented aircraft; University of Minnesota - aircraft-aerosol-
size distribution, ground-mobile laboratory; Meteorology Research, Inc. -
fully instrumented aircraft; Environmental Quality Research - pilot
ballons, forecasting; Rockwell International-pilot ballons; Environmental
Monitoring, Inc. - S0? burden with ground and airborne correlation
spectrometer; Stanfora Research Institute - ground mobile lidar; Washington
State University, Pullman - detailed hydrocarbon analysis; Argonne National
Laboratory - boundary layer studies, dry deposition; EPA - Las Vegas -
helicopter measurements, aircraft lidar; EPA-RTP - calibration, quality
control, data reduction.
3. Institution: ARB, ESRL, ORD, EPA
Investigators: William E. Wilson, Jack Durham
4. EPA Project Officer: William E. Wilson
5. Progress:
Three successful field studies were conducted - a four-week study
during summer - 1975, a two-week study during winter-1976, and a six-week
study during summer 1976. Measurements were made of power plant and urban
plumes. During the summer-!976 study the ERDA-funded, DaVinci ballon was
used as an air mass marker to measure the St. Louis plume in a LaGrangian
manner. During the last week a prototype study of a "big blob" was made to
determine optimum flight patterns for studying the development of secondary
pollutants in stagnating anticyclones.
6. Presentations, Publications, and Thesis: None
7. Plans:
Jack Durham will serve as EPA field manager for a winter-1977 field
study of an oil-fired plume.
-------
7. Plans:
1. An oil-fired plume will be studied during FY 77.
2. The major emphasis during FY 77 will be on data analysis and
reporting. An investigator's meeting will be held during the
winter of FY 77. Results will be presented at the June 1977
FIE/E Meeting and the Dubrovnik Conference, "Sulfates fn the
Atmosphere" during September 1977.
-------
1. Task Title: Management of Project MISTT
2. Objective:
To plan and direct Project MISTT, an integrated, multidisciplinary
program to study the transformation and fate of sulfur compounds
during transport.
3. Institution: ARB, ESRL, EPA
Investigator: William E. Wilson
4. EPA Project Officer: W.E. Wilson
5. Progress:
A critical review of plume studies was completed. The study
pointed out the necessity of studying plumes in four dimensions, time
as well as space. Measurements must be made as a function of time of
day as well as distance from the plume source. Conversion rates must
be determined from differences in mass flow rates. Techniques used
previously are inadequate. The S32/S34 isotope ratio technique
cannot be used because of the variety of reaction mechanisms involved;
the particulate sulfur/total sulfur ratio cannot be used because of
surface removal of gaseous sulfur dioxide.
Field studies were planned and implemented in the St. Louis area
during summer-1975, winter-1976, and summer-1976. Results from the
summer-!975 study were summarized and presented at the June 1976
Federal Interagency Energy/Environment Meeting and the June 1976 APCA
meeting. Numerous presentations of Project MISTT were made to scientific
organizations.
6. Publications, Presentations, and Thesis:
1. Wilson, W,E. Transformation and Transport of Energy Related
Pollutants. Presented at: EPA-OEMI Health Environ. Effects and
Control Tech. Aspects of Energy Research and Development Symp.
2. Wilson, W.E., R.J. Charlson, R.B. Husar, K.T. Whitby, and
D. Blumenthal. Sulfates in the Atmosphere. Presented at: 69th
Annual Meeting of APCA, June 27 - July 1, 1976, Portland, Oregon.
3. Project MISTT: Presentation to Maryland Academy of Sciences.
4. Wilson, W.E., R.B. Husar, K.T. Whitby, and D. Blumenthal. Sulfate
Formation in Power Plant Plumes. Presented at: 7th International
Tech. Meeting on Air Pollution Modeling and Its Application,
Sept. 7-10, 1976, Airlie, VA.
5. Wilson, W.E. Sulfate Formation in Power Plant Plumes. A Critical
Review. To be published.
-------
Comparison flights were performed with the correlation spectrometer of
Environmental Measurements, Inc., Washington University's sampling aircraft,
and the instrumented balloon of ERDA's Project DaVinci.
The plurne was sampled regularly by the MISTT sampling team to distances
greater than 150 km and, on occasion, to 300 km. The Labadie plume was found
to be transported long distances at night with little dilution in layers which
were separated from the ground. S02 concentrations of 0.75 ppm were observed
on one occasion at night at a distance of 50 km. Preliminary indications are
that the sulfate formation rate in the plume varies with air mass characteristics.
6. Publications, Presentations and Theses:
1. White, W.H., D.L. Blumenthal, J.A. Anderson, R.B. Husar, and W.E. Wilson, Jr.
Ozone Formation in the St. Louis Urban Plume. In: Proc. of the International
Conference on Photochemical Oxidant Pollution and Its Control, Raleigh, NC,
September 1976.
2. White, W.H., J.A. Anderson, D.L. Blumenthal, R.B. Husar, N.V. Gillani,
S.B. Fuller, K.T. Whitby and W.E. Wilson, Jr. Formation of Ozone and Light-
Scattering Aerosols in the St. Louis Urban Plume. In: Proc. of the Div.
Environ. Chern., 171st National ACS Meeting, New York, NY, April 1976.
3. White, W.H., J.A. Anderson, D.L. Blumenthal, R.B. Husar, N.V. Gillani,
J.D. Husar and W.E. Wilson, Jr. 1976. Formation and Transport of Secondary
Air Pollutants: Ozone and Aerosols in the St. Louis Urban Plume. Science.
194:187-189.
4. White, W.H., D.L. Blumenthal, J.A. Anderson, R.B. Husar and W.E. Wilson, Jr.
Formation and Transport of Light-Scattering Aerosols in the St. Louis Urban
Plume. In: Proc. of the Symposium on Radiation in the Atmosphere, Garmisch-
Partenkirchen, Germany, August 1976.
5. White, W.H. Photochemistry in Power Plant Plumes: A Comparison of Theory
with Observation. Submitted to: Environ. Sci. and Tech.
6. Husar, J.D., R.B. Husar, and E.S.Macias, W.E. Wilson, Jr., J.L. Durham,
W.K. Shepherd and J.A. Anderson. 1976. Particulate Sulfur Analysis: Applica-
tion to High Time-Resolution Aircraft Sampling in Plumes Atmos. Environ.
10:591-595.
7. Whitby, K.T.', B.K. Cantrell, R.B. Husar, N.V. Glllani, J.A. Anderson,
D.L. Blumenthal and W.E. Wilson, Jr. Aerosol Formation in a Coal-Fired
Power Plant Plume. In: Proc. of the Div. Environ. Chem., 171st National
ACS Meeting, New York, NY, April 1976.
8. Husar, R.B., N.V. Gillani and J.D. Husar. Particulate Sulfur Formation
in Power Plant, Urban and Regional Plumes. Presented at: Symposium on
Aerosol Science and Technology, 82nd National Meeting of AIChE, Atlantic
City, NJ, August-September 1976.
9. Wilson, W.E. Jr., R.B. Husar, K.T. Whitby, D.B. Kittleson, W.H. White.
Chemical Reactions in Power Plant Plumes. In: Proc. of the Div. Environ.
Chem., 17Tst National ACS Meeting, New York, NY, April 1976.
-------
10. Wilson, W.E. Jr., R.J. Charlson, R.B. Husar, K.T. Whitby and D.L. Blu-
menthal. Sulfates in the Atmosphere. In: Proc. of the 69th Annual
Meeting of APCA, Portland, OR, June 1976.
11. Husar, R.B., J.D. Husar,- N.V. Gillani, S.B. Fuller" W.H. White, J.A.
Anderson, W.M. Vaughan, and W.E. Wilson, Jr. Pollutant Flow Rate Measurement
in Large Plumes: Sulfur Budget in Power Plant and Area Source Plumes in
St. Louis Region. In: Proc. of the Div. Environ. Chem., 171st National ACS
Meeting, New York, NY, April 1976.
12. White, W.H., J.A. Anderson, W.R. Knuth, D.L. Blumenthal, J.C. Hsuing,
and R.B. Husar. Mapping Large Pollutant Plumes by Instrumented Aircraft:
Support for Project MISTT, 1974. Final Report to USEPA on Contract No.
68-02-1919 1976.
13. Meterology Research, Inc., Altadena, California. Aircraft Monitoring
Support for an Aerosol Characterization Study in St. Louis-1976 MISTT Program;
Volume I, 1976 MISTT Sampling Summary. 1975; Volume II, 1975 MISTT Data
Volume. 1976.
14. Wilson, W.E., Jr., R.B. Husar, N.V. Gillani, S.B. Fuller, W.H. White,
J.A. Anderson, and D.L. Blumenthal. Characterization of Urban Plumes.
In: Proc. of the Third Symposium on Atmospheric Turbulence, Diffusion and
Air Quality, Raleigh, NC, October 1976.
15. Gillani, N.V. and R.B. Husar. Mesocscale Model for Pollutant Transport,
Transformation and Ground Removal. In: Proc. of the Third Symp. on Atmos.
Turbulence, Diffusion and Air Quality, Raleigh, NC, October 1976.
7. Plans:
1. Sulfate flow rates will be calculated and used to estimate S02-»-S04
conversion rates. Data on hydrocarbon composition and aerosol composition
and size distribution will be studied for clues to conversion mechanisms.
2. The impactor samples will be analyzed for trace elements to document
the characteristics of the plume aerosol. Detailed meteorological analysis
will be performed to document the long range trajectories of the air masses
sampled and to document the age of the plume for each pass on selected days.
-------
SCALE, kilometers
1—200
1-150
SPRINGFIELD
MOD
r50
ILfl
ILLINOIS
WINDS
A POWER PLANT
• REFINERY
OZONE
Figure 1. Ozone concentration and light-scattering coefficient, bscat,
downwind of St. Louis on July 18, 1975. Data are taken from horizontal
traverses by MRl's instrumented aircraft. Graph baselines show sampling
paths; note that baseline concentrations are not zero.
-------
0
DISTANCE DOWNWIND, km
50 100 150
™ 1 1
A
v&2- - ""
tji\^5-t>" o
r"" ° •
• • o
0915 l?30 MOO
r ,..,..-...
^^. - " ~~ ~~* ^^ ••"• ^™" - --r
0 O
0 0
1645 1815
1
-1.0
-0.5
-200
-100
-
0
m
h-*
<
JO
0
50 100 150
DISTANCE DOWNWIND ,km
76-356
Figure 2. Traverse altitudes and pollutant flow rates in St. Louis urban plume on July 18,
1975. Data are plotted against distance downwind of the St. Louis Gateway Arch.
(a) Location of horizontal traverses; solid dots correspond to traverses shown
in Figure 1. Mixing heights were determined from aircraft soundings. Approxi-
mate time (CDT) of sampling is shown at bottom. (b) Flow rates (in excess of
background) of ozone (O3) , light-scattering coefficient
sulfur (S ) .
P
^
) , and particulate
-------
1. Task Title; Aircraft Monitoring and Analysis for an Aerosol Characterization
Study in St. Louis, Missouri.
2. Objective:
To study the transport and tne transformations undergone by sulfur
dioxide and other pollutants in urban and power plant plumes.
3. Institution; Meteorology Research, Inc. (MRI), Altadena, California
Investigator; W.H. White, D.L. Blumenthal, J.A. Anderson
4. EPA Project Officer: W.E. Wilson
5. Progress:
As part of Project MISTT (Midwest Interstate Sulfur Transformation and
Transport), MRI has used an instrumented aircraft to characterize the three-
dimensional flow of aerosols and trace gases in the St. Louis area. The
aircraft, a modified Cessna 206, was equipped for continuous monitoring of
gas concentrations (S02, 0-j, NO, NOX), aerosol indices (condensation nuclei
count, electrical chargeability, light-scattering coefficient), and meteo-
rological characteristics (temperature, relative humidity, dew point, and
turbulent energy dissipation). A sequential filter system collected high
time-resolution samples for sulfate analysis, while an array of four cascade
impactors obtained size-differentiated aerosol samples for chemical and
microscopic analysis. An onboard electrical mobility analyzer/optical
particle counter system determined the in situ size distributions of grab
samples, and evacuated canisters collected air samples for hydrocarbon
analysis.
Sampling flights were carried out on a total of thirty-nine days during
the July 15 - August 15, 1975 and July 1-31, 1976 study periods. Flight
patterns were designed to characterize cross-wind sections of large pollutant
plumes at discrete distances downwind from their sources (Figure 1).' These
cross-sectional concentration fields were then combined with data on winds
aloft, to calculate mass flow rates through each cross section (Figure 2).
Changes in the flow rate of a given pollutant with increasing distance from
the source reveal the effects of the chemical and physical transformations
occurring in the atmosphere.
The 1975 experimental program documented the existence, under steady
meteorological conditions, of a well-defined "urban plume" downwind of
metropolitan St. Louis. This plume was mapped in detail out as far as 160 km
downwind of St. Louis and was characterized at long distances by reduced
visibilities and, during the daytime, by excess ozone. Analysis of aerosol
and sulfate flow rates indicated that most of the excess light-scattering
aerosol in the plume was sulfate of secondary origin. Sulfate concentrations
in excess of 60 yg/m3 were measured during one overnight flight.
11
-------
The 1976 experimental program characterized the plume from the 2200 MW
coal-fired power plant at Labadie, MO. Measurements were made under a
variety of meteorological conditions during all phases of the diurnal cycle.
Instrumental calibration procedures were tightened this year, with calibrations
by EPA personnel of the gas monitors before and after each sampling mission,
and cross-calibration of the aircraft and RAPS systems. An improved hydrocar-
bon sampling technique eliminated difficulties encountered in the 1975 program.
12
-------
!• Task Title: Project MISTT Field Program
2. Objective:
To design, direct and implement a field program, based primarily
on aircraft sampling of precursor gases and-secondary aerosols, for
the study of transport, transformation and ground removal of atmospheric
sulfur.
3. Institution: Washington University (WU), St. Louis, Missouri
Investigators: R.B. Husar, N.V. Gillani, J.D. Husar.
4. EPA Project Officer: W.E. Wilson, Jr.
5. Progress July 1975 - October 1976:
A primary objective of Project MISTT (Midwest Interstate Sulfur
Transformation and Transport) is to investigate the in situ formation
and distribution of sulfates in large urban power plant plumes. The
design of the field program, conducted in St. Louis during the summers
of 1975 and 1976, called for a systematic deployment of several sampling
and communications aircraft, as well as mobile ground-based sampling
and meteorological support units. The experimental program was designed
to provide a data base to determine the total mass flow rate (Q) of
each measured pollutant across vertical planes normal to plume flow at
a number of increasing downwind distances from the source. The downwind
range covered was well beyond the mesoscale (100 km). The rates of
change of Q for gaseous and particulate sulfur during plume transport
permit the estimation of overall rates of S02 conversion and removal
(see report on Project MISTT Data).
Two primary instrumented sampling aircraft have been used in the
field program: a twin-engine Aero-Commander instrumented and ooerated
by WU; and a single-engine Cessna 206 instrumented and operated by
Meteorology Research, Inc. With some variations, these aircraft were
equipped for continuous monitoring of gaseous (SOp, NO, NO , 0-), aerosol
(light scattering, charge, condensation nuclei count), meteorological
(temp., R.H., dew point, turbulence), and aircraft position (altitude,
VOR, DME) parameters. These data were recorded digitally at 1 or 2 sec.
intervals on magnetic tapes. High time resolution collection of seg-
regated fine and coarse particles was performed by a sequential two-
stage filter tape sampler developed at WU. The filter samples were
subsequently analyzed on the ground by a flash vaporization/flame-
photometric detection method. The specific chemical forms of the
sulfates were also determined by a thermal analysis technique. Other
co-ordinated pollutant measureiiients were made from separate mobile
sampling platforms on the ground (sulfur, b ., aerosol charge and
correlation spectrometer [COSPEC] for SO and NCL) or in the air (COSPEC).
Ground meteorological support was provided by three mobile pilot balloon
(PIBAL) units, as well as a trained meteorologist on duty at the oper-
ations headquarters (OHQ). Aerosol size-distribution measurements were
made with the MRI aircraft using an electrical aerosol analyzer and
an optical particle counter.
13
-------
All field operations were directed from a stationary OHQ, by WU via
constant radio communication through a system which also interlinked the
field units themselves. The complex communications link was facilitated
by a radio-relay aircraft, whose presence was vital during flights
ranging beyond 100 km. The OHQ also maintained a well-equipped command
post to receive and translate real-time data into graphic plots, and,
with the help of these and continually updated meteorological reports,
provided on-line direction of the entire operation.1
Alternative flight patterns were devised depending on the availability
of one or two sampling aircraft. In 1975, the MRI aircraft was the prin-
cipal sampling unit, and was aided by a WU scout/relay aircraft. The
latter, equipped more sparsely than the former for sampling, performed
plume searching and similar scouting work ahead of the MRI aircraft in
order to save valuable sampling time. In that year, the urban plume of
St. Louis was studied (Figure 1) out to distances of over 160 km during
daytime, and over 200 km at night. The sampling aircraft performed
detailed cross-sectional mapping of the plume at each of a number of
downwind distances by making horizontal plume traverses at several ele-
vations within the plume, and augmenting these by vertical soundings.
In 1976, the emphasis was placed on mapping the Labadie power plant
plume with both sampling aircraft operating. The two aircraft were used
to perform sampling at alternating downwind distances in a leapfrog
fashion, thereby permitting a better spatial coverage and a closer
approximation of the desired Lagrangian mode of plume sampling. With
an ultra-sensitive sulfur analyzer aboard the WU aircraft, the Labadie
plume was clearly tracked down to 300 kml During 1976, a long-range
flight was also made providing air support for the flight of ERDA's
instrumented balloon DaVinci. The field program was extended by one
week to conduct three long-range test flights aimed at investigating
synoptic scale hazy air masses and plume transport in the Ohio River
valley region.
These field studies have yielded much valuable data in addition to
the development of a sophisticated operational methodology of detailed
plume studies over a long range. The aircraft studies have provided
indirect estimates of overall S0« ground removal rates during plume
transport. Direct local measurements of SOo dry deposition have also
been performed over a variety of ground cover, under different meteor-
ological conditions during day and at night, and during summer as well
as winter.
6. Publications and Presentations:
1. Husar, R.B., N.V. Gillani, J.D. Husar, S.B. Fuller, W.H. White,
J.A. Anderson, W.M. Vaughan and W.E. VMTson, Jr. Pollutant Flow Rate
Measurement in Large Plumes: Sulfur Budget in Power Plant and Area
Source Plumes in the St. Louis Region. In: Proc. 171st National ACS
Meeting, Div. Environ. Chem., New York, NY, April 1976.
2. Husar, R.B., N.V. Gillani and J.D. Husar. Particulate Sulfur
Formation in Power Plant, Urban and Regional Plumes. Presented at:
Symp. Aerosol Sci. & Tech., 82nd. National Meeting of AlChE, Atlantic
City, NJ Sept. 1976.
14
-------
3. Wilson, W..E., Jr., R.J. Charlson, R.B. Husar, K.T. Whltfay and
D. Blumenttial. Sulfates in the Atmosphere. Presented at: 69th Annual
Meeting, APCA, Portland, OR, June 1976.
4. White, W.H., J.A. Anderson, D.L.. Blumenthal, R.B. Husar, N.V. Gillani,
J.D. Husar and W.E. Wilson, Jr. 1976. Formation and Transport of
Secondary Air Pollutants: Ozone and Aerosols in the St. Louis Urban
Plume. Science 194:187-189.
5. Vaughan, W.M., R. Sperling, N.V. Gillani and R.B, Husar. Horizontal
S02 Mass Flow Rate Measurements in Plumes: A Comparison of Correlation
Spectrometer Data with a Dispersion and Removal Model. Presented at:
68th Annual Meeting, APCA, Boston, MA, June 1975.
6. Husar, J.D., R.B. Husar and P.K. Stubits 1975. Determination of
Submicrogram Amounts of Atmospheric Particulate Sulfur. Anal Chem. 47:2062.
7. Husar, J.D., R.B. Husar, E.S. Macias, W.E. Wilson, J.L. Durham,
W.K. Shepherd and J.A. Anderson 1976. Particulate Sulfur Analysis:
Application to High Time Resolution Aircraft Sampling in Plumes. Atm.
Environ. 10:591.
8. Macias, E.S. and R.B. Husar, 1976. Atmospheric Particulate Mass
Measurement with Beta Attenuation Mass Monitor. Environ. Sci. & Tech.
10:904.
9. R.B. Husar, 1976. Thermal Analysis of Aerosols. J. Thermal Anal.
10:2.
10. Dannevik, W., S. Frisella, L. Granat and R.B. Husar. S02 Deposition
Measurements in the St. Louis Region. In Preprint: 3rd Symp. on Atm.
Turb., Diff., and Air Quality, AMS, Raleigh, NC, October 1976.
11. Husar, R.B. Determination of Ambient H^SO, and its Ammonium Salts
by in situ Aerosol Thermal Analysis. Presented at: Symp. on Radiation
in the Atm., Garmisch-Partenkirchen, Germany, August 1976.
12. Husar, R.B., N.V. Gillani, J.D. Husar. A detailed report describing
the field program of Project MISTT is presently being prepared.
7. Plans:
1. Aircraft instrumentation must include meteorological and NO measure-
ments. The high sensitivity Meloy SA-285 Sulfur Analyser is currently
being calibrated for continuous in situ monitoring of particulate sulfur,
with possible on-line in situ thermal analysis of the aerosol.
2. The field operation may be improved by real-time input of telemetered
data into the computer to yield graphics in near real-time. Efforts to
further co-ordinate all the sampling units to better attain Lagrangian
plume sampling will be made in future programs.
3. Longer range flight designs will be seriously considered.
15
-------
PRIMARY
AIRCRAFT
SCOUT
..i
QM=ffc(x,y,z)U(z)dydz
plume
Figure 1. Field program components and methodology -
urban-industrial plume.
16
-------
1. Task Title: Formation of Atmospheric Aerosols - Aerosol Characteristics
Measured at Glasgow, MO. and in the St. Louis Urban Plume during the
summer of 1975.
2. Objective:
To characterize the aerosol in the St. Louis urban plume using the
EPA mobile van located 160 km north of St. Louis.
To characterize the urban plume using an instrument package aboard the
MRI aircraft.
3. Institution: University of Minnesota, Minneapolis, Minnesota
Investigator: K.T. Whitby
4. EPA Project Officer: W.E. Wilson
5. Progress:
Aerosol size distributions measured in the St. Louis urban plume can
be characterized by a single log-normal mode with ag = 2.2 + 0.2 and a
volume mean size of 0.45 + 0.06 ym. There is little contribution from
a nuclei mode except near ground sources such as the Wood River Refinery.
Calculated concentrations of aerosol sulfur in the urban plume using
measured aerosol volume concentrations and assuming sulfur in the form of
H2S04, yield values about 75% of those obtained by J. Husar using a filter
collection method.
Most of the submicron aerosol measured by the EPA van at Glasgow in
1975 can be characterized by a single log-normal mode with og = 1.78 +
0.07 and volume mean size of about 0.30 + 0.06 ym. This accumulation mode
accounts for most of the particles measured by the Aitken nuclei counter
and the optical properties of the aerosol.
Two peak ozone periods observed on August 8 and August 9 show a sig-
nificant difference in both the amount of visibility reduction and the
distribution of the associated aerosols. Table I presented the pertinent
parameters for the accumulation mode on both days. Visibility reduction
is correlated more closely with relative humidity and mean aerosol size (volume
weight) than SO? or 03. The high ^scat during the second episode is explained
by a shift in the mean size of the accumulation mode rather than the amount
of aerosol present.
Making the assumption that sulfur in the aerosol measured in situ by
the MAAS *is in the form t^SO^;, average sulfur content of the aerosol was
calculated for both days and agrees with amounts measured on August 8
using filter collection techniques (J. Husar, 1975), For August 9, however,
the calculated average amount is only 63% of the measured amount. This
could imply either different sources or different conversion processes for
the two days (Table II.)
6. Publications, Presentations, Theses: None
17
-------
7. Plans:
1. Gas calibration constants for this data have been received recently and
the problem of reading the aircraft tapes has been solved. Work on the data
from 1975 will be completed as soon as the Los Angeles roadway study is
comoleted in October, 1976.
18
-------
Table I
Typical Dist.
Time of
Date Measurement
Aug. 8,
Aug. 9,
19:00 -
20:00
20:00 -
21:00
Accumulation Mode
, _ Characteristics ,
'v D o v RH scat
um /cc um ^ % (xlO m~
48.5 0.254 1.85 51.6 2.91
78.2 0.367 1.8 70.0
13.2
Particulate Gas
Sulfur Concentrations
0 Sulfur
ppm PPm
S < 1 um
yg/m
7.0 0.104 0.027
14.0 0.106 0.018
Table II
Day
August 8
August 9
Average Measured
S < 1 um
pg/m
4.75
8.71
Average Calculated
S (accumulation mode)
Mg/m
4.81
5.52
-------
1. Task Title: Formation of Atmospheric Aerosols - Coal Fired Power Plant
Plume Studies in St. Louis, summer, 1976.
2. Objective:
To furnish, calibrate, and reduce data from an in situ aerosol analy-
zing system aboard the MRI Cessna 206.
To furnish, operate, and reduce the data from a special mobile van
that was operated on the ground under the power plant plumes being studied
by the aircraft.
3. Institution: University of Minnesota, Minneapolis, Minnesota
Investigator: K.T. Whitby
4. EPA Project Officer: W.E. Wilson
5. Progress:
Aerosol size distributions at the Labadie power plant plume were
obtained with an instrumented aircraft and the University of Minnesota's
van. The intial examination of the aerosol size distributions shows
significant formation of ultrafine aerosols in the size range smaller
than O.Olyrn. Typical nuclei mode sizes are 0.006 to 0.009pm with con-
centrations being in the 40,000 to 100,000 cm range. Even though sig-
nificant numbers of nuclei are being formed, most of the aerosol mass
being formed in the plume is being deposited directly into the accumulation
mode (Figure 1).
6. Publications, Presentations, Theses: None
7. Plans:
1. To reduce and report data by spring 1977.
20
-------
AIRCRAFT STUDY' ST. LOUIS, MO.
xie
2
1
RUN* 15 LOCATION: LftBADIE DATE' 5-JUL-76
FLIGHT TYPE -'TRAUERSE TINE' 12 = 47=18
-WDIR= RH= 57.9 U2= 1.99 32=221.24
WSPD= BSCAT= 2.13E-04 U3= 6.73 S3= 219.67
ALT=1438.2 CNC= 7.96E 04 U3-= 8.72 03= 0.015
NT= 3.23E 04 UT= 10.83 S02= 0.447
K-H)
DU
DLOGDF
0 '
.692
j f ' ' 1
| px
ei
ii rr
:•:$
vX
X-Xv
i iiiiiii i 1111111
R218 - V77771
.-.•.•'.•.
$™^^Wi$M
.1 1 10
DP
Figure 1. Typical aerosol volume size distribution measured at a distance of
6 Km from the Labadie coal fired power plant near St. Louis, Mo. on
July 5, 1976. The condensation nuclei count in the plume is 80,000
cm as compared to about 8,000 cm outside of the plume, indicating
significant nuclei formation in the plume.
21
-------
1. Task Title: Project MISTT - Synoptic Scale Haziness and Air Pollution
2. Objective:
To investigate using the national yisibility data, the spatial
extent, temporal behavior, secondary pollution content, and variability
of synoptic scale hazy air masses ('blobs') in the U.S.
3. Institution: Washington University (WU), St. Louis, Missouri
Investigators: R.B. Husar, N.V. Gillani, J.D. Husar.
4. EPA Project Officer: W.E. Wilson, Jr.
5. Progress July 1976 - October 1976:
Recent observations of high background sulfate and ozone levels
over wide rural areas of eastern U.S. have raised concern about the long
range transport and interaction of effluents from many sources. Project
MISTT field studies have already evidenced the in situ formation and
transport of aerosols and ozone in St. Louis plumes over a range of about
200 km, and the associated reduction of visibility over the exposed areas.
The study of synoptic scale air pollution is hampered by the absence of an
adequate national data base for secondary pollution. This study investigates
the suitability of national visibility data as an effective surrogate for
regional scale secondary pollution data.
Ground level visual range observations are made hourly at hundreds of
airport stations operated by the National Weather Service (NWS). The data
become immediately available via long-line telephone service, generally on
paper or paper-tape output, and are also stored on magnetic tapes for sub-
sequent delivery to the user. The spatial density of data permits meaning-
ful computer contour plotting of visibility or light extinction. A
comprehensive package of computer software has been developed which may be
driven by hourly real-time input, or stored magnetic tape input of an entire
month's data. Within minutes, the computer yields graphic visibility
contour plots, as well as surface wind plots. The programs also perform
differential shading of different visibility regions.
A detailed case study has been made of a synoptic scale air pollution
episode affecting various parts of the eastern U.S. over a period of nearly
two weeks during Summer 1975. The formation and long range transport of a
synoptic hazy 'blob1 were documented for this episode using sequential
visibility plots (Figure 1), surface winds, long-range post-facto air parcel
trajectories, national weather maps and detailed local air quality data.
It was observed that a stagnant meteorological condition, persisting for
more than two days over the high sulfur emission region of the Ohio River
valley, led to the accumulation of large amounts of aerosols and visibility
reduction to less than 6 miles over a synoptic region. Subsequent cir-
culatory air motion associated with a high-pressure cell in the region
caused the motion of the 'blob1 westward to Kansas, then up through Iowa
and Minnesota, and back to the southern Great Lakes region. At that time,
the hazy blob (<6 mile visibility) extended up to 2000 km. A subsequent
rapid southward movement of a cold Canadian front swept the blob to Florida
within two days.
22
-------
The motion of the blob as seen from visibility plots was consistent
with long-range air parcel trajectories. Satellite pictures also substan-
tiated the existence and scale of the haziness. Local air pollution
data in Missouri and Illinois verified the temporal behavior of the blob
motion and were consistent with its synoptic dimensions. Aerosol light
scattering as measured by nephelograms, and daily ozone data in St. Louis
showed remarkably good correlation with light extinction based on visibility
data. In St. Louis, 40% of the aerosol mass in the blob was measured as
sulfuric acid. Finally, hand contour plots of ozone and sulfates for
days of available data, Figure 2) showed the existence of synoptic ozone and
sulfate blobs of high concentrations coinciding closely with the hazy blobs.
A limited analysis was also performed to show the predominance of pollution
over water content as the source of haziness for R.H. <70%.
The utility of visibility reduction data as an excellent qualitative
surrogate for aerosol mass has been demonstrated. The use of this very
convenient tool in visualizing synoptic scale pollution has important
implications and should be exploited.
Publications and Presentations:
1. Husar, R.B., N.V. Gillani, J.D. Husar, C.C. Paley. Large Scale Haziness
over Midwestern and Eastern U.S. Presented at: Symp. on Radiation in the
Atm., Garmisch-Partenkirchen, Germany, August 1976.
2. Husar, R.B., N.V. Gillani, J.D. Husar. A Study of Long Range Transport
from Visibility Observations, Trajectory Analysis and Local Air Pollution
Monitoring Data. Presented at: NATO/CCMS 7th Tech. Meeting on Air
Pollution Medeling and its Applications. Airlie, VA , September 1976 (Proc.
to be issued).
3. Husar, R.B., D.E. Patterson, C.C. Paley, N.V. Gillani. Ozone in Hazy
Air Masses. Presented at: EPA Intl. Conf. on Photochemical Oxidant and its
Control, Raleigh, NC , September 1976 (Proc. to be issued),
4. Husar, R.B., N.V. Gillani, J.D. Husar, C.C. Paley, P.N. Turcu. Long
Range Transport of Pollutants Observed Through Visibility Contour Mapjs,
Weather Maps and Trajectory Analysis. In Preprint: 3rd Symp. on Atm. Turb.,
Diff. and Air Quality, Amer. Met. Soc., Raleigh, NC, October 1976.
5. Gillani, N.V. and R.B. Husar. Synoptic Haziness Over the Eastern U.S.
and its Long Range Transport. Invited Paper: 4th National Conf. on Fire
and Forest Meteorology, Soc. Amer. Foresters/Amer. Met. Soc., St. Louis, MO,
November '1976 (Proc. to be issued).
7. Plans:
1. Further automation will permit direct input of real-time data from
weather telephone service terminal into computer memory.
2. Visibility plots will be prepared at fixed intervals daily to provide
a larger scale pollution perspective, as well as to signal the onset of blob
conditions.
23
-------
3. To collect data for a second detailed case study of a suspected blob
episode relative humidity and visibility reduction during the single episode
period.
4. To assess the role of relative humidity in light extinction and visual
range reduction.
24
-------
i JUNE 25, 1975
i *
<-,
Figure 1. Sequential computer contour .plots for noon ground visibility:
solid black, <4 miles; shaded grey, 4-6 miles.
25
-------
•V..,..-
Jo.\'(£ 23, J9V5 ( \
JUNE 23, »975
-•—-"*
JULY 5, J975
JULY 5, 1975 f\
Ml >30
^ 20 to 30
IZZJ 10 lo 20
-------
1. Task Title: Processing and Analysis of Project MISTT Data
2. Objectives:
To develop and implement an interactive, graphics-oriented
computer software package for rapid processing of aircraft data.
To design the basic strategy for data analysis, and provide
guidelines for the design of an appropriate field program.
To determine rates and mechanisms of SC^-to-sulfate conversion
and pollutant removal by dry deposition.
3. Institution: Washington University (WU), St. Louis, Missouri
Investigators: R.B. Husar, N.V. Gillani, J.D. Husar
4. EPA Project Officer; W.E. Wilson, Jr.
5. Progress July 1975 - October 1976:
The data processing objective has been fully achieved with great
success. A comprehensive and versatile minicomputer software package
has been developed which permits systematic processing, and basic
analysis of the data logged on magnetic cassettes aboard aircraft,
(WU, MRI) or instrumented ground vehicles (EMI, roadway study). Parti-
culate sulfur (Sp) data are merged into the permanent data files
as soon as filter sample analyses are completed. A special feature of
the software is the rapid initial turnaround of the data within hours
of the sampling mission. This processing includes data transfer to
computer memory, calibration and instrument response time corrections,
data averaging, and production of hard copies of graphical data dis-
plays in engineering units. It provides immediate data quality check,
indicates sampling instrument malfunctions, and provides a basis for
daily interaction between the scientists and the field crew. Meteor-
ological data (pibals, visibility, etc.) are processed simultaneously.
User-oriented interactive data display-edit-integration procedures
have also been developed and used. A new software package, designed
for highly-automated production of hard copy graphics for the data
volume, is nearing completion.
The field program, as well as data analysis, are based on the
mass flow rate (Q) approach. AQ values for S02 and Sp at successive
downwind sections permit the evaluation of SOp loss-to-conversion and
to other forms of scavenging. The application of our dispersion-trans-
formation-removal model then permits the estimation of overall rates
of conversion and of removal, consistent with the observed changes in
Q. The measurements also permit the determination of pollutant ratios
(e.g. S02/sulfate). The analysis based on Q is viewed as the more
rational approach for non-conservative species. These basic concepts
have been used in a field program designed to provide detailed pollutant
measurements, as well as a completely co-ordinated meteorological data
base.
27
-------
Project MISTT data analyzed so far have indicated a substantial loss
of S02 to the ground in the mesoscale transport of low-level plumes
(e.g. urban-industrial). Tall stack emissions remain airborne for
longer distances (Figure 1). The data for both types of plumes on
hot, sunny, summer days tend to implicate the presence of ozone,
(either from in situ formation in the plume (Fig. 2a), or from
entrainment of the background air (Fig. 2b)) as being conducive to
in situ aerosol formation. The highest observed aerosol and sulfate
concentrations (bSgat>10xlO~lfm-1 and [$04] >60 yg/m3) were under night-
time conditions, with no direct evidence of ozone participation in the
reactions forming the aerosols. Data of this type are rich in informa-
tion regarding rates as well as mechanisms. Furthermore, both urban-
industrial and power plant plumes have been tracked downwind to 300
km (1976), with detailed data of direct possible significance in
regional models.
A mesoscale parametrized dispersion model has been developed to
include the effects of dry deposition, as well as pseudo-first order
gas-to-particle conversion and precipitation scavenging. The conversion
rate is allowed to depend on plume transport time, thus permitting
simulation of changing plume composition. The model also permits free
interaction between meteorology and chemistry in a non-homogeneous!y
turbulent atmosphere. Comparison of model results with measured
pollutant flow rates have yielded realistic overall rates of conversion
and removal.
6. Publications and Presentations:
1. Gillani, N.V. 1975. Data Processing, Management and Analysis
Related to Project MISTT, 1975. Report submitted to EPA Project Officer.
2. Husar, R.B., N.V. Gillani, J.D. Husar, S.B. Fuller, W.H. White,
J.A. Anderson, W.M. Vaughan and W.E. Wilson, Jr. Pollutant Flow Rate
Measurement in Large Plumes: Sulfur Budget in Power Plant and Area
Source Plumes in the St. Louis Region. In: Proc. 171st National ACS
Meeting, Div. Environ. Chem., New York, NY, April 1976.
3. Husar, R.B., N.V. Gillani and J.D. Husar. Particulate Sulfur
Formation in Power Plant, Urban and Regional Plumes. Presented at:
Symp. Aerosol Sci. & Tech., 82nd National Meeting of AIChE, Atlantic
City, NJ, September 1976.
4. Wilson, W.E., Jr., R.J. Charlson, R.B. Husar, K.T. Whitby and
D. Blumenthal. Sulfates in the Atmosphere. Presented at: 69th Annual
Meeting, APCA, Portland, OR, June 1976.
5. White, W.H., J.A. Anderson, D.L. Blumenthal, R.B. Husar, N.V.
Gillani, J.D. Husar and W.E. Wilson, Jr. 1976. Formation and Transport
of Secondary Air Pollutants: Ozone and Aerosols in the St. Louis
Urban Plume. Science. 194:187-189.
28
-------
6. Vaughan, W.M., R. Sperling, N.V. Gil lam" and R.B. Husar. Horizontal
S02 Mass Flow Rate Measurements in Plumes: A Comparison of Correlation
Spectrometer Data with a Dispersion and Removal Model. Presented at:
68th Annual Meeting, APCA, Boston, MA, June 1975.
7. Whitby, K.T., B.C. Cantrell, R.B. Husair, N.V. Gillani, J.A. Anderson,
D.L. Blumenthal and W.E. Wilson, Jr. Aerosol Formation in a Coal Fired
Power Plant Plume. In: Proc. Div. of Environmental Chemistry, Amer.
Chem. Soc., NY, April 1976.
8. Wilson, W.E., Jr., R.B. Husar, K.T. Whitby, D.B. Kittleson and
W.H. White. Chemical Reactions in Power Plant Plumes. In: Proc. Div.
of Environmental Chemistry, Amer. Chem. Soc., NY, April 1976.
9. Gillani, N.V. and R.B. Husar. Analytical-Numerical Model for
Mesoscale Transport, Transformation and Removal of Air Pollutants.
Presented at: NATO/CCMS 7th Tech. Meeting on Air Pollution Modeling
and its Applications, Airlie, VA, September 1976 (Proc. to be issued).
10. Gillani, N.V. and R.B. Husar. Mesoscale Model for Pollutant
Transport, Transformation and Ground Removal. Presented at: 3rd Symp.
on Atm. Turb., Diff. and Air Quality, Amer. Met. Soc., Raleigh, NC,
October 1976.
11. Husar, J.D., R.B. Husar, E.S. Macias, W.E. Wilson, J.L. Durham,
W.K. Shepherd and J.A. Anderson. 1976. Particulate Sulfur Analysis:
Application to High Time Resolution Aircraft Sampling in Plumes. Atm.
Environ. 10:591.
7. Plans:
During the past year analysis of aircraft data has been quite
limited. However, it will be the area of major emphasis and effort
in the next year.
1. The production of detailed data volumes will be completed for all
1975, 1976 field data collected by WU, MRI, Univ. of Minnesota and
EMI. These packages will consist of edited, averaged data in engineering
units on magnetic tape storage; tape format documentation; data volumes
of hard copy graphical displays with integrations, flight logs, sampling
and meteorological summaries, and pibal data.
2. Mass flow rates, appropriate pollutant ratios, meteorological
analyses, and model calculations and comparisons will be performed for
all appropriate data of 1975 and 1976 field programs with the following
principal objectives: a) extraction of S02-to-sulfate conversion rates
and S0£ removal rates; b) determination of dominant factors governing
the conversion rates; c) quantitative relationships between conversion
rates and incluencing factors (i.e. models of mechanisms).
3. The main mathematical model will be extended to include: temporal
variability, full utilization of meteorological data, and non-linear
conversion processes.
29
-------
7.5
u
0>
CO
cr>
*. 5.0
4.0
3.0
2.5
2.0
1.5
1.0
CO
<
01
D
U_
_l
ID
co
T 1 1 1 r 1 T i 1 r~ r
URBAN a INDUSTRIAL PLUMES
-AEROSOL
20%/HOUR LOSS RATE
AT u«5 m/sec
10 20 30 40 50 60 70 80 90 100 110 120
DOWNWIND DISTANCE, X (km)
o
UJ
f-
CO
4.0
3.0
2.0
a: 1.5
o
u.
co i.O
CO
cc
^
u.
0.5
POWER PLANT PLUMES
B
10 20 30 40 50 60 70 80 90 100 110 120
DOWNWIND DISTANCE, X (km)
Figure 1. Mesoscale depletion of sulfur mass flow rate in large plumes.
a) Rapid ground loss from urban-industrial plumes.
b) Slow depletion from power plant plumes.
30
-------
HOURS
- 250 25OO
PARTICIPATE SULFUR
i i
KRI8S5 8-14-74 10--00 LABAOIE
180
SCO
ONZ
2UO
CN
OZONE
A-'P L U H E
•*<*
*•«•«.«•«.
3
'030
538
833
1
068
260
574
068
000
000
i
SQZ
123433
124 2
Figure 2. Indication of role of ozone in plume aerosol formation.
a) In situ ozone and aerosol formation in St. Louis urban
plume, 7/18/75.
b) Possible homogeneous nucleation processes (increase in
Condensation Nuclei £ount) by entrainment of background
ozone at plume edges, Labadie, 8/14/74.
31
-------
1. Task Title: St. Louis Plume Study - Halocarbon and Hydrocarbon Measurements
2. Objective:
To make continuous halocarbon and hydrocarbon measurements at a rural
site 100 km northwest of St. Louis in order to identify the source and age
of the air mass. This information will be used, in conjunction with EPA
measurements of pollutants and Argonne measurements of meteorological para-
meters, to study the transformation of pollutants during transport.
To examine ozone concentrations in terms of the source, age, and
hydrocarbon concentrations, natural and anthropogenic, of the air mass.
3. Institution: Washington State University
Investigator: R.A. Rasmussen
4. EPA Project Officer: W.E. Wilson
5. Progress:
In July and August of 1975, Washington State University carried out an
intensive measurement program to determine the species of hydrocarbons and
their concentrations in a clearly rural location that was often influenced by
emissions from the St. Louis urban area as well as other more distant pollu-
tant sources. An instrumented field laboratory was operated at the field
site near Glascow, 111. for thirty days.
Real-time quantitative analyses of the following halocarbons were
conducted using an automated electron capture gas chromatograph: CCloF
(F-ll), CC12F2 (F-12), CHC13, CH3CC13 and CC14- Detailed C2-to-C5 and 63-
to-Ci2 hydrocarbon analysis were performed at two-hour intervals on a 24 hr.
basis, seven days a week. The intent was to discriminate natural from
anthropogenic hydrocarbons and to apply this understanding to the involved
chemistry that results in hydrocarbon oxidation products such as ozone and
aerosols.
A data report for use by other investigators was provided. An inter-
pretive report concentrating on the general character of the hydrocarbons
measured at the rural site and on the oxidant behavior in the air masses
that passed over the study site was also prepared. From the data at this
one site, four distinct situations illustrating the interplay of meteorology
and chemistry in the photolysis of urban and rural hydrocarbons, and the
consequent production of elevated rural ozone levels can be recognized:
1) Remote or background air: unambiguously clean and therefore
accepted as characteristic of air unaffected by any discernable
urban contamination;
2) Young plumes: urban pollutant plumes with easily measurable levels
of primary pollutants still reacting in transit over the rural study
site;
3) Old plumes: clearly marked fluorocarbon plumes, with most of
the reactive hydrocarbons consumed;
4) Regional pollution: no plumes noticeable, but clear evidence of
photochemical oxidation of hydrocarbons and elevated oxidant.
32
-------
Fluorocarbon-11, hydrocarbon, and weather data were used to identify
and describe these situations and to interpret the observed concentrations
of hydrocarbons and oxidant resulting from local photochemistry and transport.
6. Publications, Presentations, Theses:
1. Robinson, E. and R.A. Rasmussen. Identification of Natural and Anthropogenic
Rural Ozone for Control Purposes. Presented at: APCA Speciality Conference on
Ozone/Oxidants: Interactions with the Total Environment, March 10-12, 1976,
Dallas, TX.
2. Rasmussen, R.A., D.J. Pierotti, and J.P. Krasnec. Analysis of Halocarbons
in the Atmosphere. Presented at: 69th Annual Meeting APCA, June 27-July 1,
1976, Portland, OR.
3. Chatfield, R. and R.A. Rasmussen. An Assessment of the Continental Lower
Tropospheric Ozone Budget. To be published in: Proc. of OCED-EPA Inter,
Conf. on Photochemical Oxidant Pollution and Its Control, Raleigh, NC,
September 12-17, 1976.
4. Rasmussen, R.A. Atmospheric Halocarbon Monitoring Techniques. Presented
at: WMO Technical Conference on Atmospheric Pollution Measurement Techniques,
Gottenburg, Sweden, October 11-15,.'1976.
5. Rasmussen, R.A. 1976. Surface Ozone Observations in Rural and Remote
Areas. J. of Occupational Medicine. 18(5):346-349.
6. Rasmussen, R.A., R.B. Chatfield and M.W. Hoi den Transport of Hydrocarbon
and Oxidant Chemistcies Observed at a Rural Mid-West Site. Presented at:
"Non-Urban Tropospheric Composition." Symposium, Miami Beach, FL, November
10-12, 1976.
7. Plans
This task has been completed.
33
-------
1. Task Title: Application of Statistical and Mathematical Methods to
Air Pollution Problems
2. Objective:
To determine the feasibility of using the IBM Model to simulate tracer
experiments.
3. Institution: Northrup Technical Services
Investigator: J.H. Overton
4. EPA Project Officer: W.E. Wilson
5. Progress:
A diffusion model developed by IBM for EPA has been modified and used to
simulate the results of SFg tracer experiments carried out in St. Louis
during August of 1975. Initially, the input/output parts of the IBM model
computer program had to be modified to make it useful for the SF^ simulations.
These modifications allow for minute-by-minute input of source strengths,
and minute-by-minute output of concentrations at specified locations. The
results of four SFs tests, tests #1, 3, 4, and 5 have been simulated (Figure
1 and Table 1). During the tests SFs was released at a location, at a constant
rate, for a given period of time. Meanwhile, an automobile traveling at a
constant rate downwind of the release point collected air samples at equal
distance intervals. The samples were later analyzed for SF5. The plots are
of concentration versus distance along the collecting automobile's path.
Test #1 was a low level release 100 feet above RAMS site 111. In test
#3, the SFs was released from the KETC TV tower 1000 feet above the ground.
The relationship between the release sites and the traverse routes
(highway 40 for the data in Figure 1) is indicated in Figure 2.
In addition to the collection of SFs on tne r°ad, hourly averages were
obtained at RAMS sites. Table 1 lists the experimental and simulated values
of hourly averages at those sites. There is a general lack of agreement
between simulated and experimental values for test #1, the low-level release.
In most cases the simulated values are far too large. Better results were
obtained for the high—level release, test 13.
An attempt was made to obtain better results by varying the release
height, source location and the mixing height. The results were not
significant; thus indicating that the effects of other parameters, such as
eddy diffusivity should be investigated.
6. Publications, Presentations, Theses:
1. Overton, J.H. B.K. Lamb and F.H. Shair. A Dual Tracer Study for Validation
of Models with Respect to High and Low Altitude Sources. Presented at: The
7th Inter. Technical Meeting on Air Pollution Modeling, Aulie, VA, September
8, 1976.
7. Plans:
Project completed.
34
-------
TABLE 1. COMPARISON OF CALCULATED AND MEASURED
Concentrations of SFg (ppt)
Station
Number
101
102
103
104
105
106
109
110
112
113
114
115
116 _
117
118
119
120
121
11-12
0
-
-
0
4/0
12/279
5/0
0
6/9
0
0
0.
0
0
0
0
-
0
Test 11
Time of
12-1
2/0
6/0
0
0
0
13/206
-
2/0
36/65
-
0
0
0
0
0
0
-
0
(8/8/75)
Day - CDT
1-2
0
0
0
0
s/o
4/79
1/0
0
63/172
1/0
0
0
0
0
4/0
0
-
0/2
2-3
.
0
0
0
-
0/32
-
0
46/189
2/0
0
-
-
0
0
0
-
11-12
OA
0
0
0
0/1
0/8
0
5/0
0
0
0
6/15
0
0
Test »3
Time of
12-1
2/7
0/17
0/4
0/0
0/1
27/26
V
0
0
0
0
0
22/18
0
0
(8/11/75)
Day - CDT
1-2
0/1
26/17
0
0
0
6A1
9/6
7/12
0/3
0
0
18/22
0
0
2-3
0
8/4
0
0
0
7A
7/21
13/29
0
0
0
44/18
0
0
Single entry: Both calculated and experimental concentrations
are the same. Double entry: Experimental/calculated. Stations
not included either had faulty data, no sample taken or a value
of zero.
35
-------
350
300
250
200'
ISO
100
50
EXPERIMENT #-1 (8/8/75) HIGHWAY 40
7. 11:58 - 12:08
I
t
i
A
II
• r
i *
/
I
•*•
• .
i i i r . . . . . .
8. 1:32 - 1:42
4.
•V
1
n
i
<\
\
/. »
• \ »
/ •*•
/ ^
' •-.,
9. 1:58 - 2:C8
• EXP
+ CALC
4
\
f\
l\
• fl
/'i
i*1 '
t! '1
+• i *
/ . \
024681002468100^ woo^u
MILES ALONG TRAVERSE
EXPERIMENT #-3 (8/11/75) HIGHWAY 40
3. 12:15 - 12:39 4. 12:56 - 1:20 5. 1:42 - 2:03
1
70 •
,0-
.
50 •
£ ''>:
O.
30
21
10
0.
^
A
• i
IX I
v I
i 1
i i
1
| i
1 .
1 1
It •
i
[ ,
1
1 1
; K',
/' \ l
/ ' \«
/ 1' \
• • • •' • ' ' — i — ' r'l — i
i ft B1O1'' lAlft H
«
;• "
*•
J \
i '
< *'
\/T\
'!/ • \ ',
• */ * \ 1
/< i* \
i/'v V
/! " \
tn 1* i/. IA ifl P
• EXP
+ CALC
?/y
f / V • »
/ Y
/' V"1
// ^
i t " . i — r— i — ^-i — -*n — »
1A T » 1 4 1 «. t f 1
MILES ALONG TRAVERSE
Figure 1. Calculated and experimental concentrations of SF,.
6
36
-------
• RAPS SITES
t$ INTERSTATE ROUTES
Us) U.S. HIGHWAYS ,.
© STATE HIGHWAYS
STATE BOUNDARY
N
123
Figure 2
-------
1. Task Title: Atmospheric Boundary Layer Measurements in Project MISTT
Atmospheric Boundary Layer Measurements in Project MISTT-II.
2. Objective:
To investigate the transport and dispersive properties of the Planetary
Boundary (PBJL) »_£o>l_the_PJJ^pose j5f jjnpj^oving numerical simulations of pb'llu-
tant di stri but Tori "downwi"nd of emission sources.
3. Institution: Atmospheric Physics Section, Radiological and Environmental
Research Division, Argonne National Laboratory (ANL).
Investigator: B. Hicks
4. EPA Project Officer: W.E. Wilson and G. Holzworth.
5. Progress: k
From July 15 to August 15, 1975, three Divisions of ANL (Chemical
Engineering, Energy and Environmental Systems, and Radiological and Environ-
mental Research) cooperated in a research effort to detect pollutants
emanating from the St. Louis industrial complex at a range of 100 km, and to
observe and document those atmospheric planetary boundary layer phenomena
that influence pollutant transport over such distances.
The six-part 1975 Sangamon experiment was conducted over relatively
flat farming country near Auburn, Illinois, in order to investigate the
evolution of the PBL capping inversion between the hours of 0400-1200. To
do this, hourly radiosonde (or pibal) ascents were tracked by a digitized,
double theodolite system, the WHAT System, to give wind and temperature
profiles. Measurements made at the Galesburg, Champaign, and Auburn stations
t_o determine the geostrophic and thermal winds were supplemented by hourly
air-ways reports from the National Weather Service. Also, a network of
four acoustic sounders measured the mesoscale variations in refractive index
fluctuations near the inversion at Glasgow, Palmyra, Waverly, and Auburn.
Supporting micrometeorological data were gathered over the maize and
soybean crops grown in that area. These data included continuous measure-
ments of wind, temperature, dewpoint, ozone gradients, and net radiation.
Direct measurements of momentum and sensible heat fluxes were made by the
eddy correlation technique over both crops. In addition, line-of-sight
remote sensing of the wind field and the heat and moisture fluxes were.
made near the surface by laser scintillation and optical blurring methods.
A third part of the experiment involved measurements from a kytoon.
Tnese measurements gave high resolution profiles of wind speed and temp-
erature in the lowest 100m. Although slow balloon motions created unwanted
noise in the low frequencies, the high-frequency portion of the kinetic
energy spectrum was evaluated at various heights in the lowest 100m. Air
samples were obtained at heights above and below the inversion at different
times during the morning hours.
Besides monitoring the concentration of ozone, sulfur dioxide, nitrogen
dioxide, hydrocarbons, etc., and performing the analysis of the air samples
taken from the kytoon system, measurements were made of particulates, sulfate
specification, and oxygen-isotope ratios. An air-chemistry network was also
established, with stations at Glasgow, Auburn, and near St. Louis.
38
-------
Finally, measurements were made of turbidity by comparing the direct and indirect
components of the solar radiation. A network of stations located at St. Louis, Glas-
gow, Waverly, Famersville, Hillsboro and Auburn were deployed for this purpose.
The 1976 Sangamon experiment was conducted from July 13 to August 5, at the
same site near Auburn as the 1975 PBL experiment. The second field experiment
was to describe the diurnal cycle of the structure of the atmospheric mixed layer,
particularly in the late afternoon and evening conditions of inversion formation.
The following details will concern only those parts of the experiment that differed
significantly from the 1975 exercise.
Automatic acoustic sounding equipment was operated over a 3/4 km triangular
array in order to record spatial variations in the behavior and evolution of
the mixed layer of the atmosphere. These sounders indicated the presence of
decoupled, stable layers aloft, and provided information on the behavior of gravity
waves on the inversion layers. The breaking of such waves near the top of inver-
sions is a potential mechanism for the transfer of both pollutant materials and
thermal energy through these stable layers.
Instead of kytoon-borne sampling equipment, the second Sangamon experiment
benefited from the participation of aircraft from both Battelle Pacific Northwest
Laboratories and the EPA. Other cooperative ventures resulted in experimental
programs addressing the surface fluxes of small particles (in cooperation with
the University of Minnesota) and of ozone (University of Michigan).
During February 1976, related cooperative study (in collaboration with
Washington University of St. Louis and Environmental Quality Research, Incorporated)
was performed downwind of the Wood River refinery complex. This investigation
resulted in the first successful measurement of the vertical turbulent flux of
small particles. The measurements of particle flux, obtained as a result of
coupling a fast-response particle detector to the eddy-correlation apparatus,
showed deposition velocities that are not substantially different from those
which might be predicted for S02 flux. This casts some doubt on the
advisability of assuming greatly dissimilar values for these two cases.
6. Publications and Presentations:
1. Wesely, M.L., B.B. Hicks, W.P. Dannevik, S. Frisella, and R.B. Husar.
An Eddy-Correlation Measurement of Particulate Deposition from the Atmosphere.
Submitted to: Atmos. Environ.
2. Hicks, B.B. and C.M. Sheih. Some Observations of Eddy Fluxes within
a Maize Canopy. Submitted to: Boundary-Layer Meteorology.
7. Plans:
t
1. Further intensive studies of PBL behavior are being planned in conjunction
with several other cooperating organizations.
2. To complete a series of field experiments measuring deposition velocities
in natural circumstances.
3. To test the parameterizations developed in PBL programs over larger spatial
and-temporal scales.
39
-------
1. Task Title: Field Sampling and Analysis of Airborne Particulate Material
in Conjunction with Project MISTT.
2. Objective:
To determine the frequency of occurrence of acidic sulfate on a
regional basis and to attempt to identify those temporal and spatial
relationships that may exist in its occurrence.
3. Institution: Argonne National Laboratory, Argonne, Illinois.
Investigator: P.T. Cunningham
4. EPA Project Officer: W.E. Wilson
5. Progress:
The Chemical Engineering Division of Argonne National Laboratory
has developed techniques for collecting time-resolved, size-fractionated
samples of airborne particulate matter using Lundgren impactors and
subsequent chemical analysis by Fourier Transform infrared spectro-
scopy (FTS). The analysis is quantitative for sulfate and nitrate
ions. It also provides qualitative information on the relative amounts
of acidic sulfate (the observation of bisulfate ion and/or sulfuric
acid) and other chemical species found in the samples.
Previous studies have shown ammonium sulfate to be a major consti-
tuent of submicrometer-size ambient aerosol particles. Acidic sulfate
has also been shown to occur frequently in the Chicago, IL area.
During the MISTT project, these techniques were applied for the first
time on a regional basis in order to help elucidate the long-range
transport and transformation of sulfur compounds in the air. The
frequency, extent and magnitude of acidic sulfate episodes were to be
evaluated and correlated with other data coming from the MISTT project.
Sampling sites were established approximately 100 km apart at
St. Louis, MO; Glasgow, ILjand Auburn, IL. By using Lundgren impactors,
size- and time-resolved samples of airborne particulate matter were
collected almost continuously at these sites from July 15, 1975 to
August 11, 1975. The samples were collected with two-hour time
resolution and with four size fractions which had nominal 50% cut-points
of 10 ym, 3 urn, 1 ym..and 0.3 pm for impaction stages I, II, III and
IV, respectively.
Analysis of the submicrometer-size stage IV samples, which represent
the secondary particulate matter, has been completed and some qualita-
tive assessments have been made. Ammonium sulfate was found in varying
amounts in all stage IV samples. Widespread acidic sulfate episodes
were observed to have occurred twice during the sampling period (Fig. 1).
The time correlation for the occurrence of acidic sulfate at the
three sites suggests strongly that such occurrences are regional in
nature. The apparent diurnal variations in the degree of acidity
associated with the acidic sulfate episodes appear to be related more
to the onset of mixing associated with breakup of the nocturnal
inversion than to an increase in photochemical activity.
-------
6. Publications, Presentations and Theses:
1. Yang, R.T., P.T. Cunningham, W.I. Wilson and S.A. Johnson. 1975.
Kinetics of the Reaction of Half-Calcined Dolomite with Sulfur Dioxide
Adv. in Chem. Ser. 139:149-157.
2. Hubble, B.R., S. Siege! and P.T. Cunningham. 1975. On the Feasibility
of the CaSO^-Gas REaction for Regeneration of Sulfated Dolomite or Limestone
in Sulfur Dioxide Pollution-Control Processes. J. Air Poll. Control Assoc.
25(12):1256.
3. Cunningham, P.T. and S.A. Johnson. 1976 Spectroscopic Observation of
Acid Sulfate in Atmospheric Particulate Samples. Science. 191:77-79.
4. Cape, T.W., V.A. Maroni, P.T. Cunningham and J.B. Bates. 1976. Raman
and I.R.-Emission Studies of Some Tungstate- and Molybdate-Containing Melts.
Spectro. Acta 32A:1219-1223.
5. Holt, B.D., A.G. Engelkemeir, S.A. Johnson and P.T. Cunningham.
Oxygen Isotopy in the Formation of Sulfate Aerosols. Second International
Conference on Stable Isotopes, October 20-23, 1975, Oak Brook, Illinois.
(In Press).
6. Cunningham, P.T. and B.D. Holt. Stable Isotope Ration Measurements in
Atmospheric Sulfate Studies. International Symposium on the Development
of Nuclear-based Techniques for the Measurement, Detection, and Control of
Environmental Pollutants, March 15-19, 1976, Vienna, Austria. In Press .
7. Holt, B.D., P.T. Cunningham and A.G. Engelkemeir. Aoplication of Oxygen-
18 Analysis to the Study of Atmospheric Sulfate Formation. International
Conference on Stable Isotopes, August 4-6, 1976, Lower Hutt, New Zealand.
In Press.
8. Hubble, B.R., S. Siege!, L.H. Fuchs, H.R. Hoedstra, B.Tani and P.T.
Cunningham. 1976. The Formation of Mc^CatSO.), During the Sulfation
Reaction of Dolomite. Submitted to J. Air Poll. Control Assoc.
7. Plans:
1. Data analysis, including quantification of the neutral sulfate and
correlation with other data, will be completed for the stage IV samples.
2. The acidic sulfate episodes will be examined.
41
-------
Sun
Won
Tues
Wed
Thur
Fri
Sat
to
July 13,
1975
20
27
^ Ks^s^l
3
10
HKEC3
^sj l^fclfcs^^
E$oKSS3
14
21
28 .
1
4
1
1
11
IS 1
•si H N
|
15
c
22
[
1
29
^1 ^
E
1^
5
1
1 1
1
12
16
]
23
30
rJ^^^^^^^^^^vl
fll^SSi
b 1^1
•
6
13
1
17
1
24
31
^|^S\1
£
7
14
u
16
1
1
25
1
1 1
August 1
1
8
^^$S
t^|
15
19
1
26
cz
s$^v
2
1
9
?il^ fS^I
I\^IS8^\
|\^^ [N^|
16
' I
Auburn, 111. Neutral Sulfate
Glasgow, 111.
Moderately
St. Louie. MO. AcidicSulfate
Strongly
Auburn, 111. Acidic Sulfate
Glasgow, 111.
St. Louis, Mo.
Auburn, 111.
Glasgow, 111.
St. Louis, Mo.
Auburn, 111.
Glasgow, 111.
St. Louis, Mo.
Auburn, 111.
Glasgow, 111.
3t. Louis, Mo.
Figure 1. Sanpling Periods and Acidic Sulfate Episodes during Project MZSOT.
-------
1. Task Title: Formation of Atmospheric Aerosols - Aerosols Produced by
Combustion.
2. Objective:
To study the size distribution and concentration of primary
aerosols produced by relatively clean combustion sources operated in
compliance with air pollution emission standards.
3. Institution: University of Minnesota, Minneapolia, Minnesota
Investigator: K.T. Whitby
4. EPA Project Officer: W.E. Wilson
5. Progress:
Barsic has studied the interaction of fresh combustion aerosols
with filtered and unfiltered humid air surrounding a premixed pro-
pane-air flame. Two modes were observed in the fine particle size
range (Fig. 1). Both modes are in the Aitken nuclei size range. The
smallest mode, AN! mode, is more strongly affected by humidity.
Experiments in which the sulfur content of the fuel was varied suggest
that the AN! mode consists of sulfur compounds.
More aerosols were produced when unfiltered air was used around
the flame (Table 1).
From particle size distribution measurements made on highly dilute
diesel exhaust aerosols at idle, 1/4 load, and full load, Dolan found
size distributions showing systematic variations in the mean size of
the combustion nuclei and accumulation modes. At full load the
accumulation mode dominated, at 1/4 load both were apparent, and at
idle the nuclei mode of increased size dominated.
Verrant has developed an improved system for sampling and rapidly
diluting diesel aerosols. Using this system, aerosol size distributions
on a single cylinder Onan diesel were found to be very similar to
those measured 9 m behind a Peugeot diesel on the GM test track in
Mil ford, MI. These size distributions have a single mode in the
volume distribution at 0.2 urn. \
6. Publications, Presentations, Theses:
1. Barsic, N.J. Size Distribution and Concentration of Fine Particles
Produced by Propane-Air Combustion in a Controlled Humidity Environment.
Ph.D. Thesis. Mechanical Engineering Department, University of
Minnesota, MN. Estimated completion, January, 1977.
2. Dolan, D.F., D.B. Kittelson and K.T. Whitby. Measurement of
Diesel Exhaust Particle Size Distributions. ASME Preprint #75-WA.APC-5.
Presented at: The American Society of Mechanical Engineers Annual
Meeting, November 30 - December 4, 1975.
43
-------
3. Verrant, J.A. Development of a Dilution System for Measuring
Diesel Exhaust Particulate Matter. M.S. Thesis. Mechanical Engineering
Department, University of Minnesota, MN, September, 1976.
4. Verrant, J.A. Sampling and Physical Characterization of Diesel
Exhaust Aerosols. Submitted to: Society of Automotive Engineers. 1976.
5. Whitby, K.T., D.B. Kittelson, B.K. Cantrell, N.J. Barsic and D.F.
Dolan. Aerosol Size Distributions and Concentrations Measured During
the General Motors Proving Grounds Sulfate Study. Presented at: The
Division of Environmental Chemistry, American Chemical Society, San
Francisco, CA, August, 1976.
7. Plans:
1. The sampling and size distribution techniques developed will be
applied to the study of other clean sources of combustion aerosol.
44
-------
S
.2
.1
60%RH
AN1
A,
AN2
.001
.01
Particle Diameter, ym
-a Dp,ym
,0)
.-)
O (1)
vi e
•U 3
1-4 l-<
to o
.0. >
.2
38%RH
0
.001
/\
.01
Particle Diameter, ym
-i D
.1 P
Figure 1. Aitken nuclei mode volume distributions for fuel-rich combustion
aerosols diluted (30:1) with filtered, humidity controlled air.
Since all three distributions are to the same scale, and AV/AlogD
is plotted vs. logD , the area under each curve is proportional
to the volume of ae?osol produced. Volume distributions for lean
and stoichiometric flames are similar in the AN1 mode but do not
have the AN2 mode. The AN1 mode may be due to sulfates, while the
AN2 mode probably consists of carbon.
45
-------
Table I
%RH
40
90
Particle volume (ym /cm )
filtered unfiltered
air air
.003
.12
.015
.23
Number Mean Diameter (ym)
filtered unfiltered
air air
.0030
.0050
.0026
.0050
46
-------
1. Task Title: Aerosol Formation and Removal in Plumes.
2. Objective:
To develop comprehensive models to account for dispersion,precursor
formation, and aerosol dynamics in plumes. To carry out experimental
measurements of dry deposition and especially the effects of charge on
deposition.
3. Institution: University of Texas, Austin, Texas
Investigators: J.R. Brock, P.B. Middleton, and K. de Bower
4. EPA Project Officer: J.L. Durham
5. Progress:
The adverse effects of the atmospheric aerosol are related to the many
and complex rate processes which determine the characteristics of the
suspended particles. Development of rational control strategies, which
seek to relate ambient concentrations to primary and secondary sources,
requires models which deal with these complexities.
This project is seeking to develop useful models of the various pro-
cesses which determine the size and composition distribution of the atmos-
pheric aerosol. These various processes are summarized in a general rate
equation:
Crate of change in 1 = - prate of change )
f composition or v < due to advectionf
V.size distribution./ L J
+ f rate of change > + frate of change ) (rate of change >
(.due to dispersionj \due to coagulation) + {due to condensation J
+ /rate of change due to ) /rate of primary due to)
^homogeneous nucleation/ 1 primary sources J
+ /rate of change due to)
\sedimentation j
Propesses occurring at surfaces, such as deposition, appear as
boundary conditions. These rate relationships are coupled to rate
equations for the various chemical species participating in the aerosol
growth processes.
A numerical model, called EPOSOD, has been developed to provide a
real time simulation of aerosol size and composition. As a preliminary
effort in developing a model for secondary aerosol formation in plumes,
EPOSOD has been used to study the interaction of a plume containing a
high NO concentration with ambient levels of ozone (Figures, 1, 2, 3).
-------
Instrumentation is being assembled to determine the deposition rates
of aerosols.
6. Publications, Presentations, Thesis:
1. K. de Bower. A Method of Modelling Chemically Reactive Plumes. M.S.
Thesis, University of Texas, Austin, TX, August 1976.
7. Plans
1. Improve efficiency and stability of current numerical models.
2. Carry out dry deposition studies using high speed particle size
analyzer.
3. Carry out concurrent measurements of atmospheric electrical
parameters for direct measurement of dry deposition.
48
-------
. o'
z
o
i
o
u
-8-10
-320
0 meters
320
640
Figure 2. Simulated concentration profile of NO for traverse
through plume center at 2.3 km downwind of point
source of NO.
-840
-320
meters
320
640
Figure 3. Simulated concentration profile of 0, for traverse
through plume center at 2.3 km downwind of point
source of NO.
49
-------
0^-0.08 fp«
Figure 1. Simulation with EPOSOD Reactive Plun
Model of NO Plume Reacting with
Ambient Level of Ozone. Point
Source of NO Located at 0 KM.
Ambient Level of Ozone Assumed as
0.08 ppm.
-------
1. Task Title: Mobile Laboratory Operations in Support of Project
MISTT, July-August 1975
2. Objective:
To collect aerosol samples, pollutant gas concentrations, and
meteorological data at a site 100 km north of St. Louis, MO.
3. Institution: EPA-ERC, ESRL-ARB
Investigators: T. Ellestad; D. Dale, G. DeJong, K. Fuchs, M. Garneau,
G. Shelton (student aids).
4. EPA Project Officer: W.E. Wilson
5. Progress
Thirteen days of intensive data were collected on schedule,
with frequent local instrument calibrations and two cross-calibrations
with the St. Louis-based group. Aerosol size distribution reduction
is in progress at the University of Minnesota; gas, filter, and
meteorological data reduction is in progress at EPA. Student aids
performed about 50% of gas calibrations, 70% of data acquisition
system operation, and 80% of routine instrument operation.
5. Presentations, Publications, Theses:
Preliminary summary given at the November 4, 1975, MISTT meeting
at RTP, NC.
6. Plans:
Issue a verified data volume in December 1977.
51
-------
1. Task Title: Gas Calibration Support for 1976 MISTT Summer Field
Program, July 1976.
2. Objective:
To provide accurate and traceable gas calibrations for pollutant
gas analyzers on board several mobile sampling platforms.
3. Institution: EPA-ERC, ESRL-ARB
Investigators: T. Ellestad, R. Speer, M. Parrish, M. Bourke, J. Durham
G. She!ton (Student Aide)
4. EPA Project Officer: W.E. Wilson
5. Progress:
Calibration systems for delivering NBS-traceable concentrations
of S0£, 03, NO and N0« were assembled and verified. Calibration
services were provided for the MRI Cessna 206, the Washington University
Grand Commander, and the University of Minnesota Mobile Van on a
demand basis, generally after each flight or trip. In addition to
verifying analyzer performances and monitoring minor instrument
drifts, the frequent calibrations uncovered several serious analyzer
malfunctions, which were quickly corrected. Two cross-calibrations
with the RAPS Mobile Calibration Van were performed during the month.
Student aids were responsible for about 35% of the work.
5. Publications, Presentations, Theses: None.
6. Plans:
None, project complete.
52
-------
1. Task Title: Data Processing Support for 1976 MISTT Summer Field
Program, July 1976
2. Objective:
To process aircraft data tapes within hours of landing so that
instrument problems can be identified before the next flight.
3. Institution: EPA-ERC, ESRL-ARB
Investigator: K. Fuchs (student aid).
4. EPA Project Officer: VI.E. Wilson
5. Progress:
Aircraft cassettes were read on schedule with the ARB data
processing system, gas calibration constants were entered, and 10:1
averaging of the data was performed. Copies of the data were made
for Meteorology Research, the University of Minnesota, and ARB-ESRL-EPA.
Student aids were responsible for 100% of the effort.
6. Publications, Presentations, Theses: None
7. Plans:
None, project complete.
53
-------
1. Task Title: Relationships among Ground-level Sulfate Concentrations,
Visibility Reduction, and Meteorological Conditons.
2. Oojective:
To determine if a high sulfate episode in Wheeling, W. Va. (50 - 80
ug/m3, July 6-8, 1974) was due to local sources or long range transport.
3. Institution: ARB, ESRL, ORD, EPA and University of North Carolina
Investigators: D. Fondario, H. Jeffries, J. Saunders, and Williarp £. Wilson,
4. EPA Project Officer: William E. Wilson.
5. Progress:
Results from Phase I of the Sulfate Regional Experiment (SURE),
sponsored by the Electric Power Research Institute (EPRI), indicated a
high sulfate episode at Wheeling, W. Va. Daily, 24-hour, high volume
sampler measurements showed sulfate concentrations in excess of 30 yg/m3
from June 5-9, 1974 with a peak June 8 of 80 yg/m3. An analysis was
undertaken to determine whether this was due to local sources or long
range transport. Data utilized included long range trajectories
(24-hour and 5-day), surface weather, visibility distances, mixing heights,
and emissions. The analysis indicated that a stagnant, high pressure
system in a high emission region upwind of Wheeling accumulated pollutants
which were then transported to Wheeling by air motion. Thus it was con-
cluded that the high sulfate measured in Wheeling was the result of
pollutant transformations during long range transport.
6. Presentations, Publications, and Thesis:
1. L). Fondario, Master's Thesis: Explanations for a High Sulfate
Episode at Wheeling, W. Va., June 5-9, 1974. 1976.
7. Plans:
The thesis will be rewritten with additional long range trajectories,
published as an EPA report, and submitted for journal publication.
54
-------
1. Task Title: Mesoscale Sulfate Concentration Study
2. Objective:
To obtain 2-hour measurements of particulate sulfur and other elements
over a large geographic area for one year.
To analyze this data in terms of sulfur transformation and transport.
3. Institution: Florida State University, Tallahassee, Florida
Investigators: W. Berg, W. Nelson, J. Winchester.
4. EPA Project Officer: R. Patterson
5. Progress:
Sample collection from a 14-station network, ranging from Kansas to
New Hampshire, began in early June, 1976 and will be continued until
June, 1977. Some 800 separate week-long ''streaker" sample records will
be collected. A portion of these will be analyzed for sulfur and other
heavy elements with 2-hour time resolution by PIXE(Proton Initiated
X-Ray Emission). Some test samples have been analyzed.
6. Plans:
Several sets of streaker samples will be analyzed and the data
interpreted in terms of sources and weather patterns.
The network will be modified to include the SURE Class I stations
during summer - 1977.
7. Publications, Presentations, and Thesis: None
55
-------
APPENDIX A
A. ATMOSPHERIC PROCESSES AND EFFECTS
1. Aerosol Formation, Growth, and Removal
Formation of Atmospheric Aerosols—Parametric Measurement
of Submicron Atmospheric Aerosols, by K.T. Whitby . . .
To Investigate the Atmospheric Contribution of Biogenic
Sulfur to the Urban Load of Sulfur Aerosols, by
D.R. Hitchcock
Experimental Study of Aerosol Formation Mechanisms in a
Controlled Atmosphere, by D.L. Fox
Formation of Atmospheric Aerosols—Smog Chamber Research,
by K.T. Whitby
Smog Chamber Study of Sulfur Dioxide Oxidation and Aerosol
Formation Mechanisms, by W.C. Kochmond
Study of Vapor Pressure of Systems Forming Atmospheric
Aerosols, by G. Brown
Formation of Atmospheric Aerosols—Size Distribution Models
for Atmospheric Aerosols, by K.T. Whitby
Aerosol Dynamics, by J.R. Brock
Biogenic Emission of Aerosol Precursors, by L.L. Spiller
Metal Sulfite Complexes, by D. Lawing
2. Aerosol Characterization and Sources
Sources and Trace Metals in Urban Aerosols. Sub-Task Title:
Urban, Non-urban, and Marine Aerosol Studies, by J.W.
Winchester
Relationship of the Smog Aerosol to Pollution Sources,
by S.K. Friedlander
A Study of the Identity and Sources of Atmospheric
Aerosols, by R.G. Draftz
Analysis of Air Pollutants by Mass Spectroscopy, by
A.L. Crittenden
Chemical Characterization of Model Aerosols, by D. Mendenhall
Sources and Trace Metals in Urban Aerosols. Sub-Task Title:
Aerosols Properties Relevant to Health Effects, by
J.W. Winchester
56
-------
Aerosol Sources Program, by R.K. Patterson
Aerosol Microscopy, by J. Gerhard
Field Expedition to Phoenix, AZ, by J.L. Durham
Analytical Support for Aerosol Studies, by R.K. Patterson . .
3. Visibility and Radiation Effects
Optical Effects of Atmospheric Aerosol, by A.P. Waggoner . .
4. Heterogeneous Reactions
The Role of Gas-Solid Interactions in Air Pollution, by
H.S. Judeikis
Structure and Reactivity of Adsorbed Oxides of Sulfur and
Other Small Sulfur-Containing Molecules, by J.H. Lunsford .
Structure and Reactivity of Adsorbed Oxides of Sulfur,
by J.H. Lunsford
Reactions of Sulfur Dioxide in Aerosols, by D.M. Himmelblau .
Mass Transport Models, by J.H. Overton • .
5. Technique Development
Formation of Atmospheric Aerosols—Nonideal Characteristics
of Impactors, by K.T. Whitby
Sources and Trace Metals in Urban Aerosols. Sub-Task Title:
Development and Application of Analytical Sampling Techniques,
by J.W. Winchester
Formation of Atmospheric Aerosols—Development of a Sulfur
Aerosol Analyzer, by K.T. Whitby
Simultaneous Comparison of the EAA and the Diffusion Battery
for Atmospheric Aerosol, by J. Bricard
Determination of Sulfate Ion Concentrations in Human and
Animal Serum using High Pressure Liquid Chromatography,
by L.L. Spiller
Comparison Study of Data Collected with the Dichotomous
and High-Volume Samplers, by T. McCarthy
A Cyrogenic Procedure for Concentrating Rating Trace Gases
in the Atmosphere, by L.L. Spiller <
Collection of Atmospheric N0_ by Treated Filters, by
L.L. Spiller
57
-------
Instrumentation for Monitoring Meteorological Data, by
L.L. Spiller
Improvement of "Streaker" Technique for Automated Appendices
Collection and Analysis of Aerosols, by W. Nelson
B. AUTO EXHAUST CATALYST PROGRAM
Roadway Aerosol Studies during General Motors Sulfate
Dispersion Study, by E.S. Macias
Formation of Atmospheric Aerosols—Aerosol Size Distributions
and Concentrations Measured During the General Motors
Sulfate Study, by K.T. Whitby
Sources and Trace Metals in Urban Aerosols. Sub-Task Title:
Freeway Aerosol Aerosol Studies, by J.W. Winchester ....
Dynamics of Automotive Sulfate, by J.R. Brock
The General Motor-Environmental Protection Agency Sulfate
Dispersion Experiment in October 1975 at the General Motors.
Milford Test Track, by L.L. Spiller
Atmospheric Behavior of Catalyst-Generated Aerosols from
Source to Receptor, by J.L. Durham
58
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-77-076
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
AEROSOL RESEARCH BRANCH, ANNUAL REPORT FY1976/76A
Federal Interagency Energy/Environment Research and
Development Program
5. REPORT DATE
August 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
W.E. Wilson and C. Danskin, editors
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
10. PROGRAM ELEMENT NO.
1NE-625
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
- RTP, NC
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES A complementary report, EPA-600/3-77-080, describes research
activities funded by EPA's base program.
16. ABSTRACT
The research program of the Aerosol Research Branch includes research grants and
contracts at institutions in many parts of the United States, in addition to an
intramural program. The purpose of these projects is to study the chemical and
physical properties of aerosols, identify the mechanisms of aerosol formation and
removal, and conduct experiments to measure these rates.
The results of the research are being used (1) to establish the contribution of
the various sources to the ambient atmospheric aerosol loading, (2) to characterize
urban, natural, and primary and secondary aerosols, (3) to develop quantitative
descriptions of the generation and removal rates associated with each major aerosol
source and sink, (4) to quantify the effects of aerosol on atmospheric chemical
reactions, and (5) as a scientific basis for recommending regulatory actions concerned
with air quality improvements.
The research projects totally or partially funded by the Federal Interagency
Energy/Environment Research and Development Program are described.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
*Air pollution
*Aerosols
*Research projects
13B
07D
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
67
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
59
------- |