EPA-600/3-77-008
January 1977
Ecological Research Series
ECOND ANNUAL CATALYST RESEARCH
PROGRAM REPORT: Summary
**
Healtli tTfecis Kesearch Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2, Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal
species, and materials. Problems are assessed for their long- and short-term
influences. Investigations include formation, transport, and pathway studies to
determine the fate of pollutants and their effects. This work provides the technical
basis for setting standards to minimize undesirable changes in living organisms
in the aquatic, terrestrial, and atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/3-77-008
January 1977
SECOND ANNUAL CATALYST RESEARCH PROGRAM REPORT
Summary
by
Criteria and Special Studies Office
Health Effects Research Laboratory
Research Triangle Park, N.C. 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
HEALTH EFFECTS RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, N.C. 27711
-------
DISCLAIMER
This report has been reviewed by the Health Effects 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.
-------
FOREWORD
The many benefits of our modern, developing, industrial society are
accompanied by certain hazards. Careful assessment of the relative risk
of existing and new man-made environmental hazards is necessary for the
establishment of sound regulatory policy. These regulations serve to
enhance the quality of our environment in order to promote the public
health and welfare and the productive capacity of our Nation's population.
The Health Effects Research Laboratory, Research Triangle Park
conducts a coordinated environmental health research program in toxicology,
epidemiology, and clinical studies using human volunteer subjects. These
studies address problems in air pollution, non-ionizing radiation,
environmental carcinogenesis and the toxicology of pesticides as well as
other chemical pollutants. The Laboratory develops and revises air quality
criteria documents on pollutants for which national ambient air quality
standards exist or are proposed, provides the data for registration of new
pesticides or proposed suspension of those already in use, conducts research
on hazardous and toxic materials, and is preparing the health basis for
non-ionizing radiation standards. Direct support to the regulatory function
of the Agency is provided in the form of expert testimony and preparation of
affidavits as well as expert advice to the Administrator to assure the
adequacy of health care and surveillance of persons having suffered imminent
and substantial endangerment of their health.
New technologies for controlling emissions of pollutants to the
atmosphere are always a welcome advance in the pursuit of a cleaner
environment through research. A thorough study of these new technologies
is in order, however, to assure that the net effect on public health is
beneficial. The Catalyst Research Program, in its investigation of the
automotive oxidation catalyst, provides a sound base upon which the EPA can
make a responsible assessment of the effect on public health of this advanced
emission control technology.
H. Knelson, M.D.
i Director,
Health Effects Research Laboratory
-------
PREFACE
The Catalyst Research Program, initiated in FY 1975, is a broad
milltidisciplinary research effort to provide a sound technical basis
for evaluating the public health issues related both to the benefits
associated with the reduction of regulated emissions and to the
potential health hazards associated with any unreaulated emissions
generated by control systems. This report covers work performed
during the second year of the Catalyst Research Program plus related
work performed outside the CRP.
IV
-------
ABSTRACT
This report constitutes the second Annual Report of the ORD
Catalyst Research Program required by the Administrator as noted in his
testimony before the Senate Public Works Committee on November 6, 1973.
It includes all research aspects of the broad multidisciplinary program
including: emissions characterization, measurement method development,
monitoring, fuel analysis, toxicology, biology, epidemiology, human
studies, and unregulated emissions control options. Principal focus is
upon catalyst-generated sulfuric acid and noble metal particulate emissions.
Highlights in this report are:
• Sulfuric acid emissions from production catalyst-equipped
vehicles are lower than those predicted in the first Annual
Report.
0 Pre-catalyst baseline data on platinum levels in the environ-
ment and in representative populations are reported.
t Increases in sulfate concentrations near a freeway
have been observed.
• Data on ultrafine sulfuric acid emitted from production
catalyst-equipped vehicles are presented.
-------
TABLE OF CONTENTS
Foreword i i i
Preface i v
Abstract v
List of Tables vii
List of Figures viii
I. Introduction 1
II. Overview of Component Programs
A. Environmental Monitoring and Support Laboratory/RTP 4
B. Environmental Sciences Research Laboratory/RTP 17
C. Health Effects Research Laboratory/Cincinnati 25
D. Health Effects Research Laboratory/RTP 34
E. Office of Mobile Source Air Pollution Control/
Washington, D.C 45
III. Discussion of Program Highlights 51
IV. Appendices
Appendix A - Crosswalk Listing of FY 1975 Projects by
Laboratory and Tasks 56
Appendix B - Listing of Supplements 72
VI
-------
LIST OF TABLES
Page
I Sulfur Content of Unleaded Gasoline, Summary by
Region - June - November 1974 5
II A Comparison of Sulfur Content in Gasoline by Grade in
Los Angeles and San Francisco 6
III Lead and Phosphorus Content in Unleaded Gasoline -
June 1974 - December 1975 7
IV Summary of LACS Contractor (Rockwell) Analyses of Blind
Sulfate QC Samples 9
V Summary of LACS Contractor (Rockwell) Analyses of Blind
Lead QC Samples 10
VI S04 Emissions - 1975-1976 Catalyst Cars 18
VII Comparison of Sulfuric Acid and Sulfate Results 23
VIII Comparison of Test Conditions 26
IX Percent of Initial Lung Burden Retained with Time in
the Lungs 31
X Lethal Doses of Various Metallic Compounds After
Intraperitoneal or Oral Administration in the Rat 35
XI Sulfuric Acid Emissions from Baseline Program Vehicles... 46
XII Ranges of Sulfuric Acid Emission Levels and Gaseous
Emission Standards for Model Year 1979 49
Vll
-------
LIST OF FIGURES
Page
1 Organization of the Catalyst Research Program 3
2 LACS Study Site Composition and Elevation 12
3 LACS Data - Hi-Vol Sulfates 13
4 LACS Data - Hi-Vol Lead 14
5 LACS Data - Carbon Monoxide 16
6 Schematic Diagram of Sulfuric Acid Monitor 19
7 Location of EPA Dichotomous Samplers (Circles), General Motors
Sampling Towers (Triangles), and Mobile Laboratories at
General Motors Mil ford Proving Ground, October 1975 21
8 Distribution of Pt Detected in Tissue by Age Group (15-90)
and Sex 37
9 Lung of Mouse Exposed to Acid Mist-Carbon Particles Mixture:
Thickened Alveolar Walls as well as Thin Filamentous Septa
(a) 200X; (b) 550X 40
-------
I. INTRODUCTION
Section 202 of the Clean Air Act of 1970, as amended, required
substantial reduction in certain specified emission products from
automobiles. The automotive industry, to achieve these reductions,
chose the oxidation catalytic converter as a primary method of emission
control for model year 1975. Subsequent to this decision, EPA intensified
its research program to determine what, if any, new pollutants might be
emitted into the atmosphere as a result of the application of this
technology. Also studied were the effects of fuel composition and fuel
additives on these, as well as regulated, emissions. Results from the
EPA research program indicated that though emissions of hydrocarbons,
carbon monoxide, and certain organics would be dramatically lowered,
sulfuric acid aerosol emissions would increase, and slight emissions of
platinum, palladium, and alumina might also be expected.
Because existing ambient concentrations of sulfates in many areas
of the country have been shown to be at levels sufficient to cause
concern, and because very little information existed regarding health
effects of platinum or palladium as air pollutants, EPA initiated a
broad research program to examine the public health impact of catalyst-
emitted sulfates, platinum, and palladium.
In testimony to the Public Works Committee of the U.S. Senate,
Administrator Train specified EPA's planned program of catalyst-related
research:
1. Accelerate work on development of a reliable test
procedure for automotive sulfate emission measure-
ment.
2. Consider all feasible alternatives for automotive
sulfate emission control.
3. Improve the Agency's ability to estimate the public health
impact of sulfate and other automotive emissions.
4. Improve understanding of the atmospheric chemistry
involved in these emissions and initiate an appropriate
air monitoring program.
From these broad objectives defined in Administrator Train's testimony
of November 1973, an extensive interdisciplinary research program was
developed utilizing the resources of EPA's technical staff in the Office
of Research and Development and the Office of Air and Waste Management
as well as extramural programs with the scientific community outside the
government. The first eighteen months of effort in the program have
been completed. The initial results of the program were summarized in
the first annual report published as EPA report #EPA-600/3-75-010a-j (10
volumes) dated September 1975. This report is the second in a series
planned for annual issuance through at least 1977.
-------
The second report differs slightly from the first report in the
organization of material with the contents arranged according to the
laboratory organization under whose management the work was performed.
This change was made in order to facilitate both reporting require-
ments and identification of responsible program management for follow-up
requests for further information from report users.
Four supplements to the summary portion of this annual report
cover work performed as part of the Catalyst Research Program by the
following groups: Health Effects Research Laboratory, Research Triangle
Park, N.C. (Supplement I); Environmental Monitoring and Support Labora-
tory, Research Triangle Park, N.C. (Supplement II); Environmental
Sciences Research Laboratory, Research Triangle Park, N.C. (Supplement
III); and the Health Effects Research Laboratory, Cincinnati, Ohio
(Supplement IV). A fifth supplement covers related work performed by the
Office of Mobile Source Air Pollution Control, Washington, D.C. (Supple-
ment V). Overviews of each organization's programs are included in both
this summary report and within each supplement. In addition, Figure 1
provides a brief overview of the research responsibilities of the five
organizations participating in the Catalyst Research Program.
X . "*-
Readers familiar with the first Catalyst Research Program Annual
Report may wish to follow up on progress of projects included previously
as individual tasks within specific discipline areas. For this purpose,
a crosswalk listing of projects as treated in the 1975 annual report
with references to their status as of the currenl reporting period is
provided as Appendix A to this summary.
-------
PARTICIPATING LABORATORY
AREAS OF RESPONSIBILITY
CATALYST PROGRAM
COORDINATION OFFICE
(OFFICE OF HEALTH AND
ECOLOGICAL EFFECTS)
ENVIRONMENTAL MONITORING
AND SUPPORT LABORATORY
RTP, NC
ENVIRONMENTAL SCIENCES
RESEARCH LABORATORY
RTP, NC
HEALTH EFFECTS
RESEARCH LABORATORY
CINCINNATI, OH
HEALTH EFFECTS
RESEARCH LABORATORY
RTP, NC
OFFICE OF MOBILE SOURCE
AIR POLLUTION CONTROL
WASH, DC
I
I
• FUEL COLLECTION AND ANALYSIS
• MONITORING (LACS)
• EMISSION CHARACTERIZATION
• MEASUREMENT METHODOLOGY
• ATMOSPHERIC CHEMISTRY
• METEOROLOGY/MODELLING
• INHALATION TOXICOLOGICAL EVALUATION
OF WHOLE ENGINE EXHAUST
• TOXICITY TESTING OF EMISSION PRODUCTS
• IN VIVO AND IN VITRO TOXICITY TESTING
OF EMISSION PRODUCTS
• INHALATION TOXICOLOGY
• HUMAN STUDIES
• EMISSION FACTORS
• CONTROL TECHNOLOGY
Figure 1. Organization of the Catalyst Research Program
-------
II. OVERVIEW OF COMPONENT PROGRAMS
A. Environmental Monitoring and Support Laboratory/Research Triangle Park
The National Fuels Surveillance Network (NFSN) was established
in 1972 in accordance with Section 211 of the Clean Air Act as amended
in 1970. During the period of this report (June 1974 to December 1975)
with the assistance of the EPA Regional Offices, EMSL collected and
analyzed approximately 3,000 commercially purchased samples of gasoline
(premium, regular, leaded, and unleaded), motor oil, fuel oil, and fuel
additives. The analyses included those for more than one element, using
both isotopic dilution spark source mass spectrometry (ID-SSMS) and
instrumental neutron activation (INAA). Typical analyses for samples
collected during a 6-month period for sulfur content by region is shown
in Table I. A special effort was also conducted in support to the Los
Angeles Catalyst Study (LACS) to determine sulfur content in the Los
Angeles and San Francisco areas during the summer of 1974. These data
are summarized in Table II.
Accessory measurements were made for viscosity, Reid vapor pressure
(RVP), carbon-hydrogen-nitrogen (CHN), fluorescence indicator adsorption
(FIA), sulfur, and American Petroleum Institute (API) gravity. Multi-
element determinations were made by ID-SSMS and INAA. Analysis of single
elements was performed by atomic absorption spectrometry (AA), and compounds
were analyzed by gas chromatography (GC). A variety of standard American
Standards and Testing Methods (ASTM) chemical and physical methods was
also used.
There were three areas of activity within the NFSN relating to the
catalyst program. Assistance was provided to various EPA groups such
as the Office of Enforcement and General Counsel/Mobile Source Enforcement
Division (OEGC/MSED), the EPA regional offices, the Environmental Sciences
Research Laboratory (ESRL), Mobile Source Enforcement, Ann Arbor, and the
joint New York State-EPA study of unleaded gasoline. The results of lead
and phosphorus analyses during an 18-month period to determine compliance
with the regulations on unleaded gasoline are shown in Table III. A study
was carried out to determine the integrity of welded seam cans for shipping
unleaded gasoline samples. A paper entitled "The EPA National Fuels
Surveillance Network" was also published.
A number of quality assurance (QA) activities related to the
Catalyst Research Program are performed by EMSL. These include: (1)
routine audits of laboratory analyses performed by the LACS contractor,
(2) measurement method evaluation and standardization, (3) development
and distribution of standard reference samples and materials, and (4)
preparation of quality assurance guidelines.
-------
TABLE I
Sulfur Content of Unleaded Gasoline
Summary by Region - June-November 1974
Region
I
II
V
VI
VII
VIII
IX
Total Samples
24
14
22
23
22
23
8
Weight
Minimum
O.Q04
0.009
0.005
0.005
0.001
0.00.4
0.006
Percent
Maximum
0.089
0.042
0.094
0.073
0.075
0.052
0.076
Sulfur
Average
0.029
0.023
0.031
0.035
0.037
0.023
0.018
-------
TABLE II
A Comparison of Sulfur Content in Gasoline
by Grade in Los Angeles and San Francisco
Summer 1974
San Francisco Los Angeles
Premium
No. Samples 19 19
Wt. %S 0,009 0.026
Regular
No. Samples 15 12
Wt. %S 0.035 0.051
Unleaded
No. Samples 18 16
Wt %S 0.027 0.034
Low Lead
No. Samples 2 2
Wt %S Q.OQ9 0,042
-------
TABLE III
Lead and Phosphorus Content in Unleaded Gasoline
June 1974-December 1975
Violations
Region
I
II
III
IV
V
VI
VII
VUI
IX
X
No. Samples
19
16
23
56
81
48
67
35
22
19
Pb
0
7
0
6
0
1
8
2
1
0
P
0
0
0
0
0
0
1
1
0
3
-------
The routine audit program consists of sending the LACS contractor
blind quality control audit samples on a routine schedule to be analyzed
with the contractor's normal analyses. Audit samples for sulfate (SO^),
nitrate (NO-), and lead (Pb) analyses are sent weekly and those for
sulfur dioxTde (S02) are sent bi-weekly. Tables IV and V summarize a
portion of the SOT and Pb audit sample analyses performed by the LACS
contractor. Brief summaries of the contractor's accuracy and standard
deviation are prepared and distributed every five weeks to EPA personnel
concerned with LACS. A summary report for general distribution is
prepared every three months.
A measurement methods evaluation and standardization program
for ambient aerosol SO^ has been initiated. The work is organized into
three phases, namely: (1) a thorough literature survey of methods for
ambient SO^ measurement and a recommendation of two methods for complete
evaluation; (2) an in-depth laboratory familiarization of the two
methods; and (3) a statistically designed experimental program (sometimes
called ruggedness testing) to detect the effect of a number of important
variables on each method. At present the literature survey has nearly
been completed and a summary document is being prepared. The methythymol
blue (MTB) and the barium chloranilate methods have been selected for
further investigation.
EMSL has cooperated with ASTM Committee D2 in collaborative tests
of the analysis procedures for phosphorus (P) and lead (PB) in unleaded
gasoline. The collaboratively tested methods are ASTM D-3231 and ASTM
D-3237, respectively.
In order to support QA programs, a variety of National Bureau of
Standards (NBS) Standard Reference Materials (SRM) and EPA Standard
Reference Samples (SRS) have been prepared. These reference samples
and materials are used for calibration checks by measurement method
operators and quality control audits by operators' supervisors. In cooper-
ation with NBS, SRM's and SRS's have been developed for Pb in unleaded
gasoline. These SRM's and SRS's have been disbributed to the Regional
Offices as part of an EMSL QA technical support effort to the Mobile
Source Enforcement Division for the enforcement of the Pb and P fuel
regulation. A bulk sample of sulfur (S) in unleaded gasoline was also
developed._ This will be packaged and distributed upon request. SRS's
for Pb, S0|, and NO, on glass fiber filters were also developed as well
as a freeze-dried liquid sample of sodium sulfite (NaSO,) for auditing
the chemical analysis portion of the manual S02 measurement method.
EMSL has prepared a variety of quality assurance guidelines
both on the establishment of QA programs and on specific measurement
methods used with the Catalyst Research Program. A quality assurance
plan was prepared for the Mobile Source Enforcement Division for sample
collection and analysis of Pb and P during the enforcement of the fuels
regulation. Measurement method guidelines were completed and published
in the Environmental Monitoring Series for: (1) a laboratory method for
determination of Pb in gasoline; (2) a field method for determination of
Pb in gasoline; and (3) a laboratory method for determination of P in
gasoline.
8
-------
TABLE IV
Summary of LACS Contractor (Rockwell) Analyses
of Blind Sulfate QC Samples
Sample (yg SO^) RISC Mean (ug SO^) % Difference Mean Range % Mean Range
181
477
752
1508
2373
3857
5078
6417
264
513
749
1428
2240
3627
4777
6021
+ 46
+ 8
0
- 5
- 6
- 6
- 6
- 6
35.0
36.7
44.3
30.5
48.5
53.8
115.0
131.6
13
7
6
2
2
1
2
2
-------
TABLE V
Summary of LACS Contractor (Rockwell) Analyses
of Blind Sulfate QC Samples
Sample ug S04) RISC Mean (ug S04) % Difference a_ lOOo/RISC Mean
• • T"
121
350
804
1262
1811
_.. T_
109
320
732
1145
1626
- 10
- 9
- 9
- 9
- 10
5.5
13.4
34.3
59.7
91.1
5
4
5
5
6
10
-------
A set of eight quality assurance guidelines was prepared for
the Office of Mobile Source Air Pollution Control. Guidelines and test
precedure documents were developed for the following engine categories:
(1) light-duty gasoline powered vehicles, (2) heavy-duty diesel engines,
(3) light-duty diesel powered vehicles, and (4) heavy duty gasoline
engines. These guidelines and test procedures are available in one
document entitled "Guidelines for Quality Assurance Program for Mobile
Source Emission Measurement Systems."
In order to assess the impact of pollutant emissions from
catalyst-equipped vehicles on the ambient air adjacent to a freeway in
Southern California, a variety of pollutants are being monitored under
the LACS program by both integrated and continuous methods. The study
site composition is shown in Figure 2.
Six integrating sampling methodologies are in use. The high
volume sampler (hi-vol), using a 20x25 cm glass fiber filter, analyzed
for: total suspended particulates (TSP), water soluble sulfates (SO];),
water soluble nitrates (NOt), ammonium ion (NHt), and lead (Pb) by
standard wet chemical analysis techniques. Summary graphs of the upwind
(SUe A), downwind (SITE C), and difference (C minus A) SOJ and Pb data
obtained during the 1500-1900 hours evening rush hour are shown in
Figures 3 and 4.
Samples obtained from membrane samplers, using a 102 mm circular
filter, are analyzed for TSP, SO., NO.,, and NHt by wet chemistry, plus
9 selected elements by x-ray fluorescence (XRF). The elements are
sulfur (S), lead (Pb), aluminum (Al), silicon (Si), calcium (Ca),
chlorine (Cl), iron (Fe), zinc (Zn), and bromine (Br).
Andersen cascade Impactors, using five impactor stages made of
aluminum for aerosol size fractionation and backup filters (102 mm in
diameter) for an additional size fraction are used. Analyses on the
backup filter are by the same techniques listed for membrane sampelrs.
Dichotomous samplers, using 3 Teflon filters (37 mm in diameter)
give aerosol size fraction information in 3 ranges by a nonimpaction
method. Analyses on all filters are for SO^, NHt, strong acidity, and
the same 9 elements as obtained with the membrane samplers.
Sulfur dioxide bubblers are analyzed by the standard Federal
Reference Method.
Experimental high flowrate aerosol samplers using 2 impactor
stages and an electrostatic precipitator to obtain size fraction
information in 3 ranges with daily aerosol collection in gram quantities
for subsequent exploratory compound identification analyses.
11
-------
MET
PREVAILING WIND-
— -i^pj^ lUWtR
0'
__
s
/
y
y
>
y
y
/
y
y
SAMPLER INLETS
3-4' ABOVE
FREEWAY SURFACE
S ^
_t>
^rt^\\vr/^^^^^i\\\^\^\\
^ nn* M-
>
j
i
"A" SITE
"B" SITE
"C" SITE
D" SITE
CO ANALYZER
TOTAL SULFUR ANALYZER
NO/NO2 ANALYZER
24-hr S02 BUBBLER
24-hr HI-VOL
4-hr HI-VOL
4-hr MEMBRANE
24-hr CASCADE
AMBIENT TEMP. AND DEWPOINT
.WIND SPEED
WIND DIRECTION
MASSIVE AEROSOL SAMPLER
24-hr DICHOTOMOUS SAMPLER
03 ANALYZER
24-hr HI-VOL
4-hr HI-VOL
24-hr MEMBRANE
CO ANALYZER
TOTAL SULFUR ANALYZER
NO/NO2 ANALYZER
24-hr SO2 BUBBLER
24-hr HI-VOL
4-hr HI-VOL
24-hr MEMBRANE
24-hr CASCADE
MASSIVE AEROSOL SAMPLER
24-hr DICHOTOMOUS SAMPLER
TRAFFIC SPEED & COUNT SYSTEM
03 ANALYZER
24-hr HI-VOL
4-hr HI-VOL
24-hr MEMBRANE
Figure 2. LACS Study Site Composition and Elevation
-------
j:
"o>
cc
i-
o
z
o
o
<
o
c/3
28 -
24
20
16
12
8
0
I I ! I I I I I I I I I I I I I I I I I I I I I I I I I I
SITEC
\ , SITE A
t X
C-A
I I i 1 I I I I I 1 I 1 I I I I I I I I I I I I I I I I I
JJ ASONDJFMAMJJ ASONDJ FMAMJ JASOND
1974 | 1975 I 1976
Figure 3. LACS Data
Hi-Vol Sulfates (SO4)
Monthly Averages of 1500-1900 Hour Data
-------
14
12
o
E
"w 10
cc
h-
z
LU
o
z
o
o
8
6
I I I I I I I I I I I I I I I I I I I I I I I I I I I I I
SITEC
C-A
/ SITE A
L I I I I I I ! I I x.-r-rT I I I I I I I I I I I I I I I
JJAS. ONDJFMAMJJASONDJFMAMJJASOND
1974
1975
Figure 4. LACS Data
Hi-Vol Lead (Pb)
Monthly Averages of 1500-1900 Hour Data
1976
-------
Pollutants monitored by continuous methods are: carbon
monoxide (CO) by infrared spectroscopy; nitric oxide (NO) and
nitrogen (NOp) by chemiluminescence with ozone; and total sulfur in
the gas phase by flame photometric analyses. The dramatic cross-
freeway difference for CO during the evening rush hour is illustrated
by the graph in Figure 5.
Associated measurements are also carried out: ambient tempera-
ture and ambient dewpoint; wind speed and wind direction using sensors
at the 10 meter level; and installation of a system to monitor traffic
speed and count is in progress.
15
-------
10
I I I I I I I I I I I I r I I I I I I I I | T
E
Q,
a
8
6
DC
f-
CJ
Z
O
o
o
o
SITE C -
•' /
SITE A ^
I I I I I I I I I I I I I I I I I I I I 1 I I
0
18
3—7 pm
HOUR OF DAY
Figure 5. LACS Data
5/75
Carbon Monoxide (CO) by Hour
-------
B. Environmental Sciences Research Laboratory/Research Triangle Park
This report covers work done in the Environmental Sciences Research
Laboratory on the catalyst program from approximately the second quarter
of FY 75 to the third quarter of FY 76. Research was conducted in four
major areas: emissions measurement and characterization, atmospheric
chemistry, ambient air measurement techniques, and modeling.
All of the activity in the emissions measurement and characterization
area was geared to support the Administrator's intention to promulgate
in the spring of 1976 a sulfate emission standard for light-duty vehicles.
This work, which is reported in detail in Supplement III (Appendix B),
involved further development of emissions measurement techniques and the
establishment of baseline sulfate emission data. The effect of vehicle
type and of operating mode on sulfate emissions was studied. This work
was coordinated with related work being done at the EPA Mobile Source Air
Pollution Control Laboratory in Ann Arbor, Michigan. A summary of sulfate
emissions data under various operating conditions is given in Table VI.
The development of techniques and instrumentation to measure sulfuric
acid and other sulfate aerosols in roadways and in the immediate vicinity
of roadways has always been an important part of the catalyst program.
(It is also important to other programs, such as the control of sulfur
oxides from stationary sources.) To obtain information on the variety
of sulfate species that could be present, measurement techniques have
been developed for sulfuric acid, strong acid, particulate sulfur,
water soluble sulfate, ammonium, and metals. Figure 6 shows a schematic
design of a newly developed automatic sulfuric acid monitor. These
techniques would be applied to a sample which would be collected in such
a way so as to preserve its chemical and physical integrity during
collection and storage prior to analysis. The dichotomous sampler,
which was developed to separate particles into two size fractions during
collection, is being used for this purpose.
An invitation was given to the U.S. Environmental Protection Agency
(EPA) by General Motors (GM) to participate in a test track study at the
GM Proving Ground to measure the effect on air quality of emissions from
a fleet of catalyst-equipped vehicles under controlled experimental
conditions. The test fleet consisted of 352 low-mileage 1975 and 1976
catalyst-equipped vehicles with air pumps provided by manufacturers.
During October 1975 for about two hours a day, 350 vehicles were operated
in packs on four lanes at a speed of 50 miles per hour. This mode of
operation was equivalent to a traffic density of 5,460 vehicles an hour.
The fuel used contained 0.03 weight percent sulfur; eight vehicles were
equipped by GM to emit sulfur hexafluoride as a tracer. A vehicle was
equipped by EPA to measure particle sizes, sulfate, and sulfuric acid
17
-------
TABLE VI
S04 Emissions - 1975-1976 Catalyst Cars
(mg/mile)
Category
'75- '76 California
production cars
(Olson study)
No. Crowded Urban Highway
of Cars Fuel Freeway Si mul . Simul. Simul.
101 tank fuel
0.03% S
average
15.8 4.4 22.6
'75 49-state
production cars
(baseline study)
'76 production
Mavericks
(baseline study)
'76, 49-state
(ESRL fuel study)
Prototype
air-pump cars
(Exxon study)
11 0.03% S
0.03% S
14.9
7.9
19.8
34.7 + 6.7 13.3 ± 6.0 41.4 ± 8.3
0.02% S
0.041% S
0.059% S
0.084% S
0.019% S
NA
NA
NA
NA
NA
1.6
3.7
5.5
12.0
50.8
5.8
15.4
20.9
49.5
31.9
(40 rnph SS)
18
-------
METHANOL
INJECTOR
200 cm3/nr,in
SOLENOID
FLOW
METER
FLOW
CONTROL
-o
TEFLON
FILTER
M
FILTER
MECH
CJJ>
DRY
ZERO
AIR
r i oui_civ\j
V I VALVE
I
TEFLON
FILTER
AMBIENT
AIR
VACUUM
PUMP
I
I
JL
FLAME
PHOTOMETRIC
DETECTOR
150
cm3/min
LINEARIZER
AND
INTEGRATOR
H.
RECORDER
Figure 6. Schematic Diagram of Sulfuric Acid Monitor.
-------
on the test track. In addition to meteorological measurements, measurements
were made of sulfates, sulfuric acid, sulfur dioxide, ammonia, ammonium,
sulfur hexafluoride, and particle size at towers and in mobile laboratories
at several distances just off the test track. A diagram of the test
track showing monitoring locations is given in Figure 7.
The following conclusions can be drawn to date from the analysis of
these experiments.
t The flow rate of aerosol sulfate from the vehicle fleet
was measured by an EPA grantee. The average sulfate
emission rate per car was 0.018 g/mi which corresponds to
a conversion of about 12 percent of the fuel sulfur to
aerosol sulfate. A separate estimate by General Motors
gave an average sulfate emission rate of 0.037 g/mi which
corresponds to approximately a 27 percent conversion of
fuel sulfur to aerosol sulfate.
• Most of the aerosol mass emitted from the air injection
catalyst-equipped vehicles was in the form of ultrafine
sulfur-containing aerosol in the size range between 0.01
and 0.1 ym.
t During the background measurements before and after operation
of the vehicle fleet, this ultrafine sulfur-containing aerosol
was almost completely absent. Instead the sulfur-containing
aerosol was in the usual urban-regional fine aerosol range of
0.1 to 1 ym particle sizes. This "aged" sulfur-containing
aerosol was not acid, so it was probably in the form of
neutralized ammonium sulfate.
• The ultrafine aerosols grow into the size range of "aged"
aerosols. When the wind was across the test track (shorter
aging time) most of the aerosol from the vehicles measured 30
m off the test track was ultrafine aerosol. When the wind
blew down the test track (longer aging time) one-third to
one-half of the aerosol shifted into the "aged" 0.1 to 1 ym
range.
• Sulfuric acid aerosol was measured both inside a moving
vehicle and at an off-track site about 20 m downwind of
the test track. More than two-thirds of the sulfate
emitted by the fleet of cars was measured as sulfuric acid
at the off-track site.
20
-------
1
f
(
«
»-
»•
'^
»• —
k
CENTER
OF
MEDIAN
j E
I o
r1
_
^
2 m
30m
•
2
.•
H
t
—
*•*"*
*~
i
,
*
NORTH
20 m
_ fci 1 OTI n/irtnn r ^^rtisi in
-------
• An attempt was made to measure the potential neutralizing
effect of ammonia on sulfuric acid aerosol. This attempt
consisted of measuring both ammonium and sulfate at increasing
distances downwind from the test track. In most cases, the
ammonium-to-sulfate ratios essentially corresponded to complete
neutralization at all measurement points rather than being
consistent with gradual neutralization. Apparently, neutral-
ization occurred as an artifact during sampling and storage
and not during the transport of sulfuric acid from the vehicles
on the test track to the sampling sites. Other measurements
of acidity and sulfuric acid indicate the presence of sulfuric
acid off the roadway, but suggest partial or complete neutral-
ization 100 meters downwind. Table VII shows a summary of
sulfuric acid and sulfate results during selected sampling
periods.
• Computations by the EPA HIWAY model were compared with the
sulfate concentrations reported by GM investigators. The
computed values were in good agreement with the experimental
values when the wind was nearly perpendicular to the roadway
under unstable meteorological conditions and at wind speeds
at or above 1 m/sec. The tracer data indicate the HIWAY
model tends to overestimate by a factor of 2 to 3 for E and
F stability conditions, and by a factor of nearly 2 for
the parallel wind case.
t Neither the off-roadway sulfate measurements nor the model
results are likely to be accurate in predicting the commuter
exposure during the parallel wind case.
Modeling research now under way is designed to determine the appli-
cability of the EPA HIWAY model, or an appropriate modification of it,
to the prediction of sulfate levels in the immediate vicinity of roadways.
Work was also done on point and area sources. The work, which is reported
in greater detail in Supplement III, includes the development of a
roadway data base from a study in New York and an analysis in terms of
the EPA HIWAY model of the data generated in "The General Motors/Environmental
Protection Agency Sulfate Dispersion Experiment." The supplement also
includes a paper on the modeling effort associated with this experiment.
It is important to note that overprediction of sulfate levels in the
vicinity of roadways as found in this experiment is not unexpected. It
was recognized at the outset of this experiment that the EPA HIWAY
model was not applicable to the problem of predicting vehicle-emitted
pollutant levels in the roadway or very close to it, especially under
very low wind speed conditions. The effort was nevertheless made to
determine if the model could be adapted to this situation or if it would
suggest a route to the development of an appropriate highway model.
22
-------
TABLE VII
Comparison of Sulfuric Acid and Sulfate
Date
10/1/75
10/2/75
10/3/75
10/10/75
10/13/75
Wind
Direction
285°
330°
335°
245°
195°
Wind
Speed
km/h
15
13
8
6
12
Background
Sulfate
(BS)3
yg/m
2.75
0.59
2.27
17.19
7.55
Downwi nd
Sulfate
(DS),
yg/m
4.51
3.49
5.53
20.65
10.85
Results
(DS - BS)
yg/in3 H2S04/AS04
1.76 1.08
2.90 0.38
3.26 0.83
3.46 1.56
3.30 0.73
23
-------
In late 1975, investigators under an EPA contract began a study
in California to determine if sulfate emissions from 100 in-use
catalyst-equipped vehicles are similar to or different than emissions
from new, well-tuned vehicles. Plans call for three emission tests
per year (at approximately 4,000-mile intervals) on these consumer
owned and operated vehicles. Preliminary results, after one test
interval, show that sulfate emissions from vehicles designed to meet
California standards averaged 0.016 g/mi. This figure is considerably
less than the average of 0.035 g/mi measured in the GM study and by
dynamometer tests.
24
-------
C. Health Effects Research Laboratory/Cincinnati
In fiscal year 74, the Environmental Toxicology Division, HERL,
Cincinnati was instructed to reprogram its research effort and develop
a program for comprehensive toxicologic assessment of emissions from
automotive engines with oxidative catalytic converters in the exhaust
train. The research effort was divided into two major segments,
i.e., the assessment of biological effects in animals exposed to (A)
whole emissions from engines with and without the catalyst and (B)
single pollutants (noble metals and sulfates) associated with catalyst
emissions.
Part A: Automotive Emission Studies with and without Catalytic
Converters
The research program for the Toxicological Assessment of Mobile
Emissions (TAME) is summarized in Table VIII. Basically, the program
was designed to determine biological effects following subacute (7 days)
and longer term inhalation exposures to irradiated (I) and nonirradiated
(NI) catalytic and non-catalytic-treated emissions. Clean Air controls
(CA) and pertinent sulfuric acid (HLSCL) exposures were made where appro-
priate. This report contains data from TAME M, N., and 0 studies. Data
from the earlier TAME studies (I, J, K, L) are contained in the first
Annual Catalyst Research Program Report and in the open literature.
A comparison of the biological data from the subacute studies
indicated that when the catalyst was removed extensive histopatholo-
gical lesions were found in adult animals and a significant mortality
rate was observed in suckling rats. In the studies using catalyst-
treated exhaust no biological changes were found which could be related
to the increased sulfate emissions. The catalyst effectively reduced
carbon monoxide (CO) and hydrocarbons (HC) in the exhaust which apparently
had an effect (at least in a closed exposure system) on oxidant and nitro-
gen dioxide (N02) levels by altering the HC/NO ratio. There was a resultant
reduction in biological effects due to the exposure. The catalyst altered
the type of particulate to one which contained sulfuric acid as a major
component.
In the TAME-L study, experimental animals (rats and hamsters) were
exposed for periods up to one month to the catalyst-treated exhaust.
Lung tissues examined by light microscopy showed no detectable effects.
The scanning electron microscopy examination did not reveal any changes
in epithelial lining cells which could be related to the exposure or
emitted sulfates. An additional investigation was undertaken to deter-
mine the effects of experimental animal chamber loading (species and
numbers per inhalation chamber) and frequency of cage changes and chamber
washing on the chamber ammonia build-up and its concomitant interaction
with sulfuric acid. Data from this study served to improve experimental
design of future studies related to investigation of sulfuric acid
effect parameters.
25
-------
TABLE VIII
lexicological Assessment of the Mobile
Emissions (TAME) Studies
COMPARISO
TAME STUDIES
Test period, days
Fuel
Engine
Catalyst
Exposures
N 0
1
7
F TEST
J K
7 7
COI
L
32
MDIT
M
8.8
ION
N
39
S
O
38
Ret. Ret. + thiophene
GM 73
No
Nl
1
CA
CO
Beads
Nl
1
CA
75 Ford
Monolith
Nl
1
CA
H2S04
No
Nl
1
CA
CO
26
-------
Studies on the physiological and pathological effects were conducted
on TAME M, N, and 0. Growth rate, pulmonary function and pulmonary
pathology of young guinea pigs were examined following a 30-day continuous
exposure to catalyst-treated and non-treated automobile emissions. Details
of all TAME studies may be found in Supplement IV. Following exposures
to the catalyst-treated emissions, there was some reduction in growth
rate (0 to 20 percent). When catalytic equipment was removed, growth rate
decreased (34 to 36 percent). Airway resistance in experimental animals
was significantly greater (3 to 47 percent) in exhaust-exposed animals
than clean air controls, and lung compliance was unchanged when the
catalyst was used. However, removal of the catalyst resulted in an
even larger increase in resistance (63 to 68 percent) accompanied by a
significant decrease in compliance (35 to 39 percent), indicating bronchial
constriction. Animals exposed to H^SO,, atmospheres which were similar
in concentration and particle size to that found in catalytic emission
atmospheres, showed a 3 percent decrease in growth rate, an 18 percent
increase in resistance and no change in compliance when compared to
clean air controls. Pulmonary lesions, as examined by light microscopy,
were similar in incidence for all groups. However, those lesions seen
in the lungs of animals exposed to emissions produced without catalytic
equipment appeared more severe.
Behavioral studies indicated that exposure to both catalytic and
non-catalytic-treated exhaust resulted in a significant reduction of
spontaneous activity in rats. Blood gas analysis has shown that both
HpSO. and irradiated exhaust treated with a catalytic converter elicited
a shift toward metabolic alkalosis during exposure. In contrast,
exposure to carbon monoxide at levels comparable to that obtained in
chambers without using a catalytic converter resulted in a shift of the
blood toward acidity. The effects were less dramatic in the exhaust
chamber without the converter, thereby indicating that other components
of the non-catalyst exhaust tended to offset the action of the carbon
monoxide. It should be emphasized that blood acid-base parameters returned
to normal levels within one month after termination of all exposures.
In TAME M, lactating female rats and' their newborn offspring were
exposed to each of four treatment atmospheres (clean air, irradiated and
nonirradiated catalytic exhaust, and HpSO. mist). Tissues taken either
from the lactating females sacrificed after 4 weeks' exposure to the
catalyst-treated exhaust or from the weanling rats following 12 weeks'
exposure showed no treatment effects. In both groups there was evidence
of mild chronic respiratory disease. An -increase in hemoglobin, hemato-
crit, and total erythrocyte count was observed in the young animals
exposed to auto exhaust. The cause was not apparent but may be related
to a mild hypoxia in these groups. There were no treatment-related
effects upon body weight changes in either lactating females or their
offspring. There was no treatment-related mortality.
Developmental and growth studies in which pregnant hamsters were
exposed to irradiated exhaust using the catalytic system did not reveal
any gross teratogenic defects or embryotoxicity. However, there was a
slight delay in the onset of parturition. Postnatal growth in the
catalytic exhaust atmosphere appeared normal with the exception of a
27
-------
decreased ability to perform a postnatal reflex test (the "startle"
reflex). H^SO. aerosol maintained at the catalytic system level
resulted in a slight delay in the onset of parturition with no other
apparent effects. Non-catalytic exhaust environments were not tested.
Studies with developing chick embryos revealed increased embryonic
mortality following exhaust exposure without the catalyst, compared to
exposure to catalyst-treated exhaust; at fourteen days, mortality was 12
to 39 percent with the catalytic system compared to 51 to 55 percent
without the catalyst. The heart to body weight ratio increased 34 to 36
percent in the exhaust chambers without the catalytic system, but only
0 to 12 percent with the catalyst. Embryonic body v«eight decreased 6 to
36 percent with the catalytic system and 13 to 26 percent without it.
The liver to body weight ratio increased as much as 21 percent in both
catalyst and non-catalyst systems. FUSO, aerosol maintained at the
catalytic emission level resulted in a slight increase in mortality
accompanied by a 17 percent decrease in body weight but with no other
apparent effects. Carbon monoxide maintained at the non-catalytic
emission level resulted in a mortality of 30 percent, a decrease in
embryonic body weight of 22 percent, an increase in the heart to body
weight ratio of 28 percent, and an increase in the spleen to body weight
ratio of 37 percent.
Selected biochemical and clinical health indicators in general
showed that the use of the catalyst decreased the detrimental effects of
engine exhaust. Hematocrit, serum lactic dehydrogenase (LDH), glutamic-
oxalacetic transaminase (GOT) and lysozymes were measured in groups of
rats exposed to diluted emissions from an automobile engine with and
without catalyst; to sulfuric acid; or to carbon monoxide alone at a
level comparable to that in the automotive exhaust. An elevation in
hematocrit was observed in the animals exposed to exhaust gas without
the catalyst and in those exposed to carbon monoxide. Serum lactic
dehydrogenase activity was elevated in the groups of rats in the experi-
ment conducted without the catalyst, but no alteration was observed in
the animals from the experiment utilizing the catalyst, or in those
exposed to carbon monoxide alone. Measurements indicated that the
observed elevation of hemoglobin and hematocrit was due to polycythemia
and not to dehydration. Catalytic exhaust emissions resulted in slightly
increased serum triglycerides while serum cholesterol was not affected.
Examination of specific parameters of lipid and carbohydrate cata-
bolism such as the oxidation of C-1-palmitic acid to C02 to represent
lipid catabolism and the oxidation of C-U-glucose to represent the
breakdown of carbohydrate, revealed definite changes only in animals
maintained on a special diet containing reduced levels of Cu and Zn. The
rats receiving this special diet demonstrated decreased glucose oxidation
rates following exposure to both non-irradiated and catalytically altered
exhaust. The animals maintained on commercial rat chow did not show any
treatment effect in their ability to oxidize glucose in TAME N end 0.
The CO exposed animals in TAME 0 exhibited a decreased (15 percent)
ability to oxidize palmitate, as compared with the other groups.
28
-------
Preliminary results from tissue culture experiments demonstrated
that non-catalytic treated exhaust emissions were approximately 35
percent more toxic when compared with catalytic-treated exhaust. In
addition, sulfuric acid levels equivalent to the titratable acidity
present in the catalytic exhaust had no effect.
Functional integrity of the pulmonary aryl hydrocarbon hydroxylase
(PAHH) was studied because of its possible role in biotransformation of
hydrocarbons. In previous TAME studies, it was shown that exposure to
non-catalyst-modified auto exhaust markedly depressed specific PAHH
activity. There was a lesser but still significant depression of PAHH
along with increased relative lung mass after exposure to catalyst-
modified irradiated exhaust. In the TAME M study, pregnant hamsters and
their offspring were continuously exposed and the determinations of
total PAHH activity and relative lung mass (lung to body weight ratio)
were made in post-weanling hamsters. Body and lung weights were greater
in the sulfuric acid (S) and irradiated exhaust exposure (I) groups; as
a result, relative lung mass was not significantly different. Specific
PAHH activity was not different from controls in the sulfuric acid-
exposed group. In the irradiated exhaust-exposed group it was depressed
by about 9 percent; this depression was consistent with the pattern in
previous studies.
For TAME studies M, N, and 0, a 1975 Ford 400 CID California production
engine equipped with two oxidative catalytic converters was operated
continuously (24 hr/day) on an engine dynamometer test stand using the
California cycle. Both TAME M and TAME N utilized new engines and new
catalysts; in TAME 0 the catalytic converters were removed. In TAME M,
Engelhard Pt/Pd catalysts with American Lava monolith substrate were
used and in TAME N an identical catalyst formulation with a substrate
made by Corning was substituted. The fuel used was unleaded 91 octane
indolene with thiophene added to produce a high sulfur fuel (0.10
percent S by weight).
Comparison of the atmospheres in the'exposure chambers and the
dilution tube generated with and without the use of catalytic converter
produced the following results: (1) Major decreases in concentrations
of carbon monoxide (90 percent) and total hydrocarbons (70 percent)
occurred with the use of the catalytic converter in the exhaust system.
(2) The use of a converter caused a large decrease in sulfur dioxide
(45 percent), but a resultant increase of.sulfuric acid droplets with a
mass median diameter of less than 0.3 ym. (3) A significant decrease
in the oxidative capacity of the catalyst.occurred with use (TAME M,
45,000 miles) with a resultant increase in carbon monoxide levels and a
decrease in total particulate. The sulfate mass decreased approximately
80 percent during the course of the study. In the shorter-duration TAME N
study (39 days or 20,000 miles) only a slight CO increase resulted and
sulfate decreased 24 percent . Special procedures were followed to
prevent carburetor enrichment and possible catalyst overloading.
29
-------
The results of the Toxicological Assessment of Mobile Emissions
(TAME) studies have demonstrated that the toxicological effects of
automobile emissions are ameliorated to a considerable degree by the
addition of a catalyst.
t Pulmonary function, mortality and heart weight/body weight
ratios of chick embryos, serum enzyme levels, enzyme activity,
tissue metabolism, and histopathology studies have shown that
addition of the catalyst resulted in decreased biological
damage.
t Sulfuric acid exposures at levels comparable to that produced
by the catalyst produced few effects.
• Single pollutant studies suggested that platinum and palladium
were relatively harmless at predicted emission levels. Platinum
is rapidly excreted while palladium, although quite toxic, is
apparently only slightly absorbed when given by intragastric
route at low levels.
t It was noted that there was a decrease in the oxidative
capacity of the catalyst as miles accumulated, which resulted
in marked decreases in sulfuric acid and sulfate emissions.
t Finally, it is realized that additional data concerned
with other catalytic systems and emission products are
needed. Additional studies were proposed for FY 76 and 77.
PART B: Toxicologic Study of Auto Exhaust Catalyst Components
The second part (B) of the document presents biological findings
on the single pollutants related to catalyst emission studies. Earlier
data dealing with individual products of catalyst emissions wer.e reported
in the first Annual Catalyst Research Program Report and in the open
literature. The present data include results of the continuation of the
studies of noble metals (Pt and Pd), sulfuric acid and sulfates, environ-
mental chelates, and ozone (Supplement IV).
Whole body retention, excretion, lunq clearance, distribution ?nd
concentration of radioactive platinum ('9^Pt) in other tissues was
determined in rats following a single inhalation exposure to different
chemical forms of 191pt. The chemical forms of 191pt used in this study
were 191PtCl4, 191Pt(SOd)2, 191PtO, and 191pt metal. Immediately after
exposure most of the 19TPt was found in the gastrointestinal and respira-
tory tract. Movement of the 191pt through the gastrointestinal tract
was rapid, most of it was eliminated within 24 hours after exposure.
Lung clearance was much slower with a half-time of about 8 days. In
addition to the lungs, kidney and bone contained the highest concentrations
of Pt. Summary of lung retention data is shown in Table IX.
30
-------
TABLE IX
Percent of Initial Lung Burden of Platinum Retained with Time
in the Lungs of Rats
CHEMICAL FORM
Day Pt Metal PtO Pt(S04),
1 63.0 57.2 73.7
2 49.5 60.9 43.4
4 41.3 49.0 20.4
8 42.9 28.6
16 28.0 17.9 4.4
31
-------
- Palladium sulfate markedly affected the Incorporation of L-(3,4-
H2)-proline into non-dialyzable fractions 1n 10-day chick embryo
cartilage explants with a 55 to 65 percent reduction in uptake in a
substrate concentration range of 0.06-0.6mM. Under these conditions the
synthesis of H-hydroxyproline was almost completely inhibited. Experiments
with prolyl hydroxylase indicated a strong irreversible inhibition of
the enzyme with a competition between iron and palladium at the active
site of prolyl hydroxylase. This finding suggests a potential mechanism ,
of palladium toxicity.
The toxicity to pulmonary free cells (RFC) of sulfuric acid (FLSOJ
and palladium sulfate (PdSO») administered intratracheally was investi-
gated in rats. The amount of H2SO, solution administered was 0.45 mg
S04/kg body weight. The aqueous solution of hydrous PdS04 solution was
given at a S04 dose rate equivalent to that of the H^SO, group and a Pd
dose of 0.5 mg/kg. Twenty-four hours after dosing, the PFC were collected
by saline endobronchial lavage. The following significant treatment
effects were found in the PdSO, group: increased total numbers of free
cells, including both viable and nonviable nucleated cells, phagocytic
and nonphagocytic macrophages, polymorphonuclear leukocytes, and red
blood cells; increased number of cells with test spheres; increased
dried lung mass. No such effects were found in the H^SO, exposed group.
There were no apparent effects on percentage of nonviable cells, on
proportional phagocytic activity, or on cell size in either group.
The effect of Pt, Pd, Mg, Mn, Ca, Ce, Na, and NH, sulfates upon
succinate-dependent respiration was tested in rat liver slices and
homogenates. Cadmium, a known potent inhibitor of the mitochondrial
respiratory chain, was used in this experiment as a reference toxicant.
The results indicated that the sulfate ion in tissue slices or in a
homogenate did not affect the respiratory chain. Cadmium appeared to be
the most potent cation inhibiting 02 uptake by approximately 50 percent
as 2 x 10 M and 100 percent at 3.3 x 10 M. To achieve a 50 percent
inhibition by PdSO. more than 10 M was required. Pt appeared to be
slightly more toxic than Pd under the same experimental conditions._~0ther
cations (Mn, Mg, Ca) were not inhibitory at concentrations up to 10" M
and even appeared to have a slight stimulatory effect. No effects could
be demonstrated with low concentration of Na or NH- ions. Intragastric
administration of a single dose and of multiple doses of CdSO., Pt(S04)2,
and PdSO/, at 8 and 80 ymole per kg body weight, did not affect succinate-
dependent respiration in any of the organ tissues tested (kidney, liver,
heart, and lung). It is probable that under the experimental conditions
these metals were not absorbed in amounts sufficient to cause any effect
on the mitochondrial respiration of soft tissue organs. The in vitro
experiment suggests that Cd should have impaired this enzyme system if
absorbed in significant quantity and accumulated in the tested organs.
32
-------
Products from the combustion of tobacco, gasoline, and coal from
other pyrolytic processes are ubiquitous sources of metal binding agents
which may react with trace metals thus altering essential biological
functions. The ability of the catalyst and non-catalyst, as well as
catalytically and non-catalytically-treated auto exhaust condensate to
bind copper was demonstrated. It was shown further that the ability of
these condensates to bind copper was greater than their ability to bind
zinc, cadmium, iron, and lead. In preliminary enzyme activity studies,
it was shown that catalytically-altered auto exhaust concentrate showed
a greater inhibition of tyrosinase (a copper-dependent enzyme) than non-
catalytically- treated exhaust.
The metabolic response of lung tissue to ozone was studied in rats
and monkeys after exposure of animals to various levels of ozone (0.1 to
0.8 ppm) for 1 to 30 days. In rats, 0.8 ppm ozone exposure resulted in
a 40 to 50 percent increase in oxygen utilization by lung homogenates.
Activities of marker enzymes, such as mitochondrial succinate-cytochrome
c_ reductase, microsomal NADPH-cytochrome £ reductase and cytosolic
glucose-6-phosphate dehydrogenase, increased 40 to 70 percent over
control after 3 to 4 days of exposure, and remained elevated throughout
the continuous exposure for 30 days. In monkeys, the observations were
similar except that the magnitude of biochemical changes was relatively
smaller. Exposure of animals to lower levels of ozone resulted in
proportionately smaller biochemical changes in the lung, with detectable
effects down to 0.2 ppm. With dietary deficiency of vitamin E, ozone
changes were detected at 0.01 ppm.
33
-------
D. Health Effects Research Laboratory/Research Triangle Park, N.C.
Research which is part of the Catalyst Research Program (CRP) under
way in the Health Effects Research Laboratory at RTP may be described as
falling generally in three categories: studies of trace metals associated
with catalyst-equipped vehicles (focusing primarily on platinum compounds),
sulfate studies (focusing primarily on sulfuric acid), and a study of
emissions from consumer-owned catalyst-equipped vehicles designed to meet
Federal emissions standards. There are also other related studies such
as evaluation of in vitro screening systems which appear promising as
health effects indicators for both the pollutants associated with catalyst
vehicles and other pollutants.
t Trace Metals Research
The trace metals portion of the CRP's research program has
focused principally on platinum compounds, because this metal is commonly
used in the noble metal oxidation catalyst employed by the U.S. automotive
industry in reducing emissions to the level required by Federal law. The
concern for health effects of platinum emissions differed from that for
sulfuric acid in that it was not based upon known toxic effects of a
pollutant characterized in exhaust emissions, but upon lack of knowledge
about the toxicology of platinum compounds which might be emitted from
catalyst-equipped vehicles.
Research on platinum included both development of measurement and
emission characterization technology and also development of information
on the toxicity of various platinum compounds which might be expected
to be found in emissions from catalyst-equipped vehicles. Selection of
platinum compounds for study in toxicity testing programs was based, in
the absence of definitive data on a platinum component of automotive
emissions, on prediction of those compounds most likely to be found in
the particulate exhaust. These were platinum oxides and platinum sulfates.
The work in health related studies of platinum compounds has been
under way for nearly two years and results to date have shown that toxicity
of platinum compounds appears to be directly related to water solubility
of these compounds. Since the platinum compounds most likely to be
found in exhaust particulate are the insoluble oxides and the marginally
soluble sulfates, concern for adverse health effects from platinum
emissions is less now than at the initiation of the CRP. Table X summarizes
the toxicitity of various platinum compounds and other metal salts in
the rat as a function of the route of exposure. Interest in pursuing
platinum toxicology programs continues, however, for two basic reasons:
long-term studies on carcinogenicity, mutagenicity, and cytogenicit.y are
not yet completed; preliminary findings show possible adverse effects
from the platinum compounds being studied. Also, it has been shown that
it is possible under laboratory conditions to methylate platinum via the
same vitamin B,2 (methylcobalamin) reaction by which mercury is methylated.
34
-------
TABLE X
Lethal Doses in the Rat of Various Metallic
Compounds After Intraperitoneal or Oral Administration
Lethal Dose
(mmoles/kg)
Compound
MnCl2.4H20
PbCl2
PdCl2.2H20
PdS04
PdCl2
Ptci4
Pt(S04)2.4H20
RuCl3
Route
ip
oral
ip
ip
oral
ip
ip
ip
oral
ip
ip
oral
oral
LD10
0.56
6.3
1.6
0.39
1.56
--
—
--
0.31
0.56
0.2-
0.3
1.37
1.78
LD50
0.70
7.5
8.5
0.57
2.7
1.42
2.5
0.11
0.70
0.68
0.3-
0.4
2.2
3.2
LD90
0.87
9.0
16.8
0.82
4.8
1.8
—
—
1.57
0.82
0.4-
0.6
3.5
5.4
(mg
LD10
31
350
330
42
166
--
—
—
60
no
39-59
270
180
cation/ kg)
LD50
38
410
1760
60
290
151
490
22
136
132
59-78
430
310
LD90
48
490
3500
87
520
195
—
—
310
160
78-1
690
550
35
-------
The biological activity of methylated platinum compounds thus formed has
yet to be determined. The implications of disposal of platinum-containing
automotive parts, as well as the emissions of platinum-containing exhaust
particulate from catalyst-equipped vehicles for platinum uptake from
soil to plants and possibly into the food-chain, is also a matter of
concern to the Agency. As shown in Figure 8, platinum has been detected
in human tissue although the significance of this finding is not presently
known.
For the above two reasons -- lack of data on long-term effects of
exposure and lack of information on platinum metabolites -- the CRP
efforts in this area are important to continue. There are also some
adverse effects being noted in preliminary data from other current
studies as briefly described in the supplemental report on platinum
research: platinum sulfate has been shown to be a moderate to severe
eye irritant, and it may, at some concentrations, have an effect on
behavior which could be characterized as depressant. Other data, prelimi-
nary at best, point to other possible adverse effects which must be
carefully assessed before any final evaluation of the health effects of
possible emissions of platinum compounds from catalyst-equipped vehicles
can be made.
t Sulfate Research
The principal thrust of the sulfate toxicological research
effort is to identify toxic agents via biological screening; to study
the metabolic pathways and fate of toxic agents and identify target
organs or tissues at risk; to study the mechanisms of damage and repair;
and to develop dose response relationships. Although much ongoing
research on the toxicology of sulfate compounds was not a formal part of
the Catalyst Research Program and received support from other program
areas, the results of the total sulfate research effort have a definite
impact on assessing the hazard of catalyst emission products and are
included here. Any output from these studies will be a contribution to
construction of an improved spectrum of biological responses for use in
epidemiological studies. The primary output will be animal dose response
models which will serve as an input to the human dose response model.
Studies currently under way in HERL/RTP have provided significant
toxicological information on the health effects of sulfur oxides. In-
house investigations have continued to assess the toxicity of three
different sulfur oxide substances on the clearance of both viable and
non-viable particles deposited in the respiratory tract. The mucociliary
clearance of radiolabelled killed streptococci was significantly reduced
when,mice were exposed to HUSO, having a mass concentration of 160
yg/m , although exposure to the other sulfur oxides [NapSO,, (NH.^SO*]
had no effect on mucociliary clearance of these particles from the lungs
or nose of mice. The inhalation of H2S04, (NH4)2S04, and Na2S04 alsu
failed to alter the rate of viable streptococci from the lungs of mice.
The study indicated that neither HpSO. nor Ne^SO, had any effect on the
36
-------
SPLEEN
SUBCUT.
FAT
-
MUSCLE
AORTA
_
LIVER
LUNG
M HEART
to
g PANCREAS
ADRENALS
GONAD
BRAIN
KIDNEY
THYROID
•^
PROSTATE
• =DETECTABLE Pt
CONCENTRATION
*
• 9 •
\'^
SEX MFMFMFMFMFMFM
*
•
F
•
9
• • • • • •
*
•
0 9
9 A •
I
^m
I
MMM
•
1
|
g
i
^mm
•
^•H
•
*
^^
V W
A 0
I
7/
1
i
^•B
I
A
9
1
MFMFMFMFMFMFMFM
*
0
MM
F
M
*
^^H
F
^^•^•^M
-14
- 13
I V
- 12
-11
Q.
_ m ^
-10 Q
cc
o
- 9 tu
0
-82
- 7 <
Q
- 6 >
Q
Z
J u.
O
-46
- 3
- 2
- 1
n
M F ?
AGE 10-1516-2021-25 26-30 31-3536-4041-4546-5051-55 56-6061-6566-7071-75 76-8081-8586-9091-96 §
CO
Figure 8. Distribution of Pt Detected in Tissue by Age Group (15-90) and Sex.
-------
host's ability to vary the clearance rate of viable organisms (streptococci)
from the nose. However, the data did suggest that the viable micro-
organisms deposited in this area of the respiratory tract may multiply
more rapidly in animals exposed to (NHjpSO. aerosol. From this research,
the conclusions reached were: (1) that the action of H2S(L aerosol
might be on the ciliated epithelial airway; (2) that unaer these experimental
conditions the three sulfur oxides tested appear to have no effect on
the deep lung bactericidal host defense mechanisms; and (3) that there
is a possibility that (NH.)2S04 may actually alter the bacteriocidal
defense system in the nose of mice allowing for enhancement of growth of
the deposited microbes. Details of these studies can be found in the
supplement.
Studies on rabbit alveolar macrophages comparing the relative
toxicity of metallic sulfates and chlorides indicated that the toxicity
of the metal is the same with either the sulfate or chloride anion. On
the basis of quantitative determinations of the molar concentration of
metal resulting in net cell death in 50 percent of exposed cells as
compared to controls the following ranking of toxicity was observed: Hg >
Cd >-; V > Cu > Zn > Mn * Ni. Concentrations resulting in a net cell
death of 50 percent ranged from 0.4 mM in the case of Hg to 3 mM with
Ni. Zinc ammonium sulfate did not show a significantly different toxicity
in this system from zinc sulfate.
Crude particulate samples being tested in the system contain several
of these toxic trace elements. In some cases the net toxicity of the
crude material does not correlate well with the predicted toxicity based
on the summation of the toxicities of the metals contained within or on
the crude sample. For this reason it is important to consider the
interactions of toxic trace elements when evaluating the toxicity of
environmental samples. Initial experiments designed to elucidate and
quantitate interactions between toxic trace elements indicate that
copper protects against vanadium cytotoxicity and selenium protects
against cadmium cytotoxicity.
o
The role of HpSO* (100 mg/m ) as a co-carcinogen acting with a
known carcinogen is being studied at the New York University Medical
Center. In this study, which has been under way for about one year,
hamsters are being exposed for long periods of time to H2S04 with
multiple intubation of benzo(a)pyrene (BaP). The report found in the
supplement indicates typical daily exposure, weight changes, cumulative
mortality, as well as histological data that have been collected thus
far in the study.
A study on the effects of sulfur oxide pollutants on respiratory
function, particle deposition and bronchial clearance is also being
carried out at New York University Medical Center. Exposure of H^SO,
(mass concentration of 993-2991 yg/m) having a MMAD of 0.3 - 0.6 v>m for
1 hour showed no significant pulmonary functional changes in the test
animals. Donkeys exposed for 1 hour to (NH4)2S04 (mass concentration of
38
-------
121-1604 yg/m ) having a MMAD of 0.2 - 0.6 ym did not significantly
alter the bronchial clearance rate of inhaled ferric oxide aerosols (3 y
g). Similarly- when donkeys were exposed to rLSO. (mass concentration of
993-1364 yg/m ) having a MMAD ranging from 0.3 - 0.6 yg for 1 hour and
subsequently exposed to radiolabelled ferric oxide, no effect was evident
on the initial pattern of deposition of the particle. However, prelimi-
nary data suggest that such exposure may significantly influence (slow)
clearance of the deposited ferric oxide particle.
Research is under way at the Stanford Research Institute to determine
the biological effects of exposure to H^SO, on rats and guinea pigs.
The animals were exposed to 110 mg/m H^SO. mist with MMD of 2.3 pm
for 24 hours daily. The LDrQ for rats was achieved in 37 days whereas
the LD™ for guinea pigs, iR the same environment, was achieved in about
3 hours; During these exposures, a variety of parameters were studied
in the rat: body temperatures, weight and volume relationship of lungs,
hematological evaluation, blood pH, respiratory gas analysis and-plasma
volume measurements. Guinea pigs were also exposed to 12.5 mg/m of
HpSO/, (MMD 2.0 ym). They developed an initial tachypnea which returned
to noVmal the next day. No difference was seen in hematocrit nor in red
cell counts. An interesting observation was that if the guinea pigs
were able to survive an initial "shocking" concentration they were
"tolerant" to much higher doses that would normally have been lethal.
Studies at IIT Research Institute (IITRI), Chicago, Illinois, have
focused on the effects of single and multiple 3-hour inhalation exposures
to varying concentrations of.sulfuric acid mist in combination with 5
mg/m of carbon particles on the mouse. As was true with acid mist
alone, mice were more sensitive to acid mist and carbon particle mixtures
(A-C) than hamsters. Only minimal mortality occurred among CF, mice
after a single 3-hour exposure to 300 mg/m or five daily 3-hour exposures
to 200 mg/m A-C. Three combinations of A-C concentration and exposure
duration .resulting in the same concentration-exposure time index £CT)
were examined: 5 daily exposures at 3 hours each day to 200 mg/m ,10
daily exposures to 100 mg/m , and 20 daily exposures to 50 mg/m A-C.
Scanning electron microscopic (SEM) examination of nasal cavities,
trachea, and lungs showed that the initial concentration of A-C is a
more critical factor in tissue damage than the total number of exposures.
Exposure to acid mist alone caused damage near the top and middle of the
trachea, while the lower portion of the trachea was relatively free of
damage and the lungs were normal. Addition of the 5 mg/m carbon particulates
to the acid mist extended the damage to the lower trachea and the bronchus
of the lungs. The most severe changes, including emphysematous-like
areas in the alveoli,-were found in mice following five daily 3-hour
exposures to 200 mg/m A-C as shown in Figure 9. Histopathologic examination
of these tissues did not disclose any marked changes, indicating the
sensitivity of SEM, in detecting tissue damage.
Infectivity studies conducted at the IITRI with various A-C
concentrations demonstrated the followina:
39
-------
Figure 9. Lung of Mouse Exposed to Acid Mist-Carbon Particles Mixture: Thickened
Alveolar Walls as well as Thin Filamentous Septa (a) 200X; (b) 550X.
-------
t Increased mortalities occurred in hamsters after a single 6-
hour exposure to 300 mg/m A-C or 48 hours after intranasal
challenge with influenza virus.
• Five daily 3-hour exposures to 200 mg/m A-C immediately
before or after challenge with a viral or bacterial agent
significantly increased mortality rates of mice. A concurrent
marked decrease in clearance rate of inhaled bacteria from the
lungs was observed.
• Five^as well as ten daily 3-hour exposures 5 days/week to 100
mg/m A-C immediately after challenge with a bacterial agent
also resulted in markedly increased mortality and decreased
survival time. Significantly increased mortality and decreased
survival time was seen in mice exposed daily for 5 days to 100
mg/m A-C 24 hours before or after challenge with influenza
virus.
• Twenty 3-hour exposures, 5 days/week, to 50 mg/m A-C followed
immediately by challenge with influenza virus resulted in
significantly increased mortality and decreased survival time
in experimental mice compared to controls.
Studies of the effects of inhalation of A-C on formation of
antibody and on pre-formed antibody are also in progress at IITRI.
Mice were exposed 3 hours 5 days/week to 100 mg/m A-C before or after
vaccination with influenza A^/Japan virus. At various time intervals
after vaccination, the mice were challenged with homologous influenza
virus and mortality, survival rate, pulmonary consolidation and immune
response were measured. The results obtained to date indicate that sif-
nificantly decreased survival time and increased pulmonary consolidation
occurred in many groups of vaccinated mice exposed to pollutant compared to
vaccinated controls maintained in clean air. The primary and secondary
immune responses, as measured by hemagglutination-inhibition and serum-
neutralizing antibody levels and immunoglobulin concentrations are being
evaluated.
The effects of acid aerosols on various animal models are being
studied at the University of California, Davis. In these series of
experiments the initial studies will utilize pathogen-free rats, while
later studies will use macaque monkeys. These primates will be employed
to validate the data from rats in a species phylogenically and anatomically
closer to man and to approach the problem of pulmonary physiological
studies on a larger species using more refined methods.
Results will be evaluated using physiological, morphological and
biochemical techniques. Clearance of airways will be evaluated using
tantalum bronchography and inhalation of radiolabelled particles followed
with an Anger camera. Morphological evaluation will include use of
light, transmission electron, and scanning electron microscopy, histochemistry,
and autoradiography. Biochemical techniques are used to study the rate
and pattern of synthesis of glycoproteins.
41
-------
Morphological and histochemical studies were conducted with monkeys
which were exposed to 250-450 mg/m of H^SO. continuously for 7 days.
The animals were sacrificed and multiple sections of lung, trachea, and
nasal septum were examined by light microscopy. Sections from these
exposed animals were essentially indistinguishable from normal, unexposed
animals. Some of the guinea pigs exposed to a mean mass concentration
of 25-29 mg/m for 7 days had paucity of cilia and cilia which were shorter
than normal. This effect was more pronounced at points of airway bifur-
cation.
Biochemical studies resulted in a new culture technique for maintaining
trachea! tissue in organ culture viable for up to 5 days. Using this new
culture-jSystem, tracheal tissue from guinea pigs continuously exposed to
40 mg/m of fine H2S04 aerosol for 6-8 days. No significant increase in
incorporation rates for leucine nor glucosamine at 24 hours was observed
although a trend toward an increase was evident. Only a small number of
animals were studied.
Microbiological experiments were conducted to determine the influence
of HpSO. aerosols on immunological response and susceptibility of mice
to respiratory infections with viruses. Tracheal organ cultures and
alveolar macrophage cultures were prepared to measure the effect of
HpSO, on interferon production. The interferon titers of macrophage
cultures from exposed mice appeared to be lower than those of control
cultures. No difference in interferon production in tracheal organ
cultures was reported. At the present time, immunoglobulin and albumin
levels in lung lavages of mice exposed to sulfuric acid aerosol is being
determined.
Research in the area of respiratory physiology was devoted to three
studies: (1) baseline data on pulmonary function of non-human primates,
(2) static pulmonary mechanics and lung volumes of guinea pigs exposed
to sulfuric acid aerosol, and (3) pulmonary mechanical reflexes of
guinea pigs before and after H2$04 exposure. The exposed guinea pigs
appeared to have greater EEV, a lower compliance despite a tendency to
have larger lung capacity, decrease in respiratory frequency, and a
decrease in minute volume.
The University of Washington is conducting research on behavior and
respiratory effects of oxides of sulfur-aerosols mixtures. The first
task is to determine the interrelationship between S02 and sodium sulfate
or ammonium sulfate, and various physical environmental variables (humidity
and cold) on respiratory function of guinea pigs. The investigators are
presently completing studies on the threshold effect of S02/sodium
chloride aerosol at 80% R.H. and 22°C. The results indicate that a
certain fraction of the population studied is sensitive and responds to
the pollutant. The response does not appear to be dose-related.
42
-------
The second objective is to develop a quantitative, predictive model
for assessing the role of ammonia and physical environmental factors on
the oxidation of S02> S03, and SO. salts or acid aerosols. Mathematical
modeling of the aerosol system, including H2SO» and NH-, at concentrations
expected to exist in the lung have been performed to estimate the time
necessary for ammonia to react,with the HpSCL. The reaction times are
strongly dependent on the H?SO. mass concentration, ammonia concentration,
aerosol size distribution and relative humidity.
The third objective is to determine the respiratory physiologic
effect of. exposure to sulfates and/or acid aerosols on human volunteers
and to correlate their response to that observed in guinea pigs. Eight
volunteers have been studied. The functional measurements include: (1)
pulmonary flow resistance and compliance, (2) total respiratory resistance,
(3) maximal and partial expiratory flow, (4) closing volume and (5) lung
volume. There were no significant differences between the control and
exposed group when the data were analyzed. However, two individuals did
show an increase in resistance during the S02 - NaCl at high relative
humidity. The investigators in this project have just begun to study
patients with chronic respiratory disease. Three exposure modes will be
used: (1) S02 alone at high relative humidity (RH), (2) S02 - NaCl
aerosol at low R.H. and (3) S02 - NaCl aerosol at high R.H. The concen-
tration will be 1.0 ppm S02 ana 1.0 mg/m of NaCl.
Epidemic!ogical studies carried out by the Health Effects Research
Laboratory have indicated that levels of suspended sulfates associated
with certain adverse health effects were lower than the levels of sulfur
dioxide and total suspended particulate associated with the same health
effect. In addition, results of these studies indicate that suspended
sulfates are the pollutants most consistently associated with the aggrava-
tion of asthma. Research in this area is continuing and will focus on
ambient levels of sulfuric acid when reliable data on this pollutant
became available in sufficient volume to permit thorough study.
• In-Use Catalyst Research
The primary objective of the in-use catalyst vehicle study
being carried out by an EPA grant to the State of New York is to measure
the emission of sulfuric acid aerosol from a population of catalyst
vehicles as they accumulate mileage in normal use. At approximately
5,000 mile intervals, each vehicle will undergo a comprehensive emissions
test consisting of the following sequence: (1) a 1975 Federal emissions
test cycle (FTP), (2) a one-hour 50 mph steady cruise, and (3) a series
of up to five tests following a "sulfate driving cycle" developed by the
EPA. In addition to measuring carbon monoxide, hydrocarbons, nitrogen
43
-------
oxides, Op, and SOg, a dilution tunnel with isokinetic sample probes
will be used to collect filter samples for sulfuric acid and total
particulate mass measurements from each test segment. Analysis of
particulate sulfate mass is performed by the barium chloranilate (BCA)
method, and x-ray fluorescence for mass emission rates of ten selected
elements: lead, sulfur, phosphorous, platinum, calcium, silicon,
copper, aluminum, zinc, and iron. Fuel economy is measured by carbon
balance technique, and between test intervals by an in-line totalizing
fuel meter that will be installed on each vehicle. Tank fuel will be
collected at each test and analyzed for trace components, especially
sulfur. Prior to each test, each vehicle will be diagnostically
examined for tune-up condition, although no maintenance will be per-
formed. Most of the vehicles to be studied have been solicited from
organizations in the Albany area, but privately owned vehicles are being
incorporated to expand the population and assess personally owned
vehicular types.
The data collected from this study will be useful in determining
the emissions values to be used in modeling the sulfuric acid emission
rate from in-use catalyst vehicles. Several other correlations will
also be calculated, apparent, particularly the relation of sulfate
emissions to vehicular age, to fuel composition, and to carbon monoxide
and hydrocarbon emission rates, as all three of these factors are directly
related to catalyst activity. Testing is now under way; preliminary
data indicate very low HgSO, emissions of approximately .003 g/mi.
Regulated emissions, however, appear to be in excess of national standards;
this trend will be closely watched as the project continues.
44
-------
E. Office of Mobile Source Air Pollution Control/Washington, D.C.
The sulfuric acid emissions from current production and prototype
vehicles vary greatly as shown in Table xi.
The most important parameter in the formation of sulfuric acid
emissions appears to be the oxygen level in the exhaust gas to the
catalyst. The significant difference in sulfuric acid emissions
between the catalyst-equipped vehicles with and without air injection
is attributed to this oxygen level effect.
Current technology which has demonstrated low (below 10 mg/mi)
sulfuric acid emissions has also demonstrated the capability to certify
at the California emission levels of 0.9 HC, 9.0 CO, and 2.0 NO gm/mi.
About 20 percent of the estimated sales for 1976 in California nave non-
catalyst or catalyst without air injection control systems. Prototype
three-way catalyst-equipped vehicles, which also have low sulfuric acid
emissions, have been successfully operated to 50,000 miles at emission
levels below the California levels.
The most promising future sulfuric acid control technique is
control of the exhaust gas oxygen levels by improved fuel metering
systems and/or improved air injection systems. Oxidation catalyst,
three-way catalyst, and dual catalyst emission control systems are all
compatible with oxygen level control systems. Other important control
techniques may be developed as sulfuric acid control system development
programs are commenced. Most of the experimental work which has been
done to date has been related to the characterization of production
emission control systems, and relatively few data are available on
advanced systems, especially those designed with sulfuric acid control
in mind.
However, meeting standards more stringent than 0.9 HC, 9.0 CO, 2.0
NO gaseous emissions while controlling sulfuric acid emissions is not
precluded. The degree of difficulty in meeting more stringent HC and CO
emissions may be increased, depending on the control techniques used.
The advantages of improved air injection or improved fuel metering
are not very apparent until standards of 0.41 HC and 3.4 CO along with
HpSO, emission standards are required to be met. This is because air
injection is considered more likely to be used to meet these more stringent
HC and CO standards.
The lack of a finalized test procedure for sulfuric acid emissions
and the lack of a sulfuric acid emission standard have caused some
manufacturers to defer from starting serious development programs. The
test procedure is still being developed by EPA. Variability in test
results over the sulfuric acid test cycle, the SC7, has continued to be
45
-------
TABLE XI
Sulfuric Acid Emissions from Baseline
Program Vehicles
Type of Emission
Control System
Non-catalyst
Oxidation catalyst
w/o air injection
Oxidation catalyst
w/air injection
3-Way catalyst
Sulfuric Acid
Emissions, mq/mi*_
Range
0 to 3
0 to 118
0 to 123
0 to 2
Approximate Mean
1
8
30
1
*Milligrams per vehicle mile on the sulfuric acid test procedure, the
SC-7 with 300 ppm sulfur in the fuel. A milligram is one one-thousandth
of a gram, or about 0.00004 ounces.
46
-------
a problem for EPA and the manufacturers. This problem is expected to be
alleviated as more is learned about sulfuric acid emissions and as the
test procedure is standardized.
The following conclusions have been reached based on studies of the
available data:
• Control of sulfuric acid emissions from automobiles is still
in the infant stage of development. Many techniques
and approaches for controlling sulfuric acid emissions remain
to be explored.
• Domestic manufacturers are somewhat ahead of most foreign
manufacturers in preparing to meet sulfuric acid standards.
The clear message from the responses to EPA's request for
information on the studies of sulfuric acid emissions from the
majority of the foreign manufacturers was that they are waiting
to see what final test procedures and standards will be
proposed before they mount an effort to meet the standards.
Some of the foreign manufacturers do not even have the test
equipment needed to measure sulfuric acid emissions, let alone
have data and rational development plans, though in fairness,
some foreign manufacturers, particularly Toyota and Nissan,
have made significant contributions to the understanding of
sulfuric acid emissions despite the long lines of communication
between EPA and their research centers.
t Some manufacturers appear to be concerned about the variability
of test results, and will probably maintain that EPA has no
business setting standards until the test results are less
variable.
It is true that the test procedures for sulfuric acid testing
are relatively new and that some important parts of the feasible
certification procedures currently remain to be finalized
(especially the vehicle preconditioning). However, test result
variability for both gaseous emissions and sulfuric acid
emissions has always been a combination of both test procedure
variability (driver, sampling, analyses, etc.) and vehicle
variability (the vehicle does not perform exactly the same way
on each test). The manufacturers always strive to reduce
vehicle variability, and based on their comments and EPA's own
work, EPA strives to reduce test variability. This has always
been the case with gaseous emissions and will likely continue
to be the case with sulfuric acid emissions, although it is
true that the causes of vehicle variability during sulfate
testing are relatively unexplored now.
47
-------
• The analyses conducted in concert with this study resulted in
estimates as shown below of the sulfuric acid emission levels
that could possibly be met for various concurrent gaseous
emissions standards projecting from current emission control
knowledge.
At this point in time, the best estimates that can be given involve
the use of ranges. There are four basic reasons for this: (1) The
technology for controlling sulfuric acid emissions is just now being
considered for development. (2) There is variability in the test
results now and the test procedure is still not finalized. (3) Several
different technical approaches could be used to meet the gaseous emission
standards and their likely sulfuric acid emissions are not the same. (4)
Not many sulfuric acid emission data are available from advanced gaseous
emission control systems that were designed without consideration for
sulfuric acid emissions, let alone systems that were designed with
sulfuric acid emission control in mind.
As time goes by and the technology and understanding advances, the
ranges will, of course, narrow.
The deterioration factor assumed for the sulfuric acid emission
levels is 1.0 to reflect maximum sulfuric acid emissions at the 4,000
mile point. The lower bound of the sulfuric acid emissions in Table
VII represents the lowest technically achievable standard for sulfuric
acid at the given gaseous emission standard. Thus this maximum effort
for sulfuric acid control is assumed to force three-way catalyst technology
at the 0.41 gm/mi HC levels and no catalyst or low excess air-plus-catalyst
technology at the 0.9 gm/mi HC levels. This estimate would involve the
greatest effort on the part of the manufacturers. This also means that
it will be more difficult to certify at both the given gaseous and
sulfuric acid levels. The highest level in the range assumes only
moderate technological improvements and leaves more technological options
open to the manufacturer. This highest level also involves a much lower
risk of all manufacturers being able to certify. These ranges include
lead time, variability, and technological considerations; however, it
does not mean that all currently produced emission control systems of
each manufacturer will be capable of certification.
Table VII should not be interpreted to mean that low gaseous emission
levels cannot be achieved along with low sulfuric acid emissions.
Three-way catalysts have the potential to do both. Also, other technologies,
particularly limited oxidation catalyst approaches are still relatively
unexplored. What should be interpreted from Table XII is that it would
be more difficult for the manufacturers to certify vehicles at both
stringent sulfuric acid and gaseous emission standards.
48
-------
TABLE XII
Ranges of Sulfuric Acid Emission Levels at Various
Gaseous Emission Standards
Gaseous Emissions
g/mi, 1975 FTP
HC
1.5
1.5
0.9
0.9
0.41
0.41
0.41
0.41
CO
15
15
9.0
9.0
3.4
9.0
3.4
3.4
NO*
3.1
2.0
2.0
1.5
2.0
1.5
1.0
0.4
Sulfuric Acid Emissions
mg/mi, sulfate test cycle
H2S04
5-15
5-15
5-15
5-15
5-50*
5-50*
5-50*
5-50*
*The lead time for the introduction of three-way catalysts by all
manufacturers and the 50,000 mile durability of three-way catalysts
at these gaseous emission levels is uncertain.
49
-------
It should be recognized that, as with emission control systems for
regulated gaseous emissions, EPA does not dictate the control technology
to be used to control sulfuric acid emissions. That choice is left to
the individual vehicle manufacturers. EPA only establishes the level
that the manufacturers' vehicles are required to meet for each pollutant.
The general technical approaches now under study for controlling
sulfuric acid emissions appear to be improved fuel management, control
of oxygen level in the exhaust, and catalyst modifications. The
approaches listed above are similar to some of those also being pursued
for control of gaseous emissions control at more stringent gaseous
emission standards.
50
-------
III. DISCUSSION OF PROGRAM HIGHLIGHTS
The two events during the reporting period which most influenced
the priorities and pacing for the CRP's activities were, first, the
announcement by EPA in the spring of 1975 that the Agency was considering
a notice of proposed rulemaking for an automotive emission standard for
sulfate and, second, the subsequent announcement about one year later
that there would be no regulatory action at least for the 1979 model
year vehicles. The initial announcement of intent provided the impetus
for a heavy involvement of the Agency's emission characterization
resources toward development of a sulfate test cycle. This effort
resulted in a tentative test cycle for possible use by EPA's certification
group should an emission standard become effective.
Concurrent with the test cycle development was the continuation of
characterization of both regulated and nonregulated emissions of prototype
and production catalyst-equipped light-duty vehicles. Work conducted
under this portion of the CRP during the reporting period resulted in
data which showed the emissions of sulfuric acid from catalyst-equipped
vehicles to be substantially less than originally predicted: 1975
vehicles designed to conform to California standards (air-pump-equipped)
emitted approximately .035 g/mi H2SO-,; catalyst-equipped vehicles
designed to conform to Federal (43-state) standards emitted approximately
0.015 g/mi H9SOA. Details of these studies may be found in Supplements
I and III. * 4
In the fall of 1975, EPA participated in a General Motors roadway
experiment designed to determine sulfuric acid emissions factors and
resultant ambient air concentrations of sulfuric acid from a fleet
consisting entirely of air-pump-equipped catalyst vehicles designed to
meet 1975 California standards. Results of this dispersion experiment
which took place during October 1975, showed the vehicles' average
emission rate of sulfuric acid to be approximately .035 g/mi, confirming
earlier dynamometer test results. At the same time, results of ambient
measurements including SFg tracer studies indicated that the dispersion
model (EPA HIWAY Model) wnich had been previously employed to predict
near-roadway sulfuric acid concentrations overpredicted such concentrations
under the most adverse meteorological conditions. The tendency of the
model to over-predict concentrations near a line source, together with
the confirmation of dynamometer test data to show lower emissions of
H2$0. than had earlier been predicted, largely provided the basis for
EPA's decision in the spring of 1976 not to take action with regard to
establishing a motor vehicle sulfate emission standard for at least the
1979 model year vehicles.
During the General Motors sulfate dispersion experiment, measurements
of particle size of ambient particulate were made both inside a car on
the roadway and a short distance downwind of the roadway. These measure-
ments, together with concurrent determination of sulfuric acid levels,
led to the conclusion that the sulfuric acid emitted from the catalyst-
equipped vehicles in the study was predominately in the size range of 0.01
to 0.1 pm diameter. The contribution of near-roadway sulfuric acid from
catalyst-vehicles was found to be approximately 5 yg/m .
51
-------
The finding that catalyst-equipped vehicles can emit ultrafine
sulfuric acid aerosols may significantly affect the direction of EPA's
health effects research on sulfates -- sulfuric acid in particular.
Research now under way employs particles of sulfate/sulfuric acid in the
size range of 0.3 ym in diameter, which is the most prevalent form of
aged sulfate aerosol.in ambient air. However, the much smaller particle
of the in-roadway and near-roadway HpSO- emanating from catalyst-equipped
vehicles may have an entirely different action upon the human respiratory
system. It is hypothesized that this ultrafine aerosol may penetrate
deeper into the lung than the larger 0.3 ym respirable size sulfate
aerosol now being studied. More information is being gathered with
regard to the physical and chemical properties of the sulfuric acid
emitted from catalyst-equipped vehicles that is found near roadways.
This information, along with the development of technology for generating
and measuring ultrafine sulfuric acid aerosol will be employed in the
design of future toxicological and clinical health effects research.
In-roadway studies will also be conducted to assess the health risk of
commuter populations exposed to the ultrafine sulfuric acid aerosol.
New vehicles were used to collect data on sulfuric acid emissions
because: (1) Data could be gathered quickly for use by the Agency in
making decisions regarding regulation of emissions for those vehicles.
(The first available vehicles were employed which had little or no
mileage accumulation prior to testing). (2) The use of low-mileage
vehicles eliminates variables such as maintenance, type of fuel, and
operating mode which can significantly affect the volume and composition
of vehicular emissions.
In an effort to determine how emissions vary from new vehicles to
those actually operated by the consumer, and to determine ambient air
concentrations resulting from such vehicular emissions in the real
world, EPA is conducting several studies:
1. The Los Angeles Catalyst Study (LACS) has been in operation
since 1974 on a major freeway in Los Angeles to measure upwind
and downwind concentrations of many pollutants. Since the
meteorological conditions at this site are such that the
wind is perpendicular to the roadway a major portion of each
day, the vehicular contribution to the ambient air may be
calculated by subtracting levels of pollutants downwind
from those found upwind. Hi-vol data resulting from these
measurements show a statistically significant increase in
sulfates -- roughly 5 yg/m downwind of the freeway.
What portion of this increase may be attributed to catalyst-
equipped vehicles, heavy-duty vehicles, or artifact formation
on collection media is not yet established. Continuing
analysis of the data available, together with adjunct experiments
to identify the source of the sulfate contribution, are now in
progress. Recently developed sulfuric acid specific samplers
52
-------
will be employed at the site when available to determine what
portion of the sulfate concentration is sulfuric acid, and
the levels to which populations on and near the roadway would
be exposed.
In support of the LACS two separate studies were established
on unburned fuel: (1) the National Fuels Surveillance Network
(NFSF), and (2) the Unleaded Gasoline Enforcement Program. In
the NFSF, samples of all grades of gasoline from the ten EPA
regions were collected and analyzed for sulfur. Additional
samples from California were also collected in the San Francisco
and Los Angeles metropolitan areas over a three-month period
for subsequent sulfur analyses. In the United Gasoline Enforce-
ment Program, samples are collected and analyzed for the
regulated elements lead (Pb) and phosphorus (P), which are both
harmful to catalyst operation. Data were obtained on the number
of samples by region which exceeded the 0.05 g/mi regulation for
Pb .and the 0.005 g/mi regulation for P.
The ongoing quality assurance programs for the LACS and the
Fuels Program have maintained close control on the output data
quality. A combination of internal quality control procedures
during sampling and analysis, plus an active external audit
program, provide continuing assessment of data validity. A
short-term study has also been completed to determine the
reproducibility of LACS hi-vol measurements on a 24-hour basis.
Animal toxicology studies of sulfuric acid aerosol are under way by
EPA with both in vivo and in vitro systems; human clinical studies are
being planned. Experiments to date have employed aerosols with particles
in the size range of 0.3 m diameter most commonly found in ambient air.
To date, there are insufficient data from animal studies to show that
sulfuric acid at concentrations comparable to actual or projected ambient
levels evoke adverse biological responses. Studies of chronic exposure
and studies of effects of interaction between sulfuric acid and other
ambient air pollutants, however, are still in progress or in the planning
stages. At this time there is still insufficient information available
to determine conclusively whether sulfuric acid in the 0.3 m diameter
size range most common to ambient sulfate aerosol is a threat to public
health.
The findings from the GM dispersion study that sulfuric acid emitted
by catalyst vehicles may be an order of magnitude smaller in particle
size than aerosol which is "aged" (that is, dispersed over a period of
time in the ambient atmosphere) has spurred an interest in conducting
health effects research on sulfuric acid aerosol in the smaller particle
size range of 0.01 to 0.02 ym diameter. Such studies will not be initiated,
however, until (1) further investigation is made to identify both the
physical and chemical properties of roadway and near-roadway sulfuric
53
-------
acid aerosol resulting from catalyst vehicular emissions and the average
ambient concentrations, (2) reliable and accurate means of generating
sulfuric acid aerosol in the 0.01 to 0.02 ym diameter size range and
maintaining a given concentration level for laboratory experiments is
developed, and (3) reliable and accurate measurement techniques for
monitoring concentrations of the "ultrafine" aerosol are developed.
Until the required instrumental techniques are developed and
further information on the characterization and quantification of the
ambient ultrafine aerosol becomes available, health effects research
will continue to focus on the larger (approximately 0.3 ym) particle
size aerosol. Clinical studies of human exposure to this size particle
are still in the planning stage and are scheduled to be initiated during
FY 1977. Health effects research will be performed on the "ultrafine"
sulfuric acid aerosol as soon as the technology is available.
Sulfuric acid, though a major focus of the Catalyst Research
Program, has not been the only emission product of concern. When the
Catalyst Research Program was first initiated, there was considerable
concern over the possibility of platinum and/or palladium emissions from
the degradation of oxidation catalysts. Although these two noble metals
form the active components of the oxidation catalyst, very little was
known about health effects of the two metals.
Information from occupational exposure to platinum and palladium
gave cause for concern that any emission of platinum or palladium could
constitute a "new" environmental pollutant. Although the chemical
composition and concentrations of any platinum compounds emitted were
unknown, concern for public health spurred the initiation of a broad
program of health effects research on platinum and palladium with a
focus on platinum, which constituted the major portion of the catalyst
material. Efforts to determine the toxicity, carcinogenicity, mutagen-
icity, cytogenicity, allergic properties, and effects on immune response
were begun in FY 1975. Most research efforts concentrated on platinum
sulfate because it was predicted that soluble compounds would be more
likely to produce adverse health effects, and because sulfate concen-
trations were known to be present in exhaust from catalyst-equipped
vehicles.
Concurrently, with the health effects research, efforts to identify
and quantify noble metals both in exhaust and in environmental and
biological matrices were initiated. Studies of existing levels of
platinum in human populations and in environmental media (air, soil,
water), were undertaken to establish a pre-catalyst baseline for compari-
son with later data for emissions from automotive catalysts. Additional
research was directed toward improving analytical methodologies for
measuring low levels of platinum and palladium in a variety of matrices.
A conference was held in December 1975 to bring together those
involved in the many areas of platinum research undertaken by the CRP.
The purpose was to review progress made, to identify research gaps, and
54
-------
to set priorities for future research. Results reported at the conference
were as follows:
• Baseline studies showed that no reasonable quantities of
Pt existed in air, soil, or water.
• Occupational exposure levels were reported to be approximately
0.02 to 0.2 yg/m .
• Human burdens determined by examination of urine, blood, hair,
and feces showed no measurable Pt in any individual, though
pooled blood samples showed minute quantities.
• Autopsy data showed that a major proportion of individuals
studied had measurable amounts of Pt in varying types of
tissue.
3 3
• Exposure to 0.02 yg/m to 0.2 yg/m or higher levels can
result in measurable levels of Pt in urine.
Preliminary results from the GM study, reported by GM after the Pt
review conference, showed ambient concentrations of platinum as high as
0.03 yg/rn , a concentration which exceeds the lower values reported for
occupational levels.
Characterization of catalyst-equipped vehicular emissions showed no
measurable quantities of platinum in either the fine particulate or
gaseous fractions of exhaust; large particulate was found to contain
small amounts of platinum, but the platinum compound remained undetermined.
No accurate emission factors can as yet be calculated because analytical
methods needed to perform this work are not yet fully developed.
It has been shown that some platinum compounds can be methylated
under laboratory conditions via the same vitamin B,2 mechanism through
which mercury is methylated; consequently research should continue in
order to determine whether platinum emitted from catalyst vehicles,
however small in quantity, is biologically active.
Acute toxicological studies showed that the toxicity of platinum
compounds appears to be a function of the solubility of the compound.
Therefore, any process in the environment which might involve biotrans-
formation resulting in soluble platinum compounds is of concern. Chronic
and long-term health effects studies on platinum compounds, such as
carcinogenicity, are still under way. Results of these studies can be
important in influencing the research priorities.
Other emissions from catalyst-equipped vehicles are also under
study. Since a manganese compound is now being used as a substitute for
TEL, compounds which are likely combustion products of the manganese
additive are scheduled for toxicological evaluation during FY 1977.
Other new fuel additives which may affect catalyst emissions, and any
new catalyst formulations which employ elements or compounds for which
insufficient data exists to make a health effects assessment, will be
investigated. For example, health effects studies are planned in FY 77
on ruthenium which is under consideration for use in reduction catalyst
systems.
55
-------
APPENDIX A
Crosswalk Listing of FY 1975 Projects
by
Laboratory and Tasks
56
-------
FY 75 ROAP 21BCE
Health Effects Research Laboratory (RTP)
TASK
TASK OBJECTIVE
STATUS
en
•-J
005 Estimate no-effect level using mouse pulmonary
infectivity model (a) of appropriate Pt-group
metal compounds administered singly; and (b) of
base metal compounds administered in appro-
priate combination
006 Compare relative toxicities of Pt-group compounds
against Pb compounds using in vitro macrophage
system
007 Compare relative toxicities against Pb compounds
using in vitro conjunctiva! cell and respiratory
epithelial cell cultures -- of Pt-group compounds
008 Estimate no-effect level of Pt-grop metal compounds
using immediate and delayed allergic response in
animals
009 Compare relative cytogenicity against Pb compounds
using in vivo hamster system (a) of Pt-group
compounds (b) of base metal compounds
010 Determination of the relative mutagenicity of Pt
compounds by mammalian cell culture and plant
embryo techniques
Oil Compare relative toxicities against Pb compounds
using biochemical parameters (a) of Pt-group
compounds, (b) of base metal compounds
Ongoing
First year completed; second year cancelled due
to nonproductive results
Catalyst Program work terminated due to lack of
progress; some work on system continuing in
CSD/HERL/RTP
Ongoing
See Tasks 015 and 016
Ongoing
Completed
-------
TASK
TASK OBJECTIVE
STATUS
en
Co
012 Compare pulmonary carcinogen!city of Pt-group metal
compounds and of Pb compounds in association with
polynuclear aromatics using in vivo hamster system
014 Effects of chronic of intermittent exposure to low
levels of major catalyst attrition products or
their decay products on human pollutant burdens
015 Effects of Task 014 on irritation symptoms in humans
016 Assessment of subtle physiologic changes induced by
exposure to major catalyst attrition products or
their decay products, enzyme changes, immunologic
deficits, chromosomal aberrations
022 Comparative methyl ation chemistry of Pt-group
metals, selected base metals, and lead with sub-
sequent toxicological assessment of stable
metallic compounds
025 Analysis of animal tissue for platinum, palladium,
lead, and manganese
031 Public health impact of suspended particulate
sulfates
032 Public health impact of suspended particulate
sulfates
Ongoing
Completed
Never implemented; occupationally exposed subjects
not available for epidemic!ogic assessment due
to lack of cooperation by Pt refinery companies
Ongoing
Completed; further chemistry & toxicological
evaluation of methylated Pt compounds to be
done in combination FY 75-76 work
Completed
Lead responsibility HERL/RTP; ongoing outside CRP
Lead responsibility HERL/RTP; ongoing outside CRP
-------
TASK
TASK OBJECTIVE
STATUS
en
033 Analysis of tissue samples collected throughout
CHESS network to assess population pollutant burdens
of Pt, Pd, Ru, and Al
034 Clinical studies of human response to noble metals
035 Effect of controlled exposure to H2S04 aerosol
on immune response
036 Effect of particulate sulfates and noble metals
on human behavior
037 Effects of ambient exposure to selected chemical
particulates on the occurrence of carcinogenic or
mutagenic effects
038 Clinical studies of cardiopulmonary effect of
HpSO. aerosol
075 Toxicological evaluation of airborne respirable
particulates and mists
081 Development of sensitive biochemical and behavioral
indicators of trace substance exposure
082 Characterization and measurement of regulated sul-
fates and particulate emissions from in-use
catalyst vehicles - 1975 national standard
Completed; second phase "Research and Development of
Analytical Methods for Measuring Trace Element
Emission & Attrition Products on Mammalian Tissue"
ongoing
Never initiated.
Ongoing
Never initiated; animal work ongoing - see Task 081
Never initiated; see Task 012 for related effort
Ongoing
Ongoing
Ongoing
Ongoing
-------
TASK
TASK OBJECTIVE
STATUS
083 Analysis and evaluating photodynamic bioassay data
on organic extracts of participate atmospheric
pollutants collected by the National Air Sampling
Network
089 Tox'icological evaluation of emissions from diesel
engines
090 Study the effects of inhaled sulfates above and
in combination with S02 on pulmonary defense
mechanisms
Ongoing
Ongoing; joint effort between HERL and ESRL
Ongoing
-------
FY 75 ROAP 26AAE
Health Effects Research Laboratory (RTP)
TASK
TASK OBJECTIVE
STATUS
025 Exposure of tissue culture systems to pollutants
under conditions simulating physiologic studies
of lung and conjunctiva
026 Assessment of fuel additive emissions toxicity
via- selected assays of nucleic acid and protein
synthesis
Initial work nonproductive;being continued with
some improvement of set up of system in CSD/HERL/RTP
Completed
-------
FY 75 ROAP 21BCE
Environmental Monitoring and Support Laboratory
TASK
TASK OBJECTIVE
STATUS
ro
023 Monitor air quality along a major highway in southern
California. Utilizing existing methods, analyze water
soluble sulfate, lead, and TSP at 4 sites and CO at
1 or 2 sites. Additionally, 1 meteorology station
will be established.
024 Monitor air quality along a major highway in southern
California. Utilizing existing methods, analyze
water soluble sulfate, lead, and TSP at 4 sites.
Additionally, 1 meteorology station will be establish-
ed and total motor vehicle count (not vehicle mix)
at 1 site will be made.
055 Commercial fuels collection and analysis.
056 Standardized methods for measurement of and
collection and analysis of particulate sulfates
057 Quality assurance guidelines for measurement
methods applicable to mobile sources and fuels
and fuel additives
058 Development of standard reference materials for
emissions from mobile sources and fuels and fuel
additives
059 Collection and analysis of samples at selected
sites including sulfates, trace metals, and nitrates
060 Collection and analysis of samples at selected
sites, including sulfates, trace metals, and nitrates
Completed
Completed
Ongoing
Ongoing
Ongoing
Ongoing
Ongoing
Ongoing
-------
CO
TASK
061
062
063
064
065
066
067
068
069
TASK OBJECTIVE
Determination of various pollutants in TSP, fine
parti culates, and soil samples
Maintain national sample bank and implement data
acquisition and processing system
Expand network for collection and analysis of fuel
samples specifically in southern California in support
of catalyst field program
Survey and evaluate analytical methods pertinent to
Tasks 065 and 066
Standardized methods for measurement of exhaust and
ambient sul fates
Standardized methods for noble metals and catalyst
support materials
Develop standard reference materials for mobile
source pollutants measurements
Conduct interlatoratory performance surveys for
sul fate and catalyst- related parti culates
Monitor air quality along a major highway in southern
California. Utilizing existing methods analyze water
soluble sulfate, lead, & TSP at 4 sites and CO at 1 or
2 sites. Additionally, 1 meteorology station will be
established and total motor vehicle count (not
vehicle mix) at 1 site will be made.
STATUS
Ongoing
Ongoing
Ongoing
Completed
Ongoing
Ongoing
Ongoing
Ongoing
Completed
-------
TASK
TASK OBJECTIVE
STATUS
CT>
070 Inhouse & field evaluation of existing analytical
sampling and analysis schemes pertinent to the
determination of pollutants emanating from catalyst-
equipped automobiles
071 Same as Task 069 with the addition of traffic mix
data, TSP, size distribution at 1 station, 1 or 2
additional hi vols at a distance away from highway
and of TSP samples.
072 Handling, validation, and interpreting data from
southern California, and complex source studies,
including report writing and computer costs
073 Monitor complex sources such as street canyons,
shopping centers, and parking garages in southern
California (e.g. Disneyland) for mobile source
pollutants
080 Assist in sampling and analysis, baseline studies
085 Provide sample handling protocol for catalyst metal
analysis of a massive dust sample collected at the
LACS site
086 Develop and implement an operational system for
evaluating and collaboratively testing methods
recommended for air pollution
087 Perform x-ray fluorescence analysis of samples
from the catalyst study
088 Develop an intervention time series .model for the
Los Angeles Catalyst Study
Completed; FY 76 task specifically related to NH.
and H2SO. emanating from catalyst-equipped vehicles
Ongoing
Ongoing
Ongoing
Completed
Completed
Completed
Completed
Ongoing
-------
FY 75 ROAP 26AAE
Environmental Monitoring and Support Laboratory
TASK
TASK OBJECTIVE
STATUS
003 I Promulgation of regulations for registration of
fuels and fuel additives
004 I Initial registration of designated additives and
fuels
Ongoing
Ongoing
en
tn
-------
FY 75 ROAP 21BCE
Environmental Sciences Research Laboratory
TASK
001
002
003
004
027
028
029
030
039
040
041
TASK OBJECTIVE
Study gaseous and particulate emissions - California
1975 model year vehicles
Characterize particulate emissions, prototype
catalyst cars
Visibility effects - catalyst and non-catalyst
advanced prototype systems
Develop methodology to determine the effect of
gasoline composition and additives on emissions
control device performance
Validation of highway gaseous dispersion model for
simulation of air quality
Conduct wind tunnel experiments to evaluate current
highway model for gaseous emissions; monitor Tasks
029 and 30, prepare reports
Evaluate applicability of highway gaseous dispersion
model for mobile source particulate and aerosol
species
Develop and evaluate dispersion model for complex
mobile sources
Analysis of "unusual" emissions from current and
future mobile sources — impact of control devices
Atmospheric chemistry of acid aerosols
Personal exposure meters for suspended sul fates
STATUS
Ongoing
Ongoing
Completed
Completed
Completed
Not initiated; work plans in process to do study
for derived diffusion coefficients near highway
wake structure
Ongoing
Not initiated
Ongoing
Ongoing
Ongoing
CTl
-------
TASK
TASK OBJECTIVE
STATUS
042
043
044
045
046
048
049
050
052
Adapt methods for S02 and SO-, to mobile source
emissions measurement
Develop methods for total sulfur, sulfate, and
other sulfur compounds in particulate emissions
from mobile sources
Characterize particulate emissions from production
catalyst-equipped cars
Operate dynamometer and test equipment in support of
catalyst-related emissions method development and
characterization studies
Procure test and data acquisition equipment in
support of catalyst-related emissions testing program
Particle size, chemical characterization, formation
and growth rates of scattering roadside aerosols
Study of scavenging of S02 and sulfates by surfaces
near roadways
Smog chamber study of S02 photo-oxidation to SO.
under roadway conditions
Develop portable device for collection of sulfate
and sulfuric acid
Ongoing
Ongoing
Ongoing
Ongoing
Ongoing
CRP work completed at LACS site
Completed
Ongoing
Ongoing
-------
TASK
TASK OBJECTIVE
STATUS
en
CO
053 Develop laboratory method for collected sulfate
and sulfuric acid aerosols
054 Fabricate 12 portable samplers for measurement
of sulfuric acid
078 Characterize particulate emissions - prototype
catalyst cars
079 Characterization of roadside aerosols - particle
size, chemical composition, formation, growth, and
light scattering of roadside aerosols
089 lexicological evaluation of emissions from diesel
engines
Ongoing
Ongoing
Ongoing
Cancelled; ongoing in ESRL
Ongoing; joint effort between ESRL and HERL/RTP
-------
FY 75 ROAP 26AAE
Environmental Sciences Research Laboratory
TASK
TASK OBJECTIVE
STATUS
CTi
007 Protocol to characterize gaseous emissions as a
function of fuel and additive composition -
prototype vehicles
008 Validate engine dynamometer test protocol for
control system performance
009 Protocol to characterize particulate emissions
as a function of fuel and additive composition
010 Operate engine dynamometer test facility
Oil Acquire equipment, provide contract services;
operators, set-up, and maintenance personnel
012 Characterize current vehicle gaseous emissions
013 Characterize rotary engine emissions as a function
of lubricant composition and fuel/lubricant
interaction. Develop test protocol for nonregulated
emissions therefrom
014 Characterize alternate power systems (rotary)
gaseous emissions
017 Characterize particulate emissions - alternate
power systems (rotary). Develop protocol.
Completed
Terminated, draft unacceptable; no present
corresponding task
Terminated, no present corresponding task
Terminated, no present corresponding task
Ongoing
Completed
Cancelled
Cancelled
Cancelled
-------
TASK
TASK OBJECTIVE
STATUS
—i
o
018 Characterize detailed gaseous and particulate
emissions - non-catalytic advanced control
prototype
019 Characterize diesel gaseous and particulate emissions
021 Develop predictive model for assessing effects of
gasoline composition and additives on exhaust
species in combustion reaction studies
023 Exploratory investigation of toxic and carcinogenic
partial combustion products from various nitrogen-
containing fuel components and gasoline additives
024 Exploratory investigation of the toxic and carcin-
ogenic partial combustion product from various
oxygen- and sulfur-containing fuel components and
gasoline
028 Chemical ionization mass spectrometry of volatile
lanthanide chelates; application of CIMS to analysis
of metal chelates and other pollutants
Ongoing
Ongoing
Completed
Completed
Completed
Ongoing
-------
FY 75 ROAP 21BCE
Health Effects Research Laboratory (Cincinnati)
TASK
TASK OBJECTIVE
STATUS
013
074
075
076
077
Toxicologic evaluation of whole engine exhausts
from catalytic-controlled systems
Toxicology of respirable sulfur compounds
Toxicological evaluation of airborne respirable
particulates and mists
Comparative inhalation toxicology specific to
catalyst non-regulated emissions
Long-term, low-level, comparative inhalation
toxicology specific to non-regulated emissions
from oxidation catalysts
Completed
Ongoing
Ongoing
Ongoing
Ongoing
-------
APPENDIX B
List of Supplements
I. Health Effects Research Laboratory/Research Triangle Park, N.C.
II. Environmental Monitoring and Support Laboratory/Research Triangle
Park, N.C.
III. Environmental Sciences Research Laboratory/Research Triangle
Park, N.C.
IV. Health Effects Research Laboratory/Cincinnati, Ohio
V. Office of Mobile Source Air Pollution Control, Office of Air
and Waste Management/Washington, D.C.
. 72
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/3-?7-008
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
SECOND ANNUAL CATALYST RESEARCH PROGRAM REPORT
Summary
5. REPORT DATE
January 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Criteria and Special Studies Office
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research and Development
Research Triangle Park, N.C. 27711
10. PROGRAM ELEMENT NO.
1AA002
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Annual Program Status 6/74-12/
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Annual Report to Congress
16. ABSTRACT
This report constitutes the second Annual Report of the ORD Catalyst
Research Program required by the Administrator as noted in his testimony
before the Senate Public Works Committee on November 6, 1973. It includes
all research aspects of this broad multi-disciplinary program including:
emissions characterization, measurement method development, monitoring,
fuels analysis, toxicology, biology, epidemiology, human studies, and
unregulated emissions control options. Principal focus is upon catalyst-
generated stulfuric acid and noble metal particulate emissions.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Catalytic converters
Sulfuric acid
Desulfurization
Catalysts
Sulfates
Sulfur
Health
Automotive emissions
Unregulated automotive
emissions
Health Effects (public)
13F, B
06 T
14 B
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
21. NO. OF PAGES
81
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
73
-------
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Technical Information Staff
Cincinnati, Ohio 45268
OFFICIAL BUSINESS
PENALTY FOR PRIVATE USE. S3OO
AN EQUAL OPPORTUNITY EMPLOYER
POSTAGE AND FEES PAID
U S ENVIRONMENTAL PROTECTION AGENCY
EPA 335
Special Fourth-Class Rate
Book
If your address is incorrect, please change on the above label;
tear off; and return to the above address.
If you do not desire to continue receiving this technical report
series, CHECK HERE Q; tear off label, and return it to the
above address.
------- |