EPA 600/3 75 OlOh
September 1975
Ecological Research Series
INUAL CATALYST RESEARCH PROGRAM REPORT
APPENDICES
Volume VII
lealth Effects Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
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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 Information Service, Springfield, Virginia 22161.
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EPA-600/3-75-010h
September 1975
ANNUAL CATALYST RESEARCH PROGRAM REPORT APPENDICES
Volume VII
by
Criteria and Special Studies Office
Health Effects Research Laboratory
Research Triangle Park, North Carolina 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AMD DEVELOPMENT
HEALTH EFFECTS RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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CONTENTS
CATALYST RESEARCH PROGRAM ANNUAL REPORT
EXECUTIVE SUMMARY . .
INTRODUCTION
PROGRAM SUMMARY . . .
TECHNICAL CONCLUSIONS
Page
1
5
7
17
DISCUSSION 22
REFERENCES 45
APPENDICES TO CATALYST RESEARCH PROGRAM ANNUAL REPORT
VOLUME 1
A. OFFICE OF AIR AND WASTE MANAGEMENT
Al. AUTOMOTIVE SULFATE EMISSIONS . .
1
53
A2. GASOLINE DE-SULFURIZATION - SUMMARY
A2.1 Control of Automotive Sulfate Emissions
through Fuel Modifications 55
A2.2 Production of Low-sulfur Gasoline 90
VOLUME 2
B. OFFICE OF RESEARCH AND DEVELOPMENT
Bl. FUEL SURVEILLANCE
B1.1 Fuel Surveillance and Analysis
B1.2 The EPA National Fuels Surveillance
Network. I. Trace Constituents in Gasoline
and Commercial Gasoline Fuel Additives •
B2. EMISSIONS CHARACTERIZATION
19
44
B2.1 Emissions Characterization Summary ....
B2.2 Sulfate Emissions from Catalyst- and Non-
catalyst-equipped Automobiles 45
B2.3 Status Report: Characterize Particulate
Emissions - Prototype Catalyst Cars .... 68
B2.4 Status Report: Characterize Particulate
Emissions from Production Catalyst Cars . . 132
B2.5 Status Report: Survey Gaseous and Particu-
late Emissions - California 1975 Model Year
Vehicles 133
B2.6 Status Report: Characterization and Meas-
urement of Regulated, Sulfate, and Particu-
late Emissions from In-use Catalyst Vehicles -
1975 National Standard 134
B2.7 Gaseous Emissions Associated with Gasoline
Additives - Reciprocating Engines. Progress
Reports and Draft Final Report - "Effect of
Gasoline Additives on Gaseous Emissions". • 135
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VOLUME 3
Page
B2.8 Characterization of Gaseous Emissions from
Rotary Engines using Additive Fuel -
Progress Reports 220
B2.9 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Oxygen- and Sulfur-
containing Additives 232
B2.10 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Various Nitrogen-
containing Additives 233
B2.11 Status Report: Characterize Diesel Gaseous
and Particulate Emissions with Paper "Light-
duty Diesel Exhaust Emissions" 234
B2.12 Status Report: Characterize Rotary Emissions
as a Function of Lubricant Composition and
Fuel/Lubricant Interaction 242
B2.13 Status Report: Characterize Particulate
Emissions - Alternate Power Systems (Rotary) . .243
B.3 Emissions Measurement Methodology
B3.1 Emissions Measurement Methodology Summary ... 1
B3.2 Status Report: Develop Methods for Total
Sulfur, Sulfate, and other Sulfur Compounds
in Particulate Emissions from Mobile Sources ... 2
B3.3 Status Report: Adapt Methods for SO2 and SO3
to Mobile Source Emissions Measurements 3
B3.4 Evaluation of the Adaption to Mobile Source
SO7 and Sulfate Emission Measurements of
Stationary Source Manual Methods 4
B3.5 Sulfate Method Comparison Study. CRC APRAC
Project CAPI-8-74 17
B3.6 Determination of Soluble Sulfates in CVS
Diluted Exhausts: An Automated Method 19
B3.7 Engine Room Dilution Tube Flow Characteristics- • 41
B3.8 An EPA Automobile Emissions Laboratory 52
B3.9 Status Report: Protocol to Characterize Gaseous
Emissions as a Function of Fuel and Additive
Composition - Prototype Vehicles 89
B3.10 Status Report: Protocol .to Characterize Particu-
late Emissions as a Function of Fuel and Additive
Composition 90
B3.11 Interim Report and Subsequent Progress Reports.
Development of a Methodology for Determination
of the Effects of Diesel Fuel and Fuel Additives
on Particulate Emissions 192
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Page
B3.12 Monthly Progress Report #7: Protocol to
Characterize Gaseous Emissions as a Function
of Fuel and Additive Composition 200
B3.13 Status Report: Validate Engine Dynomometer Test
Protocol for Control System Performance 218
B3.14 Fuel Additive Protocol Development 221
B3.15 Proposed EPA Protocol: Control System
Performance 231
VOLUME 4
B3.16 The Effect of Fuels and Fuel Additives on Mobile
Source Exhaust Particulate Emissions 1
VOLUME 5
B3.17 Development of Methodology to Determine the
Effect of Fuels and Fuel Additives on the Perform-
ance of Emission Control Devices 1
B3.18 Status of Mobile Source and Quality Assurance
Programs 260
VOLUME 6
B4. Toxicology
B4.1 Toxicology: Overview and Summary 1
B4.2 Sulfuric Acid Effect on Deposition of Radioactive
Aerosol in the Respiratory Tract of Guinea Pigs,
October 1974 38
B4.3 Sulfuric Acid Aerosol Effects on Clearance of
Streptococci from the Respiratory Tract of Mice.
July 1974 63
B4.4 Ammonium and Sulfate Ion Release of Histamine
from Lung Fragments 89
B4.5 Toxicity of Palladium, Platinum and their
Compounds 105
B4.6 Method Development and Subsequent Survey
Analysis of Experimental Rat Tissue for PT, Mn.
and Pb Content, March 1974 128
B4.7 Assessment of Fuel Additives Emissions Toxicity
via Selected Assays of Nucleic Acid and Protein
Synthesis 157
B4.8 Determination of No-effect Levels of Pt-group
Base Metal Compounds Using Mouse Infectivity
Model, August 1974 and November 1974 (2
quarterly reports) 220
B4.9 Status Report: "Exposure of Tissue Culture
Systems to Air Pollutants under Conditions
Simulating Physiologic States of Lung and
Conjunctiva" 239
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Page
B4.10 A Comparative Study of the Effect of Inhalation of
Platinum, Lead, and Other Base Metal Compounds
Utilizing the Pulmonary Macrophage as an Indicator
of Toxicity 256
B4.11 Status Report: "Compare Pulmonary Carcinogenesis
of Platinum Group Metal Compounds and Lead Com-
pounds in Association with Polynuclear Aromatics
Using hn vivo Hamster System 258
B4.12 Status "Report: Methylation Chemistry of Platinum,
Palladium, Lead, and Manganese 263
VOLUME 7
B.5 Inhalation Toxicology
B5.1 Studies on Catalytic Components and Exhaust
Emissions 1
B.6 Meteorological Modelling
B6.1 Meteorological Modelling - Summary 149
B6.2 HIWAY: A Highway Air Pollution Model 151
B6.3 Line Source Modelling 209
B.7 Atmospheric Chemistry
B7.1 Status Report: A Development of Methodology to
Determine the Effects of Fuel and Additives on
Atmospheric Visibility 233
Monthly Progress Report: October 1974 255
B7.2 Status Report: Develop Laboratory Method for Collec-
tion and Analysis of Sulfuric Acid and Sulfates . • • 259
B7.3 Status Report: Develop Portable Device for Collection
of Sulfate and Sulfuric Acid 260
B7.4 Status Report: Personal Exposure Meters for
Suspended Sulfates 261
B7.5 Status Report: Smog Chamber Study of SO2
Photo-oxidation to SOU under Roadway
Condition 262
B7.6 Status Report: Study of Scavenging of SO_ and
Sulfates by Surfaces near Roadways 263
B7.7 Status Report: Characterization of Roadside
Aerosols: St. Louis Roadway Sulfate Study 264
B7.8 Status Report: Characterization of Roadside
Aerosols: Los Angeles Roadway Sulfate Study • • • 269
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Page
VOLUME 8
B.8 Monitoring
B8.1 Los Angeles Catalyst Study. Background Pre-
liminary Report
B8.2 Los Angeles Catalyst Study; Summary of Back-
ground Period (June, July, August 1974}
B8.3 Los Angeles Catalyst Study Operations Manual
(June 1974, amended August 1974)
B8.4 Collection and Analysis of Airborne Suspended
Particulate Matter Respirable to Humans for
Sulfates and Polycyclic Organics (October 8, 1974).
1
13
33
VOLUME 9
B.9 Human Studies
.194
1
B9.1 Update of Health Effects of Sulfates, August 28, 1974.
B9.2 Development of Analytic Techniques to Measure
Human Exposure to Fuel Additives, March 1974 .... 7
B9.3 Design of Procedures for Monitoring Platinum
and Palladium, April 1974 166
B9.4 Trace Metals in Occupational and Non-occupation-
ally Exposed Individuals, April 1974 178
B9.5 Evaluation of Analytic Methods for Platinum and
Palladium 199
B9.6 Literature Search on the Use of Platinum and
Palladium 209
B9.7 Work Plan for Obtaining Baseline Levels of Pt
and Pd in Human Tissue 254
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Appendix B5.1
ENVIRONMENTAL TOXICOLOGY RESEARCH LABORATORY
NATIONAL ENVIRONMENTAL RESEARCH CENTER
CINCINNATI, OHIO
STUDIES ON CATALYTIC COMPONENTS .AND EXHAUST EMISSIONS
Issued August, 1974
by
The Staff of the ETRL
J. F. Slsri., Director
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INTRODUCTION
Wellington Moore, Jr.
In July, 1973, the Division of Health Effects instructed the ETRL
to reprogram ROAP 21 AFK with major emphasis on the toxicologic assessment
of catalytic attrition products and automotive emissions which had
passed through the oxidization catalyst. Interest in the biological
effects of the noble metals (platinum [Pt] and palladium [Pd]) resulted
from the decision by the automotive manufacturers to use these metals in
the catalytic converter. These converters are designed to reduce the
concentrations of carbon monoxide (CO) and hydrocarbons (HC) in the
exhaust stream by oxidizing them into carbon dioxide and water. The
control of the concentrations of CO and HC in automotive emissions is
necessary in order for light-duty vehicles to comply with the CO and HC
emission standards set forth in the Clean Air Amendments of 1970. With
the use of Pd and Pt in automotive catalytic converters, there is the
possibility that some of the material will be emitted to- the atmosphere
or enter into other segments of the environment following degradation or
disposal of worn-out converters.
At the present time, the author is not aware of any information
concerning the chemical form of Pd or Pt which may be emitted in the
exhaust. It can be speculated that the attrition products from the
catalyst could include: 1) paniculate composed of the metals combined
with substrate material; 2) different chemical forms of Pd and Pt. A
survey of the literature indicated that there was very little information
on the toxicology of chemical forms of Pt or Pd which might be expected
-------
to occur following use of these metals in the catalyst. Likewise, there
was no information on the inhalation exposure of animals to exhaust from
automobiles containing a catalyst in the exhaust train.
The CTRL research effort was divided into two major segments: 1)
toxicological studies on catalytic metals associated with the oxidation
catalyst; 2) assessment of the biological effects of automotive emissions
which have passed through the oxidative catalytic converter.
In the noble metal studies, the soluble forms of Pd and Pt have
been used in order to ascertain some of the basic toxicological and
metabolic aspects. It is realized that the availability and metabolism
of other chemical forms or substrate material containing Pd or Pt may be
different.
It should be emphasized that ETRL has been studying the biological
effects of the noble metals for less than a year and the data should be
considered as preliminary in nature. The impact of any metal upon a
biological system is complex; however, these findings should serve as a
basis for additional research in defining the impact of the use of these
metals upon the environment. This report presents data on the ETRL
studies. A number of these studies have been submitted for publication
in the open literature.
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TOXICOLOGICAL STUDIES OF PALLADIUM AND PLATINUM
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BIOLOGICAL FATE OF 103pd IN RATS FOLLOWING DIFFERENT ROUTES OF EXPOSURE
W. Moore, Jr., D. Hysell, W. Crocker and J. Stara
It is possible that Pd used in the catalytic converter may appear
in the environment if attrition or degradation of the catalytic bed
occurs. The major routes of exposure to humans would be through inhalation
and ingestion. The purpose of this study was to determine the influence
of different routes of exposure upon absorption, tissue distribution and
excretion. Placental transfer was determined following intravenous
administration.
METHODS
Animals and Treatments
The outbred albino rats (Charles River CD-I strain) used in this
study were maintained on a commercial diet '(Purina Lab Chow) and tap
water ad libitum except where otherwise noted. The three treatment
groups consisted of:
1. Intratracheal administration
Ten fasted male rats, 180-200 g, were anesthetized with pento-
barbital sodium and placed in dorsal recumbency. The trachea was isolated
through a ventral midline cervical incision and blunt dissection of the
overlying masculature. 103PdCl2 (25 yCi in 0.1 ml saline) was injected
intratradically with a Ice tuberculin syringe and 5/8 in., 25 ga needle.
After the incision was closed, the animals were maintained in hanging
wire cages for 104 days to determine whole body retention of the
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2. Oral administration
Twenty fasted male rats, 180-200 g, were lightly anesthetized
with ether and given 25 yCi of 103PdCl2 in 0.2 ml saline by stomach
tube. Ten rats were placed in metabolism cages for collection of 24 hr.
urine and fecal samples to determine routes of excretion. The other ten
rats were sacrificed 24 hr. after dosage to establish organ distribution
of the PdCl2.
Fifteen nonfasted suckling rats, 30 g were given a single dose
of 103PdCl2 (25 jjCi in 0.2 ml saline) by stomach tube. These animals
were maintained to compare their retention of Pd with that of the adult
rats.
3. Intravenous administration
Twenty male rats, 180-200 g, were given 25 yCi PdCl2 in 0.1 ml
saline intravenously (iv) in a tail vein with a 1 cc tuberculin syringe
and 5/8 in., 25 ga. needle. Ten were sacrificed 24 hr. later for organ
distribution; ten rats were placed in metabolism cages fol- collection of
24 hr. samples of urine and feces and subsequent determination of whole
body retention. Thirteen female rats (16 days pregnant) were given 25
105PdCl iv and maintained in metabolism cages for collection of feces
and urine. They were sacrificed 24 hr. after dosage to determine organ
distribution and placental transfer of the 1^3PdCl_. An additional
group of 8 female rats were given 25 uCi PdCl iv within 24 hr. post-
parturition. The mothers and litters were maintained 25 days to determine
if the *03pd was transferred to the young via the mother's milk.
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Sacrifice and Tissue Sampling
All rats were euthanatized with an overdose of chloroform anesthesia.
Samples collected routinely were blood, heart, lung, liver, kidney,
adrenal, pancreas, abdominal fat, spleen, skeletal muscle, bone, brain,
and testicle from males, ovary from females. In the pregnant females,
4 placentas, 4 fetuses, and a pooled sample of fetal livers were also
saved. In the young rats from the milk transfer study, lung, liver,
kidney, bone, and spleen were saved. Tissue samples were placed in
preweighed glass vials for counting.
Radioactive Determinations
103PdCl2, which has a half-life of 17 days, was used in all the
studies. Immediately after dosing, whole body gamma counts were made on
all animals used in the retention studies. The animals were counted daily
for the first few days and then every other day for the duration of the
experiment. A 200-channel gamma spectrometer with a 5 in. Nal (Tl) crystal
was used for whole body counts. Tissue, urine, and feces-samples were
counted in a well-type refrigerated scintillation spectrometer.
Whole Body Retention
Analysis of the data for whole body retention of 103Pd following a
single exposure disclosed that the route of administration of the dose
significantly affected whole body retention. The percent of ^^Pd retained
with time in the rat following three different routes of administration is
presented in Figure 1. Following oral dosing, the retention curve
declined very rapidly during the first 3 days to about 0.4% of the initial
dose. The initial rapid clearance is attributed to passage of the non-
absorbed 103pdi through the gastrointestinal tract. Extrapolation of the
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-Suckling Rat
Oral
Adult
— Intratracheally
12 16 20 24 28 32" 36
Days After Dosing
Fig. 1. Whole body retention of 103Pd in adult rats
following oral, iv, and intratracheal admin-
istration. Also shewn is whole body retention
of 103pd in suckling rats following oral
administration.
7
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second component of the retention curve to the intercept indicated that
the absorption was less than 0.5% of the initial dose. Retention of
1"'?d by the suckling rats following oral administration was similar to
that of the adults; however, the amount absorbed and retained with time
was significantly higher.
The amount of 03Pd retained following intratracheal dosing was
significantly higher than that for oral dosing and also significantly
less than that for iv dosing. The greatest amount of Pd retained
with time occurred following iv administration. Approximately 10% of
the initial iv dose was retained at 76 days when the whole body counting
was discontinued.
Excretion
Radioactive counts of 24 hr. urine and feces samples from the rats
receiving the 103Pd orally showed that almost all of the 103Pd was
initially eliminated in the feces and only a trace amount was excreted
in the urine (Figure 2). With iv administration, 103Pd was eliminated
both in the urine and feces in similar quantities. Toward the end of
the study, urinary excretion exceeded fecal excretion.
Tissue Distribution
The distribution and concentration of Pd was determined for
different tissues following oral and iv dosing. Twenty-four hours after
oral dosing, detectible quantities of 103Pd were found only in the
kidney and liver. The concentration in the kidney was much greater than
that in the liver. Twenty-four hours after iv dosing, 1^3Pd was found
in all the tissues analyzed with the higher concentrations, in descending
order, occurring in the kidney, spleen, liver, adrenal, lung, and bone,
respectively.
8
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9
-------
The rats used in the whole body retention study were sacrificed 104
days post-exposure and the tissues counted. No significant amount of
*^ Pd was found in any of the tissues from the group receiving the oral
dose. In the iv dosed rats, the higher concentrations of 1"^Pd were
found in the spleen, kidney, liver, lung, and bone. For the intra-
tracheally dosed rats, the lung contained the most ^u^Pd followed by the
kidney, spleen, bone, and liver.
Maternal/Fetal Uptake
During the 24 hr. period, the pregnant rats excreted 44.2% of the
initial iv dose. The amount excreted by the pregnant rats was higher
than the amount excreted by the fasted adult male rats during the first
24 hr. period. The magnitude of the difference in J03Pd concentration
among the maternal organs and the fetuses* is best shown by the counts
per gram of tissue (Table 1).
The pattern of distribution and concentration of *O^Pd in maternal
organs was similar to that previously found in the whole, body iv experiment.
Most of the fetuses (35) contained a small amount of *-®*Pd, and the mean
value for these fetuses is given in Table 1. However, radioactive
counts for 17 fetuses from 5 litters was not significantly higher than
background counts. The same pattern of results was obtained for the
fetal livers. The amount of 103pd found in the fetuses indicated that
Pd does not readily move across the placental barrier in the rat.
The retention of l"3Pd by the post-parturient dams and pups with
time, following a single iv exposure is shown in Figure 3. It is evident
10
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Table 1. Pd in Maternal Organs and Fetuses
Tissue
Maternal organ
Blood
Lung
Liver
Kidney
Bone
Ovary
Placenta
Fetus
Fetal liver
Nfean Counts /g
3,654
29,211
319,153
588,479
18,351
29,625
58,321
757
1,429
11
-------
1C?
10
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Adult Female Rats
Suckling Offspring
8 12 16 20 24
Days After I V Dosing
28
Pig. 3. Whole body retention of 103Pd in nursing female
fats following i.v. administration and uptake of
XUJPd in suckling young via the milk.
12
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that a small amount of the *"*Pd was passed to the young via the milk.
Ttoenty-five days after dosing of the dams, the suckling rats were sacrificed
and lung, liver, kidney, bone, and spleen taken for analysis. A very
small amount of lO^Pd (10-50 counts/gram tissue) was found in the tissues.
The bone had the highest level of activity followed by the kidney; spleen,
lung, and; liver.
13
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BIOLOGICAL FATE OF 191Pt IN RATS FOLLOWING DIFFERENT ROUTES
OF EXPOSURE
W. Moore, Jr., D. Hysell, W. Crocker and J. F. Stara
Because Pt may enter various media, the purpose of this study-was to
determine the significance of different routes of exposure upon retention,
tissue distribution, and excretion. Placental transfer was determined
following intravenous administration.
METHODS
Animals and Treatments
The outbred albino rats (Charles River CD-I strain) used in this
study were maintained on a commercial diet (Purina Lab Chow) and tap
water ad libitum except where otherwise noted. The three treatment groups
consisted of:
1. Intratracheal administration
Fourteen fasted male rats, 180-200 g, were anesthetized with
pentobarbital sodium and placed in dorsal recumbency. The trachea was
isolated through a ventral midline cervical incision and blunt dissection
of the overlying musculature. 191Pt (25 nCi in 0.1 ml saline) was injected
intratracheally with a 1 cc tuberculin syringe and 5/8 in., 25 ga. needle.
After the incision was closed, the animals were maintained in hanging wire
cages for determination of whole body retention of *9*Pt.
2. Oral administration
-Seventy-one fasted male rats, 180-200 g, were lightly anesthetized
with ether and given 25 yCi of 191Pt in 0.2 ml saline by stomach tube. Six
rats were placed in metabolism cages for collection of 24 hour urine and
14
-------
feccs samples to determine routes of excretion. Fifteen animals were
used for whole body determinations. Ten rats were sacrificed on days 1,
2, 3, 7, and 14 after dosing to establish organ distribution of 191Pt.
Fifteen non-fasted suckling rats, approximately 30 g, were given a
single dose of 2§ \Ci of 19*Pt by stomach tube. These animals were
maintained for comparison with retention of Pt in adult rats.
3. Intravenous administration
Seventy male rats, 180-200 g, were given 25 pCi 191Pt in 0.1
ml saline intravenously (iv) in a tail vein with a 1 cc tuberculin
syringe and 5/8 in., 25 g needle. Six rats were placed in metabolism
cages for collection of 24 hour urine and feces samples and 15 animals
were used for whole body determinations. Ten rats were sacrificed on
days 1, 2, 3, 7, and 14 after dosing to establish organ distribution of
l^lpt. An additional 15 pregnant rats (18th day gestation) were given
25 yCi 19* Pt iv an(j sacrificed 24 hours later for determination of
placental transfer and organ distribution.
Sacrifice and Tissue Sampling
All rats were euthanatized with an overdose of chloroform anesthesia,
Samples collected routinely for counting were blood, heart, lung, liver,
kidney, adrenal, pancreas, abdominal fat, spleen, skeletal muscle, bone,
brain, and testicle from males, ovary from females. In the pregnant
females, 4 placentas, 4 fetuses, and a pooled sample of fetal livers
were also saved.
15
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Radioactive Determinations
A carrier free solution of 191*193pt*4 in 1M HCL was used for this
study. The 191Pt isotope comprised at least 50% of the total radioactive
Pt and the 0.529 MeV gamma of 19*Pt was counted in the radioactive
determinations. 191Pt has a 3-day half-life. Immediately after dosing,
whole body counts were made on all animals used in the retention studies.
The animals were counted daily for the first few days and then every
other day for the duration of the experiment. A 200-channel gamma
spectrometer with a 5 in. Nal (Tl) crystal was used for whole body counts.
Tissue, urine, and feces samples were counted in a well-type refrigerated
scintillation spectrometer.
RESULTS
Whole Body Retention
Whole body retention of ^^Pt following a single dose was affected
significantly by the route of administration. The percent of *9*Pt
retained with time following 3 different routes of administration is
presented in Figure 1. Following oral dosing, the total net gastrointestinal
excretion was extremely high resulting in a rapid decline of the retention
curve to less than 1% at the end of 3 days. Retention of 191Pt by
suckling rats following oral administration was similar to the adults
although the amount retained at 24 hours was higher (14.7% for the suckling
rats vs. 7.4% for the adults). The difference in whole body retention
probably is due to difference in the rate of movement of the *91Pt through
the gastrointestinal tract.
16
-------
60
40
0
0.
20
Percent of Initial
Retained
191
Pt
Adult
I V
Adult
s^ Intratracheally
•a J
8 12 16 20 24 28
Days After Dosing
Suckling Rat
Oral
20 r
10
32
8
Figure 1.- Whole body retention of *9lPt in adult'rats following oral, iv, and
. intratracheal administration. Also shown is whole body retention of
191pt in suckling rats following oral administration.
17
-------
The amount of 191Pt retained in the body following intratracheal
dosing was significantly higher than for oral dosing. The excretion of
approximately 50 percent of the initial dose during the first 24 hours
is attributed to mucociliary and alveolar clearance. Whole body retention
of 191Pt was the~highest following iv dosing; the short half -life
precluded an accurate determination of the biological half- life for this
metal .
Excretion
Radioactive counts of 24 hour urine and feces samples from rats
receiving 191Pt orally indicated that almost all of the 191Pt was
eliminated in the feces and only a small amount excreted in the urine
(Figure 2) . These values support the whole body data which showed that
total net gastrointestinal absorption was. low. Following iv administration,
191Pt was excreted in both the urine and feces. The urine contained a
greater quantity of the
Tissue Distribution
The distribution and concentration of Pt was determined for
different organs as a function of time following oral and iv dosing.
After oral dosing, the kidney and liver contained the highest concentrations
of l^lpt. The amount of radioactivity found in the other organs was not
significantly higher than background. The amount of ^9^Pt found in
selected tissues and the percent of the initial dose per gram following
iv dosing are presented in Table 1. Most of the tissues did not contain
levels of 191Pt appreciably higher than that found in blood. However, the
fraction of 19lPt in the plasma that is in an "available" form for
movement into the various tissues was not determined. The large amount
18
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\
\_
Urine
i/*Ac ^ n '
\y
Oral
i i i i
24 6 8 10 12 14 16 18
Days After Dosing
Figure 2. Excretion of 191Pt following iv and oral administration
19
-------
191
Table 1.
Pt Present in Rats Following A Single Intravenous Dose
1 day
2 days
7 days
14 days
Tissue
Blood
Heart
Lung
Liver
Kidney
Spleen
Pancreas
Bone
Brain
Fat
Testis
Adrenal
Muscle
i
Duodenal Segment
c/g Wet
Weight
22,147
11,819
18,432
36,848
162,227
41,085
22,208
13,146
1,150
4,487
4,186
45,439
4,798
12,725
% Per
Gram
0.91
0.48
0.75
1.51
6.65
1.68
0.91
0.53
0.05
0.18
0.17
1.86
0.19
0.52
c/g Wet
Weight
19,732
12,201
16,139
31,274
160,656
45,8T40
19,487
12,800
2,485
4,501
6,540
42,363
4,671
6,044
% Per
Gram
0.81
0.50
0.66
1.28
6.59
1.89
0.80
0.52
0.10
0.18
0.27
1.74
0.19
0.25
c/g Wet
Weight
12,774
8,805
11,180
25,732-
138,101
55,764
14,802
8,932
595
3,201
3,873
26,667
3,441
4,031
% Per
Gram
0.52
0.36
0.46
1.05
5.66
2.29
0.60
0.37
0.02
0.13
0.16
1.09
0.14
0.16
c/g Wet
Weight
7,921
4,593
5,770
4,733
30,195
20,973
3,973
5,440
265
429
1,431
6,190
2,146
1,410
% Per
Gram
0.32
0.19
0.24
0.19
1.24
0.86
0.16
0.22
0.01
0.02
0.06
0.25
0.09
0.06
-------
of 19lPt found in the kidney suggests that this organ accumulates this
element. Concentrations higher than the blood values were also found in
the liver, spleen, and adrenal. The relative low count for the brain
indicated that 91Pt was transferred through the blood-brain barrier
only to a limited extent.
Maternal/Fetal Uptake
Fifteen pregnant rats (18th day gestation) were given 25 pe Ci
191
Pt intravenously and sacrificed 24 hours later to determine placental
transfer. During the 24 hour period, the pregnant rats excreted 18.8
percent of the initial dose. The amount excreted by the pregnant rats
was approximately the same as the amount (19.3 percent) excreted by the
adult male rats during the first 24 hours period. The concentration of
191
Pt per gram for different maternal tissues and fetuses is given in
Table 2.
The data indicated that there was some transplacental passage of
191Pt, however, there appeared to be placental binding or accumulation.
*91pt was present in all the fetuses (60) counted. The hemochorial
placental barrier of rats is more easily traversed than the more complex
placental barriers found in other species of experimental animals.
21
-------
Table 2. 191Pt in Maternal Organs and Fetuses
Tissue
Blood
Lung
Liver
Kidney
Bone
Brain
Ovary
Placenta
Fetus
Fetal Liver
Mean Counts/g
10,568
17,981
43,375
127,064
9,193
792
14,639
27,750
432
1,421
% of Dose
Per Gram
0.35
0.60
1.44
4.22
0.30
0.02
0.49
0.92
0.01
0.05
22
-------
THE ACUTE TOXICITY OF PALLADIUM CHLORIDE AND PLATINUM CHLORIDE
L. Hall, J. Adams, I. Washington, K. Campbell
W. Crocker, D. Hysell, W. Moore and J. Stara
As part of the comprehensive evaluation of the toxicity of catalytic
emission products,- acute toxicity studies of Pd and Pt chlorides were
initiated. This data provides a reliable and inexpensive first estimate
of the toxicity as related to dose.
METHODS
The outbred albino rats (Charles River CD-I strain, 200-3009) used
in these studies were maintained on a commercial diet (Purina Lab Chow)
and tapwater ad libitum except where otherwise noted. Rabbits were
obtained from a local supplier and fed a commercial diet (Purina Rabbit
Chow) and tapwater ad libitum.
A. Toxicity Studies of_ Pd_ and P£
Animals were given a single dose of PdC^ or PtCl^ by one of
the following routes: 1) orally (po); 2) intravenously (iv); 3) intra-
peritoneally (ip); 4) intratracheally (itr). All solutions were prepared
in saline with no pH adjustment.
Four groups (10 animals/group) of rats were given Pd or Pt in
the drinking water and appearance, body weight and water consumption
noted. The concentrations used were 92 and 184 ppm K- PdCl4 and 235 and
470 ppm K2 PtCl4.
23
-------
RESULTS
A. Palladium Toxicity
Using the method of Diechman and LeBlanc, the approximate LD50
of PdCl was determined for iv, ip, itr, and po routes of administration.
The results are shown in Table 1.
Table 1. Acute Lethal Toxicity of PdCl
Species
Rat
Rat
Rat
Rat
Rabbit
Approx. LD50
5 mg/kg
70 mg/kg
200 mg/kg
6 mg/kg
5 mg/kg
Route
iv
ip
po
itr
iv
Marked differences in the approximate LD50 were noted among the different
routes of administration, ranging from 5 mg/kg for iv to greater than
200 mg/kg for po.
fy
Using the more precise method of Litchficld and Wilcoxon, the iv
and ip LD50 (14 days) were determined. The iv LD50 (14 days) was calculated
to be 3.0 mg PdCl2/kg with 95% confidence limits of 2.57-3.49. The slope
was found to be 1.43 with a 95% confidence limits of 1.15-1.77. The
(CHI)^ test indicated that the data were not significantly heterogenous.
Following ip administration, the LD50 was calculated to be 123.0 (91.1-
166.1) mg PdCl2/kg with a slope of 1.84 (1.04-3.27). No significant
heterogenicity was noted.
-------
Following acutely toxic iv doses of PdCl2, death occurred very
rapidly, with a sharp threshold such that if exitus did not occur within
5-10 minutes, the animals (both rats and rabbits) survived the 14 day
experimental period. CIonic and tonic convulsions were noted in rats
and rabbits. Following ip injection, necropsy findings indicated a
chemical type "burn" of the viscera in animals dying within 24 hrs.
Gross pathologic examination of ip-dosed survivors at 14 days showed
prominent peritonitis with numerous visceral adhesions.
A limited number of rats from the intravenous and intraperitoneal
studies were housed in metabolism cages and several toxicometric parameters
were measured during the 14 days observation period. Survivors of an
acutely toxic iv dose of PdCl2 exhibited a 25 per cent decrease in water
intake and urine excretion. Following intraperitoneal dosing a 7 per
cent reduction in body weight was observed with up to 80 per cent reduction
in food intake. Water intake was markedly reduced initially and then
returned to control levels or above. Proteinuria was noted in all
animals following both routes of administration. Elevated urinary
ketone bodies were observed in some animals folloxving both routes of
dosing.
In order to ascertain the effect of chemical form on toxicity, the
LD50 of K2PdCl4 and (NH4)2 PdCl4 were determined (Table 2). The LD50
when expressed in micromoles of Pd was very similar for the 3 chemical
forms.
In two groups of rats maintained for 33 days on drinking water
containing 92 ppm and 194 ppm I^PdCl^ respectively, there were no
abnormalities noted in general appearance, body weights or urinalysis.
25
-------
Table 2. Intravenous LD50 for Pd Compounds Using
the Litchfield and Wilcoxon Method
Compound
PdCl2
K2PdCl4
(NH4)2PdCl4
LD50 mg/kg
(95% Confidence)
3.0 (2.6-3.50)
6.4 (6.0-6.8)
5.6 (4.9.-6.4)
Slope
(95% Confidence)
1.43 (1.1-1.8)
1.14 (0.83-1.2)
1.31 (0.96-1.8)
LD50
yM/kg
16.9
19.6
19.7
B. Platinum toxicity
The results of a preliminary range finding study on the acute
toxicity of iv PtCl4 in rats is given in Table 3. The high incidence of
mortality at the lowest dose precluded determination of the LD50 (14 days)
However, the lowest dose would appear to be a reasonable approximation.
Table 3. Acute Intravenous Toxicity of PtCl4 in Rats
PtCl4 Dose
mg/kg
41.4
36.7
31.4
26.2
No. of Rats
per group
10
10
10
10
Cumulative
Deaths
10
9
9
4
%
Mortality
100
90
90
40
26
-------
In two groups of rats maintained for 23 days on drinking water
containing 235 ppm and 470 ppm I^PtCl/i, respectively, there was a
decrease in weight gain and water consumption. For the high dose
level the weight gain decreased 14.7% and the water intake decreased
32.3%. No gross pathological changes were found at necropsy. Additional
studies are currently in progress on Pt toxicity.
Ii± Vitro Studies
Ir± vitro protein binding studies were performed with Pd and Pt
chlorides (PdCl2 and PtCl^), using the Toribara ultracentrifugation
technique at concentrations up to 200 yg of compound/ml, using whole
plasma or plasma equivalent albumin. Protein binding was greater than
99 percent at all concentrations. Temperature and pH were found not
to affect binding.
27
-------
REFERENCES
1. Diechman, W. B. and T. J. LeBlanc. Determination of the Approximate
Lethal Dose with About Six Animals. J. Ind. Hyg. and Tox., J.A.I.H.A.
25; 415, 1943
2. Litchfield, J. T., Jr. and F. J. Wilcoxon. A Simplified Method of
Evaluating Dose-Effect Experiments. J. Pharm. Therap. 96: 99, 1949
3. Toribara, T. The Ultravilterable Calcium of Human Serum I. J. Phar.
Clin. Invest. 36: 738, 1957.
28
-------
IN VITRO EFFECT OF VARIOUS SULFATE COMPOUNDS ON
SUCCINATE-DEPENDENT RHSPIRATION
V. Finelli, M. Karaffa, M. Richards, L. McMillan and S. D. Lee
The use of catalytic converters to control hydrocarbons and carbon
monoxide in the automobile exhaust emissions resulted in an increased
output of sulfate(s).% This, along with possible emissions of noble
metals from the converter, prompted us to test comparative toxicity of
the various sulfates in an enzyme system. Succinate dependent respiration
was tested in rat liver slices incubated in Krebs-Ringer phosphate buffer
and in liver homogenate incubated in J311M phosphate buffer, pH 7.4. A Clark-
type oxygen electrode attached to a YSI Model 53 Biological Oxygen Monitor
2 3
(Yellow Spring Instrument Co.) was used to measure the 02-uptake. *
We tested the effects of various sulfates such as cadmium, palladium,
manganese, magnesium, calcium, sodium, and ammonium on the system. The
results indicated that the sulfate ion in tissue slices or in homogenate
did not effect the respiratory chain. However, among the 'cations, Cd
appeared to be the most potent inhibitor (Figure 1). Cadmium inhibited
the 02-uptake by approximately 50% at 2 X 10 M and 100% at 3.3 X 10 M.
Other cations did not show inhibitory effects at similar concentrations.
To achieve a 50% inhibition by PdS04 more than 10" M was required. Cadmium
4
ion, a known potent inhibitor of the mitochondrial respiratory chain,
was utilized in this experiment as a reference toxicant. Cadmium sulfate
was found to be at least 5,000 times more toxic to the respiratory chain
than PdSO.. As expected, other cations such as Mn *, Mg**, Ca++, Na*+
were not inhibitory at concentrations up to 10~ M, but appeared to have a
slight stimulatory effect.
29
-------
UJ
O
100
80
60
p 40
20
CSV £
-oo -8
•7
CdS04>
1
PdSCX
-5
-4
log [MeS04]
•3
•2
Figure!. Effect of CdSCX and PdSC)^ on Succinate dependent O* uptake
in rat liver homogenate.
-------
References:
1. Malanchuk, M., Barkley, N., Centner, G., Richards, M. and Slater, R.
Exhaust Emission During Steady-Speed Runs with the Catalytic Converter
in the Exhaust System, EPA, NERC, ETRL, Cincinnati, Ohio, Annual Report,
1973.
.2. Davis, P.W., "The Oxygen Cathode," in Physical Techniques in Biological
Research, Vol. 4 (W.H. Nastuk, Ed.) Academic Press, N.Y., 137, 1962.
3. Estabrook, R.W., "Mitochondrial Respiratory Control and the Polarographic
Measurement of ADP/0 Ratios", in Methods in Enzymology, Vol. 10
(R.W. Estabrook and M.E. Pullman, Eds.) Academic Press, N.Y., 41, 1967.
4. Mustafa, M.G., Cross, C.E. and Tyler, W.S., Interference of Cadmium
ion with Oxidative Metabolism of Alveolar Macrophages, Arch. Int. Med.
Symposia, 9_, 116 (1971).
31
-------
EFFECT OF NOBLE METAL COMPOUNDS ON PROTEIN SYNTHESIS
IN VARIOUS ORGANS OF RATS
S. D. Lee and R. M. Danner
Experiments were conducted to detect early biochemical effects of
intragastric administration of noble metal compounds (PdC^and Pt[SO^^)
on protein synthesis in various organs as determined by the rate of
incorporation of 14C-leucine. Experimental animals (rats) were given
PdCl (1 rag/kg body weight) 24 hr before sacrifice. Control animals
were given saline solution. All rats (control and treatment groups)
received an injection of C-leucine (140 pCi/kg body weight) through
the tail vein and were allowed to metabolize for 1 hr before sacrifice.
The C-content of purified protein in liver, kidney, lung, heart, and
blood serum were examined.
Each of the excised organ samples was homogenized with 0.25 M
sucrose (3:1 v/w). An aliquot of the homogenate was used to precipitate
protein with 10 percent trichloroacetic acid v/v. The precipitate was
washed twice with 5 percent trichloroacetic acid v/v and then twice with
95 percent ethanol. The concentration of protein was determined by the
Biuret method. Radioactivity levels were measured in a Packard liquid
scintillation spectrometer. The observed values were expressed in terms
of dpm/mg protein and percent alteration with reference to control.
As can be seen in Table 1, no change was observed in the kidney and
lung, and there was only a slight decrease in the liver. However, there
14
was a marked increase in C-leucine incorporation into the heart and
blood serum protein. The increases were 137 percent and 49 percent in
heart and blood serum, respectively.
32
-------
Table 1. EFFECT OF PdCl2 ON 14C-LEUCINE INCORPORATION INTO PROTEIN
U)
to
Item
Control
Experimental
Percent
Change
Dose (mg/kg of
body wt) and
percent change
0 mg/kd
0.5 mg/kg
Percent change
1.0 mg/kg
Percent change
5.0 mg/kg
Percent change
Liver
dpm/mg No . of
protein animals
1,484.0 4
1,361.8 4
-8.0
Table 2. EFFECT OF
Liver
cpm/mg No. of
protein* animals
1,056 6
1,374 4
+30.1
1,088 4
+3.0
1,110" 4
+5.0
Kidney
dpm/mg
protein
1,708.0
1,728.2
+1.2
Pt(S04)2
Kidney
cpm/mg
protein*
2,332
2,807
+16.9
2,477
+6.2
2,331
0
No. of
animals
4
5
Lung
dpm/mg No. of
protein animals
1,566.5 - 4
1,540.6 5
-1.7
Heart
dpm/mg No . of
protein animals
955.0 4
2,265.0 4
+137.2
Blood
dpm/mg
protein
1,877.3
2,796.5
+49.0
serum
No. of
animals
3
4
ON 14C-1-LEUCINE INCORPORATION INTO PROTEIN
No. of
animals
6
5
4
4
Lung
cpm/mg No. of
protein* animals
1,732 6
1,911 5
+10.3
2,239 4
+22.7
3,627 4
+109.4
Heart
cpm/mg No. of
protein* animals
1,355 6
1,356 5
0
1,326 4
-2.1
1,233 4
-9.0
Brain
cpm/mg
protein*
882
1,142
+29.5
1,111
+26.0
949
+7.0
No. of
animals
6
5
4
4
*Corrected for organ weight.
-------
Rats given 0.5, 1.0, and 5.0 mg/kg body weight of Pt(S04)2 exhibited
a different pattern of C-leucine incorporation into protein as depicted
in Table 2. The patterns of ^C-l-leucine incorporation into protein of
five organs were examined. The most pronounced change was observed in
the lung, where a definite dose-response was observed with increasing
concentration: incorporation of ^^C-1-leucine rose 10.3 percent for
0.5 rag/kg, 22.7 percent for 1.0 mg/kg, and 109.4 percent for 5 mg/kg
body weight, respectively.
The incorporation of C-1-leucine in kidney showed a reverse
trend: +16.9 percent for 0.5 mg/kg, 6.2 percent for 1.0 mg/kg, and no
change for 5 mg/kg body weight, respectively. The changes in the brain
showed a similar pattern to the kidney. There was a 30 percent increase
at 0.5 mg/kg body weight for liver, and no other apparent changes were
indicated. Treatment with 5.0 mg/kg body weight of Pt(S04)2 resulted in
a 9 percent deciease. Increases of about 30 percent and 26 percent for
the 0.5 mg and the 1.0 mg/kg levels were observed, respectively. Apparently,
Pt(SO.)2 at the concentrations used in this study did cause a significant
disruption in protein synthesis in organs tested.
-------
DERMAL IRRITANCY OF SEVERAL PALLADIUM, PLATINUM, AND LEAD
COMPOUNDS AND OF METHYLCYCLOPENTADIENYL MANGANESE TRICARBONYL
K. I. Campbell, E. L. George, L. L. Hall, and J. F. Stara
A necessary aspect of the general toxicologic character!zation of
potential environmental pollutants is the evaluation of dermal irritancy.
A series of such tests were performed on several palladium (Pd) and
platinum (Pt) compounds because of their relevance to catalytic automotive
emission control devices, and on two lead (Pb) compounds and the gasoline
antiknock additive, methylcyclopentadienyl manganese tricarbonyl (MMT).
The test procedure used was essentially that in standard use by the
123
National Institute of Occupational Safety and Health, ' ' a modification
of the official Food and Drug Administration procedure. In each test,
six healthy, male, albino rabbits weighing 2 to 3 kg were used. Up to
seven pairs of sites (2x2 cm) were used on the closely clipped dorsolateral
aspects of the trunk of each animal, with the sites on the right side
abraded and those on the left intact. Test materials in the solid
(powder) state (0.1-g per site) were mixed with about 0.1 ml deionized
water and spread over the site; liquid materials were applied directly
in 0.1-ml quantities. Each application was covered immediately with a
gauze patch and further secured with tape (and overwrap in one test); a
leather restraining harness was also used. After 24 hr, harnesses and
coverings were removed, and test sites were washed with mild soap,
rinsed, and dried. The skin reactions were evaluated and scored and
again 48 hr later. Skin reactions were evaluated and scored using a
-------
grading system summarized in Table 1. The assigned rating was calculated
as the average of the means from the 24- and 72-hr scores for the test
group; intact and abraded skin was rated separately (Table 2). Ratings
were interpreted according to the scheme summarized in Table 3.
Table 4 shows the materials tested, the dermal irritancy (intact
skin) and cellular toxicity (abraded skin) responses observed, and the
corresponding interpretations. Results were interpreted conservatively,
that is, based on" the test in which the most severe responses were
observed. Many of the test materials caused a delayed healing of the
abrasion lines themselves, in addition to or regardless of the standard
response criteria.
The severity of response to some of the compounds which were tested
more than once was quite variable. Skin.character and hair growth
patterns among rabbits in the specified weight range were somewhat
variable, and these could be factors in irritancy responses and evaluations,
We recommend selection of rabbits for uniformity on these additional
criteria. Close but gentle (atraumatic) clipping in preference to
shaving, and over-wrapping in preference to taping to secure the patches,
are also recommended. In addition to tests for dermal irritancy, tests
for sensitization should also be performed. Sensitizations may be far
more serious or chronic than direct irritation. They may develop at
lower and more common levels of exposure, and opportunity for development
may be greater by virtue of extended or repeated exposure by ingestion
and inhalation as well as cutaneous contact.
36
-------
For comparison, one of the authors (KIC) applied (NH^), PdCl.
and (C3H5PdCl)2 to the intact inside forearm skin in a manner similar to
that used in the rabbit tests. The 24 hr reactions were read as 2Q and
2(+), on the scale of 4 used in the rabbits, for (NH4)2 PdCl4 and
(CjH PdCl^, respectively. These scores represented somewhat different
degrees of severity of erythema and edema. The (NH*^ PdCl^ reaction
abated after removal of the patch after 24 hr so that only a faint brown
stain of the epidermis remained on the third day. The edema reaction to
(CjH5 PdCl)2 appeared to abate also, but residual effects were prolonged.
A definite brown parchment-like lesion remained for about two weeks, and
a residual erythema remained for about five additional weeks. Both test
sites itched a little during the first day, but not after removal of the
material. There was no erythematous reaction to the patches' adhesive
material, as sometimes occurred in the rabbit tests.
Table 1. EVALUATION OF SKIN REACTIONS TO TEST MATERIALS
Grade value and designation
Reaction Intact skin Abraded skin
No. irritation 0, nonirritant 0, nontoxic
Erythema (regardless of
degree) 1, mild irritant 1, mild cellular
toxin
Erythema and edema confined
to test area 2, irritant 2, cellular toxin
Erythema and edema extending
beyond test area 3, strong irritant 3, strong cellular
toxin
Eschar (deep reaction
involving dermis) 4, corrosive 4, corrosive
37
-------
Table 2. EXAMPLE CALCULATION OF TEST RATING
Intact skin reaction
(dermal irritancy)*
Item
Animal
Number:
1
2
3
4
5
6
Total :
Average :
24 hr 72 hr Total
112
Oil
213
101
123
Oil
- -
Mean
1.0
0.5
1.5
0.5
1.5
0.5
5.5
0.9
Abraded skin reaction
(cellular toxicity)*
24 hr 72 hr Total
235
123
224
213
224
112
- - -
Mean
2.5
1.5
2.0
1.5
2.0
1*0
10.5
1.8
*Dermal irritation rating for intact skin = 5.5*6 =0.9. In this
example, tho material is a nonirritant.
"""Primary irritation rating for abraded skin = 10.5f6 - 1.8. In
this example, the material is a mild cellular toxin.
38
-------
Table 3. INTERPRETATION OF SKIN TEST RATINGS
Rating
Interpretation
Intact skin Abraded skin
0 - 0.9
1 - 1.9
2-4
0 - 0.9
1 - 1.9
2-4
Nonirritant; probably safe for contact with
intact human skin.
Mild irritant; may be safe for use, but
appropriate protective measures are
recommended during contact.
Too irritating for human skin; avoid contact,
Nontoxic to cellular components of abraded
skin; probably safe for human skin contact.
Mild cellular toxins; may be safe for
abraded skin contact, provided that
protective measures are employed.
Cellular toxins too irritating for abraded
skin contact; avoidance of contact is
advised.
Mixed reactions
0 - 0.9
0
1
0.9
1.9
1 - 1.9
2-4
2-4
1 - 1.9
2-4
2-4
Safe for human skin contact.
Safe for contact with intact human skin;
may be safe for abraded skin contact when
protection is maintained.
Safe for intact human skin; contact with
abraded skin should be avoided.
May be safe for contact with intact and
abraded skin when protection is maintained.
May be safe for contact with intact human
skin when protection is maintained, but
contact with abraded skin is to be avoided.
Unsafe for contact with intact and abraded
human skin; avoid contact.
39
-------
Severity rating*
Material
tested
Intact skin
(i rritancy)
Abraded skin
(cellular toxicity)
Interpretation'1'
onized water
icgative control)
icial acetic acid
•thanoic) acid
'ositive control)
assium chloropalladite,
.PdCl,
assium chloropalladate,
,[PdCl6]
ladium chloride,
1C12
ylpal ladium chloride
mer, (C3H5PdCl)2
hlorodiamiue palladium
MTrans, Pd(NH3)2.Cl2
Ionium chloropalladite,
IH4)2PdCl4
onium chloropalladate,
H4)2PdCl6
ladium monoxide, PdO
tinum (II) dichloride,
C12
tinum (IV)tetrachloride,
C14
tinum (IV)dioxide,
02
d chloride,
C12
d monoxide
lylcyclopentadienyl
iganese tricarbonyl (MMT)
2.6
0
(0)
0
(0)
0
(0.1)
0.8
0
(0)
1.5
(3.1)
2.8
0
0.2
1.8
(2.7)
0
0
0.1
0
3.2
1.6
(1.9)
1.6
(2)
0.6
d)
1.8
0.2
(0.5)
2.5
(3.7)
3.2
0
0.6
2.6
(3.8)
0.1
0.8
Safe for human skin contact.
Unsafe for human skin contact,
Safe for intact human skin;
may be safe for abraded skin
when protection is maintained.
Safe for intact human skin;
abraded skin contact should
be avoided.
Safe for intact human skin;
may be safe for abraded skin
when protection is maintained.
Unsafe for human skin contact.
Safe for human skin contact.
Unsafe for human skin contact.
Unsafe for human skin contact.
Safe for human skin contact.
Safe for human skin contact.
Unsafe for human skin contact.
Safe for human skin contact.
Safe for human skin contact.
Safe for human skin contact.
Safe for human skin contact.
*ing in parentheses indicates the most severe test result where there was more than one
*<, those without indicate the single test rating or an average of 2 or 3 test ratings.
>ed on the most severe or single test result.
-------
REFERENCES
1. Course Manual: Toxicologic Investigative Techniques.
Occupational Health Research and Training Facility,
Division of Occupational Health, U. S. Department of
Health, Education, and Welfare, 1964.
2. Johnson, G. T., V. B. Perone, K. A. Busch, T. R. Lewis,
and W. D. Wagner. Protocols for Toxicity Determinations:
Unit 1, Acute Projects. Toxicology Branch, NIOSH,
Cincinnati, Ohio, 1973. (Draft)
3. Personal communication with V. B. Perone. July, 1973.
4. Code of Federal Regulations, Title 21, Chapter 1,
Paragraph 191.11, in Federal Register, April 1, 1973.
-------
DERMAL ABSORPTION OF 191PLATINUM+4 IN HC1 SOLUTION
K. Campbell, E. George, W. Moore, W. Crocker, and F. Truman
In conjunction with tests of dermal irritancy of platinum (Pt)
compounds, an experiment to assess transcutaneous absorption of ionic Pt
was performed. In each of 5 rabbits, 10 pi of a solution containing
191pt+4 in o.5 M HC1 was spread over a closely clipped, 1-cm square area
of dorsal skin in the scapular region. The nuclide dose was 8.36 pCi;
a Packard gamma scintillation spectrometer (Model 5375) was used for
counting. Samples of blood before application and at 4, 24, 48, and 72
hr post-application, and 72 hr terminal samples of skin (incorporating
the site of application), liver, and kidney were counted. Counts were
corrected for background and decay, expressed as counts per minute per g
of sample (except for the skin specimen, for which only total count was
pertinent), and the fraction of the original applied dose was calculated.
Results showed that at the 72-hr terminal period, on the average,
53.41 percent of the original dose was in or on the skin at the site of
application and that very small fractions appeared in the blood or in
the tissues. Of the sequential blood samples, the earliest (at 4 hr
post-application) contained by far the greatest fraction of the applied
dose (0.0074 percent); subsequent samples contained less than one-tenth
as much. Among the tissues at sacrifice, the concentration of activity
in kidney was about 2.7 times that in liver and 14.3 times that in
blood. The results are summarized in Table 1. Data from this experiment
do not permit conclusions as to total amounts absorbed versus amounts
-------
Table 1. TISSUE LEVELS OF 19lPt ACTIVITY FOLLOWING DERMAL
APPLICATION OF 191PLATINUM+4 IN HCL SOLUTION
Specimen
Counts per minute/g Proportion of dose applied, decimal, fraction xlO~6
(mean) Mean . Range Remarks
fi
Blood:
Pretreatment
Post-treatment:
*Total, based.on entire skin sample.
0-0
n=5
4 hr
24 hr
48 hr
72 hr (terminal)
Skin, terminal
Liver, terminal
Kidney, terminal
92.4
1.4
6.8
2.1
594,493*
11.35
30.3
74.0
1.24
6.60
1.82
534,100
10.25
27.0
0
0
0
0
274,000
3
6
- 240
- 3.2
- 30
- 8
- 732,000
- 16
- 48
ii
ii
ti
ii
ii
n=4
n=5
-------
lost from the skin, the fractional distribution to other tissues, and
the amounts excreted; they do suggest early minor transcutancous absorption,
with distribution to blood, liver, and kidney. There was no visible
sign of dermal irritation at the site of application.
-------
OCULAR IRRITATION OF TWO PALLADIUM AND
TWO PLATINUM COMPOUNDS IN RABBITS
D. Hysell, S. Neiheisel, and D. Cmehil
The test was performed as outlined in the Code of Federal Regulations^
(Title 21, part 191.12, revised as of April 1, 1973). Two groups of six
albino rabbits having no known ocular abnormalities were restrained and
10.0 mg of the test material was deposited on the surface of the right
eye. The left eye was maintained as a control. The animals were examined
for ocular inflammation 24, 48, and 72 hr following application of the
material.
In the case of PdO (Table 1), no reaction was noted in any of the
six rabbits. In one animal, the test material was still present in the
conjunctival sac at the end of 72 hr, but was completely covered with a
thick mucous material.
All six animals receiving PdCl showed a severe corrosive type
lesion of the conjunctiva with severe inflammation of the cornea and
anterior chamber of the eye (Table 1). This was noted at 24 hr and
persisted throughout the test period.
None of the animals receiving the platinum compounds showed any
ocular irritation.
These results indicate that at the dosage levels used, PdCl was a
severe irritant, and PdO was not. Neither of the platinum compounds
were irritating.
45'
-------
Table 1
Fraction of animals showing reactions at
specific test intervals
Compound
PdO
PdCl
PtO
PtCl
24 hr
0/6
6/6
0/6
0/6
48 hr
0/6
6/6
0/6
0/6
72 hr
0/6
6/6
0/6
0/6
REFERENCE
1. Code of Federal Regulations, Title 21, Part 191.12, Rev.
April 1, 1973
-------
THE RELATIVE EFFECTS OF PLATINUM AND PALLADIUM
6W TOJE BAT VISUAL EVOKED POTENTIAL
3, ?. LewtewsXi, T, WesseniJarp, W, Moore, and J, F, Stara
Th§ rst vigUPJ eypked potential is being utilized a.s a screen-
ing teefcfli^ye to determine the relative .short-term effects of
Vfl?i§U§ t9Xi£ agents on general central nervous system function.
then ninety anesthetized rats have been exposed to metals
platinum and palladium via intravenous injection in the
£8§t yeaff The resulting changes in the rat visual evoked potential
have &§§n en&iyzed u§ing various methods including computer averag-
ing teehniqyes,
Th§ rt§Ult§ hive indicated that this screening technique may
fe§ ifflpertBflt ifl assessing the significant acute effects of various
p§llut§nt§ §fl eentrsl nervous system function under these experimental
§enditi§n§, Table 1 indicates the threshold dose of the particular
fflital thst elieited g reproducible change in the visual evoked
petentiai in at least IP percent of the rats studied. The typical
§ff§et §b§§rv@d within the first five minutes after injection is
al§§
-------
TABLE 1
Threshold Response of
Approximately
Cation 50%(mg/kg)
Number Responding
Total Tested
Typical Effect
Observed
Co
0.010
6/9
Cd
Cr
Pd
Mn
Ba
0.50
0.70
1.0
2.0
2.0
7/13
10/15
11/20
13/18
•6/10
Pt
<10.0
0/6
Increased late (180-
500msec .^Negativity
(3) Entire amplitude
decreased(3)
Increased initial
(40-50 msec.) and
late negativity
Increased late nega-
tivity
Increased initial
and late negativity
Increased initial
and late negativity
Change in late
portion of the
evoked potential
usually an in-
creased negativity
but a decreased
.negativity was also
periodically observed.
Little effect
Therefore, the relative short-term effect of the intravenous
administration of these metals on the rat visual evoked potential may
be ranked as follows:
Co > Cd, Cr, Pd > Ba, Mn > Pt
48
-------
As a result, if a similar blood level of palladium and platinum
is assumed, it would appear that palladium has a greater effect on
general central nervous system function under the experimental condi-
tions of this particular screening technique. It should be noted
that these observed changes may not be due to a direct effect on the
central nervous system. Further experimentation is currently underway
to determine whether these effects are direct or due to indirect
factors which are the result of other physiological changes. In
addition, more quantitative and less subjective methods for determin-
ing these thresholds are currently being utilized in an attempt to
more precisely determine the relative central nervous sytem toxicity
of these metals.
49
-------
A PRELIMINARY REPORT ON THE CARDIOVASCULAR ACTIONS OF PALLADIUM
M. J. Wiester
INTRODUCTION
Palladium 'chloride (PdCl2) has been shown by Orestano to be extremely
toxic rfhen given intravenously (iv). Rabbits rapidly injected with 0.6
n>g/kg quickly died, wi^h damage chiefly to the heart. The nature of the
heart damage was not further defined, and there is very little other
information in the literature addressing this subject. The purpose of
this study is to measure the effects of palladium solutions on heart
rate, ECC pattern, blood pressure, cardiac contractility (dp/dt), and
breathing for 1 hr following iv injection.
METHODS
Sprague Dawley male rats (300 +_ 50 g) were surgically prepared 1
day before use. Surgery consisted of catherization of the abdominal
aorta with tubing (#50 P.E.) for measurement of blood pressure; tubing
(#10 P.E.) was also inserted into the femoral vein to accomodate iv
injections. Both catheters were guided through the subcutaneous tissue
to the back region, via a puncture wound through the skin to the outside.
Six small silver electrodes, fitted with micro-strip connector pins,
were inserted under the skin and sutured. These electrodes were arranged
laterally so that four were near the limbs to record the ECG and two
were on the lateral surface of the rib cage for respiratory measurements.
Following surgery, the rats were returned to their cages and given food
and water ad libitum (Purina Lab Chow and tapwater).
50
-------
For testing, an unanesthetized animal was placed in a plastic
tubular holder for the duration of the experiment, and sensor leads were
fed to a recorder (Figure 1). The measurement system is diagrammed in
Figure 2. After a 30-min stabilization or control period, the Pd
solution was injected and washed in with saline. The total volume of the
dose and wash solution was 0.75 ml, and total infusion time was 1 min.
Effects of the injection were then observed for 60 min. Control animals
were injected with 0.75 ml of saline and treated the same.
RESULTS AND COMMENTS
PdCl2 exerted an immediate cardiovascular effect in the unanesthetized
rat. The most pronounced effect was seen on the electrical integrity of
the heart. A total of 10 animals were dosed in amounts ranging from
1.14 to 5.9 mg PdCl2Ag, and in each instance, premature ventricular
contractions (PVC) were noted within 1 min after dose initiation. PVC's
were never seen during the 30-min control periods or in control animal
experiments (5 rats). Doses between 1.14 to 1.75 mg/kg resulted in mild
episodes of PVC's following the injection, with no consequential fall in
blood pressure. These arrhythmias continued for 3 to 4 min, then the
ECG stablized. This stability was dependent, however, on the quiet
state of the animal. If the rat moved or showed signs of distress,
PVC's reappeared. Rats that received doses between 1.75 and 5.9 mg/kg
experienced gross alterations in the ECG pattern following injection.
If the cardiac arrhythmias were intermittent or of such a nature as to
allow adequate filling and pumping, then the animal survived (Figure 3).
The surviving animals were able to maintain sufficient blood pressure
levels during the critical 3- to 4-min period following injection.
51
-------
F
B."_
-TT-X—V;
x «*
-»• \\ •-—-»«---—w—^ ^— **•
-*» >^x y^-*T»r>»—• >•!. «^J» »
.'• AX —
. - v
'"fc.^-' '-^ ,
4 »^
~rr*-yv'
-^•:-r-N
1
I ^'" "-^
.11: :«.
FIGURE 1. PLASTIC RAT HOLDER. HOLDER WITH RAT AND POLYGRAPH LEADS
52
-------
Pressure
Transducer
Differentiator
dp/dt
J
Impedance
Pneumograph
\
i
ECG
Preamplifier
>
r
RECORDER
Figure 2. Block diagram of recording system.
The pressure transducer is for measurement of arterial blood
pressure and is calibrated with a Hg manometer (Miller Instrument).
The differentiator records maximum rate of change of aortic
pressure (time contant of 1 msc) calibrated with an osc'iloscope.
The Impedance pneumograph monotirs rate and relative depth
of respiration (Narco Bio-Systems).
The ECG preamplifier (Grass) Lead 2 was recorded.
Polygraph: (Grass 7C)
53
-------
:.;:X'V/w/v/v
' '.""'''"'1
'<^^.^^^I^^J^^^^^
,-•'/-i/" yw i/- \f* i/~ •/- iy~ •/" v~* v^ v~ "
|w.M»wV,4»<
PfRlOD
SCO
''WWwVwWl^vV^w^vHV
1' * *' "y
C to HIM /irreR
EC»-
B. feQ &eco>JDi
•
Fig. 3 Rat £4 A. Polygraph recording 25 minutes Into the control period. Aortic blood pressure 1s 165/125.
Electronic differentation of the blood pressure signal 1s displayed as dp/dt. The upward deflection shows maximum rate
ofpressure development, which for this pressure pulse fs 3,000 mmHg/sec. dp/dt reflects the contractile state of cardli'
muscle. The respiration record shows the rate and relative depth of breathing. The ECG 1s derived from lead 2. For
this lead a prominant P wave and R wave can be defined. The Q, S, and T waves are somewhat less specific. However, th
pattern is dependable and remains unchanged throughout control periods. Heart Rate • 460 beats/min.
B. This section shows the measurements Immediately following the I.V. Injection of 2.04 mg/kg PdCl2. Gross abnormalft
can be seen in the ECG. PVC's are not frequent enough to cause a detrimental fall 1n blood pressure. Breathing was no
altered. Similar irregularities continued for approximately 3 minutes. The animal survived.
C. One hour following the Injection blood pressure had increased to 185/140 mmHg, dp/dt • 3660 mmHg/$ec., the ECG show
no groc" abnormalities, heart rate a 408 beats/min. and /• -Bathing was unchanged.
-------
The surviving rats also reestablished a stable ECG during the 1-hr
observation period, and like the low-dose animals, they were susceptible
to arrhythmias if they became agitated. Rats that succumbed after
receiving PdCl2 intravenously suffered gross alterations in the ECG
accompanied by a" precipitous fall in blood pressure. After the aortic
pressu.-e fell, breathing became erratic and the ECG continued to deteriorate
(Figure 4). Death usually occurred within 4 min after injection.
Additional ECG abnormalities (other than PVC's), that were seen after
injection of PdCl2 were extra p waves, large S waves, and various degrees
of A-V block.
Rats surviving a PdCl2 injection developed elevated blood pressures
that persisted throughout the 1-hr observation period. Systolic pressure
increased 20 to 50 mm Hg, and diastolic pressure increased 10 to 20.
Heart rates correspondingly decreased, and dp/dt changed very little.
Intravenous PdCl2 appeared to have no initial effect on respiration.
Changes in breathing were seen; however, the changes followed gross
cardiac arrhythmias and falling blood pressures. If the rat reestablished
a steady and productive heartbeat, and thus survived the injection,
breathing returned to control values and remained stable.
Palladium sulfate (PdSO^) when given to rats was found to cause
cardiovascular and respiratory effects similar to PdC^. It came to our
attention while examining effects of PdS04 solutions that on aging,
solutions became less toxic. To combat this problem, a PdS04 injection
solution was prepared at a pH of 0.5 and analyzed by a atomic absorption
throughout the period of use. Since this was not suspected while testing
PdCl4, there is some question as to the accuracy of the injected PdCl4
dose.
55
-------
A
A. COKTROU
fr,., >«»»«£
i •
•cc.
r'"
6l6»o fdtilUlE
AM ^Wj*/^WWM***
HI 11] 11| MM!,'H|:i!jj!! ,'J Imi J ,i.> i J
fttfrfffff'fffff(ff(ffttfffnrrfffffff^f>—r~
DOSf
L-rr
\ \
,g. 4 Rat 17 A. Recordir.g 30 minutes into control period - blood pressure • 125/90 mmHg. dp/dt • 3,200 mmHg/sec.
;art rate » 450 beats/min., ECG normal pattern. Breathing frequency « 132/mln. - Irregular pattern due to animal movement
. .Recording showing gross abnormalities 1n the ECG, declining blood pressure and death of the animal Immediately
blowing I.V. Injection of 2.75 mg/kg PdCl2.
-------
was administered in doses ranging between 0.5-2 mg Pd++/kg bw.
ECG changes, like those described with PdCl2, were observed during the
injection period. Initial interruption of the cardiac cycle occurred at
0.5 mg Pd++/kg bw. Animals showed deleterious changes resulting in
significant decreases in blood pressure by the time 0.9 mg/kg had been
injected. Eleven of 13 rats died during the hour following the dose.
One, which received 0.5 mg/kg, experienced only rhythmic irregularities
following injection with no sustaining symptoms. The other survivor
(1 mg/kg bw) recovered from the cardiac irregularities; however, its
systolic blood pressure increased 80 mmHg and diastolic 40 mmHg and
persisted throughout the recovery period.
Results from the preliminary experiments described above indicate
that PdCl2, or PdSO/j, when injected iv, acts as a nonspecific cardiac
muscle irritant as well as a peripheral vasoconstrictor. Since the
chloride salt strongly dissociates in solution (PdCl2 < Pd*+ + 2 Cl~),
the Pd ion itself may be the irritant. Effects seen might be due to the
release of catecho1amines or to stimulation of adrenergic receptors
located in the cardiovascular system by the metal ion.
REFERENCE
1. Orestano, G. The Pharmacologic Actions of Palladium
Chloride. Boll. Soc. Ital. Biol. Sper. 8: 1154-1156,
1933.
57
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AUTOMOTIVE EMISSION STUDIES WITH AND WITHOUT CATALYTIC CONVERTERS
58
-------
AUTO EXHAUST FACILITY MODIFICATION
R. G. Hinners and J. K. Burkart
INTRODUCTION
The auto exhaust generating system has recently been modified at
the Environmental Toxicology Research Laboratory. This paper updates
1 2
several others ' describing the earlier facilities for the production
of irradiated and nonirradiated gasoline engine exhaust-air mixtures.
In addition, this study is intended as a reference for biologically
oriented papers discussing the health effects of auto exhaust.
The toxicity assessment of mobile emissions (TAME) project represents
a series of acute and subacute bio-effect studies that test experimental
animals exposed to whole automobile-exhaust emissions with fuel additives
and/or with or without a catalytic converter. Briefly, the exhaust
gases are generated by an engine-dynamometer unit and mixed with clean,
conditioned air in a dilution system to produce the desired concentration.
The exhaust-gas mixture is divided, with one part flowing directly to
animal exposure chambers, and the remainder flowing through irradiation
chambers to other animal chambers. The recent changes that have been
made in the system include an air-dilution tube for the immediate mixing
of the entire raw exhaust emissions with conditioned air, and a large
mixing chamber after the dilution tube. This discussion also provides
information on air supply, engine cycle, fuel supply, and other minor
changes that have been made.
59
-------
Dilution Tube
The effluent from the engine exhaust system is passed into an air
dilution tube through flexible stainless steel tubing connected to the
muffler. The dilution tube is 58.4 cm (23 in) in diameter and made from
10 gauge stainless steel plate, rolled and welded. Dilution air enters
the tube through a 90° elbow from a remote supply source. Located
between the flanges of these two tube sections is a mixing baffle plate
with a 18.4 cm (7 1/4-in) diameter hole bored in the center. The incoming
dilution air is forced under pressure through this hole to mix with the
raw exhaust. The tailpipe exhaust inlet elbow enters 90° to the tube
axis and is bent 90° again, so that the flow axis of the exhaust outlet
coincides with the center line axis of the dilution tube. The exit end
of the 5.08 cm (2-in) diameter stainless steel exhaust elbow is in the
same plane as the baffle. Located on top of and outside the dilution
tube, at the baffle plate, are two quick-disconnect couplings. One
allows the end of the flexible 5.08 cm (2-in) I.D. exhaust pipe from the
muffler to connect with the dilution tube, and the other connects to the
outside atmosphere. A blank plug is installed in the disconnecting
coupling to the dilution tube when the exhaust is vented outdoors.
System back pressure at this point is 10.16 cm (4-in) water. This
feature provides the capability of varying the modes of engine operation
for aerometry and allows interruption of animal exposures.
By operating a damper in the air supply line, the dilution ratio
can be controlled. To retain the particulate matter in suspension and
prevent condensation, it is necessary to dilute the whole exhaust with
60
-------
at least 8 parts of air to 1 part of exhaust. For each pound of fuel
burned, approximately a pound of water is formed, and some condensation
occurs if the exhaust is not immediately diluted with dry air. Also to
prevent condensation, the outside of the dilution tube is insulated,
since engine room temperature often exceeds 90F, and dilution air temperature
averages 50F and 67 percent relative humidity. The main portion of the
dilution tube consists of two 2.14 m (7-ft) long flanged sections; the
tube is then reduced through a transition to a 15.24 cm (6-in) diameter
and enters the mixing chamber.
Mixing Chamber
The diluted auto exhaust enters the mixing chamber, formerly used
as an irradiation chamber, through a 15.24 cm (6-in) diameter stainless
steel pipe opening in the side wall. An e^bow discharges the exhaust in
front of and parallel with a tube-axial fan, controlled at a low rpm by
a Zero Max unit, to mix the entering auto exhaust with the chamber
atmosphere.
The chamber is 7.17 m (23 1/2 ft) long, 1.22 m (4 ft) wide, and
2.44 m (8 ft) high, with a volume of 19.34 m3 (683 ft3). The sides
consist of a framework of aluminum structural members holding metal
panels to replace the plastic windows. The aluminum sheet metal panels
are clamped and sealed by means of pressure screws and gasketed channels.
Previous studies with a reference fuel, to which had been added methylcyclo-
pentadienyl manganese tricarbonyl (MMT) as an antiknock additive, required
darkness because of the light sensitivity of the MMT. The top, bottom,
and ends of the chamber are formed of .64 cm (1/4-in) thick aluminum
plate welded on both sides at all seams to prevent leakage.
61
-------
At the end of the chamber opposite the entry port is a
15.24 cm (6-in) diameter line with a motorized damper control
vented to the atmosphere. Another 15.24 cm (6-in) diameter
outlet pipe from the chamber supplies the exhaust either to
irradiation chambers or to raw-exhaust animal exposure chambers.
A pressure sensor, which is adjustable and located downstream of the
chamber exit line, controls the motorized damper in the vent line to
maintain 5.08 cm (2-in) of positive water pressure in the chamber.
Irradiation Chambers
The photochemical reactions that result from the exposure of the
diluted^raw^exhaust to artificial sunlight take place in five irradiation
chambers. Fluorescent lighting panels composed of blue lamps, black
lamps, and sun lamps outside the chamber pass intense ultraviolet radiation
through windows of Teflon FEP fluorcarbon film. One irradiation chamber
is needed to provide the atmosphere for each animal exposure chamber.
Normal flow through the irradiation chambers is .31 m /min (11 cfm),
which results in 15 air changes per hour in the animal exposure chambers.
In some instances, however, the flow has been reduced by one-half the
normal, which, of course, doubles the irradiation time. One of the
original irradiation chambers used in previous exhaust studies has been
converted into a mixing chamber, which is described separately.
At a volume of 19.34 m3 (683 ft3) and .31 m3/min (11 cfm) flow, 43
min is needed to achieve 50 percent of inlet concentration when "building
up11 from zero. Approximately five times 43 min (3 1/2 hr) are needed to
reach equilibrium at the inlet concentration; decay time is also 3 1/2 hr.
62
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Air Supply
The air purifier unit provides, at maximum, 15.6 m /min (550 cfm)
of chemical, biologically, and radiologically (CBR) filtered and conditioned
air. Inside building air is passed through a cooling coil to lower the
temperature to 40P" (saturated at coil outlet); there is no reheating or
humidification. Therefore, if the relative humidity of the outside air
drops below 36 grains of moisture per pound of dry air, the relative
humidity in the final exposure chamber will also vary. Usually there is
no problem maintaining constant relative humidity, but occasionally on
very dry days, there is a change.
The humidifier is turned off because of the constant need for cool
dry air to mix with hot, wet raw exhaust. Exposure chambers on control
air are supplied from a separate CBR filtered source, with controls set
to maintain 72 *_ 2F and 55 +_ 5 percent humidity in the animal chambers.
The same air is also ducted to the air filter inlet of the engine being
used for the study, since a change in humidity affects the N0xemissions
from the engine.
Engine Cycle
The dynamometer driving schedule for the Chevrolet engines consists
of a repetitive series of idle, acceleration, cruise, and deceleration
modes of fixed time sequences and rates. Table 1 shows the modified
California cycle used in the fuel emission studies.
63
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Table 1. MODIFIF.D CALIFORNIA CYCLE USED IN THE FUEL
EMISSION STUDIES
Mode
Idle
Acceleration
Cruise
Deceleration
Cruise
Acceleration
Peak
Deceleration
Total
Speed, mph
0
,0 to 30
30
30 to 15
15
15 to 49
49 to 50
50 to 0
Km/hr
0
0 to 48.27
48.27
48.27 to 24.14
24.14
24.14 to 78.84
78.84 to 80.45
80.45 to 0
Time, seconds
20
14
'15
11
15
29
1.5
31.5
137 sec.
Replacement of the California cycle with the LA-4 cycle controller
was considered at one time. However, after consultation with other
experts in the field, a decision was made to continue with the California
cycle because the exhaust is being further diluted to prescribed levels
and both cycles are very similar, since they reflect transient as well
as cruise operation. The key to this research is comparative toxicity,
and either cycle is satisfactory to achieve this goal. A simple, repetitive
cycle that is easily controlled over long periods of time (weeks) is of
prime importance to toxicologic investigations.
Fue 1 Se1ect ion
The gasoline selected for use in the Chevrolet engines as a standard
reference, baseline fuel for evaluation of engine, fuel, and additive
variables was the American Oil Company's, Unleaded 91 Octane Test Fuel,
Intermediate Grade Indolene Clear. For reference, it was important that
64
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the fuel be of precise and reproducible composition and character, free
of lead and other additives (except as specifically noted), and similar
to high-volume, regular market gasoline. This gasoline has been used
for such purposes in research and development by industry and other
agencies. The lubrication oil selected was Texaco Havoline SOW, API
service specification SE. Table II represents a comparison and product
analysis of the two gasoline deliveries used for exhaust emission studies
during 1973.
Table 2. COMPARISON AND ANALYSIS OF THE TWO GASOLINE DELIVERIES
USED FOR EXHAUST EMISSION STUDIES IN 1973*
Property
.Date delivered
Quantity, gal
Octane No . , research
Octane No., motor
Lead Atm. Abs., g/gal
Phosphorus , g/gal .
Sulfur, wt. %
Aromatics, vol %
Olefins, vol %
Gum, existent, mg/100 cc
Gravity, OAPI
Oxidation stability, min.
Reid vapor pressure, Ibs.
Shipment
•1
3/30/73
2,000
91.4
82.9
0.01
0.002
0.04
25.4
11.8
0.8
61.4
600+
9.1
No.
2
10/29/73
1,500
91.3
82.. 5
0.01
0.00
0.04 '
23.5
9.9
1.0
61.5
600+
9.0
*Shipment No. 1 was used for studies G, H, I, and J.
Shipment No. 2 was used for study K with Thiophene added
to produce 0.10 percent by weight sulfur.
65
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Fuel Storage and Mandljjig
Local fire and safety regulations require flammable liquids to be
stored outside the building, so two underground fuel storage tanks were
installed on the property near a blacktop driveway. To promote chemical
stability of the fuel during storage, the tanks are maintained under
slight positive pressure, with nitrogen supplied from cylinders and
controlled by a pressure regulator. A double-acting pressure- and vacuum-
relief valve on the vent outlet compensates for changes that result from
fuel being pumped out or temperature increasing, which would alter the
pressure of the nitrogen gas cover. Each tank is of 7571 1 (2,000-gal)
capacity and equipped with an electric fuel pump rated at 56.8 1 (15gal)
per min.
Outside the building wall and next to the engine room is a 68.1 1
(18-gal) marine fuel tank sitting on a weight scale and connected to a
remote electric fuel gauge located in the instrument panel. Transportation
of the test fuel from the main underground storage supply to the 1 day
supply tank is effected by a mobile safety dispenser cart made especially
for transporting flammable liquids. The 227 1 (60-gal) capacity cart
carries the Underwriters Laboratories1 approval as a portable flammable
liquid tank and is equipped with transfer pump and grounding reel. The
cart also has a drain, and removing the pump gives access to a 10.2 cm
(4-in) handhole for reaching and cleaning the tank interior between fuel
changes. Similarly, the 68.1 1 (18-gal) marine tank can easily be
inverted for cleaning when required.
66
-------
An alteration in the composition of the reference fuel for a study
is made by the addition of the required amount of chemical to a full
cart batch. Thus studies requiring the testing of fuel additives such
as MMT or thiophcnc to increase the sulfur content can be conducted by
mixing only the amount of fuel necessary.
REFERENCES
1. Hinners, R. G. Laboratory Produced Automobile Exhaust
Facility. Biomed. Sci. Instrum. J_: 53, 1963.
2. Hinners, R. G., J. K. Burkart, and G. L. Contner. Animal
Exposure Chambers in Air Pollution Studies. Arch. Environ.
Health. 13: 609-615, Nov. 1966.
67
-------
ENGINES AND OPERATING CONDITIONS FOR CATALYTIC EMISSION STUDIES
R. G. Hinners and J. K. Burkart
During 1973, animal exposure studies were conducted in the Environmental
Toxicology Research Laboratory (ETRL), National Environmental Research
Center (NERC), Cincinnati, Ohio, to assess the relative health hazard of
automobile exhaust emitted from engines with and without catalytic
converters, using similar engine settings. Automotive exhaust catalysts
were developed to lower exhaust emissions of the three pollutants specifically
listed in the Federal Clean Air Act of 1970: carbon monoxide, hydrocarbons
(by oxidation), and oxides of nitrogen (by reduction). Three possible
conditions could result in other emissions:
1. As the hot catalyts promote the oxidation of
carbon monoxide and hydrocarbons in automotive
exhaust, converting tiiom to carbon dioxide and
water, they may simultaneously convert the organic
sulfur compounds present in all gasoline to sulfuric
acid mist and eventually to sulfates.
2. The metals used in the converter, such as
platinum and palladium, may be emitted under
conditions of catalyst degradation from the
exhaust pipe in fine particles and be suspended
in the air.
3. The total emissions may be altered and may
produce different quantities or new species.
68
-------
In order to perform the assigned tasks, this laboratory recently
acquired and installed two new engines equipped with catalytic converters
from the General Motors Company and the Ford Motor Company. The General
Motors engine (350 CID) is a 1973 production engine and has the following
controls: (1) exhaust gas recirculation, (2) an air pump, and (3) one
catalytic converter (pelletized type, noble metal oxidation catalyst).
(Catalyst by Engelhard Co.)
The Ford engine (400 CID) is a 1975 prototype, R-6 engine with R-14
calibration and the following controls: (1) exhaust gas recirculation,
(2) an air pump, (3) a fluidic spark delay valve, (4) various temperature
sensing triggers, and (5) catalytic converters of the monolith, noble
metal oxidation type (two converters of this type are required, one for
each bank of cylinders). (Catalyst by Matthey-Bishop Co.) A schematic
view of the double engine-dynamometer unit and dilution tube is presented
in Figure 1.
During the toxicity assessment of mobile emissions (TAME) (studies
H, I, J, and K), the 1973 Chevrolet engine was operated continuously for
7 days using the California cycle. Comprehensive data for comparison of
study-engine operating conditions is given in Table 1.
TAME K was designed to test emissions and bioeffects of a high-
sulfur gasoline free of other undesirable substances such as lead.
Thiophene was added to produce a sulfur content of 1,000 ppm in the
control fuel, Indolene. Sulfur compounds present in gasoline are mainly
in the form of polysulfides and thiophene compounds with an insignificant
amount of hydrogen sulfide.
69
-------
\
1 •
o,
1 I ' »
\
JlL
" II
1. Vibration Isolating Stand
2. 1973 Chev. V-8 350 C.I.D.
3. Turb.ohydromatic Transmission
4. Dynamometer Absorption Unit
5. Flywheel
6. Catalytic Converter
7. Muffler
8. Dilution Tube
9. Baffle Plate
10. Dilution Air Supply
11. 1975 Ford V-8 400 C.I.D.
12. Catalytic Converters
Figure 1. Schematic view of the double engine-dynamometer
unit and dilution tube.
-------
Table 1. COMPARISON OF STUDY-ENGINE OPERATING CONDITIONS
Item
Dates
Fuel
Engine
Engine hours
Study hours
Engine miles
Cumulative catalyst hours
Catalyst miles
Total fuel (Ib)
Fuel, Ib/hr
Exhaust Oxygen (%)
Air/fuel ratio
Oil consumption (qt)
Dilution ratio
Dilution air flow (average SCFM)
TAME H
9/10 - 17
Ref. only
'73 Chev.f
w/catalyst
62-230
168
4,600
244
4,880
1,533
9.10
4.9
-
1-1/8
8.0/1
318
TAME I
10/10 - 17
Ref. only
'73 Chev.,
no catalyst
255-425
170
8,500
244
4,880
1,545
9.08
N.A.
14.4 cycling
12.4 idle
1/2
9.6/1
305
TAME J
10/24 - 31
Ref. only
'73 .Chev.,
w/catalyst
444-615
171
12,300
465
9,300
1,601
9.40
4.2
-
1/4
8.7/1
310
TAME K
11/14 - 21
Ref. + sulfur
•73 Chev.,
w/catalyst
675-841
166
16,820
632
12,640
1,495
9.02
4.7
-
1/4
9.5/1
324
Dilution tube temperature
(average *F)
106
101
114
101
-------
Our testing procedures reported and confirmed that the addition of
oxidation catalysts to the automotive exhaust system causes an increase
in the emitted particulate material (consisting mainly of hydratcd
sulfuric acid droplets) as a result of the oxidation of organic sulfur
compounds in gasoline. Recent national averages of the sulfur content
are. between 210 and 260 ppm for premium-gasoline, and between 390 and
44.0: ppm_ for .regular gasoline. .The Indo>lene. motor, fuel used at the I5TRI
fapility had a sulfur content of 0.04 percent by weight, or 440..ppm.
72
-------
DESIGN AND SYSTEM PERFORMANCE FOR STUDIES OF CATALYTIC EMISSIONS
J. Burkart and R. Hinners
The engine used in these studies was a 1973 Chevrolet 350 C.I.D.
production model with EGR, air pump and turbo hydromatic transmission
coupled to an "eddy current" absorption dynamometer. The beaded noble
metal oxidation catalyst HN-2242 coating was by Engelhard Mineral and
Chemical Company.* New road-load data supplied by the EPA Motor Vehicle
Emissions Lab were used; they are equivalent to an increase of inertial
weight from 1542 kg (3,400 Ib) (used on a 1972 Chevrolet) to 1814 kg
(4,000 Ib). No attempt was made to adjust idle mixture, as in earlier
Toxicity Assessment of Mobile Emissions (TAME) studies A through G, and
carburetor limiters remained in place. In TAME H, the engine was run
•
as-received, except for setting idle speed, dwell, and timing. Maintenance
performed before TAME I, J, and K consisted of changing the oil and
filter, installing new points, condenser, and spark plugs, and setting
hot idle speed, dwell, and timing. In addition, before TAME K, new
spark plug wires were installed.
For each of the continuous 1-week TAME studies II through K, approximately
5470 km (3,400 miles) were accumulated on the California cycle. Separate
cumulative engine miles and catalyst miles are reported, since the
catalyst was removed in TAME I, and additional steady-speed runs (without
animal exposures) were made to characterize emissions. The dilution
ratio is determined by the ratio of average tailpipe C02 to dilute Q^.
73
-------
Because the variability of tailpipe C02 throughout the cycle is
small, the problem of obtaining a proportional sample is negligible.
Samples for CC^ detection flow at a constant 1 liter per min through a
refrigerated cooler, dessicant dryer, and paper filter to the Beckman
Infra Red Model 31S. This instrument is calibrated for 15 percent CO,
full scale and zeroed on dilution air; however, because of the cooler,
some small CO- loss in the condensate was unavoidable.
For all studies, a continuous trace at constant sample flow on two
Mosley (2-pen) recorders was made of tailpipe CO, dilute CO, tailpipe
THC, and tailpipe C02- The recordings, along with spot checks of tailpipe
oxygen and dilute CO,, monitored engine and dilution system operation.
The TAME schematic in Figure 1 shows sampling points throughout the
system, starting "ith the engine, the catalytic converter, and the
standard muffler. The numbers will be referred to for aerometry sample
identification except when exposure chambers are sampled; the chamber
number and treatment (irradiated, nonirradiated, and clean air) are
used.
Some average total particulate losses on a percentage basis are also
shown in Figure 1, starting with 100% at point 5 in the dilution tube which
was located 2.74m (9 ft.) from the raw exhaust inlet. An overall loss of
39% occurs, with the largest loss (22%) happening between points 5 and
6,2.135m (7 ft) away. The initial decrease due to the gravitational loss
of larger particles was anticipated. The reduction in duct size from
58.42cm (23 in.) to 15.24cm (6 in.) diameter was also a factor in
particulate loss.
-------
en
VENT
76%
64%
DILUTION AIR
78%^ (5)100%
MIXING CHAMBER DILUTION TUBE
IRRADIATION CHAMBERS
—061%
--O
\L
EXPOSURE CHAMBERS
%Average Total Particulate Existing
E Engine
C Catalytic Converter
M Muffler
--O Sampling Point
Nl Non irradiated Chamber
I Irradiated Chamber
Figure 1. TAME schematic showing sampling points.
-------
The size of the particulates sampled in the exposure chamber, given
as MMED (mass median equivalent diameter), varied between 0.13 and 0.40
micron, with an average of 0.29 micron. The particulatc MMED in the dilution
tube averaged 1-1/2 to 2 times larger.
The particulaitc characterization runs were made before the catalyst
studies and during a 2-mcnth study on a Mn fuel additive (CI-2) in Indolene.
For these runs a 1972 Chevrolet 350 C.I.D. was operated on the "California"
cycle and data collected at the midpoint of the study, after the system
had been conditioned. Losses vary as the character of the aerosol
changes and a different size distribution occurs from changes in engine
speed and load. This results in a different particulate loss distribution.
A change to high engine speed after a period of lower engine speed operation
shows an initial Targe loss of particulate,' due to the gravitational
losses of more large particles. The same effect is noted when much cooler
dilution air is mixed with the hot exhaust. These observations serve to
indicate the variable nature of aerosols. After this study, during the
installation of the new engine-catalyst package, the entire system was
thoroughly cleaned.
During catalyst studies, the entire tailpipe volume was mixed with
the quantities of air given in Figure 2; the resulting dilution tube
temperatures are also shown. The dilution air temperature for all
studies ranged from 48° to 55°F. Figure 3 depicts tailpipe conditions
which include exhaust oxygen content and average catalyst temperature
measured at center line of the tailpipe 2.5 cm [1 in] from catalyst
outlet. At the tailpipe, the 7-day trend during the catalyst studies
(H, J, K) was oxygen decrease, C02 increase, and catalyst temperature
increase.
76 .
-------
330
u
to
320-•
310--
z
O
i-
13
_i
O
300
DR=8/1
= 9.6/1
DR=9.5/1
012345678 012345678 012345678 012345678
TAME H TAME I TAME J TAME K
(CATALYST) (NO CATALYST) (CATALYST) (CATALYST W/
HIGH SULFUR FUEL)
012345678 012345678 012345678 012345678
DAYS DAYS DAYS DAYS
Figure 2. Dilution air flow and dilution tube temperature.
77
-------
900
< 850
u
O
800
CATAL'YST
950
900
850
12345678
TAME H
800
950
900
850
12345678
TAME J
CATALYST
WITH '
HIGH
SULFUR
FUEL
II
12345678
TAME K
6s- 0
£ 5
O
x 4
O
S 3
0.
=f 2
i
o
^ r\
\
-Vv_.
>w
-
-
.
i i i i i i i
6
5
4
3
2
1
n
»
DMA «^s
•
•
M
i i i i i i i
6
5
4
3
2
1
n
. ^^*V
^v^_-
^^
•
•
.
Days
Days
Days
Figure 3. Tailpipe conditions.
78
-------
Table 1 shows the General Motors catalyst efficiency when TAME I
(without catalyst) average emissions arc used as the basis for comparison.
Note that the catalyst is more efficient in terms of CO than of HC under
the hot cycling condition.
Some initial loss of efficiency may be due to the higher oil consumption
during TAME H; also, by the end of that study, No.. 3 plug had fouled.
Table 1. GENERAL MOTORS CATALYTIC CONVERTER EFFICIENCY
Item H J J K
Average tailpipe concentration (ppm)*
Carbon monoxide 49 4,739 354 340
Hydrocarbons (as methane) 84 946 169 153
Total percent reduction below TAME I
Carbon monoxide 99 -- 93 93
Hydrocarbons (as methane) 91 — 82 84
^Calculated from dilute concentrations multipled by dilution
ratio minus one.
79
-------
Basic specifications for the 1973 Chevrolet engine are
shown below in Table 2.
Table 2. Chevrolet Engine System
Displacement
Compression Ratio
Carburetor Type
Distributor
Mech. Adv. Unit
Vacuum Adv. Unit
Dwell
Initial Timing
Maximum Vacuum Advance
Emission Control Equipment:
1975
350 C.I.D.
8.5/1
Roch. 2GV 1-1/2 (07043114)
ff 1112168
C 4815
C6020C46914)
30°
8° ETC
I4o
Air pump
Rich tune (A/F 14.5/1)
Timed port Vac. Adv.
EGR 11633 (LF 7040437)
Data for exposure chamber temperature and relative humidity are
presented in Figure 4. The temperature profiles appear favorable,
however, the relative humidity for chambers receiving exhaust were
consistently above 60 per cent relative humidity while the reverse
was true for control air chambers.
80
-------
70%-80°FH
60%-75°Fr
50%-70°F:
IRRADIATED EXHAUST
•v Temperature
Relative
Humidity
1234567 1234567
1234567
NON- IRRADIATED EXHAUST
<60%-75°Fr-
IU
te.
50%-70°F-
i I I I i I I
1234567
1234567 1234567
I 70%-80°Fr1 ,*.
60%-75°FH
CLEAN CONTROL AIR
50%-70°F.-
i i i i i ri
1234567
DAYS
TAME I
i i r TIII
1234567 1234567
DAYS DAYS
TAME J TAME K
Figure 4. Exposure chamber temperature and relative humidity.
81
-------
EXHAUST EMISSIONS DURING STEADY SPEED RUNS WITH THE
CATALYTIC CONVERTER IN THE EXHAUST SYSTEM
M. Malanchuk, N. Barkley, G. Contner
M. Richards, and R. Slater
INTRODUCTION
In preparation for studies on the exposure of animals to the
exhaust emissions from catalytic-equipped systems preliminary runs were
made with the 350 CID Chevrolet engine operating at constant speeds.
Information was sought that would indicate the levels of constitutents
different from those of previous runs made under different engine operating
conditions. The data were needed particularly with reference to sulfur
compounds and acidity of the emissions. Preparations were made to test
for sulfates, sulT-ir dioxide, sulfuric acid* and nitrate components.
Sample procedures were adapted by making those changes necessary for
quantitative results.
EXPERIMENTAL PROCEDURE
The main effort was directed toward the sampling of particulate
matter to establish the nature of the anticipated changed character of
the particulate.
Since membrane-type filters used to collect aerosol from the
catalytic converter system deteriorated from the corrosive action of the
sample, quartz fiber material was used and found favorable for such
samplings. Not only did that material resist breakdown, it also did not
cause any changes in the nature of the aqueous extraction medium (e.g.
pH) after standing as long as 20 to 30 hr.
82
-------
The sample filters were handled in two different ways. Every
filter was weighed immediately after sampling. Some were permitted to
stand overnight to equilibrate in the room atmosphere (70-75F, 40-60
percent relative humidity) until the weight had stabilized. Because of
the large differences in initial and final weights of many of the samples,
the initial values were used to calculate the particulate concentrations
in the sampled atmospheres since those values were considered to be more
immediately representative of the existing chamber conditions. Other
filters, immediately after they were weighed following the sampling,
were placed in a measured volume of distilled, deionized water. Conductance
and pH measurements were then made to determine ion concentrations--
mainly, the acidity of dissolved samples. The aqueous extracts were
also used for analysis of particular ion radicals like the sulfate and
nitrate groups.
Analytical procedures included the barium chloranilate method and
2
nephelometry for sulfate, the phenol-hypochlorite reaction and ion-
specific electrode for ammonia and ammonium compounds, and the hydrazine
reaction for nitrate.
Bubblers containing distilled water or a weak acid solution were
used to scrub sampled atmospheres for nitrate—and for ammonium-producing
components. A sampling train of bubblers similar to that used in stack
sampling* was arranged for separation of SO2 from SO, in atmospheres
drawn from the exhaust pipe before and after the catalytic converter and
from the animal exposure chambers. The first bubbler in the train,
containing isopropanol, collected 803. The succeeding two bubblers,
containing hydrogen peroxide, collected the S02 and converted it to the
83
-------
sulfate form. In some cases, the follow-up bubblers contained totrachlormcrcurjlT
instead of peroxide to trap the S02 for analysis by the West-Gacke
method.
None of the animal exposure chambers from which the atmosphere was
sampled contained any animals. These chambers previously were hosed
down thoroughly with hot '^ater to minimize, if not eliminate, sources of
contaminating deposits.
RESULTS
The effects of different engine speeds and of different concentrations
of sulfur in the fuel are seen in the concentration values of exhaust
emission components in Table 1.
Values of gaseous components are listed first - carbon monoxide
(CO), total hydrocarbons as methane (THC), nitrogen oxides (NOX), with a
breakdown into nitric oxide (NO) and nitrogen dioxide (N02), the aliphatic
hydrocarbons of the C^-C^ group examined, olefins of the C2~C^ group,
and acetylene. Values for particulate material are listed as total
particulate and as the sulfate and nitrate concentrations in that particulate.
The first 5 columns of concentration values were obtained from the
operation of the engine with the base fuel, Indolene gasoline, and the
use of the catalytic converter unit in the immediate exhaust system.
The last 4 columns show the concentrations obtained when the Indolene
gas was "spiked" with an organic sulfur compound to double the concentration
of sulfur in the fuel; in one case, the catalytic converter unit was
retained in the exhaust system; in the second case, the unit was removed
before the run was started.
-------
Table 1. COMPARISON $r EXHAUST EMISSION'S, STEADY SPEED RU\S
Emissions
Exhaust Dilution Ratio
CO, ppm-
THC, ppm
NOX, ppm
NO, ppm:
N02, ppin
CD
VI
N-I
I
: N-I
I
: N-I
I
N-I
I
N-I
I
Aliphatics, ppn>: N-I
I
Olefins,
ppm. N-I
I
Acetylene, ppm: N-I
I
Particulate, mg/m3-diluted exhaust
N-I
I
Sulfate,
Nitrate.
mg/m3-di luted exhaust
N-I
I
mg/n^-di luted exhaust
N-I
I
Regular Indolene gasoline
with catalytic converter
15 mph
7.S/1
7 '
7
9
8
20.0
19.4
14.7
13.2
5.3
6.2
0.107
0.10S
0.450
0.426
0.025
0.025
7.20
9.60
5.20
4.33
4.80
3.01
0.32
0.01
0.01
30 mph
6.2/1
8
8
9
9
28.4
31.8
21.2
21.8
7.2
10.0
0.113
0.113
0.465
0.456
0.018
0.020
20.1
22.2
17.1
6.18
5.00
3.94
-
(7.5/1)
(7)
(7)
(8)
(8)
C23.5)
(26.3)
(17.5)
(18.0)
(6.0)
(8.3)
(0.093)
(0.093)
(0.385)
(0.377)
(0.015)
(0.017)
(16.6)
(18.4)
(14.1)
(5.11)
(4.14)
(3.26)
-
50 mph
4.9/1
10
10
4
4
102.0
104.8
71.9
63.6
30.1
41.2
0.031
0.026
0.204
0.195
0.012
20.7
49.3
44.8
6.93
4.90
2.72
0.47
0.00
0.31
7.5/1)
(7)
(7)
(3)
(3)
(66.6)
(68.5)
(46.9)
(41.6)
(19.7)
(26.9)
(0.020)
(0.017)
(0.133)
(0.127)
(0.008)
(13.5)
(32.2)
(29.3)
(4.53)
(3.20)
(1.78)
(0.31)
(0.00)
(0.20)
High-sulfur Indolene
with catalytic converter without catal>tic converte
15
8.1/1
7
7
8
8
-
-
-
0.109
0.115
0.433
0.447
0.018
0.028
23.7
28.0
21.4
13.16
11.86
10.65
0.36
0.01
0.01
mph
(7.5/1)
(8)
(8)
(9)
(9)
-
-
-
(0.118)
(0.124)
(0.467)
(0.483)
(0.020)
(0.030)
(25. 6)
(30.2)
(23.1)
(14.20)
(12.80)
(11.50)
(0.39)
(0.01)
(0.01)
15
S.0/1
491
93
21.1
20.3
13.3
9.6
7.8
10.7
-
.
-
2.5
3.0
2.5
0.54
0.49
0.49
0.2S
0.04
0.17
mph
(7.5/1)
(522)
(99)
(22. S)
(21.6)
(14.2)
(10.2)
(8.3)
(H.4)
_i
.
-
(2.67)
(3.20)
(2.67)
(0.58)
(0.52)
(0 52)
(0.50)
(0.04)
(0.18)
N-I/ Non-irradiated atmosphere, exposure chamber with
I =^-.rradiated atmosphere, exposure chamber with
-------
The samples were mainly collected from the animal exposure chambers
receiving the diluted exhaust emissions that had been exposed to the
irradiation lights (I), and those chambers receiving diluted emissions
not treated to the irradiation effects (NI). The particulatc samples
identified as diluted exhaust were collected from the exhaust system in
the immediate range of the engine.
To relate the values from the higher engine speeds and the runs
with higher gasoline sulfur to the basic 24 km/hr (15 mph) with its
7.5/1 dilution, the actual values of those runs have been adjusted to
equivalent values for a 7.5/1 dilution which are given in brackets.
Since the data apply only to single runs at each of the five different
sets of conditions (except the basic 24 km/hr (15 mph) with regular
Indolene fuel, wheie there were two runs for which the average values
were calculated), the information must be considered as tentative.
Duplicate runs will be made to establish reproducibility and to confirm
the results presented.
Nevertheless, large differences in the results between runs were
seen, which may be acceptable for what they indicate. The large increase
in the nitrogen oxides at the highest speed of 80 km/hr (50 mph) was to
be expected (see columns 1-5 of Table 1). There was a concomitant decrease
in hydrocarbons. Particulatc levels beyond the converter increased with
increasing engine speed. Apparently, particulate sulfate concentrations
remained the same at different speeds; however, they seem to make up
most of the solute of the particulate. Nitrate was present at much
lower concentrations.
86
-------
With the high sulfur (2 x) Indolcnc gas as fuel, the carbon monoxide
and hydrocarbons (total and individual) levels remained the same (columns
6 and 7). The big difference was seen in the total particulate and
sulfate contents (about three to four times as much as for the regular
Indolene gas).
The engine operating with the high-sulfur fuel but without the
catalytic converter had, as expected, much higher levels of carbon
monoxide and hydrocarbons. The nitrogen oxide levels were at similar
concentrations as those for the 24 km/hr (15 mph) with regular Indolene
fuel. The particulate levels (columns 8 and 9) were only about one-
tenth of those for the catalytic converter (columns 6 and 7). Sulfate
in the particulate was almost negligible by comparison.
Acidity measurements of the particulate from the catalytic-equipped
systems were without exception, high enough to allow for all the sulfate
to be considered present as sulfuric acid. That is to say that the
hydrogen ion concentration as (2H+), measured with a pH meter, was
greater than the sulfate (804") concentration--sometimes by a factor of
three. Such high acidity was found unaccountable on the basis of the
anionic components measured and the total particulate determined; additional
study is needed to resolve the phenomenon. An indication of relative
acidity levels with different operating conditions is shown in Table 2.
The particulate (columns 8 and 9 of Table 1) in the system without a
catalytic converter was, on the other hand, almost completely neutral as
measured by a pH meter on its aqueous extract.
Measurements of sulfur components (SOX) in the undiluted exhaust
before and after the catalytic converter showed a 50- to 90-percent
decrease of sulfur. That is to say, there was a considerable hold-up of
sulfate in the catalyst bed itself.
87
-------
Table 2. RELATIVE ACIDITY LEVELS OF EXHAUST EMISSION PARTICIPATE AT 24 km/hr (15 mph)
No catalytic converter With catalytic converter
Operating Condition high-sulfur Indolene fuel regular Indolene high-sulfur Indolene
Relative acidity
of particulate 1 65 260
Total particulate
@ 7.5/1 dilution
mg/m3 2.7 7.2 25.6
00
00
-------
REFERENCES
1. Kufta, R. J. Stationary Source Testing. Apollo Chemical
Corp., Clifton, N. J., September 1, 1972, pp. 39-51.
2. Weatherburn, M. W. Phenol-Hypochlorite Reaction for
Determination--of Ammonia. Analyt. Chem. 39: 971,
July, 1967.
3. Hauser, T. R. Method for Analysis for Nitrate by Hydrazine
Reduction. Water Research. ^: 1816, 1956.
4. West, P. W., and G. C. Gaeke. Fixation of Sulfur Dioxide
as Disulfitomcrcurate (11), Subsequent Colorimetric Estimation,
Analyt. Chem. 28: 1816, 1956.
89
-------
.Q
EFFECT OF CATALYST AND OP FUEL SULFUR CONTENT
UPON AUTO EXHAUST EMISSIONS
M. Malanchuk, N. Barkley, G. Contner, M. Richards
R. Slater, J. Burkart, and Y. Yang
INTRODUCTION
Some early studies in the automobile industry have indicated that
oxidation-typo catalysts in auto exhaust systems generated high levels
of sulfuric acid aerosol, as much as 0.1 g of the acid per vehicle mile.
It was hypothesized that the engine combustion process converted organic
sulfur compounds in the gasoline into sulfur dioxide, and that the
dioxide was oxidized by the catalyst to sulfur trioxide, which reacted
with water vapcr in the exhaust to produce sulfuric acid droplets.
Therefore, cycling speed-runs (as oppo'sed to constant-engine speed-
runs) were used for the animal exposure studies, since they more nearly
simulate automobile operation i^ the streets. Measurements of exhaust-
emission components were made to determine the levels to which the
animals in the studies were exposed. The effective changes in exhaust
composition were determined when the catalytic converter unit was added
to the exhaust system, and when high-sulfur fuel (0.10 percent sulfur)
was substituted for the reference Indolene gasoline (0.05 percent S).
Emission components present in relatively high concentrations were
monitored in much the same way as in previous runs.
90
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SAMPLING AND ANALYTICAL PROCEDURES
The instrumentation and methods used for key components of exhaust
emissions are summarized in Table 1. Atomic absorption spectrophotometry
was used for trace..metal determinations in particulate.
Particulate samples were collected on pure quartz fiber filters
after early membrane filters deteriorated from exposure to the high
reactivity of the collected sample of catalyst-treated emissions.
Bubbler and impinger samples of the atmospheres were used for
collecting ammonia- and sulfur-based gases.
RESULTS
Table 2 lists the concentrations of various engine exhaust components
measured during the series of studies of th'e catalytic converter system.
Individual hydrocarbons measured by gas chromatography are shown in
Table 3; the aromatic compounds were not measured after it was discovered
that those concentrations were so low in the atmosphere of the catalyst-
equipped system as to be near or below detection level.
Toxicity Assessment of Mobile Emissions (TAME) studies J and H,
were run under the same engine operating conditions; i.e. they were
duplicate runs. However, reference to the data of Table 1 shows considerable
differences in values between the two runs. When TAME H was performed,
the engine was probably not fully broken in, and the catalyst was quite
new; the piping system for conducting the emissions to the exposure
chambers probably had not yet attained equilibrium conditions of surface
exposure characteristics (mainly deposition of particulate and adsorption
of organic vapors) for the new engine system. TAME J, run at a later
91
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Table 1. AEROM1-TRIC CHARACTERIZATION OF EXHAUST EMISSIONS
Pollutant component Analytic method Automatic Manual Where determined
Carbon monoxide (CO) Nondispersive X EPM,* EC+
infra-red spec-
troscopy
Total hydrocarbons Flame ionization X EPM, EC
(THC), as CH4 spectroscopy
Nitrogen oxides (NOX Chemi luminescence X X EPM, EC
includes NO and N02) spcctrophotometry;
colorimetry using
Saltzman reagent
Cj to GS hydrocarbons Gas chromatography X EC
(several compounds)
Cg to CIQ aromatic Gas chromatography X EC
hydrocarbons (several
compounds)
Aldehydes, total MBTH according to X EC
Hauser
Particulates, total Filtration gravimetry X EC
mass
Part icul ate size Stage impact ion X EC
distribution: (Anderson)
aerodynamic
Photonomeric Photoclectronic X EC
(Royco)
Particulate Infra-red and X EC
composition ultraviolet
spectrophotometry
Ozone, oxidant Chemi luminescence X EC
spectrophotometry
*Exhaust or priirary exhaust: air mixture.
+Exposure chamber.
92
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Table 2. ONGINC EXHAUST EMISSION VALUES FOR
CATALYTIC CONVERTER SYSTEM STUDY
Exhaust Dilution Ratio
CO, ppm:
THC, ppm:
NOX, ppm:
NO, ppm:
N02» ppm:
Aldehydes, ppm:
Methane, ppm:
Aliphatics:
ppm C4-Cs
Olefins:
ppm C2-C^
Acetylene, ppm:
Ozone, ppm:
Particulate, mg/m^
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
Diluted
N-I
I
TAME H
8/1
7
8
12
13
11.0
11.0
8.5
8.0
2.5
3.0
-
-
-
-
-
-
Exh.
2.85
2.13
TAME I
9.6/1
551
559
110
95
11.9
5.1
6.7
0.5
5.2
4.6
10.20
14.62
1.30
1.32
13.24
9.23
3.28
3.06
0.0
0.4
1.09
0.77
3.59
TAME J
8.7/1
46
41
22
22
12.9
12.6
11.1
9.6
1.8
3.0
0.08
0.10
0.61
0.58
0.89
0.79
0.03
0.03
-
1.10
1.08
1.23
TAME K
9.5/1
40
38
18
18
12.6
11.2
10.8
9.7
1.8
1.5
0.18
0.11
6.53
6.13
0.44
0.39
0.91
0.82
0.04
0.04
-
8.10
9.30
8.75
N-I = Nonirradiated atmosphere, exposure chamber with.
I = Irradiated.
93
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Table 3. GAS CHKQMATOGRAPHIC MEASUREMCNTS OI: HYDROCARBONS, ppm
Component
n-Butane
i-Butane
n-Pentanc
i-Pentanc
Acetylene
Ethyl ene
Propylcne
Butane- 1
Isobutylene
1, 3-Butadiene
Methane
TAME
N-I
0.
0..
0.
0.
3.
6.
1.
0.
0.
0.
61
08
20
41
28.
85
81
26
63
41
0.
0.
0.
0.
3.
5.
0.
0.
0.
C.
I
I
61
08
25
40
06
10
71
08
20
08
TAME J
N-I I
0.30
0.05
0.09
0.17
0.03
0.82
0.04
Bid
Bid
Bid
0.29
0.05
0.09
0.15
0.03
0.72
0.04
Bid
Bid
Bid
TAME K
N-I I
0
0
0
0
0
0
0
6
.21
.03
.05
.15
.04
.81
.06
-
-
-
.53
0.
0.
0.
0.
0.
0.
0.
6.
18
03
05
13
04
74
04
-
-
-
13
Bid = Below level of detection.
N-I = Nonirradiated atmosphere, exposure chamber with.
I = Irradiated.
94
-------
date, when a more stable system should have been established, was
considered to have more accurate atmospheric component values than TAME H.
Therefore, the concentration values from TAME J were compared to those
from TAME I to evaluate the effect of the catalytic converter on the
makeup of the auto exhaust emissions reaching the animal exposure chambers.
That comparison is emphasized by the large percentage reduction values
of several atmospheric components, which resulted from the use of the
platinum- and palladium-coated, pelleted catalyst (Table 4), and by the
greatly reduced concentrations of individual hydrocarbons (Table 3).
Since the dilution of the raw exhaust with clean air was not as
great in TAME J (8.7/1) as in TAME I (9.6/1), the reduction values
listed in the third column of Table 4 were adjusted by a factor appropriate
to the differences in dilution values (about 10 percent of the TAME J
values) to obtain the more accurate "normalized" values listed in the
fourth column.
A barely detectible concentration of platinum (0.029 yg/m3) was
indicated in the diluted emissions of the animal exposure chamber. This
result was, of course, for a system using a catalytic converter unit
that was quite new and that was shown to be adsorbing a large proportion
of the sulfur gases in the exhaust gases.
On the basis of an average flow of 1 m^/min of raw exhaust produced
at a calculated average speed of 35 km/hr (22 mph) on the engine dynamometer,
it was estimated that the 0.029 yg Pt/m represented a loss of nearly
0.37 vg Pt/km.
95
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Table 4. COMPARISON OF EXHAUST EMISSIONS, TAME-I AND -J
Exhaust Dilution Ratio
CO, ppm:
THC, ppm:
NOX, ppm:
NO, ppm:
N02, ppm:
Aldehydes, ppm:
Aliphatics, ppm:
C4-C5
Olefins, ppm:
^2~^4
Acetylene, ppm:
Ozone, ppm:
Particulatc, mg/m3
DJ1
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
N-I
I
•il. r:>
N-I
1
TAME -I
9.6/1
551
559
110
95
11.9
5.1
6.7
0.5
5.2
4.6
10.20
14.62
1.30
1.32
13.24
9.23
3.28
3.06
0.0
0.4
ch . 1 . 09
0.77
3.59
% Concentration
reduction
TAME-J I -> J
8.7/1
46 91.7
41 92.7
22 80.0
22 76.9
12.9
12.6
11.1
9.6
1.8
3.0
0.08 99.9
0.10 99.9
0.61 53.1
0.58 56.1
0.89 93.3
0.79 91.4
0.03 99.1
0.03 99.0
1 .10
] .08
1 .21
Normalized
% reduction
value
92.4
93.3
81.9
79.0
99.9
99.9
57.7
60.0
93.9
92.2
99.2
99.1
N-I = Nonirratintcd atmosphere, c.\po:.inr cli;i:iil>t-7 v. i t h .
I = Irradiated.
96
-------
If it is estimated that there is 0.04 troy ounce of the noble metal
in the catalytic unit (1.244 g), then 0.3 x 10~* percent of the platinum
was lost per kilometer (.62 mile). Such a loss over 80,000 km (50,000
miles) of operation would mean a total loss of 2.5 percent of the
platinum originally present.
CONCLUSIONS
The incorporation of the oxidation-type catalyst in the exhaust
system resulted in drastic changes in the exhaust emissions:
a. The effectiveness of the catalyst was revealed in the
large reduction of carbon monoxide, total hydrocarbons,
and various individual organic compounds (such as acetylene).
b. Almost total elimination of aldehydes was achieved.
c. In TAME I (without catalyst), the high value of particulate
in the irradiated atmosphere along with the low value of nitric
oxide (NO) and the measured presence of ozone indicated that
a much greater photochemical reaction of hydrocarbons occurred
there than in TAME J (with catalyst). That activity was
greater in the case of the olefins than in the acetylene,
and negligible for the aliphatics.
d. Gross evidence (color and weight stability) of the particulate
in TAME I indicated that the nature of the sample was mainly
organic. The particulate in TAME J, on the other hand, was
strongly acidic, was liquid in nature, and lost significant
weight on standing. Analysis showed sulfate to be the primary
constituent. Such facts suggested the presence of sulfuric
acid as the major component in TAME J particulate.
97
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SULFATE EMISSIONS RESULTING FROM USE OF HIGH-SULFUR
FUEL IN TAME-K
M. Malanchuk, N. Barkley, G. Contner, and M. Richards
INTRODUCTION
To supplement the data on exhaust emissions from catalyst-equipped
systems in which regular Indolene fuel was used, a. high-sulfur content
gasoline was substituted in Toxicity Assessment of Mobile Emissions
(TAME), study K. In that study, a quantity of thiophene was added to
the reference Indolene fuel to provide a sulfur level twice as great
(0.10 percent) as that normally present. A more detailed analysis of
the particulate was made in order to establish the concentration of
sulfate and of the expected high acidity.
EXPERIMENTAL PROCEDURE
The high acidity of the aerosol produced in the exhaust emissions
from oxidative catalyst-equipped systems was indicated in preliminary
runs of the 350 CID Chevrolet engine. Aerosol collected from an exposure
chamber on an electrostatic precipitator plate was a water-white liquid
and proved to be very acid by pH-paper test. Also, membrane-type filters
used to sample the exposure chamber atmospheres remained an undiscolorcd
white and deteriorated upon standing several hours, sometimes to the
point of breaking into fragments.
Therefore, quartz fiber filter material (Pallflex type 2500-QAO)
was used to collect aerosol samples at all the sampling points of the
piping system. Every filter was weighed immediately after sampling.
98
-------
Some were weighed again after several hours or overnight standing to
allow for equilLbration with the room atmosphere and stabilization of
the sample weight. Others that were used for aerosol acidity measurements
Cwhole filters or portions) were then placed without delay after the
early weighing into a beaker of a specified quantity of distilled
deionized water. At least 30 min was allowed for water extraction of
the sample before the initial measurements of conductance and of pH were
made. Final measurements of ion concentration were made 16 to 40 hr
later.
The aqueous extracts were subsequently used for determination of
sulfatc (SO^"), ammonium (NH* ), and nitrate (NO, ). Sulfate was analyzed
by the barium chloranilate method, ammonium by phenolhypochlorite
reaction, and nitrate by hydrazine reduction.3
Alternate analytical methods were used in some cases to confirm the
concentrations determined. A nephelometric method was adapted to sulfate
measurement, and an ion specific electrode applied to ammonium measurement.
These methods have limited use for the present group o£ samples because
of sensitivity and reproducibility requirements.
Gas samples for nitrate- and ammonium-producing components in the
atmospheres were collected by absorption into distilled water or into a
weak acid solution. For separation of S02 from SOj, the procedure1 used
was to draw the gas through a bubbler containing isopropanol and then
through hydrogen peroxide CH2^2^ solution or through tctrachlormercurate
(TCM) contained in two follow-up bubblers. The ammonium and the nitrate
99
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product concentrations were determined by the same methods cited for the
aerosol analysis. The SO^ sulfatc in the first bubbler and the SO?
sulfate in the peroxide bubblers of the three bubbler-train were analyzed
by the chloranilatc method. The SC«2 in the TCM absorption liquid was
analyzed by the Wcst-Gacke method.
The animal (population) occupancy of an exposure chamber was noted
by the number of cages anil activity wheels. A cage might contain three
adult rats, a litter of recently born rats with their mother, or a group
of four hamsters. An activity wheel was associated with a single mouse.
A record of the animal occupancy was kept for comparison with levels of
ammonium and acidity of the particulate in the atmosphere of the exposure
chamber.
RESULTS
A condensation of the analytical values for several ionic components
is given in Table 1. Gas and particulate values are listed for the
diluted atmosphere sampled immediately after the exhaust pipe and for
the atmospheres in each of several exposure chambers.
Total particulate for TAME K is shown in the fourth column of
values of Table 2, page 3 of the article, "Effect of Catalyst and of Fuel
Sulfur Content Upon Auto Exhaust Emissions." The sulfatc value for the
diluted exhaust pipe emissions (46.5 ymol/m^) in Table 1 of this article
represents almost 55 percent of the weight of the total particulate
(8.10 mg/m^). Considering the very highly acidic nature of the aerosol
(particulate), one must assume that the sulfate is, most likely, totally
sulfuric acid. On the basis of an average emissions volume generated by
100
-------
TABLE 1. TAME K: ATMOSPHERIC COMPONENT CONCENTRATIONS, ymol/m3
Component Exhaust
Pipe
Emissions
Diluted
GAS:
(NH4+)
(N03-)
(S04=)
(S02)
PARTICIPATE:
C2NH4+) 1.6
(NO ') 0.2
(S04=) 46.5
(2H+) 170.6
"Exposure
(irradiated,
15-10 cages)
0.4
7.3
15.0
2.0
38.6
1.2
32.8'
0.2
Exposure Exposure
(nonirrad- (nonirrad-
iated, iated, no
2-0 cages) animals
0.1
2.4
28.0 ' -
0
4.6 1.1
0 0
34.3 35.0
122.9 109.9
Exposure
(irradiated,
4-2 cages +
6 wheels)
0.22
8.70
_
-
7.9
0
34.2
54.7
Exposure
(nonirrad-
iated,
2 cages +
6 wheels)
0.33
6.25
_
-
21.9
0.9
31.3
—
Exposure
(nonirrad-
iated,
12 cages)
-
_
^
-
41.2
0
25.5
0
Exposure
(irrad-
iated,
6 wheels)
-
fm
,
-
11.4
0.6
31.3
97.0
-------
the engine of 1 ro3/nnn> and an average of 35 km/hr (22 mph) equivalent
road speed for the engine operation (California cycle), the total
particulate value of the diluted exhaust was calculated as approximately
0.13 gm/km.
Actually, the*acidity is so high that at the present time, it'is
unaccountable in terms of the amount of aerosol reported. Further work
is required to explain this phenomenon. The point should be made that
those filter samples that were not used in the extraction scheme sometimes
lost as much as 50 percent of their weight after standing overnight. It was
the initial weight upon which the total particulate calculations were
made.
Although values are given for (NH4+) and (N03~) in the gas phase,
(Table 1), it is assumed that the analytical procedures are accounting
mainly for ammonia (NH3) and for the contribution of nitrogen dioxide
(N02) to these ion centration values. The SO^ in most cases is probably
a fine mist of acid aerosol in the submicron size range of 0.1 micron or
less.
The particulate analyses of Table 1 show that the aerosol in the
diluted exhaust pipe emissions (first column) is a highly acid sulfate.
The aerosol in exposure chamber No. 15 (second column) is non-acidic and
contains ammonium (2NH4 ) nearly quantitative to the sulfate (S04=)
measured. It is not unreasonable to think, therefore, in terms of the
acid (such as sulfuric acid, 1)2804) or of the salts such as ammonium
sulfate, (NH^^SO^. The amount of sulfate measured in the exposure
chambers themselves represented an average of at least 15 percent of the
sulfur present in the fuel.
102
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REFERENCES
1. Kufta, R. J. Stationary Source Testing. Apollo Chemical
Corp. Sept. 1972.
2. Weathcrburn, M. W. Phcnol-Hypochlorite Reaction for
Determination..of Ammonia. Anal. Chcm. 39: 971, July,
1967.
3. Mauser, T. R. Method for Analysis for Nitrate by Hydrazine
Reduction. Water Research. 1: 205-216, 1967.
4. West, P. W., and G. C. Gaeke. Fixation of Sulfur Dioxide
as Disulfitomercurate (11), Subsequent Colormetric Estimation.
Anal. Chem. 28: 1816, 1956.
103
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TAMP. STUDll-S ADDENDA
AEROMETRY DATA FOR TAME L
M. Malanchuk, and J. Burkart
Although the TAME-L test conditions were distinctive in many, ways,
the results have been listed alongside those of TAME-K to show the
similarities and dissimilarities of two tests that at first glance might
be considered to be very much alike.
Table I compares the test conditions. TAME-L was a continuous run
through 52 days except for a two-hour period each morning when the
engine was turned off and the exposure chambers opened to service the
test animals for clean-up of chambers and cages and for provision of
fresh food and vvatcr. That servicing necessitated a cold start-up of
the engine at 0800 each day. The automobile engine was a new unit that
was substituted for the older one used for TAME-K; that older engine
had developed oil leak problems which made it unsuitable for the TAME-L
study. The same catalytic converter was used in TAME-L as in TAME-K;
however, there was a mechanical vibrator attached to the converter in
TAME-L to simulate road vibration during the entire run.
During its nearly 700 hours of use in TAME-L, the catalyst unit
gradually increased in outlet temperature of the gas from 760°F to a
peak of 1QOO°F, leveled off at about 985°F and dropped precipitously in
temperature when the new supply fuel was introduced into the engine on
day 30. That fuel was of lower sulfur content (0.01% S by weight) and
of higher aromatics content (32 vol. %). Consequently, much more
104
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Table 1.
Comparison of Test Conditions for TAME-K and TAME-L
TAME-K
TAME-L
Test Period, Days
Hours/Day, of Engine Operation
Fuel
Engine
Engine hours accumulated,
start-end of run
Period of run, hours
Engine miles accumulated,
start-end of run
Period of run, miles
Catalyst miles accumulated,
start-end of run
Catalyst miles accumulated,
start-end of run
Total fuel consumed, pounds
7 32
24 22 w. cold start
Ref.+thiophene Ref.+thiophene
'73 Chev 350 + new '73 Chev 350 +
catalytic conv. catalytic converter
675-841
166
13500-16820
3,320
465-632
9320-12640
1495
32-718
686
640-14360
13,720
774-1460
15480-29200
6270
Overall averages for the run:
Fuel, Ibs/hr
Exhaust oxygen, percent
Dilution air flow, scfm
Dilution ratio
Dilution tube temperature, °F
Catalyst temperature range, °F
Ave. catalyst temperature,,°F
Exposure chamber temp. § percent R.H.
Nonirradiated
Irradiated
9.02
4.7
324
9.5/1
101°
835-895
859
75°F/60% R.H.
75°F/60% R.H.
9.14
3.9
335
10.2/1
96°
760-1000
892
78°F/65% R.H.
76°F/66% R.H.
105
-------
thiophene had to be added to it to bring the sulfur level to the 0.10%
concentration maintained in the earlier fuel supply.
With a clean air dilution of the exhaust gases of 10.2/1, an average
dilution tube temperature of 95°F was attained as compared to 101°F
in TAME-K with its 9.5/1 dilution ratio. Exposure chamber temperatures
and relative humidity were a little higher in TAME-L.
Table II compares the test results of TAME-K and TAME-L. The
differences in the results appear to emphasize a greater activity of the
catalyst or else a lower input from the new engine during the TAME-L
run. Carbon monoxide(CO), concentrations were about 1/4 as much in
TAME-L as in TAME-K; total hydrocarbons (THC), were about 1/2 as much.
Aldehydes, and olcfins as represented by ethylene, were considerably
reduced in keeping with the THC picture. The lower nitrogen oxide
values in a system using the oxidative catalyst could be due to the use
of a new engine (conditions).
Total particulate (aerosol) concentration showed a very substantial
increase in the dilution tube and in the nonirradiated atmosphere of the
system. The irradiated atmosphere had a much smaller degree of increase.
However, measurements of sulfate in the particulate indicated a consistently
greater proportion of water in the samples from the "nonirradiated"
exposure chambers. Much of the increased amount of aerosol in the
nonirradiated atmosphere over that in the irradiated atmosphere was due
to the greater amount of moisture in the nonirradiated sample. The
sulfate content in the irradiated atmosphere filter samples was usually
no more than 10 percent lower than that in the nonirradiated atmosphere
106
-------
TAMIE-K and TAME-L
Exhaust Dilution Ratio
TAME-K TAME-L
9.5/1 10.2/1
CO, ppm
Exp. Ch:
N-I
I
THC, ppm, as methane
Exp. Ch: N-I
NOX, ppm
Exp. Ch:
NO, ppm
Exp. Ch:
N02, ppm
Exp. Ch:
N-I
I
N-I
I
N-I
I
Aldehydes, total, ppm
Exp. Ch: N-I
I
'Formaldehyde, ppm
Exp. Ch: N-I
I
Aliphatics, ppm, C2-Cc
Exp. Ch: N-I
I
Methane, ppm
Exp. Ch: N-I
I
Olcfins, ppm, cthylene
Exp. Ch: N-I
I
Acetylene, ppm
Exp. Ch: N-I
I
Particulatc, mg/m^
Dilution Tube
Exp. Ch: N-I
I
40
38
18
12.6
11.2
10.8
9.7
1.8
1.5
0.18
0.11
0.44
0.39
6.53
6.13
0.81
0.74
0.04
0.04
8.10
9.30
8.75
9.3
10.0
10.4
9.5
8.9
8.2
8.0
7.0
0.9
1.2
0.02
0.05
0.29
0.26
6.19
6.13
0.07
0.06
21.56
11. 85 CM 7% SO/I
107
-------
samples. Specifically, out of 15 simultaneous samplings that were taken
from the "nonirradiated" and "irradiated" exposure chambers in TAME-L
and those samplings were also checked for sulfate content (such paired
samplings were taken daily, but not all were analyzed for sulfate),
every "irradiated" sample was higher in sulfate (sulfuric acid) 'concen-
tration than the "nonii-radiated" sample with but one exception—a case
of the (nearly) same an.junt of sulfate per less amount of total particulate
giving a higher concentration reading for the sulfate. This finding
resulted from having the same amount of sulfate in a smaller amount of
total particulate which would give a higher sulfate value per unit of
particulate. Accuracy of the particulate measurements could be significantly
improved with availability of a temperature + humidity controlled room
devoted to the weighing of these humidity-sensitive samples.
A plot of the day ^tozday ..particulate jconcentrat ions at three different
points in the test exposure system, Figure 1, shows a steady drop during
the period until the very end when a sudden rise occurred after a supply
of new Indolene fuel had to be introduced in order to extend the study a
few more days. The same trend is seen in the atmosphere drawn from each
of the three sampling points - the dilution tube, the exposure chamber
with the non-irradiated atmosphere, and the exposure chamber with the
irradiated atmosphere.
The CO, THC, and NOX-NO-N02 values for TAME-L in Table II are mean
values for the 32-day study based on the computer tape values recorded
during the 22-hour, engine-on period.
Various analytical methods used to measure platinum and palladium
in the filter samples collected from the diluted exhaust emissions
108
-------
during the California 7-Mode cycle runs were inclusive in establishing
the amounts of those two elements in the emissions. Concentration values
obtained by atomic absorption spectrophotometry yielded emission values
calculated as 0^1.2 yg Ft/km (0-2 yg Pt/mi). Techniques using nuclear
energy sources to induce UV fluorescence yielded values of a decade or
two as great for the platinum and also for palladium.
109
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THE INHALATION TOXICOLOGY OF AUTOMOTIVE EMISSIONS
AS AFFECTED BY AN OXIDATION EXHAUST CATALYST
D. K. Mysell, W. Moore, R. Hinncrs, M. Malanchuk
R. Miller and J. F. Stara
INTRODUCTION
This report present* data from a series of acute animal exposure
studies which were designed to assess certain health hazards of automobile
exhaust from engines equipped with or without oxidativc catalytic converters.
It is expected that these catalytic converters will be widely used by
the automobile manufacturers in order to control exhaust emission levels
of carbon monoxide (CO) and hydrocarbons (HC) . The concern, of course,
is that use of these devices might release some other noxious or toxic
substances into the environment. Three studies are discussed in this
report: TAME I, J, and K. (TAME is an acronym used by us which means
toxicologic assessment of mobile emissions). TAME I was a study of the
biological effects of whole exhaust from an automobile engine with no
catalyst, which served as a reference or baseline study; TAME J was
identical except for the addition of an oxidative catalyst to the exhaust
train; TAME K had the catalyst plus additional organic sulfur compounds
added to the fuel to maximize production of sulfate emissions. (This
paper has been submitted to Environmental Health Perspectives for publication.)
EXPERIMENTAL METHODS AND RESULTS
A. Exposure System. The exhaust emission generation system used in
these studies consisted of a 1973 Chevrolet 350 CID production engine
equipped with exhaust gas recirculation (EGR), air pump, and turhohydramatic
transmission coupled to an "eddy current" absorption dynamometer. In
110
-------
each study, the engine system was run continuously for 7 days on a
modified "California" control cycle (Table I). The gasoline used in the
Chevrolet engine as a reference fuel was American Oil Co. unleaded 91
Octane Test Fuel, Intermediate Grade Indolene Clear (Table II). Note
that in TAME K, thiophcnc was added to the reference fuel to produce a
high sulfur fuel (1000 ppm). Some of the engine operating conditions
are summarized in Table III.
In TAME J and K, the exhaust passed through a noble metal pelletizcd
type oxidation catalyst (manufactured by Engelhard Co. to General Motors
specifications) and a muffler before mixing with CBR filtered and conditioned
air in a dilution tube. The diluted exhaust was piped to a large volume
mixing chamber and then entered dynamic flow irradiation chambers lighted
to simulate sunlight so that photochemical reactions might occur. The
irradiated exhaust then entered animal exposure chambers. Additionally,
the system provided nonirradiated exhaust in the same concentration to
other exposure chambers. In each study there were clean air atmospheres
and in TAME I there was a CO atmosphere for control animal exposures.
The catalyst was removed from the system for the TAME I exposure.
Aerometry. The major components characterized in the exhaust emissions
and methods used are summarized in Table IV. Particulate samples were
collected on pure quartz fiber filters. Bubbler and impinger samples of
the atmospheres were used for collecting ammonia and sulfur based gases.
The concentration in the exposure chambers of the various emission
components are shown in Table V. The incorporation of the oxidation
111
-------
03\BLE I
Modified "California Cycle" Used in the Fuel Emission Studies
Mode
Idle
Acceleration
Cruise
Deceleration
Cruise
Acceleration
Peak
Deceleration
Speed, M.P.H.
0
0 to 30
30
30 to 15
15
15 to 49
49 to 50
50 to 0
Time, Seconds
20
14
15
11
15
29
1.5
31.5
Total 137 sec.
112
-------
TABLE II
Ccnparison and Product Analysis of the Gasoline Used for
Exhaust Emission Studies
Shipment Number
Date Delivered
Quantity, gallons
Octane Number, research
Octane Number, motor
Lead Atm. Abs. , gm/gal.
Phosphorus, gm/gal.
Sulfur, wt. %
Aromatics, Vol. %
Olefins, Vol. %
Gum, Existent, mg/100 cc
Gravity, °API
Oxidation Stability, minutes
Ried Vapor Pressure, Ibs.
#1
3/30/73
2,000
91.4
82.9
0.01
0.002
0.04
25.4
11.8
0.8
61.4
600+
9.1
12
10/29/73
1,500
91.3
82.5
0.01
0.00
0.05
23.5
9.9
1.0
61.5
600+-
9.0
Note: Shiprrent £1 used for studies I and J.
Shipment #2 used for study K with Thiophene added
to produce 0.10% by weight sulfur.
113
-------
TABLE III.
Comparison of Engine Operating Conditions
Fuel
Engine
Engine liours
Study hours
Engine miles
Cumulative Catalyst hours
Catalyst miles
otal Fuel (Ibs)
Fuel, Ifcs/hr.
Exhaust Oxygen (%}
\ir/Fuel Ratio
Dil Consumption, qts.
Dilution Ratio
Dilution Air Flow
Average, SCFM
Dilution Tube Temperature
Average, °F
TAME I
Ref. only
•73 Chev.
No catalyst
255-425
170
8,500
1,545
9.08
N.A.
'TAME j
Ref. only
'73 Chev.
w/catalyst
444-615
171
12,300
465
9,300
1,601
9.40
4.2
TAM: K
Ref. + Sulfur
'73 Chev.
w/catalyst
675-841
166
16,820
632
12,640
1,495
9.02
4.7
14.4 cycling
12.4 idle
1/2
9.6/1
305
101
1/4
8.7/1
310
114
1/4
9.5/1
324
101
114
-------
TABLE IV
Characterization of Exhaust Emissions
•Pollutant corponent
Analytic method
VThere determined*
.Carbon monoxide (CO)
Total hydrocarbons
(THC) , as CH4
Nitrogen oxides
includes MO and
C^ to C5 hydrocarbcns
(several compounds)
C6 to C10 aromatic
hydrocarbons (several
compounds)
Aldehydes, total
Particulates, total mass
Particulate size distribution:
Aerodynamic
Photonoreric
Particulate corposition
Ozone, "oxidant"
Nbndispersive EPIJ, EC
Infra-red spectroscopy
Flame ionization EPM, EC
spectroscopy
Chemiluminescence EPM, EC
spec.; coloriiretry
using Saltzman reagent
Gas chromatography EC
Gas chromatography EC
MBTH according to Hauser EC
Filtration gravirretry EC
Stage impaction (Anderson) EC
Photoelectronic (Royco) EC
Infra-red and ultra- EC
violet spectrophotcmetry
Chemiluminescence scec.
EC
*EPM - Exhaust or primary exhaust: air mixture;
EC - exposure chamber
115
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TABLE V
Engine Exhaust Emission Values for Selected Components in the
Animal Exposure Chambers
Exhaust Dilution Ratio
CO, ppm:
THC, ppm:
NOX, ppm:
NO, ppm:
NXD2, ppm:
Aldehydes, ppm:
Miphatics, ppm:
C4-C5
51efins, ppm:
C2-C4
Acetylene, ppm:
>zone, ppm:
'articulate,
mg/M3
NIa
Ib
NI
I
NI
I
NI
I
vrr
I
NI
I
NI
I
NI
I
NI
I
NI
I
NI
I
TAME I
9.6/1
651
559
110
95
11.9
5.1
6.7
0.5
5.2
4.6
10.20
14.62
1.30
1.32
13.24
9.23
3.28
3.06
0.0
0.4
0.69
3.19
TAME J
8.7/1
46
41
22
22
12.9
12.6
11.1
9.6
1.8
3.0
0.08
0.10
0.61
0.58
0.89
0.79
0.03
0.03
_
—
0.96
1.09
TAKE K
9.5/1
40
38
18
18
12.6
11.2
10.8
9.7
1.8
1.5
0.18
0.11
0.44
a. 39
0.91
0.82
0.04
0.04
-
—
6.53
5.85
= nonirradiated exhaust
I = irradiated exhaust
116
-------
catalyst into the exhaust system resulted in a large reduction in CO,
total I1C, and various individual organic compounds. In TAME I, the
photochemical reactions in the irradiated atmospheres were very pronounced
as evidenced by the presence of ozone, the low value for NO, and the
high value for particulatc. The color and weight stability suggested
the particulate to be organic in nature. In TAME J and K, the particulate
was strongly acidic, was liquid in nature, lost significant weight on
standing and contained sulfate as a primary constituent. All of this
suggested sulfuric acid as the major particulate component.
C. Biologic Systems and Effects
1. Infant mortality and body weight determinations: Groups of 10
lactating female outbred albino rats and their 2-week old offspring
(10 suckling rats/litter) were exposed to each of the treatment
atmospheres for 7 days. Animals were weighed at the beginning and
end of the study. Infant mortality was noted on a daily basis. As
may be seen from Table VI, there was a prominent effect on infant
mortality in those animals exposed to exhaust in TAME I. This was
obviously not a CO effect alone, but rather due to the combination
of biologically active pollutants. A parallel effect was noted as
far as body weight changes (Table VII) in both the adult and suckling
animals. In TAME J and K, there were not pronounced treatment
effects on either of these parameters.
2. Clinical pathology determinations: Groups of 25 adult male
outbred albino rats were exposed to each treatment atmosphere.
Five animals per treatment were removed on days 2 - 6 of the study,
117
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TABLE VI
Survival of Suckling Rats Following Exposure to
Whole Automobile Exhaust
Clean air control
Nonirradiated exhaust
Irradiated exhaust
Carbon monoxide control
1MB I
100%
23%
0%
96%
TAME J
98%
100%
100%
. TAME K
100%
100%
100%
118
-------
TABLE VII
Daily Change in Body Weight (grams) in Rat£ During Exposure
to Whole Automobile Exhaust
Lactating Female Rats:
Suckling Rats:
TAME I
CAa + 2.2
NIb - 6.7
I c -11.7
Ctf3 + 0.4
CA + 2.0
NI - 0.6
I —
CO + 1.3
•TAME J
+ 2.9
- 0.2
- 1.3
+ 2.0
+ 1.9
+ 2.1
TAME K
+0.8
+2.2
+4.6
+ 2.1
+ 2.6
+ 3.3
a: Clean Air Control Atmosphere
b: Nonirradiated Exhaust Atmosphere
c: Irradiated Exhaust Atmosphere
d: Carbon Monoxide (550 ppm) Control Atmosphere
119
-------
anesthetized, and exsanguinated by abdominal aorta cathcterization.
The clinical laboratory determinations and treatment means are
shown in Tables VIII-XI. Again a treatment effect if present occurred
only in TAME I in the exhaust exposure groups with the more - prominent
changes in the animals exposed to irradiated exhaust. The high CO
levels had some effect on the hematologic parameters but was not
totally responsible. It should be further noted that the high CO
levels produced a rather striking increase in hemolysis resistant
red blood cells which necessitated manual determinations of white
blood cell counts. No treatment effect was noted in TAMG J or K.
Because of the historical association of platinum with allergic
responses, it was particularly interesting to note no increase in
eosinophils in TAME J or K.
3. Tissue chemistry determinations: Samples of lung, liver and
kidney were collected from animals exposed to the exhaust atmospheres
for determination of platinum (Pt) and palladium (Pd). The tissue
samples were lyophilized and wet digested using aqua regia with all
nitric acid fumes being eliminated by other additions of hydrochloric
acid and subsequent heating. The digested samples were transferred
with hydrochloric acid and deionized water to a volumetric flask
with an acid concentration of 10%. After the samples were treated
with potassium iodide, the metals were concentrated by organic
extraction using mcthyl-isobutyl ketone. Fifty microliter aliquots
were analyzed using a Perkin-Elmer 503 Atomic Absorption Spectrophotometer
equipped with a GHA 2000 Graphite Furnace.
120
-------
TKBIE VIII
Treatment Mean Values for Selected Hematologic
Parameters in Male Rats
RBC/cmm (x 106) :
WBC/cmm (x 103) :
Lymphocyte : neutraphil
Ratio:
HB (gm %) :
KT (%):
CA
NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
TAME I
7.07
7.62
7.78
7.44
9.1
11.9
12.0
15.7
5.3
1.7
1.0
2.3
14.9
16.5
16.7
15.2
41.6
46.6
47.4
43.2
TAME J
7.14
7.00
7.07
9.3
9.0
8.7
5.3
5.1
5.3
14.6
14.7
14.5
40.8
41.0
40.1
TAME K
7.01
7.21
9.4
8.8
4.8
4.9
14.5
14.7
40.4
41.0
121
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TABLE IX
Treatment Mean Values for Selected Blood Chemistry
.Parameters in Male Rats
Total serum protein (gm^) :
AlfceJire phosphatase (U) :
SGOT (R-F units) :
SGPT (R-F units) :
BUN (mg%):
CA
.NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
TM»3E I
6.0
6.3
6.8
6.3
79.1
54.2
40.8
79.4
161.6
185.3
196.7
175.2
48.5
60.5
53.7
45.8
23.8
21.0
28.3
20.0
TAME J
5.8
6.1
6.0
80.9
91.4
83.4
169.7
174.4
174.8
40.0
40.7
42.0
22.5
21.8
21.4
TAME K
6.2
6.2
94.5
89.8
161.8
162.8
47.2
46.4
19.1
19.4
122
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TABLE X
Treatment Mean Values for Selected Coagulation
Tests in Male Rats
•
Platelets/cmm (x 106) :
Fibrinogen (mg/dl) :
ProthroiTibin1 time (seconds) :
Partial throrrboplastin
time (seconds) :
CA
NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
CA
NI
I
CO
TAME I
0.95
1.07
1.10
1.08
170
165
220
160
12.5
12.9
12.6
.12.3
19.9
21.7
22.4
21.3
TAME J
0.93
0.97
0.92
175
175
170
12.2
12.1
12.3
19.9
19.3
19.2
TAME K
1.02
.98
177
175
12.2
12.2
19.1
18.7
123
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XI
Treatment Mean Values for Selected Serum Electrolytic
Constituents in Male Rats
Na+ (negA.): CA
NI
I
CO
K+ (negA.): CA
NI
I
CO
(IT (ireg/1.): CA
NI
I
CO
Ca** (negA.): CA
NI
I
CO
TAME I
133.2
136.6
135.7
142.6
4.8
5.0
5.2
5.2
103.2
104.4
102.1
106.2
4.9
5.0
4.9
4.7
TOME J
140.8
141.0
141.2
5.3
5.5
5.4
105.6
104.8
105.2
4.4
4.6
4.5
TAME K
142.2
142.8
5.3
5.6
105.2
104.2
4.6
4.7
124
-------
The ]owcr limits of detectability for total Pt and Pd in a
gram of tissue were 0.2 and 0.1 ug, respectively. No Pt or Pd
could be detected in any of the tissue samples from TAME I, J, or K.
4. Morphologic pathology determinations: Tissues from adult
outbred albino rats and adult male golden Syrian hamsters exposed
to each treatment were collected and fixed in 10% formalin. Specimens
of lung, 1Lvcr, and kidney were processed, paraffin embedded,
sectioned, hcmatoxylin and eosin stained, and examined microscopically
for evidence of morphologic changes attributable to the exposure.
There were no treatment related changes in TAME J or K. In
TAME I, however, there were extensive pulmonary changes which were
more severe in hamsters and most severe in those animals exposed to
irradiated exhaust. In the nonirradiated exhaust group, the pulmonary
changes were relateable to the levels of NC^, with an increase in
alveolar macrophages at the level of terminal bronchioles initially,
followed by a proliferative phase with some apparent increase in
epithelialization of respiratory ductules, and in thickness of
alveolar septae. In the hamsters exposed to irradiated exhaust
there was a very severe acute purulent bronchitis and .bronchiolitis
which progressed to a subacute purulent bronchopneumonia by the end
of the study. Additionally, there were some degenerative changes
in renal and hepatic tissue by the end of the study in these animals.
The only lesion which could be solely related to CO "levels was extra-
medullary hcmatopoiesis in the liver of the rats after 4 days exposure.
125
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DISCUSSION
The initiating force behind use of the oxidative catalytic converter
in the automobile exhaust train is the emission standards for CO and HC
as set forth in the Clean Air Amendments of 1970. The acrometry findings
in this study would suggest that there is in fact a very marked reduction
in CO and HC levels due to the use of the catalyst.
It was further expected that the oxidative catalysts would have
minimal effect on NOX levels, which again was corroborated by these
studies. The catalyst did have an indirect effect in the exposure system
used in these studies on levels of NC>2 and other oxidants (i.e. ozone)
which constitute some of the more biologically active exhaust compounds
relative to biological effects. The reasons for this relate to findings
that at HC/NOX ratios less than 3:1, no free oxidant is formed. These
same HC/NOX ratios have a similar effect on N02 levels due to the overall
N0-N02 reaction systems. In TAME I, the HC/NOX ratio was about 9:1; in
TAME J and K the ratios were about 1.5 - 2:1. This then helps explain
the pronounced reduction in acute toxicity associated with the exposures,
rather than the lower levels of CO alone.
As noted, the oxidation catalyst did have an effect on the type of
particulate with an increase in the acidic fraction (probably sulfuric
acid). There were not any demonstrable acute biological effects in any
of the animals studied, which were attributable to these altered particulates.
The study did not rule out possible chronic effects due to long-term
exposure either as a result of the increased sulfate emissions or attrition
products of the noble metal oxidation catalyst. It is therefore imperative
that long-term studies be initiated to provide this additional information.
126
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REFERENCES
1. Clean Air Act (42 U.S.C. 1857 ct seg) includes the Clean Air Act of
1963 (P.L. 88-206), and amendments made by the "Motor Vehicle Air
Pollution Control Act" - P.L. 89-272 (October 20, 1965), the "Clean
Air Act Amendments of 1966 - P.L. 89-675 (October 15, 1966), the
"Air Quality Act of 1967" - P.L. 90-148 (November 21, 1967), and
the "Clean Air Amendments of 1970" - P.L. 91-604 (December 31,
1970).
2. Korth, M., A. Rose, R. Stahman (1964) Effects of Hydrocarbon to
Oxides of Nitrogen Ratios in Irradiated Auto Exhaust. J. Air
Pollution Control Assn. 14: 168-175.
127
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PULMONARY MICROSOMAL MIXED FUNCTION MONOOXYGENASE ACTIVITY
FOLLOWING EXPOSURE TO CATALYTICALLY-TREATED AUTO EXHAUST
L. L. Hall, I. Washington, J. Adams, K. Campbell, Y. Yang, and W. Moore
INTRODUCTION
The lung serves as a primary target organ for many air pollutants
because it is a major portal of entry for atmospheric contaminants.
Chemical carcinogenesis is of considerable concern in relation to environmental
pollutant exposure either by carcinogen or co-carcinogen exposure. The
association of microsomal mixed function monooxygenasc with carcinogenesis1
suggested the determination of effects of catalytically-treatcd auto
exhaust on this system.
METHODS -
Three hundred and sixty (360) adult male Syrian hamsters weighing
121.29 *_ .055* gms were randomized into four studies with three treatments
per study. Two studies (I,III) were performed on non-induced animals,
and two studies (II, IV) were performed on hamsters where cytochrome P-450
was induced with bcnzo(a)pyrene (BaP) (25 mg/kg intraperitoneal) twenty-
four hours prior to sacrifice. Studies I and III were performed on
hamsters exposed continuously for five days to one of the following
atmospheres: 1) clean air (CA); 2) nonirradiated (NI); 3) irradiated
(I) exhaust. Studies II and IV were performed the same except for
induction on day five and sacrificed twenty-four hours later. The
animals were exposed to the test atmospheres during the induction phase.
*Coefficient of variation
128
-------
The hamsters were anesthetized (IP) with pcntobarbital, exsanguinated
by cutting the heart, and the lungs removed jLi^ toto and quickly immersed
in cold saline (4°C). The lungs from three animals were then trimmed of
bronchi, and connective tissue weighed, and placed in cold 0.15 M KC1
for homogenization with a Willems Polytron. Mixed function monooxygenase
•f'
activity (AHH) was assayed as described by Dixon et al. (1970)
where the fluorescence of the phenolic metabolite is used as an indicator
of BaP metabolism. Homogcnate concentration of 25 mg tissue/ml and a
sixty minute incubation period were used. The results are expressed as
the fluorescence equivalent to picomoles of 3-hydroxybenzopyrene formed
per minute per mg tissue protein.
RESULTS
Table 1 shows the effect of the experimental atmospheres on hamster
body weight and the lung weight-body weight (Iw/bw) ratios. .A-statistically
significant increase (3.94%) in the Iw/bw ratio was noted in the non-
induced animals exposed to irradiated exhaust for the five day experimental
period. No significant effects in the body weight or Iw/bw ratios were
noted in either the induced hamsters or animals exposed to nonirradiated
exhaust.
Table 2 shows the effect of auto exhaust on the levels of AI-IH as
reflected by fluorescent phenolic compounds. A statistically significant
(p = .05) reduction in basal activity was found in studies I and III
(non-induced) amounting to 18.59 and 12.13 percent, respectively,
following five days exposure to irradiated exhaust. No effect was noted
in the induced animals or the non-induced animals exposed to nonirradiated
exhaust.
129
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Table 1
Changes in Body Weight and Lung Weight/Body Weight Ratios Following
Exposure to Catalyst-treated Auto Exhaust
Experiment
Treatment
No. of
Animals
Body Weight*
LW/BW*
Non-induced
Clean air controls
Nonirradiated exhaust 60
Irradiated exhaust 60
120.98 (.08)
119.15 (.10)
121.90 (.09)
0.48835 (.05)
0.48986 (.05)
0.50758 (.06)**
Induced
Clean air controls
Nonirradiated exhaust
Irradiated exhaust
60
60
60
122.00 (.08)
121,75 (.08)
121.97 (.09)
0.49196 (.05)
0.49250 (.06)
0.49268 (.06)
* Number in brackets is coefficient of variation
** Significantly djfferent from controls at p = .05 level
130
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Table 2
Effect of Catalyst treated Auto Exhaust on Hamster Aryl Lung
Microsomal monooxygenase With and Without Induction
Study Treatment
1 (without induction) Clean Air
Nonirradiated
exhaust
Irradiated
exhaust
2 (with induction) Clean Air
Nonirradiated
exhaust
Irradiated
exhaust
3 (without induction) Clean Air
Nonirradiated
exhaust
Irradiated
exhaust
4 (with induction) Clean Air
Nonirradiated
exhaust
Irradiated
exhaust
Sample Size
10
10
10
10
10
10
10
10
10
10
10
10
Mean
.0.27942
0.28298
0.22747*
.83320
.82379
.77183
.24443
.26376
.21479**
0.76066
0.77262
0.70457
Var.
.00173
.00099
.00088
.01606
.01422
.00636
.00109
.00128
.00116
.00562
.01237
.00719
Cu
.132
.136
.142
.122
* CA = NI > I at p = .05 level
** NI >1; CA = NI; CA = I at p = .05 level
131
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DISCUSSION
Due to the length of this study, repeat experiments using the five
day exposure protocol were employed to determine the effect on the basal
levels of microsomal P-450 activity and also if exposure to auto exhaust
affected the hemoprotein induction phase. In addition it was possible
to perform repeated studies to ascertain the effect variability in a
controlled fashion. The depression noted following exposure to irradiated
exhaust is consistant with our previous experience. The increase in
sample size and dual experiments confirm the existance of the depressive
effect, its repeatability , and our ability to detect the change. Although
the depression is not large, it is real and based on our previous studies,
some speculation is possible regarding its causation. Previous experiments
have suggested an inverse relationship b'etween AHH activity and total
hydrocarbon, NC^, aldehydes and olefins. However, the increased particulate
in this study could be a contributor if it contains a significant amount
of H2SO^ since the levels of the other components are quite low. No
studies on the effect of H-S04 aerosol have been published so this
hypothesis is purely speculative and arrived at by default.
The increase in lung weight-body weight ratio which was not found
in other catalytic studies, is further suggestive evidence for a particulate
effect since this study showed the largest particulate loading of any of
the previous studies. Further research is necessary to resolve this
question.
The biological impact of the reduction is microsomal mixed function
monooxygenase following exposure to auto exhaust is uncertain at this
time. The experimental data available as to how AHH relates to chemical
1 2
carcinogens is unclear, but this may be resolved in the near future. '
132
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REFERGNCI-S
1. Forina, n. M. and J. W. Daly (1974). Arenc Oxides. A New
Aspect of Drug Metabolism. Science 185, 573
2. Dixon, et al. (1970) Cancer Res. 30: 1068
3. The Second International Symposium on Microsome and Drug Oxidation.
Published in Drug Metabolism and Dcsposition 1^, 1973.
133
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BIOCHEMICAL EFFECTS OF EMISSIONS FROM AN AUTOMOBILE ENGINE
WITH AND WITHOUT CATALYTIC CONVERTER
S. D. Lee, V. N. Finelli, L. McMillan, and R. M. Danner
As a part of the toxicological studies of automobile engines with
and without catalytic converters, the Biochemistry Section, in collaboration
with Dr. Finelli of the Department of Environmental Health at the University
of Cincinnati, has studied early biochemical alterations in rats exposed
to auto exhaust emissions.
MATERIALS AND METHODS
Experimental Animals
Each exposure experiment consisted of 30 female Spraguc-Dawley
rats, each animal weighing approximately 200 g, divided into three
groups of 10 animals: Clean Air CCA), non-irradiated (NI), and irradiated
(I).
Exposure Conditions
The exposure system has been described by Hinner et al. The
concentrations of major exhaust components in the exposure chambers have
2
been described by Malanchuk et al. Temperature and humidity in the
exposure chambers were kept constant throughout the experiment at 22°C
and 50 percent relative humidity, respectively. The exposures were
conducted 24 hr a day, for 7 consecutive days. Two animal exposure
experiments were conducted using the exhaust from the same engine with
and without the catalytic converter. In addition, an experiment was
performed by exposing a group of animals to carbon monoxide alone
134
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Ccxperiment CO) at a concentration of 575 mg/m^ (500 ppm), which approximately
reflects the carbon monoxide level observed in exposure chambers when
emissions from the engine without the catalytic converter was tested.
The following parameters were determined: hematocrits, serum,
lactate dehydrogenase (LDII), serum glutamic oxaloacetate transaminase
(SCOT), and serum lysozymc. Serum LDH and GOT were determined using
DADE reagent sets (American Hospital Supply Corp., Miami, Fla.), and
lysozyme was assayed with Worthington kits (Worthington Biochemical
Corp., Freehold, N. J.). Blood samples were obtained from animals by
tail vein puncture.
RESULTS AND DISCUSSION
Figure 1 shows the drastic effects on the hematocrit of the exposure
to emissions from the engine without the catalytic converters. At the
end of the 7-day exposure, very high hematocrit levels were observed in
the experimental animals: 62.3 +_ 1.5 percent for NI, and 66.2 +_ 0.5
percent for I, as compared to a normal value of 43.2 +_ 0.9 percent for
the clean air group. During a recovery period of 3 weeks, the hematocrit
values were obtained weekly, and a gradual return to normal was seen in
the animals of both NI and I groups. The animals exposed to carbon
monoxide showed an average hematocrit of 62.5 +_ 0.9, which is equal to
the value found for the NI group in the experiment without a converter.
The hematocrit in the animals exposed to emissions from the engine
equipped with a catalytic converter did not differ from control values.
From the above data, it seems that the elevation of the hematocrit is
due to the carbon monoxide concentration in the exposure chambers. The
135
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136
-------
levels of carbon monoxide in NT and I groups in the experiment without
the catalytic converter were 551 and 559 ppm, respectively; and for NI
and I groups with the catalytic converter, the carbon monoxide levels
were reduced to 46 to 41 ppm. The increased hematocrit may be due to
polycythemia and/or dehydration. Total serum protein or albumin analyses
were not obtained, and therefore the occurrence of dehydration cannot be
confirmed; however, the data collected from histological examination of
the experimental animals revealed the presence of large numbers of
ruptured red blood cells, which may indicate a polycythenic response.
To assess organ damage in exposed animals, the activity of LHD,
GOT, and lysozyme in scrum was assayed. These intracellular enzymes are
characteristic of appropriate organs, and an increase of enzymatic
activity in serum would indicate, presumably, a leakage of enzymes from
injured cells. SCOT was not significantly elevated in any of the exposed
animals, a fact that would indicate that neither liver nor heart were
damaged by exposure to various types of emissions and to carbon monoxide.
Serum LDH was elevated in the animals exposed to emissions from the
engine without a catalytic converter. Figure 2 shows that at the end of
the exposure period, the animals from both NI and I groups showed approximately
a 200-percent increase in serum LDH activity. In the recovery period,
while the NI group values tended to return to normal, the I group values
presented an unexplained erratic behavior; moreover we cannot explain
the low value obtained in the third week for the CA group. No significant
changes in LDH activity were observed in the experimental animals when
137
-------
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Figure 2. Serum LDH activities in animals exposed
to engine emissions without catalytic converter
138
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the converter was used, or when they were exposed to CO. Serum lysozymc
activity was not assayed in the experiment conducted without a catalytic
converter; however, in the experiment with a converter, the exposed
animals did not show any statistically significant elevation. From the
above preliminary results, it appears that the target organs of the
toxic components present in the emissions from engines without catalytic
converters are probably the lungs and/or kidneys.
The introduction of catalytic converters into the automobile exhaust
system not only has reduced the levels of certain exhaust constituents,
but has effectively decreased or eliminated the biological effects
studied.
REFERENCES
1. Hinners, R. G. and J. K. Burkart. Auto Exhaust Facility
Modification. Environmental Protection Agency, National
Environmental Research Center, Environmental Toxicology
Research Laboratory, Cincinnati, Ohio. Annual Report,
1973.
2. Malanchuk, N. Barkley, G. Contner, M. Richards, and R. Slater.
Exhaust Emissions During Steady-Speed Runs With The Catalytic
Converter In The Exhaust System. Environmental Protection
Agency, National Environmental Research Center, environmental
Toxicology Research Laboratory, Cincinnati, Ohio. Annunl
Report, 1973.
3. Mysell, H. K., W. Moore, R. (.'.. MilJor, M. Mai.nu link, and
J. Stara . Comparison of liiolo}>icvi I !•.ITcrls In l.;ihor.il ory
Animals Of exposure To Auto ('.missions With .mil Without A
Use of Catalytic Converter. A paper prcscnlcil .-it the
Annual Meeting of Air Pollution Control Association,
June 9-14, 1974.
139
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l:i-M-.Ub III- I:XI'USURE TO WHOLE EXHAUST EMISSIONS
FROM AN AUTOMOBILE ENGINE EQUIPPED WITH A
NOBLE MGTAL CATALYST
W. Moore and D. Hysell
and
J. B. Boatman, D. C. Thake, J. S. Walter and S. D. Carter
Batellc Columbus laboratories
INTRODUCTION
A contract (No. 68-03-0295) was let to Batelle Columbus Laboratories
for morphological examination of lung tissues from hamsters exposed in
the TAME L study. The exposure criteria and aerometry for TAME L arc
given in other reports in this document (TAME STUDIES ADDENDA - Aerometry
Data for TAME-L). This study was designed to determine whether
detectable changes were evident in the airways of hamsters exposed to
irradiated and nonirradiated catalytic treated auto emissions. Light
microscopy and scanning electron microscopy were used to evaluate
morphologic characteristics.
METHODS
For this study, 5 hamsters were sacrificed from each of the following
groups:
Group I - nonirradiated exhaust, 14-day exposure
Group II - irradiated exhaust, 14-day exposure
Group III - control air, 14-day exposure
Group IV - nonirradiated exhaust, 27-day exposure
Group V - irradiated exhaust, 27-day exposure
Group V - irradiated exhaust, 27-day exposure
Group VI - control air, 27-day exposure
140
-------
F.;ich animal was anesthetized with sodium pcntnharbitul ip, hcparinizcd,
and trachea exposed and cannulatcd. 'Hie lungs were fixed in situ under
pressure with Karnovsky's for 30 minutes and excised and fixed an additional
60 minutes. The lungs were then rinsed free of extraneous fixative and
placed in cold buffer for transporting to Battelle. In the Battelle-
Golumbus laboratories, part of the lung (superior right lobe) was prepared
for scanning electron microscopy and part for light microscopy. All SEM
evaluations were performed with a Cambridge Mark II stcreoscan instrument
with beam accelerating voltages of 20 mv. A total of 434 photomicrographs
was taken of fine-structural detail from 122 tissue fragments for evaluation.
RESULTS
Scanning Electron Microscopy
Only minor differences could be identified betxveen specific groups
of exposed hamsters, and no areas were found in any bronchiolar surface
which could be considered to represent significant lesions or sites of
major evidence for injury. This general observation was also supported
by the evaluation of light microscopy sections.
Such differences as were observed were considered to be subjective
assessments of relatively limited areas of the bronchiolar surface areas
under higher magnification. Variation in surface topography from site
to site was characteristic of all bronchiolar surfaces examined. Marked
variations between samples from the same lung, and between animals of the
same group, were also observed. Exposure to the irradiated and non-
irradiated exhaust appeared not to have impaired the functional integrity
of the bronchiolar surfaces to a level sufficient to exert substantial
structural and morphological changes, or to result in sites of frank
lesions.
141
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Histology
There was a moderate degree of variability in morphologic features
of bronchiolar epithelium among bronchioles within a given lung, and among
lungs from different animals. The bronchiolar epithelium was generally
columnar to cuboidal with flattened epithelium evident in limited areas
of bronchioles from several specimens, including those from control groups.
Bronchiolar epithelium was generally one cell layer thick although two
or more layers were occasionally visible. There was a "piling up" of
bronchiolar epithelial cells in most specimens examined. This appearance
possibly results from contraction of the bronchiole at death or during
processing. Cellular protrusions were evident in nearly all specimens
examined being more prominent in some sections than others. These
protrusions probably represent the nonciliated cells described above and
seen in the SEM photomicrographs. There was generally a decrease in
numbers of cilia in the smaller bronchioles. Cilia at all levels were
irregular in distribution as judged by histologic appearance. There was
moderate variation in appearance and distribution of cilia within
bronchioles of a given specimen, and this variation was generally consistent
throughout all specimens examined.
The only lesions observed were minor and were noted in animals from
control groups as well as exposed groups. These lesions consisted of
small foci of mononuclear cell accumulations on the visceral pleura,
small foci of mononuclear cell accumulations adjacent to bronchioles, in
one instance a collection of ncutrophils in 3 adjacent alveoli. These
changes, due to their nature and the fact that they appeared in control
142
-------
groups with frequency similar to that of exposure groups. Changes
correlatable to the variations described from SEM evaluations were not
observed.
143
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AUTO EXHAUST TOX1C1TY AND THE RKMOVAL OF PART1CULATE
FROM THE LUNG-- CATALYTIC CONTROL DEVICE STUDIES
L. Hall, J. Adams, I. Washington, K. Campbell, Y. Yang, and W. Moore
INTRODUCTION
The pulmonary route with a surface area of approximately 70m2 is
the major portal of entry for atmospheric pollutants and therefore the
first site where toxic effects can occur. Self-cleansing mechanisms arc
necessary for maintaining the overall integrity of this system. Intoxicants
which alter this system can therefore have a profound effect on the
ability of the organ to perform its physiological role. In order to
assess the effect of auto exhaust pollutants on this system, a challenge
test using an inert particulate, titanium dioxide, for assessing the
physiological state of the protective mechanisms was performed on hamsters
exposed to nonirradiatcd and irradiated auto exhaust.
METHODS
One hundred thirty five (135) adult male Syrian hamsters weighing
approximately 120 gms were randomized into three treatment groups (45
each) with three subsets (15/set) per group. Following seven days
exposure to auto exhaust under conditions described by Hinners and
Malanchuk (see this report), the hamsters were exposed to a test atmosphere
of titanium dioxide at a mean concentration of 16.4 mg Ti02/ni3 for 7.25
hours. The test Ti02 dust had an AMMD of 0.88 yM with a og of 1.67.
Immediately following the challenge, fifteen animals from each of the
clean air control (CA), nonirradiated (NI) and irradiated (I) exhaust
-------
treatments were sacrificed with pcntobarbital, .ind the lungs removed for
titanium analysis. The remaining hamsters were returned to their respective
treatment atmosphere. Additional subsets of 15 animals from each treatment
(CA, NT, I) were sacrificed after 8 and 25 days of exposure. The lungs
were weighed, lyopholized, wet ashed and assayed for Ti by a spectrophotometric
method using 4,4-diantipyrylmethane monohydrate.* The results are
expressed as wg Ti/gm lung dry weight and as percent of initial deposition.
RESULTS
Immediately following exposure to Ti02, an average of 109.98 vg
Ti02 (65.99 pg Ti) was deposited in the lungs. This is equivalent to a
pulmonary deposition of 15.4 ml of aerosol per minute which is in good
agreement with values (11.0) estimated from the data of Fcrin (1971).*
Table 1 shows the lung burden of titanium expressed as yg Ti/gm lung
dry weight and as percent of initial deposition at 0, 8, and 25 days
post Ti02 challenge in hamsters exposed to clean air, nonirradiated and
irradiated exhaust. No statistically significant treatment effects were
observed when the data as ug Ti/gm lung were analyzed by analysis of
variance. However, when the data for each treatment were normalized to
percent of initial deposition, a significant increase (12.5%) in titanium
clearance was noted on day eight. No effect was seen on day 25, possibly
due to an unexplained larger variance in these groups. This pattern of
behavior was noted in another study (Hall eit aK, unpublished)
145
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Table 1
Pulmonary Clearance folloxving Exposure to Catalytic-Treated
Auto Exhaust: Ti02 Challenge Lung Burden
Lung Burden of Test Titanium iJg/gm/(% initial deposition)
Treatment N/CeJl Day 0 Day 8 Day 24
CA 15 561.06 519.37 412.65
(100) (92.61) (73.55)
Nonirradiated 15 588.50 532.42 392.81
Exhaust (100) (90.49) (66.74)
Irradiated 15 571.22 463.11 401.40
Exhaust (100) (80.99)* (70.27)
*Significant at p = .05
146
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DISCUSSION
Maintanence of the integrity of the pulmonary cleansing mechanisms
is of paramount importance to the well-being of the organism. Changes
in these parameters, such as increased sputum i.e. mucus production, arc
correlated with chronic obstructive lung disease.^ Experimental induction
of lung cancer in an animal model was considered a difficult task before
the discovery of administering the chemical carcinogen carried by an
inert dust. Consequently, exposure to air pollutants which effect the
pulmonary cleansing mechanism could have profound adverse effects on the
well-being of the organism.
In this study, the efficiency of the lung cleansing mechanism was
assessed by exposing the hamsters to a test dust with minimal biological
activity and very low solubility. By comparison to clean air control
animal deposition and clearance behavior, changes due to experimental
treatment can be detected by difference in initial deposition (existent
lung pathology or abnormal physiology) or changes in the rate and
extent of removal of the challenge from the lungs of the auto exhaust
exposed animals. Following continuous exposure to catalytic treated
auto exhaust for seven days, no difference in initial TiOj deposition
was found between the control and treatment groups. This would suggest
minimal or no obstructive pulmonary pathology.
An accelerated removal of the inert dust was found in hamsters
exposed to irradiated exhaust at eight days post challenge suggesting
an increase in the rate of phagocytosis-mucociliary clearance
mechanism. Twenty-five days after administration of Ti02, no difference
147
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between the controls and treatment groups were detected. This was due
to the large increase in vnriance in this time period. The significance
of this phenomenon is not known. Likewise it is not possible from this
experimental design to determine whether those parameters responsible
for the eight day affect remained changed or returned to control rates.
Further studies are necessary to ascertain any long term effects of the
observed change in pulmonary clearance and its physiological significance.
REFERENCES
1. Ferin, J. (1971) Papain-induced Emphysema and the Elimination
of Ti02 Particulates from the Lungs. Amer. Ind. Hyg. J. 34, 260.
2. Health Consequences of Sulfur Oxides: A Report from CHESS, 1970-
1971. EPA-650/1-74-004, May, 1974.
3. Sattoitti, V., F. Cefis, L. Kolb, and P. Shubik. (1965) Experimental
Studies of the Conditions of Exposure to Carcinogens for Lung
Cancer Induction. JAPCA 15, 23.
148
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Appendix B6.1
Meteoro 1 ogica 1. Mode 11 .ing: Summary
An essential step between identification of an emission
product and assessment of potential public health risk is the
ability to estimate human exposures. For pollutants specific
to the automobile, a highway air pollution model has been de-
veloped to predict stable, gaseous pollutant concentrations
under various meterological conditions at the edge of and at
substantial distances from a "simple" highway (Appendix B6.2)
Exposure predictions specific to unique catalyst non-regulated
emissions products (sulfuric acid aerosols and noble metal
participates) have been estimated utilizing this gaseous dis-
persion model. A contractural program with ESL, Incorporated
(Contract no. 68-02-1233) was undertaken in June, 1973 to assess
the applicability of this model under real-world conditions by
measurement of a gaseous inert tracer (SFcj released from a
moving vehicle. A final report has not been received at this
time.
The dispersion model discussed relates to distribution of
a stable, gaseous emission product. The validity of the exposure
estimates calculated using this model for acid aerosols or parti -
culates is not qualitatively known. In addition, application of
such a model to complex vehicular sources or downtown street
canyons is probably inappropriate. An expanded FY75/76 program
has been planned to assess the validity of the gaseous dispersion
model for estimating exposures to aerosols and particulates from
moving vehicular sources. It is also intended that a complex
source/street canyon dispersion model be developed.
149
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The attached paper "Line Source Modeling" (B6.2) was recently prepared
which discusses the Gaussian approach to modelling the line source in more
detail than previously available and shows sensitivity of the model to
several parameter changes. The paper uses the catalyst-sulfate issue as
an example, and therefore expands upon the similar usage in EPA's earlier
projections of sulfate exposures on and near major highways.
The ESL contract, discussed above, which utilizes SF, as a trace to
validate the line source dispersion model, while not in final report form,
suggests that the sigma parameters used are too small by a factor of two or
three within 100m downwind of the highway. There are also indications that
the Gaussian nature of dispersion closer than 20m to the highway should be
questioned. A more extensive discussion of the sigma problem is found in
the attached paper, "State-of-the-Art of Transportation Diffusion Calcula-
tions including Recommended Improvements" (B6.3).
ISO
-------
EPA-650/4-74-008
Appendix B6.2
USER'S GUIDE FOR HIWAY,
A HIGHWAY AIR POLLUTION MODEL
by
John R. Zimmerman
and
Roger S. Thompson
Program Element 1AA009
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, N.C. 27711
February 1975
151
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USER'S GUIDE FOR HIWAY,
A HIGHWAY AIR POLLUTION MODEL
1. INTRODUCTION
The National Environmental Policy Act of 1969 requires any Federally
funded highway construction project to be preceded by an impact statement
analyzing the effect of the proposed roadway on air quality. This report
describes a computer program, called HIWAY, for calculating air quality
levels of nonreactive pollutants produced by highway automotive traffic at
distances of tens to hundreds of meters downwind of the highway in rela-
tively uncomplicated terrain.
In making estimates of pollution concentrations for an "at-grade" high-
way , highway emissions are considered to be equivalent to a series of finite
line sources. Each lane of traffic is modeled as though it were a straight,
continuous, finite line source with a uniform emission rate. Air pollution
concentrations downwind from a line source are found by a numerical
integration along the line source of a simple Gaussian point-source plume.
Although most applications of this model will be for ground-level sources
and receptors, and for receptors close to the source where mixing height
will have almost no effect, the more general case of nonzero source and
receptor heights and inclusion of the effects of mixing height can be con-
sidered by the model.
The HIWAY model is similar to the line-source equations (5.19 and
5.20) in the Workbook of Atmospheric Dispersion Estimates (Turner, 1970)
but can also consider finite line sources at any angle to the wind.
An estimate may also be made of air pollution concentrations downwind
of a "cut section." To do this, the top of the cut section is considered to be
152
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equivalent to an area source. This area source is simulated by using a
series of ten equal line sources such that the total source strength is equal
to the total pollution emissions of the highway.
No pollution emissions module is included in the batch (card input)
version of the model. A value of the line-source strength, q (g m sec ),
AF
for each lane of traffic must be obtained from a separate computation (Beaton
et al., 1972). Line-source strength is generally a function of traffic rate,
average vehicle speed, and traffic mix (fraction of heavy-duty vehicles,
fraction of late models with emission control devices, etc.). Data input for
the HIWAY program can be accomplished in two ways: (1) through batch
mode, with data cards that follow the program deck (see Section 4 for
format) and (2) through continuous mode, that is, interactively on a time-
share computer terminal. The term interactive refers to the information
exchange between the user and the computer program in asking and
answering questions.
In the interactive version of the model, to be discussed in Section 4
and Appendix A, the user can obtain a crude estimate of line-source emission
rate for the pollutant carbon monoxide. If one does not enter emission rates
interactively, an estimate of emission rate can be determined by entering a
value for vehicle speed and traffic volume per hour for each lane of traffic.
This emission rate is representative of that for 1969 model-year automobiles
(Ludwig et al., 1970) . According to Compilation of Air Pollutant Emission
Factors (EPA, 1973) , this emission factor of 58.7 g veh"1 mi"1 for a speed
of 19.6 mi hr"1 is also representative of emissions for the vehicle model mix
near the end of 1973. See Table 3.1.1-1 in EPA, 1973.
153
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2. DESCRIPTION OF MODEL
AT-GRADE HIGHWAY
A view of an idealized four-lane at-grade highway is shown in Figure 1.
Traffic pollution emissions from each lane are simulated in the computer
model by a straight line source of finite length. As shown in Figure 1 for a
four-lane highway, the location of the highway is specified by the coordi-
nates at the centerline (from edge to edge) of the highway (points 1 and 2).
The ordering of the lanes is from left to right when one looks from point 1
to point 2. One lane or any even number of lanes from 2 to 24 can be used
in the model.
The width of the highway and its center strip must also be entered as
input data. With this information; the computer program HIWAY will assign
a finite uniform line source to each lane of traffic. These line sources are
placed at the center of each traffic lane.
A uniform emission rate, q , must be specified for each line source.
Jb
This line-source emission rate can be found if the emission factor, EF
(g veh"1 mi~ ), and the traffic volume, TV (veh hr ) , are known:
EF (g veil'1 mi'1) TV (veh hr'1)
q-(gsec~1 nT1) = :— (1)
1609.3(m mi'1) 3600 (sec hr"1)
= 1.726 x 10"7 (EF) (TV)
A value of the emission factor for vehicles can be obtained from the most
current issue of Compilation of Air Pollutant Emission Factors (EPA, 1973).
It should be noted that for many pollutants the emission factor varies with
vehicle speed.
Calculations
The calculation of concentration is made by a numerical integration of
the Gaussian plume point-source equation over a finite length. The coordi-
nates (meters) of the end points of a line source of length D (meters) ,
IBM
-------
WIND| DIRECTION
RECEPTOR
Figure 1. Overhead view of the geometry of at-grade highway as seen by the computer model.
The endpoints of the highway are specified by the centerline coordinates, (R-| ,S-|) and (R2.S2).
while the receptor coordinates are given as (R|<,S|,). Line sources (four) are indicated by
the dashed lines at the center of each lane of traffic.
155
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representing a single lane extending from point A to point B (see Figure 2),
are RA>SA and RB>SB• Tne direction of the line source from A to B is 0
(degrees). The coordinates, R,S, of any point along the line at an arbitrary
distance, i (meters), from point A are given by:
R =
+ t sin 0
(2)
s = s
(3)
NORTH
t
WIND
%SA)
RECEPTOR
(Rk,Sk)
EAST
Figure 2. Line source and receptor relationships.
156
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uiven a receptor at "jf^fc* me aownwina distance, x ^meters; , ana
the crosswind distance, y (meters) , of the receptor from the point R,S for
any wind direction , 9 (degrees) , is given by:
x = (S - Sfc) cos 0' + (K - Rfc) sin 8 (4)
y = (S - Sfc) sin 0 - (K - Kfc) cos 0 (5)
Since R and S are functions of a , x and y are also functions of I . The con-
centration, X (g m~3) , from ihe line source is then given by:
(6)
where:
U = wind speed, m sec"
D = line source length, meters
/ = point source dispersion function (Equations 7 to 9), m~*
For application of this model to a highway segment in relatively open terrain,
an approximate estimate of the wind speed, u, at 2 meters height above
ground is suitable.
For stable conditions or if the mixing height is >. 5000 meters,
where:
oy = standard deviation of the concentration distribution in the
crosswind direction, meters
o z = standard deviation of the concentration distribution in the
vertical direction, meters
z = receptor height above ground, meters
H = effective source height,' meters
157
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In unstable or neutral conditions, if °z is greater than 1.6 times the mixing
height, L (meters) , the distribution below the mixing height is uniform with
height regardless of source or receptor height, provided both are less than
the mixing height:
(8)
In all other unstable or neutral conditions:
f ='
exp - -
- H - 2NI/
+ exp - -
H
exp
_ 1 fz + H + 2NL\ 2~1
" 2 ( ^ ) \
(9)
The infinite series in Equation 9 converges rapidly, and more than four or
five sums of the four terms are seldom required.
In each of the three above equations, °y and °z are evaluated for the
given stability class and the distances x + b for oy and x + a for ° z. The
virtual distances, a and b (km) , are required to produce the initial
oz and oy (ozo and ay0) • respectively.
If z, H, or both are zero, the resulting simpler forms of Equations 7,
8, and 9 are used by the computer program.
158
-------
The value of the integral in Equation 6 is approximated by use of the
trapezoidal rule. Let A X. = D/N. Then the trapezoidal approximation gives:
X =
q
i
u
N-l
1
2
/A/)
(10)
where fa is evaluated, as appropriate, from Equation 7, 8, or 9 for t = iA £.
The distances or and y are, of course, functions of £.
For a given initial choice of the interval length, A £, the calculation is
then successively repeated with twice the number of intervals, that is,
with A £/2, A £/4 .... until the concentration estimates converge to within 2
percent of the previous estimate. This value is then used as the value of
the integral.
The above evaluation of the integral is repeated for each lane of traffic,
and the resulting concentrations are summed to represent the total concen-
tration from the highway segment.
Computer Model
The FORTRAN computer program consists of a main program, three
subroutines, and two functions. The main program handles input and sets
up a separate line source for each lane of traffic. Subroutine DBTLNE does
the integration and output of results. This subroutine calls DBTRCX, which
evaluates Equations 7, 8, or 9, or simplifications of these equations if H or z
is zero. Evaluation of Oy and a z are done by subroutine DBTSIG, which is
called from DBTRCX. Functions XVY and XVZ determine virtual distances
for a given stability class corresponding to the initial ay and initial az,
respectively.
An east-north coordinate system is used in the computer model. The
width of the highway and of its center strip, the coordinates of the centerline
of the highway, and the coordinates of the receptor(s) are input parameters.
159
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It should be noted that in Equations 4 and 5, x and y refer to a coordinate
system aligned along the wind vector (jc the downwind direction, and y the
crosswind direction). That system is distinct from the coordinate system
used for locating sources and receptors in the model.
In the basic equations given earlier (Equations 2 to 5) , units of the
coordinate system have been specified as meters for dimensional balance.
However, units of the computer coordinate system, for practicality, are in
kilometers. The user may use any convenient highway map unit if he enters
an appropriate scaling factor to convert those units to kilometers. For
example, if it is desired to use the units of meters for highway coordinates,
the scale factor should be entered as 0.001. Section 4 contains a list of the
input variables, including a brief description of each of the units by which
the input parameters must be expressed. An example of input data, as well
as the output of a run made with the example input data, is given in Appendix
A.
CUT SECTION
Estimates of air pollution concentrations at locations downwind of a
depressed highway (cut section) can be determined by considering the top
of the cut section to be an area source of pollution (Figure 3) . In the model,
this area source is approximated by using ten line sources located at the top
of the cut section. The total emission rate for the highway is first found by
adding together the emission rates for each individual lane of traffic. Then
this emission rate is distributed equally over each of the ten line sources
used to simulate the area source at the top of the cut section.
Once this has been done, the procedure used to determine pollutant
concentrations downwind of the cut section is entirely similar to the procedure
used to determine the concentrations for an at-grade highway. It should be
emphasized that these estimates of air pollution concentrations should be
made for receptors downwind of the cut section and not for locations inside the
cut section itself.
160
-------
VERTICAL CROSS SECTION OF
POLLUTION SPREADING FROM
TOP OF CUT SECTION.
Figure 3. Method of simulating dispersion from a cut section. In this illustration, there
are four lanes of traffic in a cut section with pollution emission rates q-j, q£, 93, and 04.
These emission rates are summed up and distributed equally over ten line sources placed
at the top of the cut section, \e.,t\ =(q
161
-------
3. DISPERSION FUNCTIONS
-------
where c and d (degrees) are functions of Pasquill stability class and the
normalizing distance, xo, is 1 km. Values of the parameters c and d are
given in Table 2.
Table 2. VALUES OF c AND d
USED TO CALCULATE0n
Stability class
A (1)
B (2)
C (3)
D (4)
E (5)
F (6)
Value, degrees
c
24.167
18.333
12.5
8.333
6.25
4.167
d
2.5334
1.8096
1.0857
0.72382
0.54287
0.36191
The vertical dispersion parameter value,
equations of the form:
= 9
x + a
x
o
az (meters) , is given by
(13)
where a is the virtual distance (km) to give the initial oz (meters) , and
g (meters) and h (dimensionless) are functions of stability class and also
various ranges of the distance x. When a is zero, the values are the same
as those in Figure 3-3 of Turner (1970) . Since the values of oz for x less
than 0.1 km are not given in that figure, the values of the parameters g and
h for or less than 0.1 km are given in Table 3. The values corresponding
to g and h for x at other distances can be determined by examining the
program listing for subroutine DBTSIG (Appendix B) .
Turbulence of the air produced by the motion of automobiles results in
a rapid mixing of the pollutants near the highway. This is modeled by
assuming that an initial spreading of the pollutant plume occurs over the
highway. To determine an acceptable initial vertical plume spread, data
taken near at-grade sections from various highways were used. When the
163
-------
Table 3. VALUES OF g AND h USED TO DETERMINE az
FOR DOWNWIND DISTANCES LESS THAN 0.1 km
Stability class
A (1)
B (2)
C (3)
D (4)
E (5)
F (6)
Value
g, meters
122.8
90.673
61.141
34.459
24.26
15.209
/it di men's ionl ess
0.9447
0.93198
0.91465
0.86974
0.8366
0.81558
wind direction is less than 75 degrees from the perpendicular to the highway,
it has been shown that an approximate expression can be used to determine
pollutant concentrations from an infinite line source (Calder, 1973). Solving
this expression for oz yields:
*z(x) =
C(p) u cosy
(14)
where:
oz (x) = the vertical standard deviation of plume distribution
at the downwind distance, x, from the source
C(p) = the measured concentrations at the perpendicular distance,
p (meters) , from the highway
g m
-3
Y = the angle between the wind direction and a perpendicular
to the highway, degrees
By making estimates of the line-source emission rate, q 0 , and obtaining
J6
observed data for air pollution concentrations, a plot of oz versus distance
was determined (Figure 4). From this analysis, it is seen that an initial
o z ( aZQ) equal to 1.5 meters is a conservative approximation of the vertical
-------
20
18
16
14
12
ID
g. .
o
o
100 150 200 250
PERPENDICULAR DISTANCE DOWNWIND OF HIGHWAY, meters
Figure 4. Data points used to determine an estimate of initial
-------
cross-highway spreading caused by vehicle-generated turbulence when the
wind direction is parallel or nearly parallel to the highway.
The virtual distances, a, corresponding to an initial oz of 1.5 meters
and the virtual distances, b, corresponding to an initial Oy of 3.0 meters
for each stability class are given in Table 4.
Table 4. VIRTUAL DISTANCES a AND b
CORRESPONDING TO INITIAL o-z OF 1.5 METERS
AND INITIAL o-y OF 3.0 METERS, RESPECTIVELY
Stability class
A (1)
B (2)
C (3)
D (4)
E (5)
F (6)
Distance, km
a
0.00944
0.01226
0.01736
0.02722
0.03590
0.05842
b
0.00863
0.0132
0.0210
0.0348
0.0471
0.0733
There are very few published measurements of air quality downwind
of a cut section. Nevertheless, the available data indicate that the cut-
section configuration tends to increase the dispersion of the air pollution
originating from the cut section. This is particularly true when wind
speeds are light, for then the release of heat from combustion, the long
travel time of the pollutant to the receptor, and mechanical turbulence
produced by the cut-section highway aid the dispersion. Thus , for the
cut-section case, based upon very limited data, the initial o's for wind
speeds less than 1 m sec"1 were set at 10 meters for Oy and 5 meters for
oz. It was assumed that for wind speeds greater than 3 m sec"1 the cut
section did not enhance the initial dispersion and that it was the same as
for the at-grade highway: 3 meters for oy and 1.5 meters for oz. For
speeds between 1 and 3 m see"1, the initial sigmas are linearly interpolated.
These initial o's are assumed for each of the ten lanes used to represent the
cut. The initial values of oy and oz (meters) are found from:
166
-------
'yo = 3
for u > 3 m sec
(15)
"yo = 10-7
for 1 < u<3 m sec
(16)
-------
4. PREPARATION OF INPUT DATA
CARD INPUT SEQUENCE
The arrangement of data on the input cards for the batch mode of
operation is given in Table 5. The coordinates of the roadway are in the
center of the highway (from edge to edge) . The ordering of the lanes is
from left to right when looking from point 1 to point 2.
INTERACTIVE OPERATION
The HIWAY model has been placed on the Environmental Protection
Agency's (EPA) Users' Network for Applied Modeling of Air Pollution
(UNAMAP) computer system and is accessible to EPA users. The model is
also on the UNAMAP system available to all users. For information on this
system contact: Chief, Data Management, Meteorology Laboratory, U .S.
Environmental Protection Agency, Research Triangle Park, N. C. 27711.
The self-explanatory listing produced by the model on a remote com-
puter terminal is shown in Appendix A to illustrate the operation of the
model in an interactive mode. The computer communicates to the user in
upper case letters, while the user replies in lower case letters. To initiate
the program, the user issues the command, hiway.
Operation of the model in an interactive mode is similar to batch mode
operation. To determine emission rates for the pollutant carbon monoxide,
however, the user can elect the option to use the internally generated
emission rates for carbon monoxide that are representative of the emissions
for the vehicle model mix near the end of 1973. This applies a correction
factor for vehicle speed.
168
-------
Table 5. INPUT DATA CARDS
Name
Card type 1 (1 card)
Head
Card type 2 (1 card)
RE PI
SEP1
REP2
SEP2
H
WIDTH
CNTR
XNL
Card type 3 (up to 3
cards)
QLS
Card type 4 (1 cards
can be blank for at
grade)
CUT
WIDTC
Card type 5 (1 card)
THETA
U
HL
XKST
Card type 6 (1 card)
GS
Card type 7 (any num-
ber of cards)
XXRR
XXSR
Z
Columns
1-80
1-10
11-20
21-30
31-40
41-50
51-60
61-70
71-80
1-80
1-10
11-20
1-10
11-20
21-30
31-40
1-10
1-10
11-20
21-30
Format
20A4
'
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
F10.0
Form
AAAA
XXXX.XXX
XXXX.XXX
XXXX.XXX
XXXX.XXX
XX. X
XX.
XX.
X.
.xxxxxxxxx
X.
XX.
XXX.
XX. X
xxxx.
X.
X.
XXXX.XXX
XXXX.XXX
XX.
Variable
Alphanumeric data for
heading
East coordinate, point 1
North coordinate, point 1
East coordinate, point 2
North coordinate, point 2
Height of line source
Total width of highway
Width of center strip
Number of traffic lanes
Emission rate for each lane
1, 1f cut; 0. 1f at grade
Width of top of cut section
Wind direction
Wind speed
Height of mixing layer
Pasqulll stability class
Scale factor9
East coordinate of recep-
tor13
North coordinate of recep-
tor
Height (above ground) of
receptor
Units
Map units
Map units
Map units
Map units
Meters
Meters
Meters
-
g secern"1
-
Meters
Degrees
•n sec"1
Meters
-
„
Map units
Map units
Meters
a The scale factor converts map units to kilometers.
If map units In kilometers, scale factor • 1.0
If map units 1n meters,
If map units In .feet,
If map units 1n miles,
bTo begin again with another set of data, a value of 9999. is punched for XXRR (card type 7)
following the last receptor card.
scale factor = 0.001
scale factor = 0.000305
scale factor • 1.61
169
-------
REFERENCES
Beaton, J .L., A .J. Ranzieri, and J .B. Skog (1972) . Motor Vehicle Emission
Factors for Estimates of Highway Impact on Air Quality. In: Air Quality
Manual, Vol. 2. California Department of Public Works, Division of
Highways. Sacramento, California. Report No. FHWA-RD-72-34.
April 1972. 58 p.
Calder, K .L. (1973). On Estimating Air Pollution Concentrations from a
Highway in an Oblique Wind. Atmos. Environ. 7_: 863-868, September
1973.
EPA (1973) . Compilation of Air Pollutant Emission Factors, 2nd Ed. U .S .
Environmental Protection Agency. Research Triangle Park, North
Carolina. Publication No. AP-42. April 1973.
Holzworth, G .C. (1972) . Mixing Heights, Wind Speeds, and Potential for
Urban Air Pollution throughout the Contiguous United States. U.S .
Environmental Protection Agency. Research Triangle Park, North Carolina.
Publication No. AP-101. 1972. 118 p.
Ludwig, F .L. , W .B. Johnson, A .E . Moon, and R .L. Mancuso (1970) . A
Practical Multipurpose Diffusion Model for Carbon Monoxide. Stanford
Research Institute. Menlo Park, California. Contracts CAPA-3-68 and
CPA 22-69-64. 184 p.
Pasquill, F. (1961). The Estimation of the Dispersion of Windborne Material.
Meteorol. Mag. 90(1063): 33-49, 1961.
Turner, D .B. (1970) . Workbook of Atmospheric Dispersion Estimates. U.S.
Environmental Protection Agency. Research Triangle Park, North Carolina.
Publication No. AP-26. 1970. 84 p.
170
-------
GLOSSARY
Several frequently used terms have become part of the jargon used by
air quality dispersion modelers, and these terms are defined briefly in this
section. For a more complete discussion of the concepts implied by these
terms, the reader should consult the references cited.
Stability class: Atmosoheric stability ranked according to classes, which
are given in indexes A through F (or 1 through 6), as shown in Table 1 (Pas-
quill , 1961). Class A is very unstable and is found when skies are clear and
sunny, while class F is moderately stable and occurs under calm conditions
on clear nights.
Mixing height: The height to which pollutants are actively mixed. The
air close to the earth's surface generally becomes unstable after sunrise,
resulting in a zone of vigorous atmospheric mixing in the layer of air at ground
level. The height of this layer increases after sunrise and reaches a maximum
about 4: 00 p.m. (Holzworth, 1972). For most locations close to the pollution
source, the mixing height will have very little influence on the calculation of
pollution concentration. When the receptor is located at a great distance from
the pollution source and the travel time of the pollutant from source to recep-
tor location is long, the mixing height will be the limiting height to which
pollution will spread vertically.
Receptor: A location for which it is desired to predict pollutant concen-
trations. When a model is being validated, it is necessary to obtain model
predictions at the receptor locations for which air quality data are measured.
Emission rate of a line source: An estimate of the amount of pollution being
generated by a line source (e.g. , lane of automobile traffic) . To determine this
value, two pieces of information are required: (1) the volume of traffic and
(2) the emission factor, which is dependent on vehicle speed. The emission
rate can then be determined by
q£ = (CV) (EF) (TV)
171
-------
where:
q = line source emission rate, g sec" 1 m~ *
-1 -i
EF = emission factor, g veh mi A
TV = traffic volume, veh hr"1
CV - conversion constant = 1.726 x 10" , mi hr m~ see"*
oy and az: The standard deviation of concentration distribution in the
horizontal and vertical planes, respectively. The values of Oy and 07 will
increase with downwind distance from the source of pollution as the dimensions
of the pollution plume increase. This increase in pollution plume dimension is
caused by atmospheric turbulence. The intensity of atmospheric turbulence is
in turn related to atmospheric stability. The plume growth will be greatest in
an unstable atmosphere (more turbulence) and least when the atmosphere is
stable.
172
-------
APPENDIX A. EXAMPLE PROBLEM
173
-------
INTRODUCTION
In order to clarify the procedure for using both the batch and interactive
(continuous) versions of the HIWAY model, the following test problem is solved
using both versions.
Given: Length of highway - 5 km.
Orientation - east-west.
Number of lanes - four.
Road width (edge to edge) - 46 meters.
Median width - 30 meters.
Emission rate in each lane from south to north - 0.0112, 0.0103,
0.0106, and 0.0156 g sec'1 m"1.
Wind direction - 42 degrees.
Wind speed - 3.7 in sec" .
Stability class - 3.
Find: The expected concentration at receptors along a line perpendicular
to the center of the highway segment at distances 1, 5 , 10, 30, and
50 meters from the downwind edge of the roadway (1) if the road
is an at-grade section, and (2) if the road is a cut section with the
top of the cut being 50 motors in width.
SOLUTION USING THE INTERACTIVE VERSION
Assuming that you have already logged on the computer, etc., type in the
name hiway as indicated in Table A-l. You are then given the choice of re-
ceiving a description of the model. Following that, enter the input parameters
as the model calls for them. Most of them are self-explanatory; however, a
few comments are in order:
1. When entering the mixing height never use the value 0.
2. If you do not want the effect of a limit to vertical mixing in your cal-
culation , use a large enough mixing height so that there is no chance
of its influencing your results, such as 5000 metors.
174
-------
3. When entering the receptor coordinates, remember that this program
is valid only downwind of the line source. A receptor location defined
on the line source will not give a valid answer. If you are interested
in the concentration at the edge of the highway, use a downwind dis-
tance greater than 0.1 meter from the edge of the highway and the
result will be valid.
4. The coordinates for the ends of the roadway segment are assumed to
be in the center of the road (from edge to edge).
5. The ordering of emission rates is for lanes in order from left to right
when looking from point 1 to point 2.
The results for the at-grade section are given following the entry of
receptor coordinates. For convenience, the center of the roadway has been
placed 0.023 km north of the origin in this example so that the edge of the
road is on the axis and the y coordinate of the receptor is the distance from
the edge of the road. The roadway and receptors could have been placed
at any location.
The option to run the model for a new receptor location (LOG) , change
the road type (TYPE) , or to end the program (END) is given after the
results.
In the second part of the problem, the road type (cut) , the width
(50 meters) , and the location of the road (to again place the edge of the
road at a y coordinate value of zero) are changed. The results for the cut
section are shown following the entry of data. Note that the concentrations
are in micrograms per cubic meter (UGM/M**3). The part per million (PPM)
column is a conversion from micrograms per cubic meter for the pollutant
carbon monoxide. The part per million column would be incorrect for any
other pollutant.
If you decide to continue and change the receptor locations (LOG) ,
remember that the receptors must remain downwind from the downwind
edge of the roadway.
175
-------
SOLUTION USING THE BATCH VERSION
The batch version requires at least seven input cards. Depending upon
the number of receptor points and number-of problems to be run , there may
be more. The format for each card is given in Table 5. Table A-2 lists the
input for the example problem; Table A-3 lists the results. Note that for
the cut section the sixth and seventh fields (columns 51 to 70) in card type
2 were left blank. Also note that the card with 9999. for the variable XXRR
is only used if more than one set of input data are used. A card like this
does not follow the last set of input data. As in the interactive version, the
parts per million column is only valid if carbon monoxide is the pollutant
being modeled.
176
-------
Table A-l. EXAMPLE OF INTERACTIVE VERSION OF HIWAY
hiway
DO YOU WANT A DESCRIPTION OF THE EPA "HIWAY" MODEL
BEFORE APPLYING IT7CYES OR NO)
yes
l.THE EPA "HIWAY" MODEL COMPUTES IMERT POLLUTANT CONCENTRATIONS IN THE
VICINITY OF A ROADWAY ON A SHORT TERM BASIS (HOURLY AVERAGES) USING
THE GAUSSIAN PLUME FORMULA! ION. IF MORE THAN ONE RO'\DV'AY IS PRESENT,
SUPERPOSITION APPLIES. THE MODEL CAN BF. USED F™> AT GRM1E \MD CUT
SECTIONS FOR RECEPTOR DISTANCES OF TENS TO MUNDREOS OF METERS DOWNWIND
OF THE LINE SOURCE IN RELATIVELY UMCOMPLICATE" TERPAI'l.
2.THE COORDINATE SYSTEM IS -VROAMnRH SMC" THAT THE K^XIS INCREASES FPOM
.WEST TO EAST WHILE THE Y-AXIS HCPRASES FPOM S^UTH TO MOOT!'.THE UNITS
RELATEH TO HIGHWAY "RASUPEMEMTS ARE INDICATED P,Y ^ SCAL* CACTOR OF
USER UNITS TO KILOMETERS. TMC MOST F&EOljrmY USFH FACT*nS ARE:
UMTS SCALE r/v^Tnp
KILOMETERS 1.0
METERS O.nQl
FEET 0.000^05
MILFS 1.6i
SCALE FACTOR UNITS *\PPLY EXCEPT 1'HEH ^THED H'MTS APF SPECIFICALLY
REOIJESTED.
3.THE EMISSION TATA IS nEPEMDF.MT n'l VFMIHLF SP^EO^YOES ANn MUM3ER OF
VEHICLES^ANO EMISSION CONTROL DEVICES.THE PROGRAM WILL GENERATE AN
EMISSION RATE BASED OM A'J ESTIMATE OF AVERAGE ROADWAY SPEED AND
VOLUME OF TRAFFIC. UTERNATIVELYXTHF USER CA'J ELECT TO SPECIFY HIS
OWN EMISSION RATES IN GRAMS PER SECOND-METER.THE LMTER APPROACH IS
HIGHLY PREFERABLE SINCE THE INTERNALLY GENERATED RATE IS BASED UPON
A SPECIFIC AUTOMOBLE MIX (END OF 1973) WHICH DOES NOT APPLY ACCURATELY
IN MOST CASES. EMISSIONS (GM/SEOM) ARE ENTERED IN ORDER FROM LEFT
TO RIGHT WHEN LOOKING FROM POAD END PT 1 TO END PT 2.
4.ROAD COORDINATES ARE THE ENDPOIMTS OF THE HIGHWAY CENTER LINE.
l/l.'ID DIRECTION IS DERIVED BY MEASURING CLOCKWI SE(EAST) FROM
DUE NORTH.(E.G..WIND FROM NORTH IS 0 DEGREES;EASTERLY WIND IS 90.)
5.THE PROGRAM CONTAINS THE OPTION TO EVALUATE ANY NUMBER OF
RECEPTOR LOCATIONS AND/OR TYPES op ROADS.
6.YOU MUST SEPARATE MULTIPLE INPUTS WITH COMMAS.
7. FOR MOST APPLICATIONS,THE HEIGHTS OF THE RECEPTOR
SOURCES ARE USSUMED TO RE THE SAME.
-------
a 3
Table A-l (continued). EXAMPLE OF INTERACTIVE VERSION OF HIWAY
DO YOU WANT A DESCRIPTION OF THIS VERSION OF "HIWAY"?(YES nR MO)
no
ENTER SCALE FACTOR (USER UN ITS/KI LOf'ETER).
1
ENTER LINE(ROAD) ENDPOINTS.(ORDERED PAIPStXT,Y1,X2,Y2)
2.5,.023/-2.5/.023
ENTER EMISSION HEIGHT. (METERS)
0
ENTER WIND DIRECTION (DEG). NORTH IS ZERO.
ENTER WIND SPEED (METERS/SEC).
3.7
ENTER MIXING HEIGHT (METERS).
1000
ENTER PASQUILL-TURNER STABILITY CLASS (1-6).
ENTER THE NUMBER OF LAMES.
k
DO YOU WISH TO ENTER YOUR OWN EMISSION RATES?(YES OR NO)
yes
ENTER LINE SOURCE STRENGTH VECTOR.(A VALUE FOR EACH LANE)
.0112,.0103,.0106,.0156
IS THIS A CUT SECTION? (YES OR MO)
no
ENTER HIWAY WIDTH (METERS).
1*6
ENTER WIDTH OF CENTER STRIP (METEPS).
30
ENTER NUMBER OF RECEPTOR LOCATIONS "HSI RED.(MAXIMUM OF 25)
5
ENTER RECEPTOR COORDINATE SETS.(X*Y IN SCALE FACTOR UMITS;Z IN METERS)
0,-.001,0,0,-.005,0,0,-. 010,0
0,-. 030,0,0,-. 050,0
-------
Table A-l (continued). EXAMPLE OF INTERACTIVE VERSION OF HIWAY
HtWAY VERSION: 71*250
ENDPOINTS OF THE LINE SOURCE
2.500, .023 AND -2.500, .023
EMISSION HEIGHT IS 0.000 METERS
EMISSION RATE (GRAMS/SECONO*METER) OF k LANE(S)
.112-01 .103-01 .106-01 .156-01
WIDTH OF AT-GRADE HIGHWAY IS 46.000 METERS
WIDTH OF CENTER STRIP IS 30.000 METERS
WIND DIRECTION IS l»2. DEGREES
WIND SPEED IS 3.7 METERS/SEC
STABILITY CLASS IS 3
HEIGHT OF LIMITING LID IS 1000.0 METERS
THE SCALE FACTOR IS 1.0000 USER UNITS/KM.
•vl
VO
RECEPTOR LOCATION HEIGHT COMCEMTRAT1OM
X Y Z (H) UGM/M**3 P»M*
.0000 -.0010 .0000 I»UI»9. 3.871
.0000 -.0050 .0000 3831* 3.333
.0000 -.0100 .0000 329U. 2.866
.0000 -.0300 .0000 218U. 1.900
.0000 -.0500 .0000 1669. 1.U52
* PPM CONCENTRATIONS CORRECT FOR CARBON MONOXIDE ONLY.
-------
Table A-l (continued). EXAMPLE OF INTERACTIVE VERSION OF HIWAY
YOU HAVE THE OPTION TO RUN THE MODEL FOR A NEW RECEPTOR LOCATION
(LOO,OR TO CHANGE THE ROADWAY TYPE,OR TO END THE PROGRAM.
ENTER LOC, OR TYPE, OR END.
type
ENTER LINE(ROAD) ENDPOINTS.(ORDERED PAIRS:X1/Y1/X2/Y2)
2.5/.025/-2.5,.025
ENTER EMISSION HEIGHT. (METERS)
0
ENTER WIND DIRECTION (DEG). NORTH IS ZERO.
k2
ENTER WIND SPEED (METERS/SEC).
3.7
ENTER MIXING HEIGHT (METERS).
1000
ENTER PASnUlLL-TURNER STABILITY CLASS (1-6).
3
ENTER THE NUMBER OF LANES.
k
DO YOU WISH TO ENTER YOUR OWN EMISSION RATES?(YES OR NO)
yes
ENTER LINE SOURCE STRENGTH VECTOR.(A VALUE FOR EACH LANE)
.0112,.0103,.0106,.0156
IS THIS A CUT SECTION? (YES OR NO)
yes
ENTER WIDTH OF TOP OF CUT. (METERS)
50
ENTER NUMBER OF RECEPTOR LOCATIONS DESIRED.(MAXIMUM OF 25)
5
ENTER RECEPTOR COORDINATE SETS.U&Y IN SCALE FACTOR UNITS;Z IN METERS)
0,-.001,0,0,-.005,0
0,-.010,0,0,-.030,0
0,-.050,0
-------
Table A-l (continued). EXAMPLE OF INTERACTIVE VERSION OF HIWAY
HI WAY VERSION: 71*250
ENDPOINTS OF THE LINE SOURCE
2.500, .025 AND -2.500,
EMISSION HEIGHT IS .000 METERS
EMISSION RATE (GRAMS/SECOND*METER) OF
.112-01 .103-01 ,106-OT
WIDTH OF TOP OF CUT SECTION IS 50.000 METERS
WIND DIRECTION IS 1*2. DEGREES
WIND SPEED IS 3.7 METERS/SEC
STABILITY CLASS IS 3
HEIGHT OF LIMITING LID IS 1000.0 METERS
THE SCALE FACTOR IS 1.0000 USER UNITS/KM.
025
I* LANF.(S)
.156-01
00
RECEPTOR LOCATION
X
.0000
.0000
.0000
.0000
.0000
Y
-.0010
-.0050
-.0100
-.0300
-.0500
HEIGHT
Z (M)
.0000
.0000
.0000
.0000
.0000
UGM/M**3
3891*.
31*52.
301*0.
2107.
1636.
CONCENTRATION
PPM*
3
3
2
388
003
61*5
1.833
1.1*23
* PPM CONCENTRATIONS CORRECT FOR CARBON MONOXIDE ONLY.
ENTER LOC, OR TYPE, OR END.
end
-------
Table A-2. CARD INPUT FOR EXAMPLE PROBLEM
12345678
12 34 56 78 90 12 34 56 78 9012 34 56 78 9C12 34 56 78 90 12 34 56 78 90 12 34 56 78 90 12 34 55 78 90 12 34 56 7890
00
to
AT -G RA DE
2.5
.0112
C
42
1
.0
.0
.C
JJ
.C
9999.
CUT-SECT
2.5
.0112
1
42
1
.0
.0
mC
.0
.0
SECTION
.023
.0103
3.7
-.001
-.005
-.010
-.030
-.050
ION
.025
.0103
50
3.7
-.001
-.005
-.010
-.030
-.050
EXAMPLE
-2.5
.0106
10 CO
.C
.0
.0
.0
.0
EXAMPLE
-2.5
.0106
10 CO
.0
.0
.0
.0
.0
FOR HIUAY
.023
.0156
USERS MANUEL
.0
46 .C
30.0
FOR HIUAY
.025
.0156
USERS MANUEL
.0
12 34 56 78 9012 34 56 78 9012 34 56 78 90 12 34 56 78 9012 34 56 78 90 12 34 56 78 90 12 34 56 78 9012 34 56 78 90
12345678
-------
Table A-3. EXAMPLE OF BATCH VERSION OF HIGHWAY
3XQT HIUAYBATCH.KZ
AT-GRADE SECTION
EXAMPLE FOR HIWAY USERS MANUEL
00
U)
HIWAY VERSION: 74250
ENDPGINTS OF THE LINE SOURCE
2.500. .023 AND -2.5DOt .023
EMISSION HEIGHT IS . COC METERS
EMISSION RATE (GR AMS/SECOND *METER ) OF 4 LANE(S)
,112-Cl .103-01 .106-01 .156-01
WIDTH OF AT-GRADE HIGHWAY IS 46.0 M
WIDTH OF CENTER STRIP IS 3D.C M
WIND DIRECTION IS 42. DEGREES
WIND SPEED IS 3.7 METERS/SEC
STABILITY CLASS IS 3
HEIGHT OF LIMITING LID IS 1000.C METERS
THE SCALE OF THE COORDINATE 'AXES IS l.CCCC USER UNITS/KM,
RECEPTOR LOCATION
.0000
.CCQG
.ococ
• 3CCC
.ccco
- .0 Cl C
-.ccsc
- .0 10 0
-.0300
-.0500
HEIGHT CONCENTRATION
ZCM) UGM/METER«*3 PPM •
.CCCC 4449. 3.671
.0000 3331. 3.333
.0000 3294. 2.866
•COCO 2184. 1.900
.0000 16C3. 1.452
• PPM CONCENTRATIONS CORRECT FOR CARBON MONOXIDE ONLY.
-------
Table A-3 (continued). EXAMPLE OF BATCH VERSION OF HIGHWAY
CUT-SECTION
EXAMPLE FOR HIUAY USERS MANUEL
oo
HIUAY VERSION: 74250
ENDPOINTS OF THE LINE SOURCE
2.500. .C25 AND -2.500r .025
EMISSION HEIGHT IS .000 METERS
EMISSION RATE { GR AM S/ SECOND *METER> OF 4 LANE UGM/METER»»3 PPM *
.OOCO 3394. 3.338
.0000 3452. 3.CC3
.QCOO 3C4C. 2.E45
.0000 2107. 1.333
.0000 1S36. 1.423
* PPM CONCENTRATIONS CORRECT FOR CARBON MONOXIDE ONLY,
-------
APPENDIX B. FORTRAN SOURCE PROGRAM LISTING
FOR BATCH VERSION OF HIWAY
185
-------
00
C HIV AY - NEW VERSION - JUNE 1974
C THIS PROGRAM CALCULATES THE CON CENTRA
COMMON /SOL/ QLN(25)tHLN(25) f RAQ<25)tSA
• SYON tSZONt CONC50)
COMMON /REC/ RR( 51 >r SR (51) rZR< 51 >
COMMON /ME A/ THETA rUtKST tML
COMMON /PUT/ XXRR(51)»XXSR<52J »QLSI25)tH
DIMENSION Z(51)
IVERS=74250
IRD=5
IWRI - S
C READ HEADER CARD
10 READCIRDt500tEND=19C)HEAD
500 FORMAT C20A4)
WRlTECIWRItSlOlHEAD
510 FORMATC'C1 t/t20A4t/)
WRITE! IWRI?520)IVERS
520 FORM AT CO HIUAY VERSION :• t!6)
READ(IRDrS40.ENO=190l REP1 tSEPlt REP2 iSEP
540 FORHATC8F10.0I
C REPltSEPl ARE THE COORDINATES OF AN E
C SOURCE IN SOURCE COORDINATES.
C REP 2. SEP 2 ARE THE COORDINATES OF THE
C LINE SOURCE IN SOURCE COORDINATES.
C H IS THE EFFECTIVE EMISSION HEIGHT OF
C yiDTH IS THE HIGHWAY WIDTH (MI FOR AT
C CNTR IS THE WIDTH OF THE CENTER STRIP
C XNL IS THE NUMBER CF LANES FOR THE AT
URITE(IURIt550)REPltSEPltREP2tSEP2
550 FORM ATI' ENDPOINTS OF THE LINE SOURCE* t/
• F9.3 t« t» tFg.St* AND" tF9. 3» •• »»F9.3)
NL=XNL
URITEtlURItSEOH
560 FORMAT C* EMISSION HEIGHT ISSF3.3.' MET
URITE(IURIt570)NL
570 FORM ATI* EMISSION RATE C GR AM S/SECO MO«MET
RE AD IIRD t510 I ( QL SC I) tl=l tNL)
HON FROM A LINE SOURCE
M25l»RBQ(25)fSBQ(25lt
EADC20»tIWRI
2t H»WIDTHtCNTR»XNL
NO POINT OF THE LINE
OTHER END POINT OF T HE
THE SOURCE IN METERS.
GRADE
(Ml
-GRADE HIGHWAY.
ERS* I
ER) OFS 14 t' LANE( S) *)
HI WAY 1
HI WAY 2
1 HIWAY 3
HI WAY 0
2 HIWAY 5
3 HIWAY 6
4 HIWAY 7
5 HIWAY 8
6 HIWAY 9
7 HIWAY 1C
8 HIWAY 11
HIWAY 12
9 HI WAY 13
10 HIWAY 14
11 HIWAY 15
12 HIWAY 16
13 HIWAY 17
14 HIWAY 18
15 HIWAY 19
16 HIWAY 20
HIWAY 21
HIWAY 22
HIWAY 23
HIWAY 24
HIWAY 25
HIWAY 26
HIWAY 27
HIWAY 28
17 HIWAY 29
18 HIWAY 30
HIWAY 31
19 HIWAY 32
20 HIWAY 33
21 HIWAY 34
22 HIWAY 35
23 HIWAY 36
24 HIWAY 37
-------
00
vj
C QLS IS THE LINE SURGE STRENGTH (GRAMS/SEC ON0*METER) HIUAY
VRITE(IURIt58G>(fiLS
-------
oo
oo
WRITEC IWRI .620)05 50 HIWAY 75
620 FORMAT (• THE SCALE OF THE COORDINATE AXES IS ttF10.4.» USER UNITS/ 51 HIWAY 76
• KM.'// ) HIWAY 77
WR IT E( IW RI r6 30 ) 52 HIWAY 78
630 FORMAT tlHOf' RECEPTOR LOCATION HEIGHT CONCENTRATION'./. 53 HIWAY 79
• • X'flOXt'Y Z(M) UGM/METER**3 PPM • •) HIWAY 8C
RA=REP1*GS 54 HIWAY 81
RB=REP2«GS 55 HIWAY 82
SA=SEP1»6S 5E HIWAY 83
S3=SEP2*GS 57 HIWAY 84
WL= CWIDTH-CNTR)/XNL 58 HIWAY 85
IF (C OT .G T. C. ) GO TO 80 59 HIWAY 86
7C SYON=3. 60 HIWAY 87
SZONrl.5 61 HIWAY 88
GO TO ICC 62 HIWAY 89
8C IF (U.GT. 3. 1GO TO 70 63 HIWAY 90
IFdl.LT. 1. 1 GO TO 90 64 HIWAY 91
OUK= (U-l.l /2. 65 HIWAY 92
SYON=10.-7.»DUM 6E HIWAY 93
SZON=5.-3. 5*DUM 67 HIWAY 94
GO TO Ifl C 68 HIWAY 95
90 SYON=10. 69 HIWAY 96
SZON =5. 70 HIWAY 97
100 CONTINUE 71 HIWAY 98
DELR=RB-RA 72 HIWAY 99
OELS=SB-SA 73 HIWAY100
DIST=SGRTC DELS*DELS+DELR*DELR) 74 HIWAY101
NLIM=NL/2 75 HIWAY102
ALIM=NLIM 76 NIWAY103
00 110 IO=ltNLD1 77 HIWAY104
A=ID 78 HIWAY105
DL=( -C.5)*CNTR + < (-1J *ALIM-0. 5* A) *WL 79 HIWAY106
DUK=DL*0 .001/01ST 80 HIWAY107
RAQ( ID )=RA*OELS*DUM 81 HIWAY108
RBQ( ID »=RB+DELS*DUM 82HIWAY109
SAQ( ID )=SA-OELR*DUM 83HIWAY110
S8G( ID *rS8-DELR*DUM 34 HIWAY111
-------
CO
10
QLNIID1=QLSIID>
HLNIIDI=H
110 CONTINUE
NS=NLIM*1
AS=NS
DO 120 ID=NS»NL
A=IO
DL=0.5.»CNTR+C0.5+A-AS)*HL
DUM=DL*O.C 01/0 1ST
RAQCID)=RA+D£LS*DUM
RSQCID I=RB*0£LS*DUM
SAQ( ID)-SA-OELR*DUM
SBQ(ID1=SB-DELR»DUM
QLN(IOI=QLS(ID)
HLN(ID)-H
120 CONTINUE
K=NL
ICHK=1
N=l
130 READ (IRD ?5
IF CXXRRC N) .GE.9999.160
IF (N -5 1) 1C Ot 14 Ct 1HO
140 URITEf IWRIf64Q)
64C FORMAT ClHCtf THE NUHBLR OF
• TEKPTEO TO READ THE 51ST.
150 1C HK =2
GO TO 170
160 RR (N>=XXRR(N)*6S
SRfNt=XXSRCNl*6S
ZR(Nr=ZINI
N=N»1
60 TO 130
170 N=N-1
00 180 IOUH=lfN
180 CONCIOUHn=0.
C K IS NUMBER OF LINE SOURCES
C N IS NUMBER OF RECEPTORS
i£ND=15C IXXRRI N) tXXSRf N) tZ(N )
TO 170
RECEPTORS IS
COMPUTATIONS
LIMIT ED
UILL BE
TO 50. YOU HAVE
HADE FOR 50.* )
85
86
87
88
89
30
91
92
93
94
95
96
97
98
99
100
101
10?
103
101
105
106
107
AT 108
109
110
111
112
113
114
i.15
116
117
118
HIHAYl!
HIHAY1
HIWAY1
HZWAY1
HIWAY1
HIWAY1
HIUAY1
HIMAY1
HIWAY1
HIWAY1
HIVAY1
HIWAY1
HIUAY1
NIVAY1:
HZWAY1
HIWAY1
HIHAY1
HIWAY1
HIUAY1
HIWAY1
HIUAY1
HIUAY1
HZUAY1
HIUAY1
HIUAY1
HIUAY1
HIUAY1
HIVAY1
HIVAY1
HIM A Yl
HIVAY1
NIVAY1
HIVAY1
HIUAY1
HIUAY1
HIWAY1
HIHAY1
-------
10
o
CAUL DBTLNEIK.N) 119 HIHAY149
URITEf IWRItGSDI 120 HIM A Yl 50
650 FO RH AT (1 HO .'* PPM CONCENTRATIONS CORRECT FOR CARBON MONOXIDE: ONLY 121 HiyAYlSl
*.*) HIUAY152
60 TO (10*190) tICHK 122 HIWAY153
190 CALL EXIT 123 HIUAY154
END 124 HIUAY155
22 COMMENT CARDS 9 CONTINUATION CARDS 34 NUMBERED STATEMENTS
-------
35
40
45
46
SUBROUTINE DBTLNEI NQ »NR)
COMMON /SOL/ QLNC25)tHLN(25> tRAQ(25) tSAfl (251 tRBQ (2 5) tSBQ (2 5) »
SYONtSZONtCONf 50)
COMMON /REC/ RRI 51 ) t SR C5 II tZRC 51 »
COMMON /WE A/ THETA tU.KST tHL
COMMON /PUT/ XXRR(51)*XXSR(51) tQLS(25) tH EA D( 20 )t IURI
DIMENSION XST(ll).YSTCll)
XCR, S) =
-------
NJ
17
48
49
C
100
105
110
115
120
125
13 C
135
14 C
145
150
155
ISO
165
170
175
ido
185
URITEC IWR:
FORMATI1H
60 TO 465
DE LR =R 2- R]
DELS = S2
Yl = YCRli
Y2 = YIR2i
IF(YlrY2)
IF Yl :
IF (C OS T *
IF CC OS T -
IF (DEL R +
IF (DEL R -
SLOC = SR!
RLOC = Rl
GO TO 20 G
SLP = DEL!
IF (SLP 11 31
SLOC = SRI
RL OC = ( SI
60 TO 200
IF (S IN T *
IF (SIN T -
IF (DEL R +
IF (DELR -
SLP = DEL!
RLOC = RRI
SLOC = SU
60 TO 200
IF (D EL R +
IF (DELR -
RLOC =• Rl
SLOC -
-------
RLOC = (SLOC - SREC) * SINT/COST * RREC 71 HIWAY22
60 TO 200 72 HIUAY22
190 TATH r S BIT/COST 7J HIUAY23
C TATH IS TANGENT (THETA) HIWAY22
SLP = DELS/OELR 7* HIWAY22
C SLP TS SLOPE OF LINE SOURCE. HIUAY2;
RLOC = (RREC/TATH * SI - SLP»R1 - SREC I/ O. ./TATH - SLP I 75 HIWAY2:
SLOC = (RLOC - RREO/TATH * SREC 76 HIWAY2.1
C RLOC. SLOC IS LOCUS OF UPWIND VECTOR FROM RECEPTOR AND LINEAR HIWAY2-
C EXTENSION OF LINE SOURCE. HIWAY2:
200 XLOC - X (RLOC. SLOC} 77 HIWAY2*
IF ( XLOC 1255.255.205 78 HIUAY24
C XLOC IS POSITIVE IF LOCUS IS UPWIND. HIWAY2'
2C5 IF (S 2-SI 1210 .210.215 79HIWAY2'
210 SMAX = SI 80 HIWAY21
SMIN = S2 31 HIWAY2*.
60 TO 220 82 HIUAY2*
215 SMAX r S2 83 HIWAY2*
SHIN -SI 84 HIHAY2*
220 IF (R2-R1 )2 25 .225 .230 85HIHAY2^
225 RNAX - Rl 86 HIUAY2!
RMIN = R2 87 HINAY2!
60 TO 235 88 HIUAY2!
230 RMAX r R2 89 HIUAY2!
RMIN - Rl 90 HIWAY2!
C SEE IF UPWIND LOCUS IS ON LINE SOURCE. HIUAY2!
235 IF (RLOC-RMIN 1255 >2 40 1240 91HINAY2!
240 IF (R MAX- RLOC 1255 t245t245 92 HIWA-T2!
245 IF (SLOC-SHIN)255 .250.250 95 HIWAY2!
25C IF (SMAX- SLOC J255 .260.260 94HIUAY2!
255 INDIC = 1 95 HIWAY2C
C I NO 1C =1 FOR NO LOCUS ON LINE SOURCE. HIHAY2C
XA = XI 96 HIMAY2C
YA = Yl 97 HIUAY2C
XB - X2 98 HIMAY2C
YB = Y2 99 HIUAY2C
60 TO 300 100 HIUAY2C
-------
260
C
30 0
C
305
310
C
C
C
C
315
320
325
C
IN QIC = 2
XA
YA
XB
Y8
01
DI
DI
IF
cu
60
00
ox
DY
PR
KN
XI
YI
KN
DO
XS
YS
XZ
XY
CA
60
IF
IF
KN
60
I NO 1C =2 FOR LOCUS ON LINE SOURCE.
= XI
= Yl
= XLOC
= 0.
SX = XB - XA
SY r YB - YA
SI - SQRT (DISX*DISX * DISY»DISY)
DEI IS LEN6THIKM) OF LINE CONSIDERED.
CO IS I) 31 C. 305.310
RR = 0.
TO «»35
I = DISI*1 000. 720.
ONE -HALF IS INCLUDED IN THE 20.
DDI IS ONE-HALF TIMES 1/10 OF OISI (Ml.
= DISX/10.
= DISY/10.
EV =0.
TRL = 1
- XA
= YA
T = 0
355 I - 1.11
STORE EACH XI ,YI.
TC I) = XI
T(I) = YI
= XI + XV ZL
= XI * XV YL
LL D BT RC XI UZ >Z »H .HL. XZ >X Y. YI »K ST .AN. M. SY .S Z» RC )
T0( 315.335) .KNTRL
IF RC IS ZERO. CONTINUE UNTIL RC IS PCS HIVE.
(RC) 350.350.320
(I -113 25 .325. 330
TRL = 2
TO 345
RESET POINT A TO LAST ONE PREVIOUS.
1C1 HIUAY267
HIUAY268
ID 2 HIUAY269
1C3 HIWAY270
1C 4 HI HA Y2 71
105 HIUAY272
106 HIWAY273
107 HIWAY274
108 HIWAY275
HIWAY276
1G9 HIWAf277
liO HIUAY278
111 HIWAY279
U2 HIWAY280
HIUAY281
HIWAY282
Ii3 HIWAY283
114 HIWAY28U
115 HIWAY285
lj.6 HIUAY286
117 HIWAY287
118 HIUAY288
119 HIUAY289
120 HI WAY 2 90
HIWAY291
121 HIWAY292
122 HIWAY293
123 HIUAY294
124 HIUAY295
125 HIWAY296
126 HIWAY297
HIUAY298
127 HIHAY299
128 HIHAY300
129 HIWAY301
130 HIWAY3C2
HIUAY303
-------
<£>
tn
THIS SEGMENT IS 0
330 XA = XSTCI-11
YA = YST(I-1,|
KNTRL = 2
60 TO 345
335 IF(RC}34Ct340t345
C RESET POINT B IF REACH ZERO CONCENTRATION.
340 XB = XI
YB = YI
60 TO 360
345 KNT = KNT + 1
350 XI - XI * DX
YI = YI + DY
35 5 CO NT IN UE
360 IF (KNT )37C .370 1365
365 IFCKNT-6)300»300t390
C IF GET TO 370 t CONC. FROM
370 GO TO (375t38Ct385)t INDIC
375 RC = 0.
60 TO 465
380 FIRST r 0.
60 TO 450
385 RC = FIRST
60 TO 460
390 CONTINUE
C 00 A TRAPEZOIDAL INTEGRATION
C IT IS LIKELY THAT A OR B HAVE
40 0 DISX = XB-XA
01SY = YB-YA
01 SI = SORT! DISX«DISX +
C 0 IS I IS DISTANCE! KM 1
DELD - D IS I* 100.
C DELD IS 1/10 DISI IN METERS.
OX - DISX/10.
DY = DISY/10.
SUM - 0.
XOUM - XA
YOUM - YA
131 HIUAY304
132 HIWAY30!
133 HIUAY30f
134 HIUAY301
135 HIUAY30C
HIUAY30!
136 HIHAY31C
137 HIUAY311
138 HIUAY312
139 HI HA Y3 12
140 HXUAY3U
141 HIWAY31!
142 HIVAY31C
143 HI HA Y3 11
144 HI HA Y3 1C
FROM
BEEN
A TO 3 IN TEN STEPS.
REDEFINED.
DISY*DISY)
FROM A TO B
145 HIUAY32C
146 HIUAY321
147 HIUAY322
148 HIUAY322
149 HIUAY324
150 HIUAY32S
151 HIUAY32C
152 HIUAY321
HIUAY32C
HIUAY32S
153 HIUAY33C
154 HIUAY332
155 HIUAY332
HIUAY332
156 HIUAY334
HI WAY 335
157 HIUAY336
158 HIUAY331
159 HIUAY33C
160 HIUAY335
161 HIUAY34C
-------
XZ = XDUM * XVZL
XY = XDUM * XVYL
CALL DBTRCX(UZ.Z.H»HLt XZtXY. YDUMtKST»AN» Mt SY »SZ. RC >
SUM = SUM * RC/2.
DO 4C5 I = It9
XDUM = XDUM « DX
YDUM - YDUM + DY
XZ = XDUM •»• XVZL
XY = XDUM + XVYL
CALL DBTRCX(UZtZ»H.HL»XZfXY. YDUM.KSTtAN. Mt SYtSZtRC »
405 SUM = SUM + RC
XDUM = XDUM + DX
YDUM = YDUM + DY
XZ = XDUM + XVZL
XY = XDUM + XVYL
CALL OBTRCX(UZtZ,H»HL»XZtXY. YDUMtKSTtANt M, SY »SZf RC>
SUM = SUM + RC/2.
£ C INTEGRATED VALUE IS CURR.
CURR = SUM * DELD
ILIM = 1C
C FIRST ESTIMATE COMPLETED HERE.
410 PREV = CURR
C EVALUATE FOR POINTS IN BETWEEN THOSE 4. RE AD Y EVALUATED.
DELD 3 DELD/2.
XDUM = XA * DX/2.
YDUM = YA * DY/2.
DO 415 I = 1.ILIH
XZ = XDUM •» XVZL
XY - XDUM + XVYL
CALL DBTRCXCUZtZrH.HLtXZtXY. YDUMiKST.ANt Mt SY tSZt RC I
C NOTE ADD THESE TO RC*S FOUND ABOVE.
SUM = SUM + RC
XDUM = XDUM •>• DX
415 YDUM - YDUM + DY
CURR = SUM » DELD
C SECOND ESTIMATE COMPLETED HERE. ALSO FOUR TH ,S IXTH .ETC .
TEST = ABS((CURR-PREV)/CURRJ
162
163
164
165
166
157
168
169
17 C
171
172
17 J
174
175
176
177
178
179
180
132
183
184
185
186
187
188
189
19C
191
192
193
HIUAY341
HIUAY342
HIUAY343
HIWAY344
HIUAY345
HIWAY346
HIUAY347
HIUAY348
HIWAY349
HIUAY350
HIWAY351
HIWAY352
HIUAY353
HI WAY 3 54
HIWAY355
HIWAY356
HIWAY357
HIWAY358
HIUAY359
HIUAY360
HIUAY361
HIWAY362
HIUAY363
HIUAY3G4
HIUAY365
HIUAY366
HIUAY367
HIUAY368
HIUAY369
HIUAY37G
HIWAY371
HI WAY 3 72
HI WAY 3 73
HIUAY374
HIUAY375
HIWAY376
HIWAY377
-------
IO
c
120
C
425
C
430
C
435
440
445
450
I
IFCT
ILIH
PRW
E
DELD
DX =
DY =
XOUH
YDUM
00 4
xz =
XY =
CALL
SUN
XDUH
YDUM
CURR
T
TEST
IF (
ILIM
DX =
DY =
GO T
A
T
F
ES
25
X
X
0
455
GO
RC
GO T
FIRS
IN 01
XA -
YA =
XB -
Y8 =
GO T
RC =
HI
TE
0
D
0
T
0
= C
TO
T
C
MI THIN* PIN OF LAST VALUE
-------
460 COM NC1=CONINCI+RC»QL
470 CONTINUE
COM NC 1=1. OE+6«CON CNC1
CL SS =0 .0 00 87 «C ON INC >
URITE( IURIt660)XXRRfNCI»XXSR(NC) tZRlNCIt CON(NC).CLSS
660 FORHATflH t3 (FlO .4 t2X) iFlO .0 iFlfl .3 >
465 CONTINUE
RETURN
END
227
228
229
230
231
232
233
234
235
HIUAY415
HIUAY416
HIUAY417
HI WAV* 18
HIWAY419
HIUAY420
HIWAY421
HIWAY*22
HIUAY423
32 COM It NT CARDS
CONTINUATION CARDS
74 NUMBERED STATEMENTS
10
CO
-------
ID
SUBROUTINE OBTRCX CUiZ tH.HLt X. XY tY .KST »A N» Ht SY tS Zt RC I
C THIS IS THE 1972 VERSION OF DBTRCX.
C SUBROUTINE DBTRCX CALCULATES CHI/Q CONCENTRATION VALUES t DBTRCX
C CALLS UPON SUBROUTINE DBTSI6 TO OBTAIN STANDARD DEVIATIONS.
C THE INPUT VARIABLES ARE....
C U WIND SPEED CM/SEC)
C Z RECEPTOR HEIGHT CM)
C H EFFECTIVE STACK HEIGHT CM I
C HL=L HEIGHT OF LIMITING LID (Ml
C X DISTANCE RECEPTOR IS DOWNWIND OF SOURCE (KM)
C XY X+VIRTUAL DISTANCE USED FOR AREA SOURCE APPROX. CM)
C Y DISTANCE RECEPTOR IS CR OS SUING FROM SOURCE CKMI
C KST STABILITY CLASS
C THE OUTPUT VARIABLES ARE...*
C AN THE NUMBER OF TIMES THE SUMMATION TERM IS EVALUATED
C AND ADDED IN.
C RC RELATIVE CONCENTRATION CSEC/H«*3)
C INRI IS CONTROL CODE FOR OUTPUT
IURI - 6
C THE FOLLOWING EQUATION IS SOLVED —
C RC = I1/(2*PI*U*SIGMA Y'SIGMA Z)>* IE XP f-0.5* CY/SIGMA Yt*«2l)
C IEXP 1-0. 5*11 Z-H1/SIGMA Z 1* *2 1 * EX Pf-0 .5 *( IZ+H )/SIGM A Z) **2)
C PLUS THE SUM OF THE FOLLOWING d TERMS K TIMES IN=1« I —
C TERM 1- EXPC-D. 5*1 (2-H-2N LI /SIGMA Zl*»21
C TERM 2- EXP<-D.5* UZ+H-2ND/SIGMA ZI**2I
C TERM 5- EXP t-C.5» UZ-H+2ND/SIGMA Z1»«2I
C TERM d- EXP«-D.5*UZ*H*2NLJ/SIGMA Z)»*2I
C THE ABOVE EQUATION IS SIMILAR TO EQUATION 15.8) P 36 IN
C WORKBOOK OF ATMOSPHERIC DISPERSION ESTIMATES WITH THE ADDITION
C OF THE EXPONENTIAL INVOLVING Y.
C IF THE SOURCE IS ABOVE THE LIDt SET RC = 0. t AND RETURN.
IF CH-HL)302.302t30d
302 IF ( 2-HL)300t3CCi30
304 IF I Z-KL)30f 3C6t3C6
306 URITEflWRIt 3C7)
307 FORMAT (IHO.'BOTH H AND Z ARE ABOVE THE MIXING HEIGHT SO A RELIABL
• E COMPUTATION CAN NOT BE MADE.*)
5
6
7
HIWAYd2d
HIWAYd 25
HI HA Yd 26
HI WAY* 27
HI WAY* 28
HI HA Y* 29.
HIWAY*30
HI WA Yd 31
HIWAY*32
HIWAY*33
HI WAY* 3*
HI WA Yd 35
HI HA Yd 36
HI WA Yd 37
HIWAY*38
HI WA Yd 39
HI HA Yd dO
HIWAYddl
HI HA Yd d2
HIWAYdd3
HI WAY***
HIWAYddS
HIWAYddG
HIWAY**7
HIUAYddS
HIWAYdd9
HI WA Yd 50
HI WA Yd 51
HI HA Yd 52
HI WA Yd 53
HIWAY*5*
HIUAYdSS
HIUAY*58
HI WA Yd 57
HI WA Yd 58
HIWAYd59
HI WA Yd 60
-------
NJ
O
o
30
C
c
30 C
C
310
C
C
C
C
5
C
c
6
3Gf
C3 = H«H
IF (C 3- 50
A2= 1. /E
WADE
RC = A2/
M = 1
RETURN
A2 = Q.
A3 = 0.
CA = Z-H
CB = 7«iH
IS LESS THAN 1 METERt SET RC=0.
-------
ISJ
O
C3 = OA*CA/C2
C4 = CB*C8/C2
IF 1C 3- 50 .) 40 7» 40 Bt 40 8
407 A2 = 1./EXPIC3)
408 IF 1C 4-SO.) 40 9* 411*411
409 A3 = 1./EXPCC4)
C HADE EQUATION 3.1.
411 RC = IA2 * A3I/I 6.28318*U*SY*SZ*CL>
H = 2
RETURN
C IF SIGMA-Z IS GREATER THAN 1.6 TIMES TH
C THE DISTRIBUTION BELOW THE NIXING HE IS
C HEIGHT REGARDLESS OF SOURCE HEIGHT.
7 IFCSZ/HL - 1.619*9*8
C WADE EQUATION 3.5.
8 RC = l./(2.5066*U*SY*HL*Cl>
N = 3
RETURN
C INITIAL VALUE OF AN SET = 0.
9 AN = 0.
IF 3Ot 340*40
C STATEMENTS 40 TO 250 CALCULATE RC t THE
C USING THE EQUATION DISCUSSED ABOVE. S
C VARIABLES ARE USED TO AVOID K£ PEAT ING
C CHECKS ARE MADE TO BE SURE THAT THE AR
C EXPONENTIAL FUNCTION IS NEVER GREATER
C -50). IF *AN* BECOMES GREATER THAN 45
C PRINTED INFORMING OF THIS.
C CALCULATE MULTIPLE EDDY REFLECTIONS FOR
40 Al = 1«M6.28318*U«SY*SZ«C1)
C2 =2 •• SZ *S Z
A2 = 0.
A3 - C.
CA - Z-H
C8 = Z«H
C3 - CA*CA/C2
C4 = C8*C8/C2
E MIXING HEIGHT*
HT IS UNIFORM WITH
RELATIVE CONCENTRATION.
EVERAL INTERMEDIATE
CALCULATIONS.
GUMENT OF THE
THAN 50 (OR LESS THAN
t A LINE OF OUTPUT IS
RECEPTOR HEIGHT Z.
33 HIWAY*98
34 HIUAY499
35 HIU/tYSOO
36 HIWAY501
37 HIWAY502
38 HIWAYS03
HIUAY504
39 HI WAYS 05
40 HIHAY506
41 HIWAY507
HIUAY508
HIUAY509
HI WAYS 10
42 HIWAY511
HI HAYS 12
43 HI WAYS 13
44 HIUAY514
45 HIUAY515
HIWAY516
46 HIWAY517
47 HI WAY 518
HIWAY519
HIWAYS20
HIWAY521
HIWAYS22
HIWAYS23
HIUAY524
HIWAY525
HI WAYS 26
48 HI WAYS 27
49 HIWAY528
50 HIWAY529
51 HIWAY530
52 HIWAY531
S3 HIUAY532
54 HI WAY 5 33
55 HIUAY534
-------
o
KJ
60
80
90
110
120
130
150
160
180
190
21 C
220
240
250
C
340
IF C C3-50. )60t 80»80
A2 =1 J EX Pf C3 )
IF (C 4- 50 .190. 110 .110
A3 =1 ./ EX PC C4 I
SUK=0.
TH L = 2. • HL
AN=AN*1.
M - 0.
AS = 0.
AS = 0.
A7 = 0.
C5 = AN*THL
CC = CA-C5
CD = C&-C5
CE = CA+C5
CF - CBfCS
C6 =. CC*CC/C2
C7 = CD*CD/C2
C8 = CE*CE/C2
C9 = CF»CF/C2
IF (C&- 50.) 130.150.150
A4 =1 ./ EX P( C6 1
IF (C 7- 50.) 16 C« 18 0,180
AS =1 ./ EX Pt C7 )
IF 1C 8- 50.) 190. 210.210
A6 =1 ./ EX Pf C8 )
IF (C 9- 50.) 220t 240.240
A7 =1 ./ EX Pt C9 }
T=Aft+AS+A6+A7
SUM=SUH«-T
IF (1-0,01)250,120,120
RC=A1* (A 2+ A3* SUM)
M = 5
RETURN
CALCULATE MULTIPLE EDDY REFLECTIONS
Al - l./I6.28318*U«SY*SZ*Cl)
A2 = 0~.
FOR GROUND LEVEL RECEPTOR H
56
57
58
59
60
61
62
63
64
65
66
67
68
69
7D
71
72
73
71
75
76
77
78
79
80
81
82
83
84
35
86
87
88
89
90
91
HIUAY535
HI HAYS 36
HIWAY537
HIWAY538
HIUAY539
HIUAY54Q
HIHAY5H1
HIUAY512
HIUAY543
HIUAY5W
HIUAY545
HZUAY546
HIUAY547
HIUAY548
HIWAY549
HIWAY550
HIWAY551
HI WAYS 52
HIUAY553
HIUAY55
-------
ISJ
O
00
C2 = 2.*SZ»SZ
C3 = H«H/C2
IF 1C 3- SO .) 360. 41 Of 110
360 A2 = 2./EXPIC3I
410 SUM = 0.
THL = 2. * HL
420 AN = AN * 1.
A4 = 0.
A6 = 0.
C5 = AN* THL
CC - H-C5
CE = H * C5
C6 - COCC/C2
C8 - CE*CE/C2
IF 1C 6- 50 .) 430* 480. 480
430 Aft = 2./EXPIC6I
480 IF(C8-50.1490t540t540
490 AS = 2./EXPIC8!
540 T = Aft * A6
SUM - SUM + T
IF (T -0 .0 1) 550. 42Ot 420
550 RC = Al * IA2 + SUM I
M = 4
RETURN
END
92 HIWAY572
93 HI WAYS 73
94 HI WAYS 74
95 HI WAYS 75
96 HIWAY576
97 HI WAYS 77
98 HI WAYS 78
99 HIWAY579
100 HI WAYS 80
101 HZ WAYS 81
102 HI WAYS 82
103 HIUAY583
104 HI WAY 5 84
105 HI HAYS 85
106 HIWAYS86
107 HIWAY587
108 HIWAYS88
109 HIWAY589
110 HIHAY590
111 HIUAY591
112 HIWAY592
113 HI WAYS 93
114 HI HAYS 94
115 HIUAY595
116 HIHAY596
56 COMMENT CARDS
1 CONTINUATION CARDS
41 NUMBERED STATEMENTS
-------
NJ
o
SUBROUTINE DBTSIG (X tXY. KST* SY *SZ)
011C NS ION XA(7)*X8C2>*XO(5)*XE(8)*XF(9)*
• AM 6) *BD(6) »AE19) .BEf 9) tAF( !0>t BF(1Q)
DATA X A/.5 ..4..3 ,.25..2. .15. .17
DA TA X B/ .4 t. 2/
DATA XD 730. tlD. t3.t 1. t.3/
DATA XE /40. *20. »1C. *4..2. .1...3*. I/
DATA XF /60. .30. .15. *7.*3. .2..1. *.7..2/
DATA A A /453.85* 346. 75 .258 .89* 217. 41 .179
DATA B A /2.1166.1.7283.1.4G94.1.2644.1.1
DATA A B /109. 3 0.98 .483 .90. 67 3/
DATA BB /1.0971.0. 98332. 0.931987
DATA AD /4 4. 05 3* 36 .6 50 .3 3. 50 4. 32 .093 .3 2.
DATA BO /C.51173*0.56589*0.60486*0.64403
DATA A £ /47.618*35.420*26. 970.24.7C3.22.
• 24. 26 /
DATA BE /C .29592 .0.376 15 *C.467 13 .0.50527
» 0.81956 .0.83667
DATA AF /34. 219* 27.074*2 2. 651*17 .8 36 .16.
* 14. 45 7t 15 .209 /
DATA BF /O . 21716 .0. 274 36 .0 .32681 *C . 41507
• 0.6 84 65 tO.7 8407 tO.81558 /
GO TO (10*20*30*40.50*6G)*KST
C STABILITY A HOI
10 TH - t 24 .167 - 2.5334*ALOG CXY) 1/57.2958
IF I X.GT.3.11) 60 TO 63
DO 11 ID = 1.7
IF (X.GE. XA(ID) I 60 TO 12
11 CONTINUE
ID = 8
12 SZ = A At B)> » X »* BAIID)
60 TO 71
C S TA BI LI TY B ( 20 1
20 TH - (18.333 - 1 .8096*AL06 (XY) 1/57 .2958
IF (X.6T, 35.) 60 TO 69
DO 21 E> - 1.2
IF ( X.6E.XBIID1) 60 TO 22
AA (8 },BA(8>.ABC3). BB (31,
.52. 170.22.158 .08.122.87
262. 1.09 32*1.0542 *.944 7/
093* 34.4597
.0.81066.0.869747
53 4* 21 .6 28 .21. 62 8 . 23 .3 31 »
.0 .5 7154 tO .6 30 77 • 0 .7 56 60 »
18 7. 14 .8 23 *1 3. 35 3 » 13 .9 53 »
•0 .464 90 *0 .545C3 .0 .6 3227 •
1
2
3
4
5
6
7
8
9
10
11
12
13
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
HI WAY 5 97
HIWAYS98
HI WAYS 99
HIWAY60C
HIUAY6C1
HIUAY602
HIWAY603
HI WAY 6 04
HIWAY605
HIUAY606
HIUAY6C7
HIMAY608
HIUAY6C9
HIUAY610
HIWAY611
HI WAYS 12
HIWAY613
HIWAY614
HIUAY61S
HI HA Y616
HIWAY617
HI WAY 618
HIWAY519
HIWAY620
HIWAY621
HIWAY622
HIWAY623
HIWAY624
HIWAY625
HIWAY626
HI HA Y6 27
HIWAY628
HIUAY629
HIWAY63C
HIHAY631
HIWAY632
HIWAY633
-------
KJ
o
en
21 CONTINUE
ID = 3
22 SZ = ABC ID I * X
60 TO TO
C STABILITY C I
30 TH = ( 12 .5 - 1 .0
SZ - 6 1* 111 *X *
60 TO 70
C STABILITY D I
40 TH = ( 8.3333-0.7
DO 41 ID = 1.5
IF ( X. GE.XDUD))
41 CO NT IN UE
ID = 6
42 SZ = A Dl ID I • X
60 TO 70
C STABILITY E I
5C TH = ( 6. 25 - 0.5
DO 51 ID = 1.8
IF I X. 6£.XEIID)1
51 CONTINUE
ID = 9
52 SZ = AE(ID) * X
60 TO 70
C STABILITY F I
60 TH = C 4. 1667 - 0
DO 61 ID = 1.9
IF ( X. GE.XF(IDI)
61 CONTINUE
ID = 10
62 SZ = AFC ID I • X
GO TO 70
69 SZ = 5000.
60 TO 71
70 IF I SZ .6 T. 5000.1
71 SY = 1000. • XY
RETURN
*• BB(ID)
30)
857»ALOGCXY) )/57 .2958
* 0.91465
40)
2382*ALOGf XY))/57.295B
GO TO 42
• * BD(IO)
50)
4287*ALOGf XY 1) /57. 2958
GO TO 52
** BE! ID)
60)
.36191 «ALO61 XY)) /S7.2958
GO TO 62
• * BFIID)
SZ = 5000.
* SIN(TH)/C2.15 * COSITHU
31 HIUAY634
32 HIUAY635
33 HIUAY636
34 HI WAYS 37
HI HA Y6 38
35 HI WAYS 39
36 HIUAY640
37 HIUAY641
HIUAY642
38 HIUAY643
39 HIUAY644
40 HIHAY645
41 HIMAY646
42 HIWAY647
43 HIUAY64B
44 HIUAY649
HIUAY650
45 HIUAY651
46 HIUAY652
47 HI WAYS 53
48 HIUAY654
49 HIWAY655
50 HIUAY656
51 HIWAYS57
HIWAY658
52 HIWAY659
53 HIUAY660
54 HI WAYS 61
55 HIWAYS62
56 HIWAYS63
57 HIWAYS64
58 HIWAYS65
59 HIWAY666
SO HIWAY667
61 HIWAYS68
62 HIWAYS69
63 HI WAYS 70
-------
END
S COMMENT CARDS
5 CONTINUATION CARDS
6* HIUAY671
19 NUMBERED STATEMENTS
KJ
o
FUNCTION XVY ISYOtKSTI
GO TO Cl*2t3>4t5t6)fKST
1 XVY = (SYO/213.) ••1.1148
RETURN
2 XVY - IS YO/155.) ••1.09 7
RETURN
3 XVY r ISYO/1C3.) ••1.092
RETURN
4 XVY = CSYO/68. )**1.G76
RETURN
5 XVY r ISYO/50. )**1.G86
RETURN
6 XVY = (SYO 733. 51 ••1.08 3
RETURN
END
1 HI WAYS 72
2 HIUAY673
3 HIWAY674
4 HIWAY675
5 HIWAY676
6 HIVAY677
7 HIWAY678
8 HIWAY679
9 HIUAY680
10 HIUAY681
11 HIWAY682
12 HIWAYS83
13 HIUAY684
14 HIUAY685
15 HIUAY686
0 COMMENT CARDS
0 CO NT IN UAH ON CARDS
6 NUMBERED STATEMENTS
-------
NJ
o
C
10
11
12
C
20
21
22
DATA
DATA
DATA
DATA
DATA
DATA
DATA
DATA
SB
SD
SE
SF
A A
AB
AD
AE
FUNCTION XVZ (SZC.KST)
DIMENSION SA(7)fSB(2)t SD(5),SE(8
AR 10 >»CA<3).C3<3).CD(6 )»CE(9),
DATA SA 713.95.21.40.29.3.37.67.
720.23.40.7
712.09.32.09.65.12.134.9
/3 .534 18 .6 98 t21. 62 8t 33 .4
74.093.10. 93.13. 953.21.6
/I 22 .8 .1 58 .08. 17 Q. 22 .1 79
790.673.98.483.109.37
734.459.32.093.32.093.33
/2 4.26 .2 3. 331*21.6 28 .21.
• 4 7. 61 8/
DATA AF 715.209.14.457.13.953.13
* 27.074.34.2197
DATA C A 71 .0585. .948G*.9147*.887
DATA CB /I .073 .1.017..91157
DATA CD 71.1498.1.2336.1.5527.1.
DATA CE /I .195 3. 1.2202.1.3217.1.
* 3.37937
DATA CF 71.2261.1.2754.1.4606.1.
• 3.6448.4.60497
60 TO (10f 20»30»40.50.60)»KST
STABILITY A(10)
DO 11 ID = 1.7
IF (SZO.LC.SAUDI I 60 TO 12
CONTINUE
ID = 8
XVZ =ISZO/AAfID) l**CAf 101
RETURN
STABILITY B (20)
DO 21 ID - 1.2
IF ( SZO.LE.SB(IO)) 60 TO 22
CONTINUE
ID = 3
XVZ = (SZO/AB(ID))**CB(ID)
RETURN
USFC9).
CF(10)
47.44.71
.251.27
89.U9.76
27.26.97
.52.217.
.501.36.
628.22.5
.953.14.
9. .7909.
6533.1.7
5854.1.7
AA <8 ),A3<3)»AD(6 )» A£ 19 )•
.16. 104.CS/
7. 79 .0 7. ID 9. 3. 14 1. 85 /
6. 4C..54.89.68.84. B3 .2 5/
41 .258.39.346.75.453 .857
650. 44.C53/
34 »2
-------
to
o
00
C STABILITY C I 30 )
30 XVZ r (SZO 761. 141)** 1.09 33
RETURN
C S TA BI LI TY D C 10 )
40 DO 41 ID = 1*5
IF CSZO.LE, SD1ID) ) GO TO 42
41 CO NT IN UE
10 = S
42 XVZ = (SZO/ADCID )) **CDfID)
RETURN
C STABILITY E I 50 I
50 DO 51 ID = 1*8
IF f SZO.LE.SECIDM GO TO 52
51 CO NT IN UE
ID = 9
52 XVZ = CSZO/AECIO M»»CE(ID)
RETURN
C STABILITY F (SO)
60 DO 61 ID = 1*9
IF (SZO.LE. SF(ID) ) GO TO 62
61 CONTINUE
ID = 10
62 XVZ = CSZO/AF(IDn**CF(ID)
RETURN
END
HI WAY? 24
31 HIUAY725
32 HIWAY726
HIWAY727
33 HIWAY728
34 HIWAY729
35 HIWAY730
36 HIWAY731
37 HIUAY732
38 HIUAY733
HIWAY734
39 HIWAY735
40 HIWAY736
41 HIWAY737
4? HIUAY738
43 HIWAY739
44 HIUAY74C
HIUAY741
45 HIWAY742
46 HIUAY743
47 HIUAY744
48 HIUAY745
49 HIWAY746
50 HIWAY747
51 HIUAY748
6 COMMENT CARDS
5 CO NT IN UAH ON CARDS
16 NUMBERED STATEMENTS
-------
APPENDIX B6.3
LINE SOURCE
MODELING
by
0. -Bruce Turner*
Environmental Applications Branch
Meteorology Laboratory
To Be Presented by L. E. Niemeyer* at the
5th Meeting of the Panel on Modeling
Of the NATO Committee on the
Challenges of Modern Society
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, N. C. 27711
* On Assignment from the National Oceanic and Atmospheric Administration,
U.S. DeparLinent of Coraicrce
-»no ,
-------
LINE SOURCE MODELING
ABSTRACT
This paper discusses estimation of air pollutant concentrations
from line sources such as highways and airport runv/ays. Emphasized
is the Gaussian plume approach applicable v/her. there is undisturbed
horizontal flow from the source to the receptor. Results are given
for an example of the estimation of particulate sulfate concentrations
from motor vehicles. Sensitivity to atmospheric stability and to the
angle betv/een wind direction and source orientation is shown. Sufficient
comparisons have been made with field measurements to give some degree
of confidence in the use of this model.
210
-------
INTRODUCTION
This paper discusses the estimation/of air pollution concentrations
that result from line source emissions. Highways and airport runways
are examples of such line sources. To estimate concentrations from
these line sources, several different approaches have been used. These
include use of Gaussian models and of cell models. Inputs to the models
require information concerning the source geometry and its emissions,
the meteorological conditions, and also the location of the receptor
points. One of the primary needs for a line source model is to estimate
concentrations from linear highway segments. These estimates are used
in preparing environmental impact statements. Of major interest for
impact statements are the meteorological conditions and angle of the
wind with the roadway that lead to the highest concentrations.
An additional use of line source models is to determine the environmental
Impact of aircraft emissions from runways and taxiways.
APPROACHES
There are several different approaches to simulating dispersion
from line sources. The approach that will be emphasized here is the
use of Gaussian dispersion models. The Gaussian models assume that
the distributions of pollutants in the crosswind and vertical directions
are Gaussian or bell-shaped distributions. The Gaussian approach is
limited to situations where the wind flow is horizontal and parallel
to the ground, and a single representative wind speed can be chosen.
211
-------
Situations that have been considered using the Gaussian model are
"at-grade level" roads and also roads in "cut-sections." In the case
of the "cut-section" roadway, it is assumed that the flow above the
cut is essentially horizontal and estinates are only made for receptor
points outside the cut.
Depending upon the angle betv/een the wind direction and the roadway,
and also upon the length of the roadway, either simple formulae or
numerical integration procedures are used to estimate the concentrations
at receptors. These are discussed below.
In applying the Gaussian model to highway segments, a separate
line source and emission rate are used for each lane of traffic. To
account for the initial dispersion in the turbulent wake behind each
vehicle, an initial distribution of pollution is also assumed.
Air quality estimates are needed for averaging times of 1 hour
or longer because of the averaging times of the air quality standards.
Therefore, emissions averaged over hourly time periods are used. The
averaging is done by determining total vehicle flow for each hour and
the appropriate emission factor to obtain the average emission over
each one-hour time period. Different emission rates can be used for
each lane of traffic based on the number of vehicles using that particular
lane.
212
-------
Other approaches, such as the grid a'pproach, as used in the EXPLOR
Model, (Sklarew, Fabrick, and Prager, V972) have also been applied to
line sources. Cell models, using diffusivities for the dispersion,
can account for variations in flow and the increase of wind speed
with height. However, these will not be discussed in this paper.
INPUTS TO THE MODEL
There are three important inputs to the line source model. First,
the location of the source and the emission rates must be known. In
the case of a highway segment the coordinates of the end points of
the segment, the number of lanes, the total width of the highway, and
the width of any median are required. Emissions for each lane separately
are entered as grams per second per meter of length. This line source
emission rate, q&, can be found if the emission factor EF (g veh km" )
and the traffic volume TV (veh hr ) are known. The following equation
similar to that from Zimmerman and Thompson (1974) is used:
.""I !.._"" I > TII / i_ i_ ~i
(g sec'V1) = EF ( g veh"' km"1) TV (veh hr"1)
1000.(m km"1) 3600 (sec hr"1)
2.78xlO'7 (EF) (TV)
213
-------
A value for the emission factor can be obtained from the Second Edition
of Compilation of Air Pollutant Emission Factors (EPA, 1973). Vlhen
vehicle speed is known and different from that used in the reference,
a multiplier correction factor is used.
The second category of input is meteorological conditions. Wind
direction, wind speed, stability class, and mixing height are required
for each hour. Since mixing height is the top of the neutral or unstable
layer, it is not a valid concept for situations where stable conditions
exist in the layer of atmosphere near the ground. Therefore, a value
for mixing height is not considered for stable conditions.
The third classification of input is the location of receptors.
The East and North coordinates and the height above ground (usually
zero) are needed.
Calculation of Concentrations
For the special situation of the wind direction perpendicular to
the line source with the end points of the line at some distances from
the location of interest, the Gaussian Model is a simple equation:
_ q*
x = \f~ u oz(x + a)
(1)
This and all other equations presented here are for the case where both
the line source and the receptor are at ground-level, x is tne concentration,
214
-------
q is the emission rate, u is the v/ind speed, and a is the dispersion
parameter value dependent upon distance from the source and stability
class. The distance from source to receptor is x. a is the virtual
distance to give the required initial o (discussed below).
Calder (1973) has given a modified equation to use when the line
source can still be regarded as infinite in length but the v/ind deviates
from the perpendicular. Deviations as much as 75° from the perpendicular
can be handled in this v/ay for very long line sources (about 15 to 20 km).
The equation used is:
x ~ « - sin a u a£(x + a) '2'
where a is the angle between the wind direction and the orientation
of the line source and x, which is the distance from the receptor to
the point on the line source directly upwind, is found from:
x = d/sin a
where d is the perpendicular distance of the receptor from the line
source. If more than one lane of a roadway is being simulated, the
equation must be applied to each lane independently and the resulting
concentrations summed.
215
-------
When the wind direction is close to that of the line source, or
the line source can no longer be regarded as infinite so that end effects
may occur; Calder's approximation is no longer valid. The calculation
of concentration must be made by a simple numerical integration of the
Gaussian plume point source equation over a finite length. The coordinates
of the end points of a line source of length L extending from point A to
B (see figure 1) are R., S. and Rfi, Sg. The direction of the line source
from A to B is B. The coordinates R, S of any point along the line at
the arbitrary distance x. from point A is given by:
R = RA + 8. sin £
S = SA + ft cos @
Given a receptor at R^, $k, the downwind distance, x, and the
crosswind distance, y, of the receptor from the point R, S for any wind
direction 0 is given by:
x = (S - Sk) cos 0 + (R - Rk) sin 0
y = (S - S. ) sin 0 - (R - R.) cos 0
IN K
Since R and S are functions of £, x.and y are also functions of £.
The concentration, x from the line source is then given by:
216
-------
X =
U
xp(-yV2ov)dA
where a and b are the virtual distances required to produce the initial
az apd <*v respectively.
The trapezoidal approximation to the integral is found by the
following. Let Afc = L/M
where:
u
exp -
fi =
-y2ClA£] 1
m 2o 2(x[iA£]+b)J
N-l
n fi
1=1
(3)
For a given initial choice of the interval length, M, the calculation
Is then interatively repeated with twice the number of intervals, that
1s, with AH/2, AA/4 ..., until the concentration estimates converge to
within some specified limit of accuracy. This value then represents
the true value of the integral.
217
-------
Figure 2 gives guidance on which equation or procedure to use for
receptors near a specific line source. For v/inds perpendicular to the
source, equation (1) can be used over a wide area. Equation (2) can
be used over a smaller area. The size of both of these areas increases
with length of the line source. Also the angular range for which
equation (2) applies, changes somewhat with source length.
The initial dispersion caused by the down wash or v/ake effect behind
each individual vehicle is considered in the model by assuming an initial
a (horizontal dispersion parameter) value of 3 meters, and an initial
a (vertical dispersion parameter) value of 1.5 meters at each point
along the line source. This is depicted in Figure 3.
SPECIFIC EXAMPLE
The example discussed here relates to particulate sulfate
concentrations produced by automobiles. Most gasoline marketed in
the United States contains a small amount of sulfur. In order to meet
automobile emission standards for carbon monoxide and hydrocarbons,
catalytic-converters are scheduled for use on a number of 1975 model-
year automobiles. The converter will oxidize carbon monoxide and
hydrocarbons to water vapor and carbon dioxide. It will also oxidize
the sulfur in the exhaust to sulfur trioxide which will rapidly convert
to sulfuric acid due to the high humidity in the exhaust. Sulfuric
acid mist and other sulfate aerosols will result.
218
-------
Measurements of atmospheric sulfate ,have been related to adverse
health effects in various studies (Finklea, 1973). It is therefore
desirable to estimate sulfate particulate levels at receptor locations
near busy roadv/ays. Since associated health effects have been compared
with 24-hour measured air quality levels, it is desirable to make the
estimates with the model for up to 24 hours.
•An estimate of emission rate of sulfate from catalytic equipped
vehicles was first obtained from the mobile source air pollution control
experts. Computations were then made on the assumption that 25% of the
vehicle miles traveled on the roadway segment v/ere by vehicles equipped
with catalytic converters. A segment of expressv/ay, 10 lanes in width,
(43 meters wide including a 3 meter median) and 2 kilometers in length
was chosen as the source. Traffic flow rate at the busiest time of
day was assumed to be 2,000 vehicles per hour per lane.
Estimates of hourly concentrations v/ere made for a day having rather
typical meteorological conditions, and for a day with adverse meteorological
conditions. Receptor locations, perpendicular to the mid point of the
2 km highway, v/ere considered at 3, 50, and 500 meters av/ay from the
downwind edge of the highway. Computations v/ere made with the wind
perpendicular to the highway segment. Computations were then made varying
the angle of wind direction to the highway in order to determine what
angle produced the maximum concentration at each specific receptor. The
results of these short term estimates with an everaging time of one
hour are shown in Table 1.
219
-------
Computations of 24-hour sulfate concentrations at each receptor
were then made, varying both meteorological conditions and the volume
of vehicles, hour by hour. Realistic vehicle flow rate variations
were obtained from highway experts. The hourly meteorological conditions
'used were from a 24-hour period of airport data. This 24-hour period
was selected for its light wind speeds, stable conditions, and small
variability in wind direction. An orientation of the highway segment
was chosen so that there was some cross-expressway component of the
wind in the same direction during most of the 24 hours. The temporal
variations in concentrations at the various receptors'are shown in
Figure 4. Average estimated 24-hour concentrations during this period
at the receptor distances of 3, 50, and 500 meters are 11, 5, and 0.2
_3
ygm , respectively. Although this computation may not represent the
worst situation, it can be considered as an adverse situation with
regard to size of highway, amount of vehicular traffic, and meteorological
conditions.
MODEL LIMITATIONS AND CONFIDENCE LIMITS
The application of the Gaussian line source model is restricted
to cases where there is horizontal flow and a representative mean
wind can be determined between the source and the receptor. The influence
of local roughness which is caused by trees or buildings close to the
roadway is not included in this model. It is assumed that the surroundings
220
-------
are nearly-level open country. The dispersion parameter values o
and a , are basically extrapolations to shorter travel distances of
the dispersion parameter values for the Pasquill stability types used
in Workbook of Atmospheric Dispersion Estimates (Turner, 1970).- Therefore,
these may be slightly in error due to local roughness. The initial
mixing zone due to the turbulence behind vehicles is estimated from a
very limited amount of data and could be subject to change with availability
of future field studies. Changing the stability classification by one
cl.ass will change the concentrations by 10 to 20% close to the source
and as much as a factor of 2 at distances greater than about 1 km.
Including other sources of error, the accuracy of the model is that
estimates might be expected to be within field measurements by a factor
of 3 to 5.
There have been some limited comparisons of calculations with the
model and field measurements. These comparisons have not been sufficient
in number to validate the model with regard to the full range of stability
classes or the entire range of possible angles of the wind with the roadway
The initial a's and the dispersion parameter values themselves are subject
to change in response to further field measurements and consideration
of local surface roughness. The model should not be applied to highway
locations on a fill or built upon elevated columns above the ground
surface because in these situations the flow can not be considered
horizontal.
221
-------
MODEL SENSITIVITY
'The model assumes concentrations are inversely proportional to
wind speed. As mentioned previously, change of stability class will
cause considerable changes in concentration. Figure 5 shows the
concentrations at receptor locations downwind of the line source for
various stability classes for the case of perpendicular winds. A
four lane highway 19 meters wide with a 3 meter median was used for
this exercise. The highway segment is 5 kilometers long with the
receptors perpendicular to the center of the segment. So as to be
normalized for the emissions and wind, emissions for each lane were
assumed to be 1 g sec" m and wind speed was set at 1 m sec .
Figure 6 shows the concentrations at receptor locations at the same
distances from the identical line source but for wind direction only
10° from the orientation of the line source. Figure 7 shov/s the change
in concentration as the angle of the wind with the source orientation
changes for different receptor positions. The same source is used as for
Figures 5 and 6. The stability used was class E. Note that for
receptors close to the highway, the maximum concentration occurs with
small angles of the wind to the source orientation. For receptors at
greater distances from the source, the maximum concentration occurs
with a larger angle. Although larger, these angles are still quite
small, being only 17° from parallel with the line source for a receptor
500 meters from the source.
222
-------
CONCLUSION
Line source models are useful for estimating concentrations from
traffic on highway segments and airport taxiways and runways. A model
based on the familiar Gaussian assumptions can be used for the full
range of receptor locations and wind orientations with the line source
for situations v/here the wfnd blows horizontally along the ground surface.
These assumptions are most completely fulfilled for at-grade roadways
with no significant obstructions to the flow at the side of the road.
Although not completely validated for the full range of stability and
wind angle situations, sufficient comparisons have been made with field
measurements to give some degree of confidence in the use of this model.
For more complex highway configurations other approaches such as the
use of cellular models are in order.
ACKNOWLEDGEMENTS
The author is indebted to Larry Niemeyer, Karl Zeller, Lea Prince,
Susan Godfrey, and Floyd Jenkins for their comments and assistance.
223
-------
REFERENCES
Gaidar, K.L., 1973: On Estimating Air Pollution Concentrations
From a Highway in an Oblique Wind, Atmos. Environ. 7, 863-868 (Sep 73)
Environmental Protection Agency, 1973: Compilation of Air Pollutant
Emission Factors. Second Edition. EPA Publ. No. AP-42. Research
Triangle Park, NC (Apr 73)
Finklea, J.F., 1973: Conceptual Basis for Establishing Standards.
Proceedings of the Conference on Health Effects of Air Pollutants,
October 3-5, 1973, p 686, United States Senate Publication 93-15,
U.S. Government Printing Office, Washington, D.C. (November 1973)
Sklarew, R.C.; Fabrick, A.J.; and Prager, J.E., 1972: Atmospheric
Simulation Modeling of Motor Vehicle Emissions in the Vicinity of
Roadways. Presented at the 1972 Sunnier Computer Simulation
Conference, San Diego. June 14-16.
Turner, D.B., 1970: Workbook of Atmospheric Dispersion Estimates
Environmental Protection Agency Publ. No. AP-26, Research Triangle
Park, NC 84 p.
Zimmerman, J.R.; and Thompson, R.S., 1974: User's Guide for HIWAY,
A Highway Air Pollution Model. Environmental Protection Agency.
Environmental Monitoring Series EPA-650/4-008 (Jun 74).
224
-------
TABLE 1
ONE-HOUR ESTIMATED SUSPENDED PARTICULATE SULFATE AND SULFURIC ACID CONCENTRATIONS
IN THE VICINITY OF A BUSY TO-LAME EXPRESSWAY.*
ISJ
KJ
in
Distance from
Edge of Expressway
(meters)
3
50
500
Concentration (yg m )
Normal Meteorology Adverse Meteorology
Wind
Perpendicular
Wind at
Worst Angle
2.1
1.3
0.3
5
2
0.3
Wind
Perpendicular
Wind at
Worst Anale
20
19
5
88
33
6
* Assumes 25% of the vehicle miles traveled on a busy 10 lane expressway 2 km long (20,000
vehicles per hour at 30 ml hr" ) are by vehicles equipped with oxidation catalyst devices
emitting 0.05 grams of sulfuric acid or sulfate per vehicle mile. Other 75% of vehicle
miles emit no sulfuric acid or sulfate.
-------
NORTH
(RA,SA)
WIND
RECEPTOR
(R, S)
(RB,SB)
EAST
LINE SOURCE AND RECEPTOR RELATIONSHIPS
226
FIGURE 1
-------
EQUATION (2) CAN BE USED FOR THE AREA
WITH LINES BETWEEN THE PLUMES FROM THE
END POINTS.
-------
ASSUMED INITIAL CONCENTRATION PROFILES IN THE HORIZONTAL AND VERTICAL
RESULTING FROM INITIALcry OF 3, AND INITIAL<7Z OF 1.5
FIGURE 3
-------
DURING 24 HOURS AT 3 DISTANCES FROM A HlGSi.'.AY
KJ
KJ
10 LANE HIGHWAY
2 km LONG
43 metors WIDE
3 meter MEDIAN
RECEPTORS PERPENDICULAR
TO_CENTER OF LINE
EMISSION'S AND
METEOROLOGY
VARIED HOUR BY HOUR
4 6 8
10 12 ,14'
TIME
16 18 20 22 24
FIGURE 4
-------
X AS A FUNCTION OF DISTANCE FROM ROAD FOR 6 STABILITY CLASSES
(PERPENDICULAR WINDS)
I
5 10 50 100 SCO
PERPENDICULAR DISTANCE OF RECEPTOR FROM LINE SOURCE .(nT)
1COO
FIGtJRF 5
-------
•X AS A FUNCTION OF DISTANCE FROM ROAD FOR 6 STABILITY CLASSES
(WIND AT ANGLE OF 10° WITH LINE SOURCE)
ISJ
OJ
50 100
500 : 1000
-------
KJ
UJ
KJ
10
s
•k
X
XAS A FUNCTION OF ANGLE OF THE WIND WITH LINE SOURCE
FOR 5 RECEPTOR DISTANCES
-I .1 I !
0 5 10 15 20 25 30 35 40. 45 50 55 60 65 70 75 80 85 SO
ANGLE OF WIND WITH RESPECT TO ROADWAY ORIENTATION, degrees
FIGURE 7
-------
AKPLNUIX B7.1A
Status Report
Development of a Methodology to Determine the
Effects of Fuel and Additives on Atmospheric Visibility
The initial work to study the effects of fuel and fuel additives on
atmospheric visibility is being conducted by the Calspan Corporation. The
Calspan Corporation contract is for a laboratory study to develop the
measurement methodology and to use the recommended methodology for study
of visibility reduction by emissions from automobiles using a "standard
EPA fuel additive study reference fuel" and additives. The work is to be
conducted in three phases: (1) methodology development (including test
facility development), interim report on methodology development and
recommendation,and (3) the application and methodology tests with auto-
mobiles using the reference fuel and the additives CI-2 and F-319.
The test facilities for the study have been completed, the methodology
development tests have been completed (phase 1), and an oral interim report
recommending the measurement method has been presented (phase 2).
The results of the methodology tests indicate that the atmospheric
visibility-reducing potential of exhaust emissions is primarily dependent
on the HC/NOX ratio of the emissions. The combustion products with the
highest HC/NOX ratio produce the most visibility reduction.
At present, a contract overrun is being negotiated for completing the
third phase work. The overrun was due to unexpected delays in preparation
of facilities for the study, slow stabilization of vehicle performance,
and the lengthy sample test periods of 24 hours.
During the phase 3 part of the program,the exhaust emissions from a
1971 catalyst-equipped Ford automobile will be tested to determine the
effect of the catalyst on the visibility effects of the emissions.
233
-------
FIGURE 1 : ORIGINAL VEHICLE EMISSION TEST SCHEDULE
MILEAGE ACCUMULATION. THOUSANDS OF MILES
KJ
W
-t
<
VEHICLE NO. 1
VEHICLE NO. 2
VEHICLE NO. 3
) 1 2 3 4 5
III 1
-t A fr't- A/?
r> r> A o
« o ^ c B/?
*^ Y
LEGEND
1. O " MILEAGE CONDITIONING TEST (SINGLE TEST)
2. A - REPRODUCIBILITY DEMONSTRATION TESTS
(TRIPLICATE TESTS)
3. A - ENDOLENC 0
B " ENDOLENt 0 + 0.5 GM/GAL TEL
C - EPA REFERENCE FUEL
D • E»A REFERENCE FUEL + 0.5 GM/GAL TEL
6 7 8 £
1 ' '
A f\ f*. j
B • ** — -
A o o '
1r -t n Id
/\ ^^\ ^^ 1
« •« \^^^^^^^^\J^^^^^^^^-
} 10 1
I
-
> O i
I r> t
a H n m-
1** U/J *"(
O t
NOTES:
1. AN UNSPECIFIED NUMBER OF
PRELIMINARY TESTS WILL BE
PERFORMED DURING THE FIRST
TWO THOUSAND MILES
2. EACH ENGINE WILL BE CLEANED
AND A NEW EXHAUST SYSTEM
INSTALLED AFT ER THF. FIRST SI)
THOUSAND MILES.
4. a = CHF.VRON F-310
fl ~ ETHYL CI-2
-------
FIGURE 2 REVISED VEHICLE EMISSION TEST SCHEDULE
MILEAGE ACCUMULATION, THOUSANDS OF MILES
(A)
012 34567
II 1 1 1 1 1
vehicle No. 1 t A
f*\ f^ ^ A
t> {J {J Li
O O O •"•
1 1 1 1
Performance Date: 9/24 10/15 11/12 12/10
LEGEND
1. O • MILEAGE CONDITIONING TEST (SINGLE TEST)
2. A - REPRODUCIBILITY DEMONSTRATION TESTS
89 10 11 12 13
II III
O— • * " Y O O~ Y
1 i 1 1 1 |
1/7 3/18 4/8 LTO BE DETERMINED
P INTERIM REPORT
NOTES:
1. AN UNSPECIFIED NUMBER OF
PRELIMINARY TESTS WILL BE
PERFORMED DURING THE FIRST
14 If
c J
« C6 J
rt -A
U ti
, D8 ^
A
— n— — A
I
1 1
AFTER J
(TRIPLICATE TESTS)
A - INDOLENE 0
B - INDOLENE 0 + 0.5 GM/GAL TEL
C " EPA REFERENCE FUEL
D - EPA REFERENCE FUEL + 0.5 GM/GAL TEL
a - CHEVRON F-310
/? - ETHYL CI-2
SEVEN THOUSAND MILES
2. EACH ENGINE WILL BE CLEANED
AND A NEW EXHAUST SYSTEM
INSTALLED AFTER THE FIRST TEH
THOUSAND MILES.
-------
.NO
2
5
6
7
8
9
o o
AUTO EXHAUST -»- NATURAL AIR (200:1)
AUTO EXHAUST + NATURAL AIR (200:1)
AUTO EXHAUST + NATURAL AIR (200:1)
AUTO EXHAUST + NATURAL AIR (200:1)
AUTO EXHAUST + NATURAL AIR (200:1)
NATURAL AIR ONLY
RH
35%
35%
35%
80%
80%
80%
CARC
CARC
CARC
CAR A
CAR A
at
E
6
8 10 12 14
IRRADIATION TIME (MRS)
16
18
20
22
Figure 3>
EFFECT OF VARIATIONS IN NATURAL AIR ON TEST RESULTS
236
-------
NO
4r~i— .-
r
10 O C
11 j\' • £.
12 o c
50 i
40
30
20
_i
10
u
a
85
5
4
3
2
1
(
L
f
] AUTO EXHAUST + FILTERED AIR (200:1)
) AUTO EXHAUST + Fl LTERED Al R (200:1 )
i AUTO EXHAUST + FILTERED AIR (200:1) + 0.8 ppm SO2
> AUTO EXHAUST + FILTERED AIR (200:1) + 0.9 ppm SO2
'
0
^'
-^
\
\
1
x
3^
1
\
\A
\
^
— :=-H
V _
^x
"v
5
L— -
t
t
Q--.
A^
^__.
-a —
xx
**>,
.
-10 -
K>1 .,......_..
^^^O
RH
35%
80%
35%
80%
4
^===1
"-<
CAR A
CAR A
CAR A
CAR A
!
i
i
|
^ — -
t
i
i
» ..^.TT-
12
) 2 4 6 8 10 12 14 16 18 20 22
IRRADIATION TIME (HRS)
Figure
EFFECT OF RELATIVE HUMIDITY AND ADDED SO2 ON TEST RESULTS
237
-------
NO
t
4
11 "
1* .
12"
1C
.0 D
.0 0
A A
' A A
RH
AUTO EXHAUST + FILTERED AIR (200:1)
AUTO EXHAUST + FILTERED AIR (500:1)
AUTO EXHAUST + FILTERED AIR (200:1) + 0.8 ppm SO2
AUTO EXHAUST + FILTERED AIR (500:1)+ 0.12 ppm SO2
AUTO EXHAUST + FILTERED AIR (200:1) + 0.9 ppm SO2
AUTO EXHAUST + FILTERED AIR (500:1) + 0.09 ppm SO2
35%
30%
35%
30%
80%
75%
CAR A
CAR A
CAR A
CAR A
CAR A
CAR A
4 6 8 10 12 14
IRRADIATION TIME (HRS)
16
18 20
22
Figure 5 EFFECT OF DILUTION RATIO . RELATIVE HUMIDITY AND ADDED SO2
ON TEST RESULTS.
238
-------
- - - - -
AUTO EXHAUST + FILTERED AIR (200:1) + 0.8 ppm SO2
AUTO EXHAUST + FILTERED AIR (500:1) + 0.12 ppm SO2
0 AUTO EXHAUST + FILTERED AIR (1000:1) + 0.05 ppm SO2
D AUTO EXHAUST + FILTERED AIR (500:1) + 0.04 SO2 +
0.7 ppm HEXENE
A 0.08 ppm SO2 + 0.7 ppm HEXENE
RH
35%
30%
30%
CAR A
CAR A
CAR A
30% CAR A
v>
-j
CO
V)
>
14 16 18 20
IRRADIATION TIME (HRS)
22
Figure fo EFFECT OF DILUTION RATIO, ADDED HYDROCARBON AND SO2
ON TEST RESULTS
239
-------
O -O HEXENE-1 <2cc) + 0.07 SO2 DEC 5. 73
HEXENE-1 <2cc) + 0.035 SO2 + 2.1 NO FEB 1, 74
50
40
30
20
s
M
fl
1
_____
91
I
' ~~t
1
1 (
\
\
i
1 r
t>.
\
\
I
1 1
'x>
N
| 1
\
!__.
i
^o
>»,
i
i r
X^
1
"•--o
1
~o
I
0246
8 10 12 14
TIME (MRS)—i-
16 18 20 22
Figure 7 COMPARISON OF HEXENE-1»SO2 IRRADIATION WITH AND WITHOUT
THE ADDITION OF NO
240
-------
TABLE 1
METHODOLOGY REPEATABILITY TESTS - CARS A, B 6 C
TEST
Car A
Car A
Car A
Car A
Car B
Car B
M Car B
~* Car B
Car C
Car C
Car C
Car C
#1
#2
#3
#4
#1
#2
#3
#4
n
#2
n
#4
CONDITION*
300:1
300:1
300.1
300.1
+
300:1
300:1
300:1
300:1
+
300:1
300:1
300:1
300:1
+
+ 0.05
+ 0.05
+ 0.05
+ 0.05
3 cc HC
+ 0.05
+ 0.05
+ 0.05
+ 0.05
3 cc HC
+ 0.05
+ 0.05
* 0.05
+ 0.05
3 cc HC
so2
so2
so2
so2
so2
so2
so2
so2
so.
so.
so2
so2
T
72°
78°
80°
79°
65°
73°
70°
74°
72°
70°
70°
o
70
RH
33%
25%
>22%
26%
28%
29%
28%
26%
23%
27%
28%
28%
N0i
3.53
3.90
3.87
3.65
3.50
3.55
3.46
3.72
3.58
3.42
3.46
3.70
N0f
1
1
1
1
1
1
1
1
1
1
2
.92
.68
.64
.90
.56
--
.20
.02
.40
.60
.76
.12
VIZ after 23 hrs
10.7
18.5 \
20.5 /
7.9
19.0 |
22.8 >
20.5 j
8.0
I7.il
18.0 \
14.0 j
3.4
Engine Failure
, 19.2 +1.3
20.8 +2.0
16.5 +2.5
*
411 test samples irradiated for 23 hrs
For all non-lead tests (i.e., Car A + Car B) avg visibility = 20.3 +2.2 mi
-------
FIGURE fc REPEATABILITY TF.STS FOR 300:1
A
DILI/FION - CAR A (NON-LEAD GAS)
242
-------
CAN
az
243
-------
FIGURE (0 REPEATABILITY TESTS FOR 300:1 DILUTION - CAR C (LOW-LEAD GAS)
tOL C,
2%
-------
2.8
2.4
2.0
1.6
2
o
1.2
0.8
0.4
BEGIN USING ADO TIVES
4 6
MILES(x103)
10
12
Figure U HYDROCARBON EMISSIONS VS MILEAGE ACCUMULATION
245
-------
5.6
4.8
4.0
3.2
O
8
2.4
1.6
0.8
. —-S-
B
•A
;B
B
B
B
--J
c
b
©'
b
B
r
3 BEGI
BEGIN
USING ADDITIVES 13
. UJ
o
_i
OL
cc
6
MILES (x 10-5)
10
Figure )?» CARBON MONOXIDE EMISSIONS VS MILEAGE ACCUMULATION
12
246
-------
5.6
4.8
4.0
3.2
2.4
1.6
0.8
BEGIN USING ADDITIVES
4 6
MILESU103)
10
12
Figure
NOX EMISSIONS VS MILEAGE ACCUMULATION
247
-------
TABLE I.
METHODOLOGY REPEATABILITY TESTS - CARS A, B 6 C
Visibility in miles
Test
Car A
non-
lead
fuel
„ p!310
00
Car B
non-
lead
fuel
+
Cl-2
Car C
low-
lead
fuel
+ CI-2
#18
#19
#20
#21
#22
#11
#13
#15
#16
#17
#23
#24
#25
#26
Condition
300:1 + 0.05 SO,
il *
II
II
300:1 + 0.05 SO,
+ 3 cc HC
300:1 + 0.05 S02
ri
300:1 + 0.05 SO,
* 3 cc HC
300:1 + 0.05 SO,
i ii ^
it
300:1 + 0.05 SO-
+ 3 cc HC
T
°F
78
77
77
79
80
67
71
74
80
78
70
75
76
83
RH
46%
32%
41%
55%
43%
39%
31%
40%
36%
40%
36%
48%
49%
51%
N0i
ppm
2.94
4.10
3.78
2.91
3.58
3.45
3.55
3.47
3.30
3.27
3.68
3.20
3.32
2.97
N0£
ppm
1.30
2.20
1.90
1.21
1.28
1.64
1.78
1.62
1.35
0.90
1.57
1.13
1.29
--
HC
ppmC
3.15
2.50
2.95
3.30
8.05
3.60
3.55
3.90
3.75
8.85
5.25
5.25
5.00
10.8
after 23 hours irradiation
HC/NOx
1.07
0.61
0.79
1.13
2.25
1.04
0.97
1.13
1.13
2.70
1.43
1.64
1.51
3.63
April (10,000 mi)
21. 8-j
||;5|, 26.4+12
17.0-'
7.0
21.8-v
"•J 1 19.8 +3.1
16.8 r
17.8^
6.0
9.4>
7.7 \ 8.9 +1.2
9.8J
3.5
Feb
10
18
20
7
19
22
20
8
17
18
14
. (8000 mi)
.7
f} 19.2+1.3
.9
•°1
.8 C 20.8 +2.0
.0
.0 V 16.5 +2.5
.0 J
-------
tt'i
10
-------
B-1B91
-------
-------
50
40
30
20
t
10
9
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252
-------
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253
-------
Figure \7 PROGRAM SCHEDULE AND CUMULATIVE COSTS - REVISED 9/10/73
TASK
PHASE I
• PLANNING & INITIAL
TESTING OF METHOD
• EFFECTS OF CHAMBER
QT 7TT fl TrMVTTOr^TvrN/f TT1SJT A T
CONDITIONS
• VALIDATION OF EXPERI
MENTAL TECHNIQUE
PHASE II
• INTERIM REPORT AND
ORAL REVIEW
PHASE III
• REPEATABILITY &c
DEMONSTRATION TESTS
• EFFECTS OF EPA REF-
ERENCE FUEL & ADDI-
TIVES ON VISIBILITY
• MONTHLY & FINAL
REPORTS
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projected expenditures
actual expenditures
-------
APPENDIX B7.1B
DEVELOPMENT OF A METHODOLOGY TO DETERMINE
THE EFFECTS OF FUEL AND ADDITIVES
ON ATMOSPHERIC VISIBILITY
MONTHLY LETTER REPORT
FOR PERIOD COVERING SEPTEMBER 1974
By: W. C. Kocmond
Contract No. 68-02-0698
10 October 1974
Prepared for:
Environmental Protection Agency
Durham, North Carolina
255
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• INTRODUCTION
One of the provisions of the 1970 amendment to the Clean Air Act
stipulates that the Administrator of the Environmental Protection Agency
(EPA) may require a fuel or fuel additive manufacturer to conduct specific
tests in accordance with accepted test methods and procedures to determine
the effect of such emissions on the public welfare or on the emission control
performance of a vehicle. The contribution of these emissions to reduced
visibility in the atmosphere is related to this problem and therefore must
also be considered. In order to anticipate possible regulatory measures,
a methodology is required for assessing the effects of fuels and/or fuel
additive combustion products on atmospheric visibility. It is the objective
of this investigation to develop such a methodology.
In this monthly report, a brief description is given of progress
for the month of September, together with plans for the coming month.
• PROGRESS TO DATE
During September and early October, engine tear down procedures were
completed on Cars A and B and mileage accumulation was started. New exhaust
systems were installed on both vehicles and all combustion chamber deposits
were collected for EPA inspection and analysis. A decision to replace the
heads from Car A with those from C (no longer slated for tests on this pro-
grams) was made after noting that the valve guides in Car A were wearing
abnormally. This condition could have posed a threat to proper engine opera-
tion after additional mileage accumulation.
A 1973 Ford Torino with a catalytic converter was delivered to Calspan
from the EPA during late September. The car is being operated on lead-free
reference fuel in the same manner as A and B during the mileage accumulation
period. All vehicles will be given an emissions test after the 1000 mile
point is reached.
256
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Work was completed during September on the air conditioning system
which will be used to supply controlled humidity air to the carburetors of
the vehicles during emissions tests. The system, which consists of a 1 ton
air conditioner, reheat coils, blowers and appropriate ductwork, has been
tested over a wide range of humidities and temperatures and is operating satis-
factorily. Humidities between 30% and 80% can be reliably obtained by regu-
lating the amount of heat that is supplied to the nearly saturated cold air
within the ductwork. The system will be used during the first emissions
series scheduled for late October.
• PLANS FOR THE COMING MONTH
Mileage accumulation will continue during October and the first
emission series will be performed on the test vehicles late in the month.
A total of 3000 miles will be driven on Cars A and B before additives are
introduced into the fuels. The catalytic converter equipped Ford will
operate on reference fuel throughout the period.
Because of delays in completing the lighting modifications to the
Calspan smog chamber, methodology tests will not be started until early
November. The vehicle emission test schedule anticipated for the remainder
of the program is shown in Figure 1.
257
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FIGURE 1. REVISED VEHICLE EMISSION TEST SCHEDULE
MILEAGE ACCUMULATION, THOUSANDS OF MILES
Performance Date:
/IS 1
lll/
9/24 10/15 11/12 12/10 1/7 3/18 4/8 11/1 11/22 12/13 1/3 1/31
INTERIM
REPORT
1.
2.
LEGEND
O • MILEAGE CONDITIONING TEST (SINGLE TEST) 1.
A - REPRODUCIBILITY DEMONSTRATION TESTS
(TRIPLICATE TESTS)
A • INDOLENE o 2.
B • INDOLENE 0 + 0.5 GM/GAL TEL
C - EPA REFERENCE TJEL
NOTES:
AN UNSPECIFIED NUMBER OF
PRELIMINARY TESTS WILL BE
PERFORMED DURING THE FIRST
SEVEN THOUSAND MILES
EACH ENGINE WILL BE CLEANED
AND A NEW EXHAUST SYSTEM
INSTALLED AFTER THE FIRST TEH
THOUSAND MILES.
4. a - CHEVRON F-310
/? - ETHYL CI-2
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APPENDIX B7.2
DEVELOP LABORATORY METHOD FOR THE COLLECTION AND
ANALYSIS OF SULFURIC ACID AND SULFATES (21 BCE - 053)
The primary source of atmospheric sulfuric acid aerosols and sulfates
is the burning of fossil fuels that contain sulfur compounds. Photochemical
and catalytic reactions in the atmosphere produce additional quantities of
sulfuric acid and sulfate. The United States will be emitting much more
sulfuric acid and sulfate into the atmosphere as a result of the catalytic
converter that must be installed on all 1975 vehicles. In addition, the
burning of more coal with a high sulfur content will compound the sulfuric
acid-sulfate problem. The toxicity of sulfuric acid aerosols and their
ever-increasing input to the atmosphere makes it imperative that a reliable,
specific, and sensitive sulfuric acid and sulfate method be developed.
A contract is being written entitled "Development of Methodology and
Instrumentation for the Assay of Sulfuric Acid and Sulfates in Ambient Air."
It should be in the Contracts Office by the end of August 1974 and hopefully
proposals will be received for evaluation and contractor selection by
November 1974.
259
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APPENDIX B7.3
DEVELOP PORTABLE DEVICE FOR COLLECTION OF SULFATE
AND SULFURIC ACID (21 BCE - 052)
Sulfuric acid and sulfate present in the atmosphere constitute severe
health hazards. The emission and consequently the adverse effect on human
health of increasing amounts of these pollutants caused by the increasing
use of catalytic converters on automobiles can properly and reliably be
assessed only if accurate and reliable collection methods exist. Presently
available samplers and sampling techniques for sulfuric acid and sulfate are
unsatisfactory, mainly because no provisions have been made to check or
prevent the conversion of S02 to sulfuric acid and/or sulfate on the collec-
tion medium nor to prevent interactions of hydrocarbons, photochemical
oxidants, and a host of airborne catalytic substances with the sulfur oxides.
The purpose of this task, therefore, is to evaluate present sampling
methods and to develop a compact, efficient, and economic portable collection
device for sulfuric acid and sulfate whereby artifact formation is prevented
and precursors of sulfuric acid and sulfate are not collected as sulfuric
acid or sulfate so that the values of yg/m^ of these two pollutant species
are accurate values representing the true amounts of sulfuric acid and
sulfate at the site of collection.
Task 052 is presently in the planning stage and no RFP has yet been
issued. It appears that the target date for completion of the task
(July 1975) as listed in ROAP 21 BCE is premature and unrealistic, and it
is suggested that it be rescheduled.
260
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APPENDIX B7.4
PERSONAL EXPOSURE METERS FOR SUSPENDED SULFATES
(21 BCE - 041)
This program will include development of devices to collect particles
so that analysis for H2S04 may be performed shortly after the sample is
deposited on the collection surface. This collection device after initial
testing could be converted to a miniature personnel dosimeter, if we can
demonstrate that the sulfuric acid collected will maintain its integrity
until the collector is returned to the laboratory for analysis.
261
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APPENDIX B7.5
Smog Chamber Study of SO? Photo-oxidation to $04 Under Roadway Conditions
This is a contract task performed by Calspan Corporation. The task
calls for smog chamber experimentation to determine the dependence of
sulfate formation on the sulfate precursors, in simulated roadway atmo-
spheres. This work is coordinated with another contract effort at Battelle,
concerned with sulfate formation in city-wide and rural atmospheres.
Detailed design and coordination of the two efforts was finalized in an
EPA-Calspan-Battelle meeting held in RTP, NC in June, 1974. Calspan is
now completing a first phase of the study, concerned with delineation of
effects from certain chamber design and procedural factors upon the data
sought. Information to be ultimately generated in this project will
provide £ measure of the extent to which S02 is expected to be converted
into sulfate in a typical roadway atmosphere.
262
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APPENDIX B7.6
STUDY OF SCAVENGING OF SO? AMP SULFATES BY SURFACES
NEAR ROADWAYS (PE 1AA002, POAP A21BCE Task 049)
This is a new task that will be performed under contract. An
RFP should be out in September and the contract awarded in December.
Existing diffusion models do not include pollutant removal
mechanisms at surfaces although empirically determined distribution
parameters (oz, ay) very likely account for this effect. Roadway
and adjacent surfaces may act as significant sinks for auto produced
SO2 (controlled by eddy diffusivity) while not acting in the same
way for fine (<.ly) aerosol t^SOi, (controlled by Brownian movement
through boundary layer). These effects should be determined and
incorporated into diffusion models.
The contract will call for four related research efforts. These
efforts are (1) theoretical diffusion modeling to estimate the
relative effects of surfaces as sinks for reactive gases and aerosols,
(2) laboratory controlled experiments to determine magnitude of these
effects on various surfaces for SC>2 and I^SOi^ aerosols, (3) field
controlled experiment (measuring concentrations from controlled
emissions over uniform surface such as unused airport runwayX, and
(4) correlating deposition rates on various surfaces with concentration,
emission, and meteorological data near high traffic density roadways
to verify controlled experiment findings.
263
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APPENDIX B7.7
Characterization of Roadside Aerosols
St. Louis Roadway Sulfate Study
Grant, Husar, Washington University, St. Louis, Missouri
The objective of this study is to determine the changes in sulfate
aerosol, sulfuric acid mist, and other aerosols components due to the
introduction of cars equipped with catalysts. This will differ from
the Los Angeles study in that it will be performed in a city with
higher SO. background, lower oxidant, and different meterologlcal
conditions. Sulfate size distribution, S0_/ sulfate ratio, 2-hour
sulfate and other elements, and acidity will be measured upwind and
downwind of a beltway with approximately 250,000 vehicles a day
traffic.
The elemental analysis will be performed by Winchester, Florida
State University, 1'allsihasse. Husar, at Washington University, will
make water soluble sulfate and acidity measurements for both roadway
studies.
This program will be coordinated with other studies in St. Louis
which are part of the RAPS program. It is expected that meteorological
and vehicle emission data will be available from RAPS.
264
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21BCE-40 3RD 61ABZ Atmospheric Chemistry of Acid Aerosols
ROAP 21AKB, Determination of the Character and Origin of Aerosols,
contains a number of programs relevant to the problem of acid aerosols.
The ROAP output is described as follows:
Contribution of the major sources to atmospheric aerosols,
quantitative descriptions of the generation and removal
rates associated with each major source and sink, character-
ization of urban, natural, primary source and secondary
source aerosols, scientific data for fine particle criteria
and standards, quantification of the effects of aerosols
on atmospheric chemical reactions.
The ROAP approach is described as follows:
Determine physical and chemical properties of source, ambient,
and natural aerosols; use this information to infer the con-
tribution of the various sources to the ambient atmospheric
aerosol loading; determine generation and removal rates for
important sinks and sources; measure effects of various aerosols
on atmospheric chemical reactions; study gas-particle conversions
and particle removal processes. Establish the relation between
photochemical aerosol concentrations and concentrations of
controllable precursors. Special attention will be given to
sulfates, nitrates, Cd and Pb.
-------
This ROAP contains a number of programs which are of special
interest to the Catalyst Program.
1. Photochemical Generation of Acid Aerosols from SO . Smog
^
chamber studies are being conducted to resolve current problems over
the rate of the direct photochemical generation of sulfuric acid
mist from SO . Reported rates vary from a low of no reaction reported
by Friend to a rate of 6% per hour obtained in the Battelle Smog
Chamber. Studies will be conducted to determine the reasons for the
variation in reaction rates and to determine the mechanism of this
reaction.
2. Indirect photochemical or chemical conversion of SO to
sulfuric acid mist. Laboratory studies have been conducted on the
olefin, ozone, SO system which indicate that sulfuric acid mist
is formed by the oxidation of SO by a biradical or zwitterion, a
reactive species formed from the reaction of ozone plus olefin.
A mechanism has been derived for this process and rates recommended
for the photochemical model of sulfate formation from this system.
Further work will be performed to obtain more accurate rates and
mechanisms. Additional studies will be made to determine rates and
mechanisms for other conversion mechanisms. Smog chamber studies
are being conducted of the olefin, NO , SO system. Studies this
X fc
year will be with propylene. The data from the smog chamber studies
will be used to improve and validate the photochemical smog model.
3. Liquid dropplet reactions. Studies are being conducted to
determine the rates and mechanisms and effects of catalyst such as
266
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metal salts and ammonium on the conversion of SO to sulfate in
liquid dropplets or liquid aerosols of various types. It is felt
that this heterogenous mechanism may be very important both in
power plant plumes and in the conversion of SO to sulfate during
long range transport. It may also be important near roadways under
conditions in which fog is formed.
4. Surface reactions. Studies are being conducted to determine
the chemical structure of SO absorbed on atmospheric particles and
to measure the rate of conversion of SO_ to sulfate on a variety of
atmospheric particles and surfaces.
5. Size distribution measurement. Both impactors and particles
counting techniques are being used to determine the size distribution
of aerosol generated by automobiles and other sources and at various
points in the atmosphere.
6. Aerosol Dynamics. Theoretical and experimental studies are
being conducted on the nucleation of sulfuric acid mist and the con-
densation and coagulational growth of sulfuric acid particles.
7. Humidity effects. The size of the sulfuric acid aerosol
depends strongly on the relative humidity. Sulfuric acid particles
will grow if the relative humidity increases above about 20%.
An experimental appartus is being constructed to allow measurements
of the aerosol growth and theoretical calculations are being developed
to calculate the aerosol growth under conditions of relative humidity
from 20-100%. This may be specially important in determining lung
deposition. Sulfuric acid mist from automobiles is thought to be in
the fine particle range with estimates from .02 to .3 for the mass
267
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mean diameter. These particles will probably be carried into
the lung during breathing. If they were inert a large percentage
of them would be expected to escape from the lung. However, the
sulfuric acid dropplets will grow in the high humidity of the
respiratory system and will be deposited on the lung or bronchi
tissue by impaction.
8. Sulfate compounds. An insitu technique has been developed
and used in the field which provides qualitative differentiation
between sulfuric acid droplets, ammonium bi-sulfate, NH HSO , and
ammonium sulfate,,(NH )-SO .
9. Aerosol generation. Techniques have been developed for
generating sulfuric acid mist in the .1 to .3 micron size range for
use in animal exposure studies.
10. Sulfate analysis. Techniques have been developed using
flash vaporization and flame photometric detection to measure either
total sulfur compounds volatile at 800°C or total water soluble
sulfur compounds. This technique is sensitive down to a few
nanograms of sulfur and can be used to make very short time measure-
ments of sulfur containing aerosols.
268
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APPENDIX B7.8
CHARACTERIZATION OF ROADSIDE AEROSOLS
Los Angeles Roadway Sulfate Study
Grant: Winchester, Florida State University
Tallahassee, Florida
The primary objective of the first phase of this study is to
obtain pre-catalyst, baseline information on aerosol characteristics
to permit assessment of changes caused by catalyst equiped automobiles.
Of special interest is the sulfate/SO ratio, the size distribution
of the sulfate aerosol, and the acidity of the aerosol. The baseline
data will be obtained by monitoring the ambient air adjacent to a
heavily traveled highway before the 1975 model year, catalyst
equipped automobiles are on the road. A series of tests will be
conducted along a Los Angeles, California, freeway early in September,
1974, to provide some of the baseline information. Analyses for
elements, sulfate, acidity and size distribution will be correlated
with SO and CO concentrations and meteorological data obtained in
the QAEML study. Later in the fiscal year, after catalyst equipped
cars are present in the automobile mix, the study will be repeated
to determine the changes caused by catalyst cars.
Aerosol particles will be collected as a function of particle
size, using cascade impactors of the single orifice Battelle design,
and of time, using Jensen-Nelson "streaker" Nuclepore filter samplers.
Six impactor fractions from <0.25 to >4 vim diameter will be collected
over 8-16 hour sampling intervals, and unfractionated aerosol will
be sampled by "streaker" with 2 hour time resolution. Some samplers
will be activated by a wind direction sensitive switching device.
Samplers will be taken at established stations operated by the EPA
269
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in Los Angeles along a freeway where SO , CO, and wind velocity are
monitored during aerosol sampling. For periods of optimum meteorological
conditions, aerosol samples will be selected for elemental analysis
using proton-induced x-ray emission (PIXE) with the view of relating
observed atmospheric concentrations to sources along the freeway
and in directions toward and away from the ocean. These results
may provide a baseline for future measurements to evaluate the freeway
as a source, especially of particulate sulfur compounds. Duplicate
impactor and streaker samples will be taken for determination of water
soluble sulfate by flash vaporization followed by flame photometric.
Low pressure impactor runs will be made to determine the size distribution
in the range 0.05 to 1.0 microns.
We can expect, to find the following results:
The PTXE analytical technique permits quantitative measurement of
S, Cl, K, Ca, Ti, Fe, Zn, Br, and Pb in most aerosol samples of 1 m
air volume from urban areas, and V, Cr, Mn, Ni, Cu, and As may be
determined as well. The present work will focus on sulfur and the
elements which can be related to it. Relations of the following kind
will be looked for in the data from this baseline study:
If future particulate sulfur is derived from auto exhausts, assuming
it is formed during the combustion of unleaded gasoline, its secular
increase should be correlated with a secular decrease in atmospheric
lead. There, the present extent of correlation of particulate sulfur
with lead, especially as a function of particle size, may be a crucial
part of the baseline information in this study.
Future acid sulfate additions along the freeway may cause chemical
270
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reactions in the ambient aerosol, especially if sufficient time is
available for particle interactions in the atmosphere. Volatility
of Cl and Br by acidification is one type of reaction which may occur.
Therefore, future sulfur increases may be accompanied by decreases
in Cl and Br concentrations and in the relative Br/Pb of automotive
exhaust particles. Present correlations between these elements should
be part of the baseline.
The ambient aerosol is affected by natural sources at sea, which
generate large amounts of large particle chloride, and sulfate, and
on land, which generate large particles of soil composition, including
Fe and Ti, and additional urban sources may also be operative, affecting
the concentrations of Pb, Br, S, and other elements, especially in
small particle size ranges. The baseline study, through statistical
treatment of the data, will examine the relationships among all the
elements measured so that the net freeway contributions to the aerosol
may be evaluated. Future studies will be compared with these general
baseline relationships.
Samples of fine and coarse aerosol will also be collected for
determination of total acidity. This will give an indication of the
amount of acid currently present in roadway aerosol. Analysis of
samples for acidity and water soluble sulfate willbbe performed at
Washington University, St. Louis. This program will include FIXE
analysis of samples collected in St. Louis for the St. Louis
Roadway Sulfate Study.
271
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9 PERFORMING OR~ANIZATION NAMC AND ADDRESS
Health Effects Research Laboratory
Office of Research 8 Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
EPA-600/3-75-01Q h
I TITLE AND SUBTITLE
ANNUAL CATALYST RESEARCH PROGRAM REPORT
Appendices, Volume VII
6. PERFORMING ORGANIZATION CODE
I. AUTHORISI
0. PERFORMING ORGANIZATION REPORT NO.
Criteria and Special Studies Office
1. lit I.I I n.n 'P ACCESSION NO.
,. HI POUT DATE
September 1975
IO. PMC.GUAM ELEMENT NO.
1AA002
11. CONTRACT/GRANT NO.
17. SPONSORING AGENCY NAME AND ADDRESS
Same as above
13 TYPE OF REPORT AND PERIOD COVERtO
^nmjaj^ Program Status 1/74-9/J
14 SPONSORING AGENCV CODE
EPA-ORD
Ib. SUPPLEMENTARY NOTES
This is the Summary Report of a set (9 volumes plus Summary).
See EPA-600/3-75-010a thru OlOg & OlOi and OlOj. Report to
Congrtss.
16. ABSTRACT
This report constitutes the first Annual Report of the ORL) 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 charac-
terization, measurement method development, monitoring, fuels analysis,
toxicology, biology, epidemiology, human studies, and unregulated emissions
control options. Principal focus is upon catalyst-generated sulfuric acid
and noble metal particulate emissions.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Catalytic converters
Sulfuric' acid
Uesulfurization
Catalysts
Sul fates
Sulfur
Health
li.lDENTIFIEHS/OPEN ENDED TEMMS
Automotive emissions
Unregulated automotive
emissions
Health effects (public)
i. COGAU I n.lil/(.inii|i
'I. LUI r n i Bur ION STAFLMCNT
Available to public
19 StCURITY CLASS (I tut Ht parlf
10 SECUMTtV CLASS (Tim page)
Unclassified
21. NO Of PAGES
278
72. PRICE
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