EPA-650/3-74-010
NOVEMBER 1974
Ecological Research Series
1
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Research reports of the Office of Research and Development, 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:
I. 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.
Copies of this report are available free of charge to Federal employees,
current contractors and grantees, and nonprofit organizations - as
supplies permit - from the Air Pollution Technical Information Center,
Environmental Protection Agency, Research Triangle Park, North
Carolina 27711; or, for a fee, from the National Technical Information
Service, Springfield, Virginia 221 61 .
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EPA-650/3-74-010
PROCEEDINGS OF THE SOLVENT
REACTIVITY CONFERENCE
Atmospheric Chemistry and Physics Branch
Chemistry and Physics Laboratory
Program Element No. 1AA008
ROAP No. 21AZJ-02
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, N. C. 27711
November 1974
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
11
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TABLE OF CONTENTS
MORNING SESSION CHAIRMAN: B. DIMITRIADES
Page
1. Opening Remarks
B. Dimitriades, EPA, NERC-RTP, CPL 1
2. On-going Research in Chemistry and Physics Laboratory
on Pollutant Transport and Transformation
A. P. Altshuller, EPA, NERC-RTP, CPL 2
3. Emission Trends and Pollutant Transport
R. E. Neligan, EPA, OAQPS, MDAD 5
4. The Concept of Reactivity and Its Possible Applications
in Control
B. Dimitriades, EPA, NERC-RTP, CPL 13
5. EPA Critique of R. 66 and Appendix B
F. Porter, EPA, OAQPS, ESED 23
AFTERNOON SESSION CHAIRMAN: A. LEVY
1. Reactivity Classifications of Organics
A. Levy, Battelle-Columbus 29
2. An Experimental Protocol for Reactivity Measurement
C. W. Spicer, Battelle-Columbus 29
3. Critique of Solvent Reactivity, R. 66 and Appendix B
W. L. Faith, Consulting Engineer 30
4. Development of a Study Program (Research Needs)
A. Levy, Battelle-Columbus 32
SUMMARY-CONCLUSIONS 33
LIST OF ATTENDANTS 35
TECHNICAL REPORT DATA SHEET 41
m
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MORNING SESSION
1. Opening Remarks -- B. Dimitriades, EPA
Dr. Dimitriades extended a welcome to all conference attendants
and spoke briefly on the background activity that culminated in the
conference.
Staff members of the Chemistry and Physics Laboratory of EPA's Office
of Research and Development have been thinking about the problem of solvent
emissions and about the possibility and desirability of using reactivity in the
control of such emissions. Such concern was instigated by two developments:
(a) Recent smog chamber studies suggested that the reactivity classi-
fication of organics 1n the widely used Los-Angeles-County-Rule 66 is
incomplete and at points wrong, (b) It was realized that reactivity
criteria were not used consistently in existing EPA regulations—such
an inconsistency being in principle at least, undesirable. With these
developments in mind, an EPA committee of Solvent Reactivity Experts
was established and began having conversations with the private sector
for the purpose of exploring some relevant questions on the subject
of reactivity and its application in solvent emissions control.
The first conclusion reached from these conversations was that
EPA should take a close look at whatever data were available on reactivity
of organics and, based on such data, attempt to classify organics into
reactivity classes more correctly than was done previously. This was
done in 1973 and results were described in a first-draft document
that was circulated and reviewed extensively. That document also
included a discussion of possible methods by which reactivity
criteria could be applied in control, as well as a discussion of
associated problems and research needs. For a period of several
months following the circulation of the document, response was received
covering viewpoints from the entire technical community in the country;
that is, from federal and state government, private industry and
trade associations, and academic institutions. Such response ranged
widely, from severe criticism to enthusiastic endorsement. Some of
the criticism was judged to be unjustified. Other criticism, however,
was well-taken, and has changed somewhat EPA's thinking
and conclusions. Therefore, one of the reasons for EPA's interest
in this conference is the desire to take the opportunity to present
EPA's thinking on the subject, in the light of the response received
thus far.
There have been other developments in the past year that
are relevant to and of interest in this conference. Thus, the belief
that pollutant transport phenomena are important has become stronger. Also,
speculations have been made—speculations unsupported by direct evidence
but nevertheless rational—that such transport phenomena reduce
the differences in true or effective reactivity among all but a few
organics. Linking the reactivity concept with pollutant transport
introduces a new perspective that certainly deserves attention.
1
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2. On-Going Research ui EPA's Chemistry and Physics Laboratory on
Pollutant Transport and Transformation -- A. P. Attshuller, EPA
Dr. Altshuller first offered some comments setting the theme
and scope of this conference. He emphasized that:
(a) The validity of the Ox-HC curve used by EPA as the basis for
determining control requirements is irrelevant to this conference.
The conference is intended to deal with questions of "what to do"
and "how we do it", following determination of control requirements--
a determination that may or may not be based on EPA's Ox-HC curve.
(b) Reactivity-based control regulations have been in use and,
presumably, have been accepted. Therefore, the question "to use or not
to use" reactivity criteria is irrelevant; what is relevant is the question
of "whether we should improve, and how to improve regulations."
(c) Deficiencies or gaps in existing knowledge and research
needs, while within the scope of the conference, should not be discussed
in the context of whether they are prohibitive or not. The question
to be emphasized is "what do we do now to improve control regulations
with the knowledge we have now."
Following these comments, Dr. Altshuller discussed oxidant
transport phenomena and their impact on the oxidant-reactivity of
organic substances.
Oxidant as defined in the EPA air quality criteria is the gross oxidant
measured by the KI method and corrected for nitrogen dioxide and sulfur
dioxide interference. Ozone is the predominant oxidant, but the
peroxyacyl nitrates present will contribute somewhat to the total
response of a colorimetric oxidant analyzer.
Oxidant formation is particularly sensitive to the ratio of
organics(HC) to nitrogen oxides (NO ) present as reactants in the air.
Oxidant does not start forming at measurable concentrations until.
essentially all of the nitric"oxide (NO) present is converted to
nitrogen dioxide (N02). Reducing the HC-to-NOx ratio slows down the
tate of conversion of NO to NOg and the rate of formation of oxidant.
The lesser the ability of an organic substance to participate in
oxidant formation, the more sensitive it is to a given ratio or
nitrogen oxide concentration, and the longer it takes for oxidant to
be formed at appreciable levels. However, rather substantial varia-
tions in composition of atmospheric organic mixtures toward lower
•activity are necessary in order to reduce oxidant formation
significantly. Care is required in interpreting laboratory smog chamber
results on single hydrocarbons or simple mixtures since these systems
are used primarily to demonstrate maximum ranges of effects of
compositional changes.
As discussed above, reduction in the HC-to-NOx ratio or reduction
it t e photochemical reactivity by compositional changes slows down
rather than eliminates the formation of oxidant. Only a small number
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of organic substances have been demonstrated to have negligible
ability to participate in oxidant formation. Even paraffinic hydro-
carbons such as butanes or pentanes participate in oxidant formation
and only a small amount of a more reactive organic, if present, can
accelerate oxidant formation appreciably.
These circumstances suggest that changes in reactant ratio or
organic composition which can reduce oxidant concentration levels near
the origin of high emission loadings may not reduce oxidant further
downwind. Therefore, control measures that work to the advantage of
the urban area where they are initiated may not be effective
50 of 100 miles downwind. Measurements in the Southern California
Ajr Basin, as well as studies around Houston, in Texas, ;(conducted
by Washington State U,) and in the Midwest (conducted by RTI)
indicate that urban plumes containing oxidant at or above the air
quality standard can fumigate other urban areas or rural areas well
downwind. The range of downwind transport of oxidant in urban
plumes is under continuing experimental investigation.
The experimental approach commonly used to develop reactivity
scales for organic substances is the use of smog chambers. In most of
these studies, a fixed initial concentration of each of a series of
organic substances is irradiated using simulated solar radiation with
a fixed initial concentration of nitrogen oxide. Such chambers normally
are operated as static systems at constant light intensity, temperature,
and humidity.
Most of these smog chamber experiments have been conducted at a
two-to-one ratio (HC:NOX) of reactants. In dicussing the results of
such studies, insufficient emphasis was placed on the arbitrary nature
of the choice of a two-to-one ratio of reactants. This selection of
ratio would not be important if the oxidant yields and dosages were
almost independent of reactant ratio. However, there are "lower"
reactivity organic substances, such as ji-butane and formaldehyde, which
yield little oxidant at lower reactant ratios and large amounts of
oxidant at higher reactant ratios. Conversely, many "higher"
reactivity substances, such as propylene and m_-x.ylene, yield large
amounts of oxidant at lower reactant ratios and smaller amounts of
oxidant at higher reactant ratios. In part, this difference results
from the slower rate of conversion of NO to N0£ by "lower" reactivity
organic substances, being compensated for at higher reactant ratio
by the smaller amounts of NO which are available for conversion to
N02- At the higher reactant ratios, the "higher" reactivity organics
cause a rapid conversion of NO into N0£ followed by NOg consumption
which, in turn, causes the production of oxidant to cease. In contrast,
the "lower" reactivity organics continue to participate in the
generation of ozone over a longer time period, resulting thus in
high yields and dosages of oxidant.
Emphasis is being placed on high ratio conditions since these
are more likely to be associated with large sources of emissions of
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organic solvents, petroleum and petrochemical production and related
industrial processes. Plumes associated with such emission conditions
may produce oxidant more slowly than automobile exhaust, but over a
longer distance and for longer periods of time. Therefore, the
substitution of "lower" for "higher" reactivity organic substances may
assist the local air pollution situation but may not assist as much
in reducing oxidant exposure at downwind locations.
What types of studies can contribute to resolving these problems?
Field experiments can be designed to differentiating between
anthropogenic and natural cau.ses of oxidant. formation. Selection of
appropriate sites should assist in differentiating between mobile sources
and stationary sources of organic emissions in terms of oxidant forma-
tion. Field measurements are urgently needed in which the plumes
from large extended individual sources of organic emissions are followed
downwind to measure oxidant formation as a function of organic
concentration and composition. Such plumes are likely to have higher
ratios of organics to nitrogen oxides than do the plumes from-high
traffic density areas. •
Properly designed smog chamber experiments can assist materially.
Proper selection of reactant ratios, long irradiation periods, and
simulation of atmospheric dilution should provide the conditions to
better evaluate the significance of low and high reacitivty
organic substances in oxidant formation under transport'conditions.
Smog chambers also can be used to compare the effect on oxidant
formation of changes in reactant ratios with changes in solvent-
composition.
While speculation may be premature, it is possible that additional
studies will indicate that elaborate reactivity scales are unnecessary.
The more important differentiation needed is likely not to be between
"moderate" and "high" reactivity substances. The important differen-
tiation may be between reactive and essentially unreactive substances.
For example, the determination of which paraffinic hydrocarbons can
be considered as essentially non-reactive or of low reactivity under a
wide range of conditions is of particular importance, since paraffinic
hydrocarbons constitute an important group of substances with respect
to control of organic emissions from solvent use., petroleum production,
refining and marketing (including vapor losses at the wholesale and
retain levels of use), and the production of petrochemicals-.
Another research tool which should be applied is chemical kinetic
modeling. Considerable progress is being made in verifying the applica-
"inty or sucn moaeis witn smog cnamoer experiments, unce veririea tne
kinetic model can be used to supplement experimental results by
computing results for conditions not covered by the experimental
desiqn. The model should be useful in treating reactivity problems.
In applying the outputs of these several approaches we may find
it useful to differentiate between relatively isolated urban areas
•".Tip Acting on lightly populated and vegetated areas downwind compared
tc closely clustered communities possibly involved in fumigation of
each other on a significant number of occasions each year. In the former
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case the type of reactivity schemes already developed may continue to be
aoolicable. In the latter cases new accroaches mav be necessarv.
Discussion
Questions were raised from the floor (N. J. Butler, Reynolds
Metal Company) regarding the role of natural hydrocarbon emissions
in the atmospheric photochemical reaction. Dr. Altshuller responded
that EPA 1s presently conducting field studies directed at these
questions. He expressed the viewpoint that a small amount of oxidant,
probably no more than 50 parts per billion, may form from natural
hydrocarbon. If higher values of oxidant are observed in rural areas,
then one needs to ascertain whether an urban plume is contributing to
the measured oxidant. Terpenes react very fast and are capable of
producing photochemical aerosol. However, there are no indications
as yet that terpenes contribute significantly to oxidant formation.
Natural hydrocarbons other than terpenes may also have a role; however
each case should be looked at individually.
Mr. Lebron (Maryland Bureau of Air Quality) remarked that
aerometric data in Baltimore indicated that the level of hydrocarbon had
no effect on oxidant level; rather it was the morning NOX that
correlated well with oxidant. Dr. Altshuller responded that he would
be reluctant to accept these conclusions. Precursor effects are coupled
with several factors and it would be very difficult to statistically
delineate such coupling. Further, Washington, D. C. data, examined by
EPA, did not seem to lend support to Mr. Lebron's conclusions.
Mr. Zimmt (NPCA) commented that the data that had been accumulated
on transport effects had been obtained mostly for reactive hydrocarbon
mixtures. There have been no studies on how low reactivity mixtures
would react, to substantiate such effects. Dr. Altshuller agreed
that there have been no case studies of transport effects for low
reactivity mixtures.
In response to questions from the floor, Dr. Altshuller explained
that there are studies currently under way dealing with city-countryside
interactions. The Washington State University, under EPA contract, and
EPA are studying the effect of urban emissions on countryside air quality;
also, the Coordinating Research Council has contracted Washington State
University to study the effect of natural organic emissions on urban
air quality.
3. Emission Trends and Pollutant Transport -- R. E. Neligan, EPA
Mr. Neligan expanded on what Dr. Altshuller discussed concerning
long distance transport studies. He discussed in detail a study in
the mid-west area of the United Sates. Figure 1 shows the study area.
Both ground monitoring stations and aircraft sampling were employed.
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Table 1 is a summary of the oxidant concentrations obtained at the four
monitoring stations. Figure 2 shows the oxidant aircraft measurement.
Table 2 shows the rural ozone measurements.
Mr. Neligan discussed also EPA estimates on the mobile and
stationary hydrocarbon emissions for 1970 and 1990 and stressed the
growing relative importance of the stationary source emissions in
future years. Table 3 shows these values for several U. S. cities.
These predictions were based on the equation:
(Q. x Gf x Rf)sc
(1) Psc = -— x 100
jX Gfx Rf)
sc
Where Psc = percent contribution for source category
Qi = base year emission inventory - 1970
G.C'= growth factor for source category, computed
Rf = Predicted emission reduction factor - 1990
Table 4 gives the ratio of mobile and stationary source emissions for
the years 1970 and 1990.
Discussion
Mr. Starke (Shell, Houston) asked whether in long distance transport
phenomena natural hydrocarbons might have a greater impact on ozone
measured at the monitoring site than the man-made emissions. Mr. Neligan
responded that there are several possibilities that would have to be
considered. For example, ozone may be transferred down from the
stratosphere; also natural hydrocarbons may give rise to ozone in the
.02 to .03 ppm range. Adding those two sources together it could
produce up to .05 ppm of ozone from natural sources. If higher con-
centrations of ozone are measured then one must ask where does the
ozone come from. Mr. Starke pursued his question further by suggesting
that it might be possible that man-made sources contribute, for example,
one unit whereas natural sources contribute ten units of ozone. Dr.
Altshuller and Dr. Bufalini responded with comments suggesting that
the field studies now conducted under EPA sponsorship will look into
these possibilities. They suggested specifically that the summer
program in the midwest is designed to determine the importance .
of transport of ozone and ozone precursors. Detailed hydrocarbon
analysis as well as ozone and nitrogen oxide measurements will be
made at several sampling locations in the midwest. This includes ground
a'd vertical sampling. The detailed hydrocarbon analysis should make
it possible to determine the importance of nautral sources of ozone
precursors. The area under study will cover Cincinnati, Dayton,
Wilmington, Columbus, Canton, and Pittsburgh with several rural sites.
Mr. Neligan added, in response to Mr. Patrick's (Union Carbide)
question, that in these studies attention will be given to the air
circulation patterns in the areas where these measurements will be
made.
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MICHIGAN
LANSINGo
DETROIT
wise.
MILWAUKEE
£___——- -——4"-^ VEL£
l ~
i
' | coLinuevs
ILLINOIS J INDIANA J OHIO
•SPRINGFIELP, mD,;MPOLIS \
I I
NEW YORK
BUFFALO HART\ORC«>
\CONN.
PEORIA
„,} ^-w—x r VIRGINIA'^/
i y' o 'Wf /
/ 0FRANKFORT \ CHAKLESTW'}
"'-""*"* XUWISBURG?/* V|RG|N|A
e RALEIGH
NORTH CAROLINA
y .^jwatf r- NQRTH CARQ
$ TENNESSEE ,*x CHARLOTTE
( J ?
f* —" i_——"»
MEMPHIS —-•»——^•""yr ^^ \
Figure 1. Rural oxidant study area.
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CO
Table 1. 51HMARY OF POLLUTANT CONCENTRATIONS, 6/26/73 TO 9/30/73
MEAN
MAX.
STD. DEV.
CASE COUNT
McHENFttT
(HOI
149 /LC /m3
330 jztj/m3
56 /u|/m3
I,62J!
KANE
JRLY OZONE C
130 p.q /m
270/zg/m3
57 /ig/ m3
2,131
COSHOCTON
ONCENTRATION
112 /ig/m3
340/ig/m3
63 /ig/m3
1,785
LEWISBURG
S)
105 ^g/m3
250/^g/m3
54 /^g/m3
1,663 ;
MEAN.
MAX
STD. DEV.
CASE COUNT
( -10URLY
NITROGEN DIO
II ^g/m3
40/xg/m3
8 /^g/m3
1,869
•
XIDE CONCENTF
21 ^g/m3
70 p.q/ m3
15 p.q / m
2,043
NATIONS )
16 p.q /m
60yu.g/m3
15 p.q / m
1,699
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CO
5
u
d
03
UI
o
ID
9000
.046
OZONE CONC. (ppm)
SEPT 12, 1973
— -070-
O54
.058.
.031
.043
A
LEWISBURG
(1653 EOT)
E 4000
3000
2000
1000
.082£(.082)
McHENRY
A (1146-1200 EOT)
LEWISBURG Av.
(1036-1112 EOT) KANE
(1250-1315/1425 EOT)
(.084)
A
COSHOCTON
(1537-1600 EOT)
iVISL
A RDU {0936 EOT)
A R D U (1755 L
i
200
400 600
NAUTICAL MILES
Figure 2. Ozone aircraft measurement
800
900
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Table 2. RURAL OZONE STUDY
Station
MeHenry
Kane
Coshocton
Lewisburg
Oxidant Concentrations
Max. Value
0.18
0.15
0.18
0.13
99%
0.16
0.13
0.17
0.12
% of time
Above Stds.
78
65
46
39L
10
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Table 3. ESTIMATED HYDROCARBON EMISSIONS
(1000 tons/year)
Mobi1e
Stationary
AQCR
Los Angeles
San Francisco
Houston
New York
Washington, D.C.
Beaumont
Phoenix-Tucson
1970
829
372
326
1160
221
69
117
1990
133
57
48
166
40
10
24
1970
339
257
274
361
47
152
85
1990
593
400
407
342
98
157
174
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Table 4. HYDROCARBON EMISSION DISTRIBUTION
AQCR
Year
Los Angeles
1970
1990
San Francisco
1970
1990
Houston
1970
1990
New York
1970
1990
Washington, DC
1970
1990
Beaumont
1970
1990
Phoenix-Tucson
1970
1990
Percent of Hydrocarbon
Mobile
71
18
59
12
54
11
76
33
82
29
»"i t
0 1
6
58
12
Emissions
Stationary
29
82
41
88.
46
•8$
24
67
18
71
69
94
42
88
12
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4. The Concept of Reactivity and Its Possible Applications in
Control — B. DimTtri ades, EPA
The concept of reactivity has been around for several years and
discussions of its definition, .significance, application, etc. have
been presented in a number of published reports. Of this elementary
information, three facts or. premises need to be stressed here:
1. Of the several reactivity manifestations caused by organic
pollutants, only one is of direct interest here: The one responsible
for the maximum oxidant levels found in the atmosphere.
2. The reactivities of organics can be measured only by laboratory
techniques (smog chambers); atmospheric data analysis offers no promise.
3. Organic emissions differ widely in reactivity.
Because these premises are crucial to the follow-up treatment of the
subject, they will be discussed here in some detail.
The first premise has perhaps obvious validity, considering that
oxidant is the only photochemical pollutant for which there is an air
quality standard, and for which the designated abatement approach is
based on control of organic emissions only. Nevertheless, two points
must be stressed here:
(a) While the linkage of the organic emissions with the oxidant
problem is used as the basis for deriving numerical control require-
ments, this linkage in itself is not the only reason for wanting to
control organic emissions. It is certain that control of organic
emissions will result in reduction not only of oxidant but also of
other photochemical smog symptoms. This comment is made because there
have been attempts made to degrade the need for HC control by
questioning the validity of the oxidant standard.
(b) Reactivity has been defined in terms of the max. 1-hour
concentration of oxidant observed during the 6-hour smog chamber
test. This "max-1-hour-concentration" definition was adopted simply
because the same definition is used for the air quality standard
for oxidant, However, this does not mean that this is the only
acceptable definition. For the purpose of defining and expressing
the reactivity of an organic, one can use any kinetic or concentra-
tion entity that can be measured in smog chamber test, and that can
be shown to relate quantitatively to the maximum oxidant concentration.
The second premise (that reactivity can be measured only by smog
chamber techniques) is an obvious one. It is also an important one
to keep in mind for the following reasons. In some applications, the
limitations pf the smog chamber techniques are prohibitive only
because there exists an alternative, superior method. This is, for
example, the case with the study of the oxidant-precursor relationships;
in such study the aerometric data analysis method is more valid than
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the smog chamber method. However, in the case of reactivity measurement,
the limitations of the smog chamber method are not necessarily
prohibitive; such limitations should be judged bearing in mind that
the smog chamber method is the only alternative available.
The third premise (that organics differ widely in reactivity) is
one the validity of which could be challenged, as explained next; In past
and present practices,, the maximum-oxidant reactivity of an organic i'
is measured by irradiating for 6 hours in a smog chamber pure air
containing prescribed levels of the test organic and NO. Oxidant
begins to form and accumulate only after, all of the NO has been oxidized
into NO^. Within this fixed 6-hour period then, organics which convert
the NO into N0£ very slowly, do not necessarily yield all the oxi.dant
they can yield. They could yield their maximum oxidant .concentrations
tf test conditions were different, e.g., if they were irradiated for
longer than 6 hours. Therefore one could speculate that under prolonged
irradiation conditions, as e.g. in transported city air, all but very
few organics might manifest similar reactivities, rather than a. wide
range—and this of course would question the utility of the reactivity
concept.
So, there are questions that challenge the validity of the third
premise. Nevertheless, the existing evidence, although it raises
questions, clearly does not invalidate the premise. Under conditions
prevailing within an urban area—where the problem really .is— the
existing reactivity data certainly have some validity. Under transport
conditions, i.e., under prolonged irradiation, some thought-to-be.
unreactive organics may exhibit higher reactivity, .but there is no
reason to believe that the reactivity range within the reactive organics
should shrink drastically— at least, this is not what existing knowledge
on reaction mechanism suggests.
Reactivity Classification of Organics •
In an EPA effort to classify organics into reactivity classps.
the main body of data used was obtained from three sturHpt;; thp Rattoiio
the Shell, and the SRI reactivity studies. Data. were also taken from
other studies— HEW, BuMines, General Motors and Los Angeles County.
S nee these studies used different smog chambers and conditions, all
reactivity data were expressed in terms of toluene equivalents, in the
hope that this would permit pooling of data from all studies. However,
despite this normalization, the reactivity values. still differed
considerably from study to study. For this reason, the classification
was done separately for each of the three sets of data— Battelle.
i, bKJ — and results were combined subsequently.
Examination of the data suggested that the organics tested could
be classified within 5 classes, as shown in Table 5. The 5-group
classification was dictated by the degree of agreement among the
three studies. Better agreement would have permitted classification
into more than 5 groups; worse agreement would have. the opposite
effect. The degree of agreement varied. Thus, the Battelle and
Sliell studies correlated well, Whereas the correlations
14
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with the Battelle and the Shell data were poor. This poor correlation
of the SRI data with the other data prompted some of the reviewers
of this EPA study to recommend that the SRI data not be included
in the reactivity classification work. While such a recommendation
has its merit, one must also consider that:
(a) the poor correlations between SRI and Battelle and Shell
may reflect mostly the small number of correlation points;
(b) the SRI show good internal consistency;
(c) if the number of reactivity classes is reduced to 5
(and even better to 3) the disagreement of the SRI set with the other
sets of data does not cause prohibitive problems; and
(d) the SRI study provides data for several organics not tested
by others (Table 5). In conclusion, while the question of the SRI data
inclusion is an open one, it was nevertheless decided to proceed
with this first effort to do the reactivity classification, including
the SRI data. Results are shown in Table 6.^ The only inconsistencies
in this classification are caused by the data on isopropyl alcohol
and i-butyl acetate. The Battelle data for these two organics suggest
a Class-I classification, whereas the SRI and Shell data suggest
classification in higher classes.
i
Based on the numerical ratings shown In Table 6, overall numerical
ratings were derived for the 5 classes and are shown in Table 7.
Class I is meant to include those organics that can be exempted from
control.
Application of Reactivity Criteria in Control
There are two approaches to emission control:
(a) The "air quality management approach"
(b) The "best practicable means" approach
By the air quality management approach, control requirements are
determined so as to achieve the air quality standards withou^ considering
availability or cost of control technology. The "best practicable
means" approach requires emissions to be controlled to a level that
is technically and economically feasible. Thus, the "air quality
management" approach has a more rational basis but it may not be
feasible; whereas the "best means" approach is feasible but it may
not achieve the desired air quality improvement. Obviously a
combination of the two approaches is also possible, perhaps with
advantage, as described next.
First, the overall percent reduction (of ambient organics)
required should be calculated using either EPA's Appendix J (Federal
15
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Register, Aug. 14, 1971) or another method. Then, rather than
controlling all emission sources uniformly, each emission source is
controlled to a different degree as shown in equation (1):
(l-b)rtotal(Source)total = (l-b1)r1(Source)1 + .... + (l-b.)r. (Source) . (1)
where ID,- designates the degree of control to be applied on the
respective source; r%- is the reactivity of the emission mixture from
each source; (Source)-,- designates emission rate; and b is the
required degree of control, as calculated from Appendix J. Such b,-
is to be a function of three things: (a) Reactivity of emission mixture
from repsective source; ( b) relative contribution to total emissions
load; and (c) control technology available. [Note: Whereas bj depends
on reactivity of emissions before control'- was applied, rj represents
reactivity of emission left uncontrolled]. Thus, several sets of b-j-
values could be developed, depending on the circumstances in the control
region. The only requirement that must be met is that the set of
bj-values should be such that equation (1) is satisfied. How one
goes about determining the optimum set of bj-values is an open
question at this time. In a first effort to answer this question -.
t'PA has awarded a contract to conduct a case study using as the case
site the Southern California air basin. The contractor will gather
••'•"iventory data and will attempt to develop a set of bj-values, taking
in co consideration the three pertinent factors mentioned: reactivity,
illative strength, and control technology available. Needless to
say, the main objective in this study is not to develop reactivity-
related emission standards. Rather, it is hoped that by going
through this exercise of developing reactivity-related standards,
fhe feasibility and merits of such standards will be explored and
unforeseen problems will be identified.
Q"estion-Problems in Application of Reactivity Criteria in Control
The fundamental questions to be asked here are whether a rigorous
ar d systematic application of reactivity criteria in control is feasible
a. H whether it really and truly has an advantage over the control
rejulations now in use. The answer to these questions would depend on
t' e answers to three other questions:
(1) Are the inventory data available sufficiently detailed to
'- Tnit a reactivity assessment of the emission mixtures from the
jrio-js sources? Reactivities of emission mixtures cannot be
'jst''r.ted unless the mixture composition is known.
'2) Assuming emission composition is known, how accurate is the
n of mixture reactivity from mixture composition?
(3) In the event that application of reactivity criteria
will ^equire different degrees of control upon the various sources
fan /iow required, what would the benefit from such change be?
-------
Question (l)--on detail of inventory data available—cannot
be answered reliably at this time. While the data available may not
be sufficiently detailed to permit application of the 5-group
reactivity classification scheme, they may be adequate for use of the
2-group classification. We expect to have an answer to this question
in the near future, as a result of a contract effort—an effort
directly addressed to the sufficiency of the inventory data available.
Question (2)--on the accuracy of the reactivity calculations--
cannot be answered precisely at this time. Present practice is to
calculate the reactivity of a mixture from component mole fractions
and component reactivities using the linear summation method.
It is submitted here that the error in such calculations cannot be
prohibitively large. Organics range in reactivity by more than an
order of magnitude; the calculation error certainly is much less than
that. Nevertheless, EPA is currently studying this question; there is
an on-going modest effort to use photochemical modeling techniques to
calculate mixture reactivity from individual component data.
Question (3)—on the benefit to be derived from application of
reactivity criteria—cannot be answered now. However, ar^ answer
may be had in the next few months, as a result of an on-going EPA-
contract effort on this subject.
All in all, it appears that the uncertainties concerning benefits
and the problems in applying reactivity criteria in control depend
on how rigorously or with how much detail these reactivity criteria
are to be applied.
Discussion
Questions were raised in regard to the Appendix J curve which was
referred to in Dr. Dimitriades' presentation. Dr. Dimitriades
responded that this is a curve published in Federal Register issue
of August 14, 1971, and is a guideline to calculate the hydrocarbon
control required to reduce oxidant.
In response to other questions, Dr. Dimitriades indicated that the
reactivity data available for the various organics, represent the
ability of the organic to produce oxidant on a mole basis rather than
on a weight basis. In response to whether this might create a bias
toward a heavier weight compound, Dr. Dimitriades suggested that he
didn't believe so. This problem,, if indeed, present, could be solved
relatively simply through numerical calculations.
Ms. Brunelle from Los Angeles County asked how strongly would
EPA feel about the use of oxidant alone as the basis for reactivity.
Dr. Dimitriades responded that there is no other choice at present
since the oxidant problem alone provides the legal basis for hydro-
carbon control.
17
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In response to other questions Dr. Dimitriades indicated that
the newly suggested reactivity classification of orgam'cs will be
included in the proceedings from this conference.
Dr. Dimitriades also discussed the EPA contract effort to explore
the development and use of reactivity criteria in control. Mr. Malkin
asked whether in this contract there will be a complete inventory of
the "benefits" to be obtained as a result of the use of such criteria.
Dr. Dimitriades responded that the only benefit considered in the
contract study is the oxidant reduction itself. In the discussion that
followed, Mr. Malkin clarified that he meant to ask whether there were
indeed benefits in terms of health effects as a result of the oxidant
reduction. Dr. Altshuller responded that there is evidence that ozone
indeed exerts health effects. Mr. Malkin objected to that and he made
reference to an EPA study cited in the report "Environmental Quality -
1974" (by Council on Environmental Quality) in which the cost of health
damage by oxidant/03 was given a zero dollar-value. Dr. Altshuller
agreed that this seemed to contradict the very bases of the air quality
standard for oxidant/Ch, but he insisted that regardless of the dollar-
value given to health damage by oxidant, the evidence of oxidant-
induced health effects was sufficiently compelling to lead to the
development of a health related air quality standard for oxidant.
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Table 5. REACTIVITY CLASSIFICATION OF ORGAN ICS
CLASS j
(Nonreact'ive)
C,-C- paraffins
Acetylene
Benzene
Benzaldehyde
Acetone
Methanol
Tertiary-alky! alchols
.' '*
Phenyl acetate
Methyl benzoate
Ethyl amines
Dimethyl formamide
Perhalogenated hydrocarbons
CLASS II
(Reactive)
Mono-tertiary-
alkyl benzenes
Cyclic ketones
Tertiary-alkyl
acetates
2-nitropropane
CLASS III
(Reactive)
C.+-paraffins
Cycloparaffins
Styrene
n-alkyl ketones
Primary- & Secondary-
alkyl acetates
CLASS IV
(Reactive)
Primary- & secondary-
alky 1 benzenes
Dialkyl benzenes
Branched alkyl
ketones
Primary- & secondary-
alkyl alcohols*
N-methyl pyrrolidone Cellosolve acetate
N,N-dimethyl
acetamide
Partially halo-
genated paraffins*
Partially halogenated
olefins *
CLASS V
(Reactive)
Aliphatic olefins
a-methyl styrene
Aliphatic aldehydes
Tri-& tetra-alkyl
benzenes
Unsaturated ketones
Diacetone alcohol
Ethers
Cellosolves
* Tested by SRI only.
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Table 6. SUMMARIZED REACTIVITIES AND CLASSIFICATION OF SOLVENTS
Reactivity, Toluene Equivalents
Battelle SRI Shell
Solvent Range Avg Range Avg Range Avg Class
Paraffins (including 0.4-0.6 0.5 0.9-0.9 0.9 0.8-1.0 0.9 III
cycloparaffins)
Olefins
Aliphatic 1.3-1.5 1.4 - - 1.8-3.1 2.4 V
Styrene 0.7 .0.7 - - - III
a-methyl-Styrene 1.5 1.5 - - - - V
Aromatics
Benzene 00 0.2 0.2 I
Primary-, secondary-Alkyl 0.9-1.2 1.0 1,0 1.0 1.0-1.2 1.1 IV
Benzenes
Tertiary-Alkyl Benzenes 0.6 0.6 - - 0.5-0.5 0.5 II
Dialkyl-Benzenes 1.0 1.0 - - 1.3-1.7 1.5 IV
Tri-, tetraalkyl Benzenes 1.5 1.5 - - 3.2 3.2 V
Ketones
Acetone 0 0 - - 0.1 0.1 I
n-Alkyl Ketones 0.5-0.8 0.65 0.9 0.9 0.9-1.4 1.1 III
Branched Alkyl Ketones 1.0-1.8 1.4 0.9-1.0 0.95 1.3 1.3 IV
Cyclic Ketones 0.2 0.2 0.5 0.5 0.5-0.6 0.5 II
Unsaturated Ketones 1.5-1.7 1.6 - - - - V
Alcohols
Methanol I
Primary-, secondary-Alkyl 0.2 0.2 1.1-1.2 1.2 0.6-1.451.1 IV
Alcohols (C>1)
tertiary-Alkyl Alcohols - - - - 0.30.31
Diacetone Alcohol '-4 1.4 1.7 1.7 - - V
Ethers
Diethyl Ether - 2.5 2.5
Tetrahydrofuran 1.9 1.9 . - - 1.4 1.4 V
Ethyl Cellosolves 1.5 1.5 1.9 1.9 - - V
Esters
?r-!rary-, secondary-Alkyl 0.2 0.2 0.7-1.4 1.0 0.8-1.0 0.9 III
Acetates
Tertiary-Alky! Acetates - - - 0.5 0.5 II
Cello^olve Acetate - - 1 1 1 .1 - -IV
Pherv Acetate 00 - - - - I
Methyl Benzoate 00 - - - - I
20
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Table 6 (continued). SUMMARIZED REACTIVITIES AND CLASSIFICATION OF SOLVENTS
Reactivity, Toluene Equivalents
Batelle SRI Shell
Solvents Range Avg Range Avg Range Avg Class
Ami nes
Ethyl Amines 0.1-0.2 0.15 I
N-Methyl-Pyrrolidone 0.7 0.7 - - - - III
N,N-dimethyl-Formamide - - 0.2 0.2 I
N,N-dimethyl-Acetamide - - - - 0.95 0.95 III
Halocarbons
Perhalogenated . - - 0.5-0.5 0.5 - II
Partially Halogenated - - 0.8 0.8 - - III
Paraffins
Partially Halogenated - - 1.4 1.4 - IV
Olefins
Nitroalkanes
2-Nitropropane 0.2 0.2 0.7 0.7 - - II
21
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Table 7. NUMERICAL REACTIVITY RATING
IN THE 5-CLASS CLASSIFICATION OF ORGANICS
Class Rating
I 1.0
II 3.5
II 3.5
III 6.5
IV 9.7
V 14.3
22
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EPA Critique of Rule 66 and Appendix B -- F. Porter, EPA
Most overall emission control strategies which have been advanced
to reduce ambient atmospheric levels of photochemical oxidants are
based on either a "Rule 66" approach or an "Appendix B" approach. A
"Rule 66" approach recognizes to some extent the wide variation in
"reactivity" of various classes of hydrocarbons. The primary emphasis
of a "Rule 66" approach is to limit the emission of a few hydrocarbons (of
high reactivity) much more severely than the emissions of most hydrocarbons
(of low reactivity). Thus, this approach concentrates more on changing the
character of hydrocarbon emissions rather than reducing emissions and
is based on the premise that hydrocarbons of low reactivity do not
significantly contribute to the formation of photochemical oxidants.
An "Appendix B" approach on the other hand tends to overlook the
wide variation in reactivity of various classes of hydrocarbons. The
primary emphasis of an "Appendix B" approach is to severely limit the
emission of all but a few hydrocarbons into the atmosphere. This approach is
based on the premise that all hydrocarbons, whether of high or low
reactivity, will contribute to the formation of photochemical oxidants
over a long time period.
"Rule 66" was developed and initially implemented by the LAC-APCD
in mid-1966 and subsequently amended in late 1971 and late 1972. The
adoption of "Rule 66" by the LAC-APCD represented a major effort to
reduce the formation of photochemical smog by reducing emissions of
hydrocarbons. Throughout the development of "Rule 66", the LAC-APCD
consulted closely with many of the industries affected by these
regulations and as a result, although many of the industries questioned
the need and desirability of "Rule 66", it was ultimately accepted as
a "workable" and feasible approach to reduce the formation of photochemical
smog. Currently, the "Rule 66" approach has been adopted in one form or
another, as the basis for that portion of the State Implementation
Plan dealing with the attainment and maintenance of the National
Ambient Air Quality Standards for Photochemical Oxidants, in some
twelve states.
"Appendix B" was developed by EPA and promulgated in August 1971,
as part of the Requirements for Preparation, Adoption and Submittal of
Implementation Plans in Federal Register 36 FR 15486. "Appendix B"
reviewed the degree of emission control which could be attained with
regard to specific air pollutants emitted from various industrial sources.
The emission limitations presented, represented at that time EPA's
judgment of the degree of emission control which could be attained
with reasonably available emission control technology. The intention
of EPA was not to require or encourage states to adopt "Appendix B"
23
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but to provide a general base of knowledge with regard to the extent
by which emissions could be reduced from various industrial sources.
Thus, the intention of EPA was that the knowledge provided by "Appendix
B" would serve as a general background against which states could make
emissions control decisions and develop emission regulations for inclusion
in their Implementation Plans, tailored to their specific problems and
needs. Currently, the "Appendix B" approach has been adopted in one
form or another, as the basis for Implementation Plans submitted to
EPA, by some twenty-seven states.
Both "Rule 66" and "Appendix B" therefore serve as the basis for
a number of State Implementation Plans. In this regard, both approaches
will be implemented to various degrees in a number of states as a
means of reducing and controlling ambient concentration levels of
photochemical oxidants in the near future.
In any critical review of the effectiveness of a "Rule 66" or
an "Appendix B" approach to reducing and controlling the formation of
photochemical oxidants, the major conclusion that emerges is that
neither approach by itself can be judged to be totally effective at
this time. A "Rule 66" approach, as exemplified by the regulations
currently in effect in Los Angeles County, represent a rather sophisti-
cated approach. The wide variation in reactivity of various classes of
hydrocarbons is recognized to some extent; the possible increase in
reactivity of hydrocarbons under adverse processing conditions such
as incomplete combustion and the general undesirability of permitting
uncontrolled emissions of hydrocarbons of low reactivity from very
large emission sources, one recognized to some extent. In addition,
the recent and continuing development of new technology in the area
of surface coatings such as water-based, high-solids and powder
coatings, is encourgaed to some extent.
Even in its most sophisticated form, however, as mentioned earlier,
the primary emphasis of a "Rule 66" approach is to limit the emissions
of hydrocarbons of high reactivity much more severely than the emission
of hydrocarbons of low reactivity, thus concentrating more or, changing
the character of the emissions, rather than reducing them. The ultimate
ambient concentration levels of photochemical oxidants, which are eventually
r-ached in a local area over a period of time, depends on their accumula-
t.on. This however, depends on a number of interrelated, competing and
complex mechanisms, many of which are not well understood. Generally,
it would appear that hydrocarbons of low reactivity permit a number
of factors which tend to decrease the accumulation of oxidants in a
local area, such as internal-mixing and dispersion within the local
aw sphere and transport by favorable meterological conditions from
the local area, to take effect to some extent. Thus, in specific
areas, under favorable topographical and meteorological conditions,
this approach could be an effective means for reducing local ambient
concentration levels of photochemical oxidants. In many other areas
however, this approach could be completely ineffective and all
hydrocarbons emitted into the atmosphere could be expected to contribute
to local concentration levels of oxidants.
24
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To the extent that a "Rule 66" approach can be credited with
reduction or control of local ambient concentration levels of photo-
chemical oxidants in the immediate area in which this approach is
implemented is, of course, consistent with the overall goal on
the national level of reduced ambient concentration levels of photo-
chemical oxidants. However, in judging the effectiveness of a
"Rule 66" approach at the national level-, consideration must be given
to the effect of this approach on area-wide ambient concentration levels
of oxidants, in addition to the effect on local concentration levels.
A low reactivity rating does not necessarily mean that a particular
hydrocarbon does not contribute to the formation of photochemical
oxidants. If hydrocarbons of low reactivity contribute little to local
photochemical oxidant formation, as a result of transport from the
immediate area by favorable meteorological conditions for example,
this implies that they may contribute to local oxidant formation in
other areas. The extent to which this phenomena might lead to high
ambient concentration levels of oxidants in surrounding local areas,
would depend on a number of complex factors, among them, the degree
of dispersion among these areas and the residence time in each.
Initial investigations into the effect of dispersion and transport
of hydrocarbons and photochemical oxidants from local areas to
surrounding areas, appears to indicate that this phenomenon can be
a significant contributing factor to high local ambient concentration
levels of oxidants in these surrounding areas. If a "Rule 66"
approach were implemented in a particular area and this contributed to
high local oxidant concentrations in surrounding areas, this would
have to be viewed as an unacceptable approach, even if it lead to
some reduction of local oxidants concentrations in the immediate area.
From an overall viewpoint therefore, while a "Rule 66" approach
may be a very sophisticated approach in terms of recognizing a number
of factors which bear on local ambient concentration levels of
oxidants, it is based on the premise that hydrocarbons of low reactivity
contribute little to local oxidant formation and that local oxidant
formation is essentially a function only of local emissions of hydro-
carbons. This fails to recognize that under many conditions, all
hydrocarbon emissions could be expected to contribute to local
oxidant formation. It also fails to recognize that the transport of
hydrocarbons and oxidant from surrounding areas into local areas may
be a significant factor contributing to high local oxidant concentration
levels. In this case, the implementation of a "Rule 66" approach in
surrounding areas could be expected to magnify the adverse effect of
this transport phenomenon and could lead to higher local oxidant
concentration levels.
An "Appendix B" approach to reducing and controlling the formation
of photochemical oxidants, as exemplified by the August 1971 Federal
Register, represents a rather pragmatic, if somewhat unsophisticated
approach. Essentially, all hydrocarbon emissions are treated equally,
in that the same degree of emission reduction is required irrespective
of the relative reactivities of various classes of hydrocarbons emissions.
25
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In addition, little consideration or encouragement is given to the
recent and continuing development of new technology in the area of
surface coating such as water-based, high-solids and powder coatings.
The primary emphasis of an "Appendix B" approach., is to reduce
all emissions of hydrocarbons to the greatest possible extent, through
the use of readily available emission control technology. As mentioned
earlier, the basic premise underlying this approach $s that all
hydrocarbons whether of high of low reactivity, will contribute to
the formation of oxidants over a long time period. Consequently, while
this approach may acknowledge that a few specific hydrocarbons are
completely unreactive and that emissions of these hydrocarbons need
not be reduced, given the fact that most hydrocarbons are reactive,
the wide variation in reactivity of various hydrocarbons is of little
importance. Thus, the basic premise of this approach treats all
reactive hydrocarbons equally and leaves no options to relate emission
reductions in some fashion to relative reactivities.
At the time "Appendix B" was formulated within EPA9 the possibility
that transport of oxidants and hydrocarbons from surrounding areas into
local areas might be a significant factor contributing to high local
ambient concentration levels of oxidant, was not recognized. Thus,
"Appendix B" as "Rule 66", was developed on the premise that local
e.mbient concentration levels of oxidants resulted from local emissions
of hydrocarbons. The basic difference between these two appraoches being
essentially that "Rule 66" considered hydrocarbon reactivity to be a
significant factor bearing on the ultimate concentration levels of
oxidants attained in a local area, whereas "Appendix B" considered this
factor of less significance in view of the total quantities of
hydrocarbons emitted into the local atmosphere.
In light of today's recognition of the possible adverse effects
on local ambient concentration levels of oxidants, due to the phenomenon
ov transport of oxidants and hydrocarbons from surrounding areas into
a local area, an "Appendix B" approach seems more suitable than a
"rluie 66:: approacn tor coping with this situation. Alt-hnnnh rnnron+naiiy
'V.ppencnx tr mignt appear to be the most desirable approach to follow.,
full implementation of this approach in all cases could present consider-
f'^lj difficulties.
Hydrocarbons are emitted from a vast number of sources, both in
t'Vms of number and physical variety. There is no single, universal
emission control technique. Rather there are a number of differing
emission control techniques that vary in their adeauacv t.n limit
cm biuns rrorn source to source and from hydrocarbon to hydrocarbon.
The closest technique to being universal is incineration. However,
under todays' constraints of limited fuel availability and high fuel
prices, it is likely that this emission control technique may only
represent a viable, practical alternative if vast heat recovery and
utilization is possible.
26
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In the particular area of organic solvents and surface coatings,
reformulation of coatings to water-based, high-solids or powder
coatings appears to be a potentially useful technique to reduce emissions
of hydrocarbons. Yet developments in this area appear to be embryonic
in many cases and the specifications that many coatings must meet
require extensive and time consuming test programs. Similar problems
also appear to exist in many other areas and with many other emission
control techniques.
In regard to full implementation of either a "Rule 66" approach,
or an "Appendix B" approach, therefore, it appears that while an
"Appendix B" approach might be more desirable conceptually, it could
give use to a number of problems in specific situations. Implementation
of a "Rule 66" approach on the other hand, would likely give rise to
few problems since it has proven both generally acceptable to
industry and "workable" over the past eight years in Los Angeies County.
However, it should be noted that in some areas, a "Rule 66" approach
might not result in a significant reduction in local ambient concen-
tration levels of oxidants and might even result in significant
increases in ambient concentration levels of oxidants in surrounding
areas, due to transport of hydrocarbon's^and oxidants to these areas.
The EPA goal in this matter, of course, is to achieve significant
reductions in ambient concentration levels of photochemical oxidants in
order to achieve and maintain the National Ambient Air Quality
Standards for Photochemical Oxidants throughout the United States.
Long-range this appears to imply the need for a reduction in hydrocarbon
emissions to the greatest extent possible. Consequently, an "Appendix B"
approach to photochemical oxidants appears necessary over the long
term to maintain the Ambient Air Quality Standards; although in a few
specific, isolated areas, where transport phenomenon would not give
rise to problems in other areas, a "Rule 66" approach might prove
adequate.
From an air pollution control viewpoint, it would be most desirable
to implement an "Appendix B" approach as completely and as soon as
possible. However, it appears that this course of action could give
rise to a number of problems in specific situation. Consequently, over
the short-range, while an "Appendix B" approach should be implemented
as fully as possible, in those situations where the implementation of
an "Appendix B" approach is not a viable alternative, a "Rule 66"
approach should be implemented as an interim measure. However, adequate
precautions should be incorporated in those areas where a "Rule 66"
approach is implemented, to encourage and insure continued development
of technology to accommodate the ultimate implementation of an
"Appendix B" approach within a reasonable time frame.
27
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Discussion
Comments from the floor suggested tha the EPA "Appendix B" is
unreasonable in that, e.g , it does not exempt the unreactive acetone
from control. Also questions were raised regarding the rationale of
the Rule 66 restriction that organic emission from a single source
should not exceed 3000 Ib/day. While no answers were given to these
questions, Ms. Brunnelle of LAAPCD stressed that the Rule 66 was intended
for use in LA only and that the Rule sought to limit only those emissions
that would cause a pollution problem only within LA. In questions
regarding the utility of diffusion models in predicting pollutant
dispersion, Mr. Neligan responded that the models now in use are applicable
for dispersion distances no longer than 30-40 miles. Mr. Neligan
further stressed that one does not need a diffusion model to see that
pollutants are being transported; if a model does not predict such
transport, then something must be wrong with the model.
Mr. Zimmt (NPCA) commented that the repeatedly made statement that
"the organic pollutants that survive the within-city irradiation will
react after they are swept out of the city" is only speculation.
Mr. Zimmt also offered the National Paints and Coatings Association
viewpoint on the discussion subject, summarized as follows:
"There are three parts to the emissions control problem:
(1) Need for emissions reduction
(2) Viable control techniques
(3) Reasonable compliance schedule.
Some parts of the country have adopted Rule 66 when there was no
demonstrated need for emissions reduction and when viable control
techniques were not available.
NPCA endorses Rule 66 as an inducement to develop new "low
emissions" coatings. Solvent removal by treatment is technically and
financially not feasible.
NPCA suggests switching to low reactivity solvents until new
solvents or techniques are ready."
Questions were also asked about EPA's efforts, if any, to identify
non-photochemical sinks of organic pollutants. Dr. Dimitriades
responded that while there are several EPA studies on fate of
pollutants, he was not aware of any studies specific for HC. He added
that if such sinks exist, to all probability, they would reduce only
the long term effects of the organic emissions; there are no
indications that urban emissions, while within the urban area, would
be appreciably affected by such sinks.
28
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AFTERNOON SESSION
1. Reactivity Classification of Organics -- A. Levy, Battelle-Columbus
A number of solvent reactivity studies were reviewed mainly
with the intent of examining strengths and weaknesses in reactivity
classification. First, consideration is given to the use of reactivity
as a control procedure relative to total reduction of organic emissions.
Consideration is then given to the various definitions of reactivity,
with special attention as to how the various reactivities relate to
one another. Detailed examination was then made of oxidant reactivity data
from several programs. It is shown that when HC/NOX ratios are comparable
oxidant reactivity is also comparable, even when absolute concentration
levels are varied. Correlation analyses also compare favorably under
similar chamber conditions. Special attention is directed to the importance
of background mixtures in evaluating reactivity, especially In bringing
out the influence of synergistic effects in simple, binary solvent systems.
It is on this basis that linear summation rules are examined and shown to
be wanting. Lastly, some examples are presented which illustrate the
pronounced effect of HC/NOX ratio on reactivity. It is concluded that to
be able to generalize solvent reactivity concepts, so they may be applied
more broadly in terms of chemical structure, a more rigorous chamber
procedure for evaluating solvents is needed.
Discussion
The question was asked whether svnergistic effect would cause
organic mixtures to manifest higher or lower reactivities than expected.
Dr. Bufalini explained that the answer depends on the HC-to-NOx ratio
factor. If the HC-to-NOx ratio is constant, then the synergism usually
has a positive effect, i.e., a mixture of organics is more reactive than
the individual component reactivities suggest. To the question whether
this relates to need for NOX control, Dr. Bufalini responded that NOX
control requirements are based on entirely different considerations.
In response to Mr. Romanovsky's inquiries, Mr. Levy stated that
reactivity manifestations that do not correlate to oxidant yield are not
of much interest at the present time. Mr. Romanovsky took exception
to this viewpoint. He explained that organics should not be judged
solely by their oxidant yields; rather, they should be judged by the
degree to which they participate in atmospheric reactions since such
participation will ultimately lead to formation of objectionable pollutants.
2. An Experimental Protocol For Reactivity Measurement— C. W. Spicer,
Battelle-Columbus
Many investigations have been carried out over the years on the
photochemical smog reactivity of solvents and other organic materials.
There has never been a consistent procedure, however, which attempts to
maximize both the realism of the reactivity assessment and the efficiency
of the operation. Thus, investigations have been carried out using a
variety of experimental conditions which very likely affect the results
or the study. Examples cited are variations in the initial organic to
29
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nitrogen oxides ratio, the concentration or loading of the organic
studied, and the effect of the presence of other hydrocarbons on the
reactivity of the specie of interest. Discussion of these three variables
is aimed at demonstrating their effect on organic reactivity and especially
on realtive reactivity. The point of this part of the discussion is
that future reactivity studies should consistently employ a known set of
predetermined experimental conditions so that reactivity results are
more directly comparable. The experimental conditions should be chosen
so as to represent as closely as possible actual atmospheric reactivity
conditions.
Due to the long list of organics which should be investigated
in a future reactivity study, it is imperative that an efficient reactivity
procedure be employed. A method whereby a large existing smog chamber
is broken down into 4 to 5 smaller chambers through the use of Teflon
compartments is discussed. Particular emphasis is placed on the effi-
ciency of the operation, e.g., 4 or 5 simultaneous smog chamber experi-
ments could be run in 1 day, and the low cost of implementing such a
procedure. The chamber, light bank, and instrumentation would remain
unchanged; the instruments would be automatically cycled among the Teflon
compartments for maximum efficiency. The use of background mixtures
in future reactivity studies will also be discussed and a specific
replacement scheme will be suggested.
Discussion
Dr. Dimitriades asked for clarification regarding the reactant
concentrations to be adopted in the reactivity measurement protocol.
Dr. Spicer responded that reactant concentration conditions would be
decided upon at a later time.
Mr. Zimmt (NPCA) inquired whether plastic film bags could be used
as smog chambers. Mr. Levy responded that choice of wall material is
dictated by wall effect considerations. In a generalized sense, small
smog chambers cause wall effects that can in turn cause interferences,
especially in photochemical aerosol studies. Dr. Dimitriades added
that recent studies at Lockheed (under CRC-EPA contract) indicated that
wall material and surface-to-volume ratio are smog chamber design
parameters that affect smog chamber results significantly and that,
therefore,.they should be considered carefully in development of a
reactivity measurement protocol.
3. Critique of Solvent Reactivity, Rule 66. and Appendix B_ -- W. L. Faith,
Consulting Engineer
Dr. Faith agreed that a sound and definite regulation should be
developed to control emissions of photochemically reactive compounds
into the atmosphere. He further agreed that the amount of control
should bear a reasonable relationship to the relative "reactivity" of
the emitted organic compound. Dr. Faith stressed that organic vapors
emitted not in mixture with NQX do not pose a photochemical pollution
problem. He also expressed his belief that control of stationary source
emissions in Los Angeles did not prove to be of any benefit to local air
quality. Dr. Faith proposed the following type of regulation:
30 •:
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"Emissions should be classified as follows:
1. High reactivity - organics mixed with NOX in stated
ratios prior to emission.
2. Moderate reactivity - all non-aromatics containing a
carbon-carbon double bond, and all di-substituted and higher
aromatics.
3. Low reactivity - all non-aromatics not containing a
carbon-carbon double bond, and not in Class 4; toluene.
4. Negligible reactivity - compounds now in Appendix B.
"Within each class, degree of control should be related to
volatility, e.g., (a) > 1 mm Hg, (b) 0.1 - 1 mm Hg, (c) 0.0 - 0.1
mm Hg, (d) < 0.01 mm Hg.
"Also control the emissions for a given evaporated solvent
to a similar degree as other organic emissions.
"Set up a referee system and test protocol to establish
relative reactivity of specifically questioned compounds and
relate their relative reactivity to 2 or 3 standard compounds,
e.g., propylene, toluene, and isopropyl alcohol."
Discussion
Mr. Neligan (EPA) took strong exception to Dr. Faith's contention
that control of stationary source emission in LA during the late 1950's
has been of no benefit to local air quality. Mr. Neligan explained that
such a conclusion could hardly be substantiated in view of the fact that
the emission increment caused by growth of both mobile and stationary sources
had more than offset the decrement achieved by control.
Mr. Sussman (Ford) commented that based on existing regulations, one may
conclude that only the 6-9 a.m. emissions need to be controlled (Mr. Sussman
later in the session stated that his suggestion was facetiously offered). Dr.
Dimitriades responded that such conclusion was based on misinterpreation of
the regulations.
Dr. Dimitriades made reference to Dr. Faith's statement that organic
emissions discharged without NOX present no problems, and asked whether Dr.
Faith shared the opinion voiced earlier in the session that the natural —
rather than man-made—organic emissions may be largely responsible for the
oxidant problem. Dr. Faith responded that the naturally emitted organics,
in his judgment, are not part of the problem.
Questions were also addressed to the speaker regarding the role of NOX
and of pollutant transport in oxidant formation. Dr. Faith responded that
N0x--and not hydrocarbon--is the oxidant precursor that should have been
controlled from the beginning of the control efforts. Further, he disagreed
with Mr. Neligan's comment that a significant portion of the oxidant problem
at Indio, California, is caused by Los Angeles emissions; he submitted that
31
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the problem is caused by local emissions. Mr. Neligan said that the Palm
Springs-Indio area was violating the oxidant standard more than twice
as frequently as were stations in Los Angeles County according to
CARB reports and the maximum values were approximately the same level.
In addition, hydrocarbon emissions in Los Angeles County were about 15
times greater than in San Bernardino County, and 20 times greater than
in Riverside County.
4. Development of a Study Program (Research Needs) — A. Levy, Battelle-
Columbus
Mr. Levy suggested a research program aimed at updating the current
status of organic solvent reactivity. A prospectus was presented to
the attendees outlining a proposed program. The program would have two
principal objectives. The primary objective would be to evaluate and
correlate the photochemical smog reactivity or organic solvents with
chemical structure. A secondary objective would be to expand and broaden
current knowledge on the influence of parameters on reactivity. In order
for such a program to be of maximum value to both industry and government,
it was suggested that a new reactivity procedure be developed for use in
this new program. This new procedure would make it possible to evaluate
a solvent under a variety of conditions by simultaneously carrying out
the irradiation of several systems in a multi-chamber facility, this program
would be operated through an Advisory Committee representing the sponsoring
groups. The hope was also expressed the EPA would provide one or two
people to serve in an ad hoc advisory capacity to this committee.
The suggested program would be a two year program, starting about
September 1974.
Discussion
Questions were asked from the floor regarding EPA's input to the
design of the proposed program. It was specifically asked whether and
how would EPA use the information output from this program. Dr.
nimitriades (EPA) responded that EPA cannot be expected to make any
commitment regarding its future stand on the subject of reactivity.
He stressed, however, that at present, EPA is r.ctivelv interested in
the concept and use of reactivity and will certainly pay close attention
to the proposed effort and its findings. Responding further to questions
from the floor, Dr. Dimitriades indicated that EPA will consider
establishing formal liaison withthe planned activity and will make a
decision shortly.
To other questions regarding specific objectives and scope of
the contemplated study, Mr. Levy responded that such points would be
discussed at a later time, after the general intent of the study and
its desirability are established.
Mr. Zinmt suggested that the proposed study be designed so as to
develop information relevant to the type of atmosphere expected at
the time the study is to be completed. This led to questions regarding
duration of proposed study; Mr. Levy indicated that he would recommend
a program at least 2 years long.
32
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SUMMARY-CONCLUSIONS
The concept of photochemical reactivity and its present use in
solvent emissions control strategies was reexamined for validity,
utility, and desirability. Such reexamination was instigated by
a number of recent developments, including the following:
1. EPA realized that reactivity criteria are not used consis-
tently in existing control regulations—such an inconsistency
being, in principle at least, undesirable.
2. Recent smog chamber studies showed that some thought-to-be-
unreactive organics are in actuality reactiye--a reversal
that invalidates the reactivity classification (of organics)
in the widely used Los Angeles County Rule 66.
3. It has become increasingly evident that pollutant transport
does occur, and that such transport enchances formation of
oxidant from low reactivity organics.
4. EPA realized that the present emphasis on control of the
mobile source emissions will eventually make solvents and
the other stationary source emissions the predominant emission
problem.
Except for one dissenting opinion, there was general agreement
that control of solvent vapors and of other organic emissions from
stationary sources is necessary, and that use of reactivity criteria
on such control is, in principle, sound. The dissenting opinion was
that solvent vapors, as well as any other organic emissions that are
emitted unmixed with NOX, do not pose a photochemical pollution
problem.
In regard to use of reactivity criteria in control, EPA contended
that present practices, as reflected in the predominantly used Los
Angeles County "Rule 66" and EPA's "Appendix B" reactivity related
guidelines, are not totally satisfactory. Thus, Rgl,e 66 is lacking
in two respects: First, its reactivity classification of organics is
inaccurate, the error being in the direction toward less stringent
control. Second, it assumes that organics of unknown reactivity are
non-reactive--an assumption that is probably wrong and that again
leads to less stringent control. Appendix B is lacking in that it
assumes that all, except very few, organics are equally reactive--
an assumption that is known to be wrong and that it causes inflexibility.
Viewpoint from the solvents and paints manufacturers and users did not
disagree with these contentions; however, it also emphasized that in
the course of the years during which Rule 66 was the only reactivity
related control regulations, manufacturing and trade practices have
been shaped so as to make compliance with Rule 66 feasible. Further,
33
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enforcement of an Appendix-B type new regulation, requiring drastic
emission reduction by treatment, will incur serious economic penalties and,
more importantly, will hamper development of other, environmentally
much more advantageous products and processes, such as water-based and
high-solids coatings.
Recent findings concerning occurence and effects of pollutant
transport appear to provide additional support to the "all-organics"
control concept advocated by Appendix B. Thus, under the prolonged
irradiation conditions occurring in transported air masses, it is very
probable that the "less reactive" organics are induced to form as
much oxidant as the "more reactive" ones. Therefore, to alleviate
oxidant problems both in the vicinity of the.emission source and in the
downwind areas, nearly universal control of organics, as prescribed
by Appendix B, is more effective than the more selective control
prescribed by Rule 66. In support of this conclusion, air pollution
control officers from LA County stressed that Rule 66 was indeed
conceived and designed to cope solely and specifically with the
photochemical pollution problem within the LA air basin; no considera-
tion was given to transport induced problems outside the basin. In
view of these developments regarding pollutant transport, EPA is now
inclinded to think that an "area-wide" approach to control may be
advantageous over the "region-wide" approach now in use.
Regarding the need for more rigorous and consistent use of
reactivity criteria in control, EPA offered some conceptual specifics
on such use. Thus, it was suggested that control requirements for
each source type should be calculated taking into consideration
(a) the degree of total hydrocarbon control required for the region
or area, (b) the relative strength of the source, (c) the reactivity
of the emissions, and (d) the availability of control technology.
EPA is not convinced that implementation of such an application of
reactivity criteria is feasible at this time. Questions regarding
the actual benefits from and problems in such application are still
open, although they are being studied.
rJiially, suggestions tor future research needs were offered and
discussed. EPA presented a new reactivity classification of organics,
based on existing smog chamber reactivity data. It was agreed that
reactivity data for additional organics are needed. It was further
agreed, that research is needed to obtain more reliable techniques
for calculating reactivities of emission mixtures.
34
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Robert F. Adams
Diamond Shamrock Corp.
P. 0. Box 500
Deer Park, TX 77536
Ph. 713-479-2301, ext 129
LIST OF ATTENDANTS
J. J. Bufalinl
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 549-8411, ext 2374
A. P. Altshuller
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C 27711
Ph. 549-8411, ext 2191
Donald P. Andrew
State of Maryland
Bureau of Air Quality Control
610 N. Howard St.
Baltimore, Md. 21201
Ph. 301-383-3122
Abel Banov
American Paint Journal
370 Lexington Ave. (Rm. 813)
New York, N.Y. 10017
Ph. 212-532-7753
F. M. Black
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 549-8411, ext 2323
R. C. Bourke
Detroit Diesel-Aliison GMC
P. 0. Box 894, S20
Indianapolis, Ind. 46206
Ph. 317-243-4147
Jonathan L. Bowen
Hooker Chemical & Plastics Corp.
Niagara Falls, N. Y.
Ph. 716-285-6655, ext 540
' rnneth A. Bownes
Inmont Corp.
925 Allwood Road
Clifton, N. J. 07012
Ph. 201-773-8200
Margaret F. Bruneile
L. A. County APCD
434 3outh San Pedro St.
Los Angeles, CA 90013
Ph. 213-974-7532
Marijon Bufalini
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 549-8411, ext 2728
N. J. Butler
Reynolds Metals Co.
6601 W. Broad St.
Richmond, Va. 23261
Ph. 282-2311, ext 2547
John Calcagni
2113 JFK Federal Bldg.
Boston, Mass. 02203
Ph. 617-223-4636
John E. Campion
Avery Products Corp.
415 Huntington Drive
San Marino, CA 91108
Ph. 213-682-2812
Raymond J. Connor
National Paint & Coatings Assn.
1500 Rhode Island Ave. N. W.
Washington, D. C. 20005
Ph. 202-462-6272
James D. Crowley
Eastman Chemical Products, Inc.
Kingsport, Tenn. 37662
Ph. 615-246-2111, ext 3312
G. W. Daigre
Dow Chemical
P. 0. Box 150
Plaquemine, LA 70764
Ph. 504-348-6591, ext 373
R. S. Davidson
Reynolds Metals Company
Packaging Research Division
10th & Byrd Sts.
Richmond, VA 23219
Ph. 804-649-1411, ext 7815
35
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Oliver Degarmo
Monsanto
800 N. Lindbergh
St. Louis, Mo. 63166
Ph. 314-694-4878
Joseph A. DeSantis
Environmental Protection Agency
JFK Federal Bldg.
Boston, Mass. 02203
Ph. 617-223-4449
Basil Dimitriades
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-549-8411, ext 2706
Marcia Dodge
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 9199-549-8411, ext 2374
Robert H. Duzy
Union Carbide
270 Park Ave.
New York, N. Y. 10017
Ph. 212-551-4914
Timothy J. Dwyer
U. S. EPA Region II
26 Federal Plaza
New York, N. Y. 10007
Ph. 212-264-9Rnn
John J. Eichler
State of Connecticut DEP
165 Capitol Ave.
Hartford, Conn.
Ph. 203-566-3223
W. D. Erskine
Va. Air Pollution r.nntmi p^^rd
ytn St. Office Bldg.
Richmond, VA
Ph. 804-770-2530
W. L. Faith
Consulting Engineer
San Mori no, CA
William D. Faulkner
Calgon Corp.
Box 1346
Pittsburgh, Pa. 15230
Ph. 412-923-2345
Dean C. Finney
Eastman Chemical
Kingsport, Tenn.
Ph. 615-246-2111
Don R. Goodwin
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-688-8146, ext 271
Robert E. Grimm
The Dayton Tire & Rubber Co.
P. 0. Box 24011
Okla. City, Okla. 73132
Ph. 405-745-3421, ext 212
H. R. Guest
Union Carbide Corp.
Box 8361
80 Charleston, W. Va. 25303
Ph. 304-747-5481
James K. Hambright
Fulton Bann Bldg.
Harrisburg, Pa.
Ph. 717-787-4324
Phi np Hanst
tnvironmental Protection Aqency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-549-8411, ext 2201
W. C. Holton
Battelle
505 King Ave.
CuluniDus, umo 43201
J. K. Hudgens
Ford Motor Co.
Mt. Clemens Paint Plant
400 Groesbeck Highway
Mt. Clemens, Michigan 48043
Ph. 313-468-2681, ext 254
36
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Harold L. Jensen
Manager, Environmental Control
Warner Lambert Co.
201 Tabor Rd.
Morris Plains, N. J. 07950
Ph. 201-540-2641
Kenneth D. Johnson
Mpg. Chemists Assn.
1825 Connecticut Ave. N. W.
Washington, D. C. 20009
Ph. 202-483-6126, ext 244
William L. Johnson
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-688-8146, ext 474
W. E. Kemp
Koppers Co. Inc.
440 College Park Drive
Monroeville, Pa.
Ph. 391-3300,ext 5544
Steven Landon
Washex Machinery Corp.
5000 Central Freeway
Wichita Falls, Texas 76306
Ph. 816-855-3990
Felipe Lebron
Md. Bureau of Air Quality Control
610 N. Howard St.
Baltimore, Md. 21201
Ph. 301-383-3148
Lawrence S. Leonard
The Lilly Co.
P. 0. Box 1821
High Point, N. C. 27260
Ph. 919-885-2158
Art Levy
Battelle
505 King Ave.
Columbus, Ohio 43201
Beryl Van Lierop
Armstrong Rubber
500 Sargent Drive
New Haven, Conn. 06507
P'i. 203-777-7401
Roland C. Lingle
1717 English Rd.
High Point, N. C. 27260
Ph. 919-885-2157
Harry F. Macrae
Amsco Div. Union Oil of Calif.
4822 Albemarle Rd.
Charlotte, N. C. 28205
Ph. 704-536-0134
W. P. Mahoney
Ball Corp.
1509 S. Macedonia
Muncie, Ind. 47302
Ph. 319-284-8441
Gabriel Mai kin
134 Lister Ave.
Newark, N. J.
Ph. 201-344-1200
Russel L. Maycock
Shell Chemical Co.
One Shell Plaza
Houston, Texas
PH. 713-220-2686
William J. McFarland
General Motors Tech. Ctr.
Warren, Mich. 48090
Ph. 313-575-8609
H. R. McNair
Union Carbide Corp.
270 Park Ave.
New York, N. Y. 10017
Ph. 212-551-2222
Ellen Mil ford
Whittaker Corp.
P. 0. Box 891
Lenoir, N. C. 28645
Ph. 704-754-9081
Ronald Mueller
EPA Region IX
100 California St.
San Francisco, Calif. 94111
PU. 415-556-2332
James D. Mulick
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-549-84411
37
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Kenneth J. Murray
Exxon Chemical Co.
P. 0. Box 536
Linden, N. J. 07036
Ph. 201-474-2649
Robert Neligan
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C.
Ph. 919-688-8146
Robert C. Miles
Uniroyal, Inc
Oxford Management & Research Center
Mjddlebury, Conn. 06749
Ph. 203-573-2387
James L. Nolan
Rhode Isliand Div. of
204 Health Building,
Providence, RI 02908
Ph. 401-277-2808
Air Pollution
Davis St.
Control
Malven L. Olson
Indiana State Bd. of Health
Division of Air Pollution Control
1330 W. Michigan St.
Indianapolis IN 46206
Ph. 317-633-4814
Joseph Padgett
Environmental Protection Agency
Mutual Bldg.
Durham, N. C.
Ph. 919-688-8146, ext 204
David R. Patrick
Environmental Protection Agency
Research Triangle Park, N. C. 27711
Ph. 919-688-8146, ext 474
Robert R. Patrick
Union Carbide Corp.
i-ix 8361
G_). Chas., W. Va. 25303
Ph. 304-747-4985
Robert J. Ph'.illips
General-Motors Technical Center
Warren, Mich. 48090
Ph. 313-575-8609
R. H. Pdi>rer
Battelle
505 King Ave.
Columbus, Ohio
Fred Porter
Environmental Protection Agency
Research Triangle Park, N. C. 27711
Thomas R. Powers
Esso Research & Engineering Co.
P. 0. Box 51
Linden, N. J. 07036
PH. 201-474-2548
Louis Proulx, Jr.
Conn. Dept. of Env. Prot.
State Office Bldg.
Hartford, Conn. 06115
Ph. 203-566-4312
John H. Rains
Ethyl Corp.
Research & Development
Box 341
Baton Rouge, LA 70821
Ph. 504-357-4361
Jerry Romanovsky
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-549-8411
J. C. Ruehrmund
Va. Air Pollution Control Bd.
9th St. Office Bldg.
Richmond, Va.
Ph. 804-770-2530
Frank Ryan
Rubber Mfgr's. Assn.
1901 Penn. Ave.
Washington, D. C 2000P
PH. 202-785-2602
Dallas W. Safriet
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-688-8146, ext 497
38
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Jay Shah
Gravure Research Institute
22 Manhasset Ave.
Port Washington, N. Y. 11050
Ph. 516-883-6670
John Sigsby
Environmental Protection Agency
National Environmental Research Center
Research Tirangle Park, N. C. 27711
Ph. 919-549-8411
R. D. Sites
St. Clair Rubber Co.
1765 Michigan Ave.
Marysville, Mich. 48040
Ph. 313-364-7424
Clete M. Smith
PPG Ind
No. 1 Gateway
Pittsburgh, Pa 15222
Ph. 412-434-2404
Stan Sorem
Shell Oil Co.
100 Bush St.
San Francisco, CA 94106
Ph. 415-392-5414
C. Spicer
Battelle
505 King Ave.
Columbus, Ohio
Lester L. Spiller
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
PH. 919-549-8411, ext 2729
Dr. Frank Spuhler
Texas Air Control Board
3520 Shoal Creek Blvd.
Austin, TX 78758
PH. 421-5711, ext 442
Edward W. Starke
Shell Oil Co.
One Shell Plaza
Houston, TX 77001
Ph 713-220-3239
Victor H. Sussman
Ford Motor Co.
Rm 628W Parklane Towers
1 Parklane Blvd.
Dearborn, Mich.
Ph. 313-323-2895
Larry L. Thomas
National Paint & Coatings Assn.
1500 Rhode Island Ave.
Washington, D. C. 20005
PH, 202-462-6272
Fred Troppe
1200 Firestone Pkwy
Akron, OH 44317
Ph. 216-379-6168
A. M. Twilley
c/o Ford Motor Co.
Room F-3005 AADGO
P. 0. Box 1586
Dearborn, Mich. 48121
Ph. 313-594-0343
Gerald W. Wallace
Lilly Research Laboratories
Indianapolis, Ind. 46206
Ph. 316-261-4074
R. G. Weisz
Amoco Chemicals Corp.
Box 400
Naperville, 111. 60540
Ph. 312-420-5035
R. G. Weldele
Eli Lilly & Co.
Indianapolis, Ind 46206
Ph. 291-261-2303
Manfred Wentz
International Fabricare Institute
8001 Georgia Ave.
Silver Spring, Md. 20910
Ph 301-589-2334
Elmer P. Wheeler
/Monsanto Co.
800 N. Lindbergh Blvd.
St. Louis, Mo. 63166
Ph. 314-694-2196
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Ron Venezia
Environmental Protection Agency
National Environmental Research Center
Research Triangle Park, N. C. 27711
Ph. 919-549-8411
John C. Yates
Engineering Science Inc.
7903 Westpark Dr.
McLean, VA 22101
Ph. 703-790-9300
R. E. Yeatts
RJR Archer, Inc.
B. G. Development Center
33rd & Shorefair Dr.
Winston-Salem, N. C.
Ph. 919-548-3738
Werner S. Zimmt
El DuPont Co.
Marshall Laboratory
Box 3886
Philadelphia, Pa. 19146
Ph. 215-463-3000
40
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-650/3-74-010
3. RECIPIENTS >CCESSIOWNO.
4. TITLE AND SUBTITLE
I. REPORT DATE
November 1974
Proceedinqs of the Solvent Reactivity Conference
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Basil Dimitriades
8. PERFORMING ORGANIZATION REPORT NO.
9.
PERFORM.LNG ORGANIZATION NAME AND ADDRESS
Research Triangle Park, N. C. and
Battelle
Columbus, Ohio
10. PROGRAM ELEMENT NO.
1AA008
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
Chemistry and Physics Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The concept of photochemical reactivity and its present use in solvent emissions
control strategies was reexamined for validity, utility, and desirability. Such
reexamination was dictated by recent developments, including new experimental
evidence on reactivity of organics and the realization that existing reactivity-
related regulations are inconsistent among themselves. It was generally agreed
that solvents and other stationary source emissions must be controlled and that
use of reactivity criteria on such control is, in principal, sound. EPA offered
comments suggesting that the recently verified pollutant transport phenomena
would tend to make Appendix B-type regulations more effective relative to the
widely used Rule 66 regulation. Another consequence of pollutant transport is that
the relatively unreactive organics are induced to form as much oxidant as the reactive
ones. Therefore, an appropriate reactivity classification of organics should be
based on considerations related to pollution problems caused both within a region
and in the downwind areas.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
air pollution
photochemical reactions
solvents
emission
organic compounds
regulations
hydrocarbons
nitric oxides
nitrogen dioxide
piumes
ozone
test chambers
LAC-APCD Rule 66
EPA-Appendix B
Reactivity Classifica^io
Control Strategies
Stationary sources
Pollutant transport
13B, 4A, 7C
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
44
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
41
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