VOLUME 3
COMMENTS ON THE
ADVANCE NOTItE OF PROPOSED RULEMAKING
"OZONE - DEPLETING CHLOROFLUOROCARBONS
PROPOSED PRODUCTION RESTRICTION"
BY THE
ENVIRONMENTAL PROTECTION AGENCY
SUBMITTED BY
E. I. DU PONT DE NEMOURS & COMPANY (INC.)
WILMINGTON, DELAWARE
JANUARY 5, 1981
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VOLUME 3
Table of Contents
X. APPENDICES (Continued)
A. - F. See Volume 2
G. Ranking Compounds by Potential for Ozone
Depletion - "Permit Pounds" G-l-9
H. Scope of Proposed Regulation H-l-13
I. Economic Incentives Regulatory Options 1-1-39
J. Chlorofluorocarbon Production and Emissions J-l-16
K. Industry Funded Fluorocarbon Research
Program - Effect of Chlorofluorocarbons on
the Atmosphere (CMA/FPP) K-l-77
L. Uncertainties - Chlorofluorocarbon Effects
and Stratospheric Ozone (SRI Report) L-l-8
XI. BIBLIOGRAPHY XI-1-47
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X. APPENDIX G
RANKING COMPOUNDS BY POTENTIAL
FOR OZONE DEPLETION
G-l
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Ranking Compounds by Potential
for Ozone Depletion
Table of Contents
1. INTRODUCTION 3
2. DU PONT RANKING SCHEME 5
3. COMPARISON OF DU PONT vs. EPA
RELATIVE RANKING SCHEMES 8
G-2
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Ranking Compounds by Potential
for Ozone Depletion
1. INTRODUCTION
It is the chlorine in CFC molecules which is
hypothesized to lead to the catalytic destruction of ozone.
Different CFCs potentially contribute different amounts of
chlorine to the stratosphere. Therefore, Rand introduced the
concept of "permit pounds" in its Draft Report [Rand, 1979]
to reflect this difference between the various CFC compounds
under assessment. Du Pont commented in its critique of the Rand
Draft Report [Du Pont, 1980c] that the ranking concept made
sense in that it would allow focusing of regulatory attention on
those compounds with the greatest environmental damage potential
and would permit better evaluation of the effectiveness of
competing policy designs.
However, we also noted [Du Pont, 1980c] that
although the Rand system of "permit pounds" was a good first
step, it was an oversimplification of the relative potential
environmental impact of individual compounds. We offered an
alternative approximation which we believed to be more rigorous.
In the ANPR, EPA has retained the concept of
relative ranking ("permit pounds") but has incorporated a
relative quantitative ranking which we believe is in error. The
ANPR references Lawrence Livermore Laboratory (LLL) as the
source of its ranking. We have tried unsuccessfully over the
past 2 months [Hapka, 1980] to obtain this data from EPA to
enable a comparison to our earlier work. Conversations with LLL
personnel [Woebbles, 1980] have confirmed our preliminary
analysis that EPA's ranking is not correct, and is not based on
the Livermore group's best assessment of the problem.
G-3
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Ranking Compounds by Potential
for Ozone Depletion
We have discussed this analysis with the Livermore
group, and agreed on the methods which should be applied.
Subsequently, we have updated and improved our analysis using
the best available published data. .We submit the results herein
[see Table 1] . The differences between the Du Pont and EPA
ranking are not trivial [See Table 2], having potentially
profound implications for the ability of the producers to supply
CFCs if the proposed regulations were promulgated.
G-4
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Ranking Compounds by Potential
for Ozone Depletion
2. DU PONT RANKING SCHEME
The relative potential environmental impact of
CFCs on ozone is related to both emissions of the respective
CFCs and their individual potentials for causing ozone
depletion. In developing a ranking of the "relative ozone
depletion potential" of the individual CFCs, we have examined
the relevant factors and found that one must consider: a) the
CFC molecule chlorine content by weight, b) the rapidity of
release of chlorine from the CFC molecule in the atmosphere
(i.e. atmospheric lifetime), and c) the efficiency of this
released chlorine in depleting ozone (primarily determined by
the altitude at which chlorine is released). This latter factor
had been overlooked in previous assessments by both EPA and Du
Pont, but has now been determined to have significant impact on
the results.
Determining chlorine content by weight is a
straightforward calculation, but the latter two effects are
intimately tied to model results, so will require periodic
updating as inputs to the models are refined.
The entire problem may be addressed with a model
in one of two ways: a) A steady-state model calculation may be
made for a given annual release, say one million tons, of a
single CFC. Calculated ozone depletion from the model runs for
each CFC may then be compared to yield the relative depletion
potential of each CFC, b) Alternatively, the annual emissions
of a given CFC may be adjusted in a series of calculations to
determine how many pounds are necessary to give a particular
value of potential ozone depletion, say 5 per cent. The pounds
required for differnt CFCs may then be compared to yield
directly the relative depletion potentials.
G-5
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Random Compounds by Potential
for Ozone Depletion
Du Pont has chosen the latter method, whereas the
Livermore group [Wuebbles, 1980] has chosen the former. The
two methods are roughly equivalent, although the intimate
connection between the method and the model employed is likely
to lead to slight, but inconsequential differences in the
results.
The relationship to models also leads to a slight
complication for CFC-22 (and for any other hydrogen-containing
CFC which reacts in the troposphere with hydroxyl (OH)
radical). This is true because it is likely that the models are
currently overestimating OH concentrations in the lower
atmosphere, (See Appendix E) and, if so, the models are
underestimating the atmospheric lifetime of CFC-22 and,
therefore, its chlorine contribution to the stratosphere.
The model-calculated lifetime of CFC-22 is
approximately 12 years, whereas most other estimates are in the
range of 15-20 years. A calculation of "ozone depletion
potential" of CFC-22 based on the current model calculated
lifetime of CFC-22 gives a very small depletion potential. We
have taken a conservative position and adjusted the lifetime of
CFC-22 to 20 years, i.e., we have assumed that more CFC-22
reaches the stratosphere (to release chlorine which potentially
may react with ozone) than the models currently calculate. This
leads to the value reported in Table 1. It should be emphasized
that the reported "relative ozone depletion potential" for
CFC-22 is conservatively very large. It is entirely possible
that the depletion potential is actually smaller, which would
allow even more substitution of CFC-22 for other CFCs under any
permit pound-type system.
G-6
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Random Compounds by Potential
for Ozone Depletion
The critical point regarding CFC-22 is that the
depletion potential cited by EPA is greatly overestimated. A
correct treatment must account for both lifetime and altitude of
chlorine release. We note further that such a treatment
actually increases slightly the "relative ozone depletion
potential" for CFCs 12, 113, 114, and 115, compared to the EPA
values. We believe that the reported factors herein are a
better representation of the relative potential threat to the
ozone by individual CFCs than previously performed.
G-7
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Ranking Compounds by Potential
for Ozone Depletion
3. COMPARISON OF DU PONT VS. EPA RELATIVE RANKING SCHEMES
The Du Pont numbers, derived as discussed in the
preceding section, are presented below and compared to those
advanced by the EPA.
Table 1
Ranking of CFCs by Calculated
Relative Ozone Depletion Potential
(Normalized to CFC-11)
Compound EPA Ranking Du Pont Ranking
(ANPR)
CFC-11 1.00 1.00
CFC-12 0.79 0.84
CFC-113 0.77 0.82
CFC-114 0.49 0.61
CFC-115 0.20 0.35
CFC-22 0.18 0.03
The next step is to translate these relative rankings into
equivalent CFC pounds, based on CFC-11 = 1.0.
Table 2
Compound EPA Equivalent Du Pont Equivalent
PoundsPounds
CFC-11 1.00 1.00
CFC-12 1.26 1.19
CFC-113 1.36 1.22
CFC-114 2.04 1.64
CFC-115 5.00 2.86
CFC-22 5.56 34.00
G-8
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Ranking Compounds by Potential
for Ozone Depletion
Thus, under the EPA numbers, CFC producers would
be allowed to manufacture 5.6 pounds of CFC-22 in place of 1.0
pound of CFC-11 with no net increase in potential harm to
stratospheric ozone. However, under the Du Pont numbers, CFC
producers would be allowed to manufacture 34^ pounds of CFC-22 in
place of 1.0 pound of CFC-11, over a six-fold increase. This
difference is critical because CFC-22 has the potential for use
as an alternate to CFC-12 in a number of large volume
applications.
G-9
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X. APPENDIX H
SCOPE OF PROPOSED REGULATIONS
H-I
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Scope of Proposal
Table of Contents
Page
1. INTRODUCTION 3
2. JUSTIFICATION FOR PROPOSING TO CONTROL
ONLY CFCS? 4
3. JUSTIFICATION FOR PROPOSING TO CONTROL
ALL CFCS? 6
4. COUNTERPRODUCTIVITY OF PROPOSING TO
CONTROL POTENTIAL FLUOROCARBON ALTERNA-
TIVES - WHY REGULATE A POTENTIAL
SOLUTION? 9
5. JUSTIFICATION FOR NOT EXEMPTING
NON-EMITTING CFC USES FROM THE PROPOSAL? 11
6. SUMMARY 13
a-2
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Scope of Proposal
1. INTRODUCTION
The only justification for regulation of a chemical by
EPA is the need to control the production, use or disposal of the
chemical in order to reduce risk to human health or the
environment (hopefully on a cost/benefit basis) arising from
current practices. After a risk is identified, a regulation may
be devised to control the risk. The regulation should focus on
the source of the risk and it should be demonstrated that the
regulation will, indeed, reduce or control the risk — else why
regulate?
Opposite this logic, we find EPA's ANPR proposals for
the control of CFCs to be seriously deficient in both logic and
justification. In this section we question EPA's justification
for 1) proposing to control all CFCs, yet neglecting other
compounds of potential concern opposite stratospheric ozone
depletion, 2) including all CFCs regardless of lack of techni-
cally supportable findings that all CFCs are of significant risk
to stratospheric ozone, 3) including in the proposal scope
compounds which potentially are part of the solution to CFC
depletion of ozone (if it occurs), rather than a significant part
of the problem, and 4) not exempting CFC uses which result in no
emissions, when the stated concern is over the potential effect
of CFC emissions, not the use.
H-3
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Scope of Proposal
2. JUSTIFICATION FOR PROPOSING TO CONTROL ONLY CFCS?
The Clean Air Act is concerned with potential damage to
stratospheric ozone from halocarbons or other sources. The NAS
examined CFC-11 and CFC-12 and to a lesser extent other potential
sources of ozone depletion. Yet EPA states in the ANPR:
"Potential ozone depleters found outside the CFC
chemical family may eventually require regulatory action
as well. However, the present set of regulations would
be limited to CFCs only because there does not exist
sufficient information on other depleters,"...
This statement should be contrasted with the NAS finding that:
"Atmospheric measurements indicate that methyl chloro-
form is contributing between a quarter and half as many
chlorine atoms to the stratosphere as are CFC-11 and
CFC-12. If it gains increased usage, as a substitute
for other solvents in degreasing and coating operations
it may well become the largest source of stratospheric
chlorine." [NAS, 1979b, p. 45].
Further information on the potential effect of methyl
chloroform on stratospheric ozone is available from an EPA spon-
sored conference [EPA, 1980b] specifically on this subject.
It is arbitrary and capricious to include in the ANPR
proposal CFC-22 and all other commercial and as yet uncommercial-
ized CFCs (for many of which there does not exist quantitative
information opposite any threat to the ozone - See section 3) ,
and simultaneously exclude methyl chloroform for the same reason
— especially in the face of information available to the EPA
from its own conference on methyl chloroform, and the NAS1
expressed concern that methyl chloroform may well become the
largest source of stratospheric chlorine.
H-4
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Scope of Proposal
A quantitative illustration of the arbitrary nature of
EPA's proposal is developed below, in Table 1. Utilizing the
concept of relative ranking of compounds by their potential
effect on stratospheric ozone ("ozone depletion potential" or
permit pounds - See Appendix G) , the potential threat to
stratospheric ozone is compared for CFC-11, CFC-12, CFC-22 and
methyl chloroform. It is seen that the calculated relative ozone
depletion potential of methyl chloroform is three times that of
CFC-22 (0.09 compared to 0.03). When total world releases of the
compounds are figured in, methyl chloroform presents a potential
threat to the ozone about 20 times that of CFC-22.
Table 1
Calculated Depletion Potentials and Relative"
Calculated Environmental Impacts for Selected Halocarbons
Relative
Depletion
Compound Potential
, g77
(10 pounds)
Calculated Relative
Environmental Impact
(Relative depletion
potential
x world release)
Relative Environmental
Impact
(Ratio to CFC-22=1)
CFC-11
CFC-12
1.0 (a)
0.84 (a)
674
830
674
697.4
156.7
162.2
Methyl
Chloroform 0.09 (b)
CFC-22
0.03 (a)
930
144
83.7
4.3
19.5
1.0
(a) Calculated by Du Pont - see Appendix G.
(b) Calculated by Du Pont in a manner identical to that described in
Appendix G for CFCs. The atmospheric lifetime of methyl chloro-
form in those calculations was 8 years.
a-J
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Scope of Proposal
3. JUSTIFICATION FOR PROPOSING TO CONTROL ALL CFCS?
EPA states in the ANPR:
"EPA believes that any regulation of ozone depleters
should be as comprehensive as possible, consequently
this regulation would address all CFCs." (emphasis
added).
Notwithstanding that if the regulation is to be compre-
hensive methyl chloroform should not be excluded , we question
the scientific justification for including all CFCs under the
proposal.
Is EPA's belief sufficient or is technical support
required? Technical support for EPA's proposed regulatory scope
is not evident in the reference most often cited by EPA — the
1979 NAS report [NAS, 1979a] . As EPA correctly states in the
ANPR:
"NAS examined only two CFCs, CFC-11 (trichlorofluoro-
methane) and CFC-12 (dichlorodifluoromethane) because
they represent the vast majority of all CFCs produced."
(emphasis added).
''"Part of our concern is that methyl chloroform competes in the
marketplace with one of the CFCs proposed for regulation
(CFC-113). Were CFC-113 to be regulated, many users would
switch to methyl chloroform.
H-G
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Scope of Proposal
In fact, none of the assessments of potential future
stratospheric ozone depletion have included any CFCs except
CFC-11 and CFC-12. Further, to our knowledge, CFC-113, CFC-114,
CFC-115 (all included in EPA's scope) have never been thoroughly
studied by EPA or others specifically opposite the potential of
these compounds for ozone depletion. And CFC-22 has been given
only a cursory examination — acknowledged by EPA in the ANPR:
"NAS also briefly considered CFC-22 (chlorodifluoro-
methane) but excluded it from the analysis because as a
partially halogenated compound, its likelihood of
reaching the stratosphere before dissociating is much
less than that of fully halogenated compounds."
(emphasis added).
It is telling that EPA follows this statement in the ANPR with
the statement:
"However, the findings by NAS on the ozone depletion
potential of CFC-11 and CFC-12 are relevant qualita-
tively for all chlorofluorocarbons" (emphasis added).
Notwithstanding that no technical support is offered for
this conclulsion, we question the justification for a regulation
based on a qualitative finding. To what extent will EPA's
proposal reduce the alleged risk from CFCs -113, 114, 115, and
22? No risk determination has been made for any CFCs except
CFC-11 and CFC-12.
Without study of the potential effect on ozone from all
CFCs, any regulation must focus only on CFC-11 and CFC-12 (the
only CFCs studied), although as we note elsewhere (Sections III,
IV and V) even the extensive studies of CFC-11 and CFC-12
performed to date do not support a finding of unreasonable risk
from these compounds.
An even more bizarre aspect of EPA's proposed "shotgun"
approach is that the Agency's formula (cnclxFyH2n + 2-x-y; x> °'
11-7
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Scope of Proposal
y > 0 to bound the regulatory scope goes to extreme limits. A
rigorous following of this formula would mean that even high
molecular weight polymeric compounds would fall under the
proposed regulatory restrictions if they contained any trace of
chlorine (x is defined as >• 0 and n is unlimited) even though
these materials are nonvolatile with no potential for CFC
emissions.
Last, the proposed regulatory scope would include a
number of compounds which, through their potential future use,
could provide part of the solution to the problem (if it exists)
of ongoing use and emissions of potential high risk CFCs such as
CFC-11 and CFC-12. This is discussed in the next section.
H-8
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Scope of Proposal
4. COUNTERPRODUCTIVITY OF PROPOSING TO CONTROL POTENTIAL FLUORO-
CARBON ALTERNATIVES — WHY REGULATE A POTENTIAL SOLUTION?
Not only is there little or no current scientific or
risk justifiction for any potential regulation of CFCs to extend
beyond CFC-11 and CFC-12, but the broad proposal in the ANPR to
include "all alkanes that contain at least one chlorine and one
fluorine, including CFC-11, CFC-12, CFC-113, CFC-114, CFC-115 and
CFC-22, as well as several other CFCs not presently manufactured
or manufactured only in very limited quantities" embarks EPA on a
course that will impede and limit the development and application
of potential alternatives to the currently used CFCs thought to
present the greatest risk.
As an example, in Section VIII and Appendix B, we note
that CFC-22, CFC-141b and CFC-142b show technical promise as
refrigerants or blowing agent replacements for the currently used
CFC-11 and CFC-12 — replacements which due to a different
chemical structure would drastically reduce the potential for
stratospheric ozone depletion. However, by including these
compounds in its regulatory scheme, EPA has severely reduced
incentives to develop or use these compounds as replacements in
the aforementioned CFC-11 and CFC-12 uses.
Again taking CFC-22 as an example, we showed in Appendix
G that a pound of CFC-22 was approximately only 1/34 the
potential risk to the ozone of a pound of CFC-11 and only
approximately 1/29 the potential risk of a pound of CFC-12. Were
the need to arise, even partial substitution of CFC-11 and CFC-12
by CFC-22 could reduce several-fold the risk to the ozone.
li-S
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Scope of Proposal
Consistent with this objective, EPA states in the ANPR
it would structure regulation "...in such a way as to provide
incentives for industrial users to shift from those CFCs
[hypothesized to be] most harmful to the stratosphere toward
those CFCs posing a lesser [theoretical] threat." Yet the
Agency's proposal does not create the incentive to use CFC-22 (as
an example) so much as it creates a disincentive to use it,
because it too is being regulated. So long as a potential
alternative like CFC-22 is under the proposed overall cap on CFC
production, users will be reluctant to convert to its use due to
uncertainty over whether it would be further restricted in coming
years. (See Section VII). If the Agency desires to create an
incentive for users to convert from CFC-12 to CFC-22 (a step
yielding an approximate 29-fold per pound decrease in potential
risk to the ozone), CFC-22 should be exempted. Other reasons for
exempting CFC-22 are provided in other parts of this Appendix.
In a recent letter from EPA to a Congressional
representative [Wellford, 1980] it was stated:
"The Agency is studying methods to stimulate the devel-
opment of substitutes for all [CFC] applications...."
Not only are we not aware of any such studies but what
the Agency has proposed creates a disincentive to use potentially
satisfactory alternatives, not a stimulus.
a-10
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Scope of Proposal
5. JUSTIFICATION FOR NOT EXEMPTING NON-EMITTING CFC USES FROM
THE PROPOSAL?
In its ANPR summary of the ozone depletion theory, EPA
states:
"The continued worldwide release of CFCs is therefore
troublesome...." (emphasis added).
and uses as a Section heading:
"The Risks of Continued World Chlorofluorocarbon
Emissions" (emphasis added).
Through all reports and discussions on the issue to
date, it has been understood that the use per se of CFCs posed no
problem to the stratospheric ozone layer, but that emissions of
CFCs (from products and processes) which eventually were
transported into the stratosphere were of concern. This is in-
herently obvious. The potential problem is in the stratosphere.
Therefore, only those CFCs reaching the stratosphere are of con-
cern. Refrigerators and auto air-conditioning systems do not get
into the stratosphere. CFC emissions from these and other uses
may.
Further support for the logic for exempting non-emitting
uses may be found:
• In the Rand Report (in its discussion of economic
incentive approaches to regulation):
"The only exemptions from the tax that would be
recommended by efficiency and effectiveness criteria
would be for CFCs used in applications where there are
no emissions, such as when the CFC is used as a
precursor for producing other chemicals that do not
deplete ozone." [Rand, 1980, p. 240].
H-II
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Scope of Proposal
• And even more tellingly, in EPA's Development Plan -
"Chlorofluorocarbons - Phase I" [EPA, 1980e, p. 8]:
"Some CFCs are used as intermediates in the manufacture
of non-ozone depleting substances. This use of CFCs
should probably only be controlled to the extent that
CFCs are released during the process."
Yet inexplicably, the ANPR does not provide for the
exemption of non-emitting CFC uses — in fact, does not even make
mention of them.
The major CFC use resulting in no emissions is CFC-22 as
an intermediate in the production of fluoropolymers. The end
products are not potential ozone depleting substances.
Therefore, this CFC use should be exempted from the proposals and
all assessments and projections of production, use and emissions
should exclude this and like CFC uses.
H-12
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Scope of Proposal
6. SUMMARY
• Any proposed rule should be restricted to CFC-11 and
CFC-12 because:
a) There is no technical support for EPA regulating
all CFCs when all technical studies to date have
restricted their assessments 'to CFC-11 and CFC-12.
Further, EPA has made no risk assessment of the
potential effect on the ozone of any CFCs except
CFC-11 and CFC-12, nor demonstrated how the proposed
rule would reduce risk from these other compounds.
CFC-22, in particular, presents a very small
potential risk compared to CFC-11 and CFC-12.
b) EPA's proposed rule scope would cover all
technically promising fluorocarbon alternative
compounds. This creates a disincentive for further
developement and will restrict potential use —
results which are counterproductive to the Agency's
stated goal of reducing the use of potential high
risk CFCs (e.g., CFC-11 and CFC-12) through the
creation of a stimulus to encourage the development
and use of substitutes for CFC applications.
c) The use of CFCs which result in no emissions,
such as the use of CFC-22 as a chemical inter-
mediate, pose no potential threat to the ozone layer
and, therefore, should be excluded from any further
regulatory consideration.
• There is no justification for EPA regulating CFCs
while ignoring the ozone depletion potential of
other compounds, such as methyl chloroform.
H-i
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X. APPENDIX I
ECONOMIC INCENTIVES
REGULATORY OPTIONS
1-1
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Economic Incentives Options
TABLE OF CONTENTS
PAGE
1. INTRODUCTION 4
2. BACKGROUND 7
a. Mandatory Controls 7
b. Economic Incentives Options - The "Why"
and the "How" 8
c. Arguments Against Economic Incentives Options 11
i. Double Burden 11
ii. Small Firm Argument 12
iii. State Versus Federal Requirements 12
iv. Transfer Payments Create Inflationary
Pressures 13
v. Political Problems 13
vi. Legal Problems 15
3. RAND'S ESTIMATING PROCEDURES 17
a. Data Uncertainties 17
b. Discounting Procedures 19
c. Administrative Costs of Regulation 21
d. Impact of Uncertainty on Choice of Optimal
Incentive Design 23
4. OPTION DESIGN IMPLICATIONS 25
a. Designs Should Reflect Different Potential
Environmental Impacts of Compounds 25
b. Design Control Point - Production, Use or
Emissions 26
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Economic Incentives Options
Paqe
c. Transfer Payments 28
i. Uncompensated Transfer Payments 28
ii. Reduce Transfer Payments 29
iii. Compensated Transfer Payments 30
d. Market Structure Effects of Regulatory Design 33
e. Risk Trade-offs 34
f. Diminishing Returns 35
OPTION IMPLEMENTATION AND ADMINISTRATION ISSUES 36
a. Uncertainty Concerns 36
b. Mechanics of Implementation 37
c. Legal Issues 38
i. Taxes 38
ii. Marketable Permits 38
1-3
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Economic Incentives Options
1. INTRODUCTION
Our ability to take a stance on economic incentives
regulatory options is limited due to the newness of these
concepts and the unavailability to date of adequately detailed
potential structures on which to base our analysis.
We agree there are numerous problems and inefficiencies
associated with traditional command and control regulations as
they have been imposed historically. And many of the theoretical
arguments advanced in support of the economic incentives
aproaches are appealing, at least at first glance. However, once
one progresses beyond a theoretical or conceptual examination of
the incentives options, it becomes obvious that they too have
practical limitations. Careful consideration of design,
implementation and administration issues reveals that these
concepts, while seemingly efficient and simple at face value,
have associated with them complex policy problems and questions.
From our examination to date, we are concerned there are
numerous and interrelated legal, hidden cost and efficiency pro-
blems associated with the potential implementation and adminis-
tration of these concepts. There also is a natural reluctance to
commit one's business to the experimental evaluation of untested
theoretical concepts. Regulation often has produced results and
inefficiencies not readily foreseeable from pre-application
examination. It follows that any new regulatory intervention
ought to be carefully thought out before it is implemented. As
an example, even if incentives policies result in less of a
straight-jacket than direct controls (as theorized), nevertheless
they can be applied in a way that would leave society worse off.
In the chemical industry, we require that theory be put
to test; first on the lab bench, then in a pilot plant or test
market, prior to committing to full scale product or process
1-4
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Economic Incentives Options
introduction. We question the wisdom of jumping from economic
theory to real world fluorocarbon production and use without
first obtaining some practical experience with these concepts in
an area with much less potential impact. When the economic,
energy conservation and safety importance of CFC products are
considered, the wisdom of such an action is further questioned.
The concepts should be tried out on a limited basis and the
experience assessed before committing to the full scale-up which
fluorocarbons would represent.
We also have a fundamental concern over the potential
broad-based implications of this form of regulation to the
balance between business and the regulatory arm of government.
It may be argued that these concepts minimize regulatory control
of industry and are economically efficient through their reliance
on the operation of the marketplace. But the use of these
concepts represents a potential for ever-increasing control in an
area heretofore the province of business and the consumer.
Pollution control is a well defined area in which business,
government and environmentalists seem to be progressing towards a
workable balance. Policies — no matter how theoretically sound,
or well intentioned — which potentially expand this arena into
economic control of the marketplace, should be examined carefully
and approached with caution.
The analyses we have seen to date provide more questions
than workable solutions. We feel that neither EPA nor Rand have
addressed adequately the areas of policy design, implementation
and administration, or their implications (although the Rand
researchers do identify many of the potential problem areas and
suggest substantial further work).
Part of the problem we experience is the lack of
adequate option detail for analysis. Without detail which
addresses identified questions and concerns, it is extremely
1-5
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Economic Incentives Options
difficult for us to perform the required analysis from our
perspective. Until specific detailed proposals are developed
which would allow the evaluation of the legality, difficulty and
costs of complying with incentives options compared to tradi-
tional command and control options, we must hold our opinion or
££j. __ The potential problems must be
addressed publically by EPA, though the creation of detailed
hypothetical option designs, with allowance for comment by
industry and other interested parties, prior to implementing any
of these options.
1-6
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Economic Incentives Options
2. BACKGROUND
The following presents our understanding of the problems
with mandatory controls, the "why" and the "how" of economic
incentives controls, followed by some of the arguments against
incentive options. Our comments in the following sections are
based upon this understanding.
a. Mandatory Controls
Mandatory controls, or command and control options, are
the basic technique used over the last decade to regulate air and
water pollution. They are targeted at particular activities in
individual industries. v
It is argued that these options are cost inefficient in
attaining environmental goals such as CFC emissions reduction due
to inherent inflexibility. Some activities regulated by
mandatory controls may require large expenditures to reduce
emissions by modest amounts, whereas other activities, if given
the same expenditure, would show large reductions. Further,
under such controls, the cost per pound of emissions reduced may
rise rapidly for a given activity as the control standard is
approached, whereas a comparable expenditure in another activity
could produce greater reductions.
Yet, under command and control options, industries or
individual firms within the targeted industries could not trans-
fer expenditures between each other (either inter- or intra-
company or industry), in order to attain the greater efficiencies
in emission reduction versus cost available elsewhere.
An additional concern with mandatory controls is the
problem of enforcement. Regulations targeted to specific
emissions activities within specific industries must be enforced
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Economic Incentives Options
at the point of control. In the case of CFCs, this could mean
enforcing standards in thousands of use locations.
It also is argued that once a firm has met a control
standard there is no incentive for the firm to reduce use beyond
the standard, nor for competitive reasons, to spend monies for
innovation which would lead to lower use.
b. Economic Incentives Options - The "Why" and the "How"
In recognition of the limitations of command and control
options, economists have long argued for the use of economic
incentives policies. These policies are theorized to function by
effectively raising the prices users must pay for their polluting
activity, thus making the control of the activity economically
attractive.
In the case of CFCs, were the cost of using them to be
higher due to a regulatory policy which increased their price,
users would seek ways to reduce their purchase and/or to use them
more efficiently. Use reduction could be achieved through
product or process substitution or increased conservation, and
use efficiency could be increased through recapture and reuse.
Under these options, the degree of use or emission
reduction desired could be controlled simply through adjustment
of the economic penalty imposed on the chemical's use. At higher
cost penalties, firms would find it attractive to make greater
expenditures to further limit the use of the chemical.
Theoretically, the optimal point of economic disincentive on the
use activity would be the premium at which an increase in the
cost of reducing the use would be equal to the decrease in the
environmental damage that would result from the chemical's use.
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Once the desired policy outcome is decided upon, the
policymaker could step back and limit further involvement to a
monitoring of the degree of goal attainment, followed by an
adjustment (up or down) of the use premium as needed to meet the
preset goal. This would minimize the need for direct monitoring
and enforcement of controls on the behavior of individual firms
and industries.
More importantly, it is argued that such a scheme would
allow the individual firms and industries to decide upon the most
economically sensible course of action for their circumstances.
Some, lacking the technology or resources to make much headway in
the use reduction, would pay the penalty. Others would find it
attractive to substantially reduce their use to avoid the
penalty, often going beyond any standard set under command and
control.
In short, it is argued that under such a system, firms
will operate in their own best economic interests with the net
result that the overall use or emissions goal will be met more
efficiently — i.e., at lower cost — than would be the case
under a system in which specific steps or controls were required
without consideration of the individual capabilities and
motivations of those affected.
This is because command and control steps generally are set at
some average point of technological and economic achievability
so as not to be so stringent that they prove unworkable or
result in massive business failures.
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The two incentive policies most often discussed are
taxes and quotas. A tax would be imposed on the use of CFCs,
resulting in the user paying the CFC producer the normal supply
price plus a tax penalty for each pound of CFC purchased, thus
creating an incremental incentive (determined by the size of the
tax) to reduce the use of the chemical. The control agency would
raise or lower the tax in response to the quantity of CFC
purchased, relative to its policy goal.
A quota system would start from the supply side of the
equation. If a quota on CFC production or sale were imposed,
some sort of premium price mechanism would evolve to allocate the
reduced amount of CFCs among the competing uses. Whether the
producers themselves effected this through price increases, or
the users through buying and selling permits for the right to
purchase the limited quantity of CFCs, makes little difference in
theory. The net effect would be that the effective price of
using CFCs would increase, thus creating an incentive to reduce
their use. Many theorists favor the later approach, terming it a
"marketable quota system." The users would market among
themselves the permits for CFC purchase. The permit price would
reflect the supply availability and serve to allocate the limited
CFC among the uses based on value-in-use or essentiality. The
control agency would simply raise or lower the production or
sales quota of CFCs to meet its policy goal.
Theoretically, the same reduction in use, at the same
cost, could be achieved using either permit quotas or taxes —
i.e., for a given use reduction goal, either option should result
in the effective increase in CFC price being the same, thus
reducing CFC use by like amounts. However, it is important to
note that the theoretical equivalence between taxes and quotas is
dependent on markets being purely competitive and on quotas not
being used to reduce competition. [See section 4-d].
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c. Arguments Against Economic Incentives Options
Many of the concerns raised about the use of economic
incentives regulatory options result from the absence of detailed
descriptions of how these options would work and an understand-
able reluctance to have untested, theoretical concepts applied to
important industries. Prior to satisfactory resolution through
option design and trial testing, these concerns remain arguments
against the use of economic incentives approaches.
i. Double Burden
Any system which required the paying of a charge (taxes
or permit bids) would remove monies that would otherwise be used
on emission control.
It takes time for a firm to analyze its abatement
possibilities, design or decide on new equipment, and place in
operation new technology. Given the need for this lead time, any
charge applied the first few years would be a double burden:
money would have to be spent for the incentive charge, even
though there may be no reasonable action a firm could take to
reduce its emissions in this period; and monies would have to be
spent in this period for steps to reduce emissions over the long
run.
As a solution, the gradual phase-in of incentives
options, to allow industry time to effect emission reduction
steps before having to pay a penalty, has been suggested. We
believe all regulations should be phased-in over a reasonable
time frame in order to minimize the economic impact of com-
pliance.
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Economic Incentives Options
ii. Small Firm Argument
Those firms too small to afford emission reduction
equipment would still have to pay any charge, but without any
potential for eventually offsetting the charge cost through
emission reduction. The net result is that these firms pay more
for doing what they have always done — but this increased cost
would not be offset by any reduction in emissions, immediate or
longer-term. Consequently, small firms' costs would increase
relative to other firms. This would have the effect of shifting
demand away from small firms towards other firms and, in the
extreme case, put the smaller firms out of business.
One suggested solution is to 'exempt small firms from a
charge system. But exemptions would significantly complicate the
very design and enforcement attributes which make the incentives
options attractive. Once the regulatory agency begins granting
exemptions, an incentives policy is likely to lose its theoret-
ical property of achieving any desired reduction of CFCs at the
lowest achievable compliance cost.
iii. State Versus Federal Requirements
The primary argument for economic incentives options is
that if an economic disincentive to pollute is created,
individual firms, acting in their own best economic interests,
collectively will reduce polluting activity much more efficiently
than were each firm to be required to meet set control standards.
Were such a system in place on a Federal level, but individual
States still allowed to issue traditional command and control
regulations, the economic efficiency of the incentives option
could be destroyed. The Federal system would be designed to
permit firms to reduce emissions in the manner and to the degree
economically justified. Yet State issued command and control
steps could significantly undermine this economic rationale. For
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instance, a firm could be required by the State to put in
equipment making no economic sense to the firm, yet then have to
pay a Federal charge penalty for not having made the best
economically justified decision.
It is an overstatement to say that Federal and State
controls would present a strictly additive burden because a State
command and control reduction regulation would reduce the Federal
charge payments. However, there would be the potential that the
State regulations would partially negate the very efficiencies
touted for the incentives approach. Clearly, harmonization of
Federal and State options must be carefully examined.
iv. Transfer Payments Create Inflationary Pressures
It is argued that taxes or permit fees to government by
industry are simply transfers of wealth within the economy.
Since such payments do not use up real resources and are
eventually returned to the economy, it is claimed they do not
directly contribute to inflation. This argument is supported by
the formal definition of inflation which relates it to an
expansionist monetary policy.
However, these transfer payments would represent a real
cost of doing business to industry and would be reflected in
product prices. Consumers equate price increases to inflation
and social pressure for increased wages would result. If this
pressure exists under a monetary policy that does not restrict
the money supply, the price increases caused by the charges
indirectly lead to inflation.
v. Political Problems
• A tax or a permit fee system could be subject
to political manipulation. Due to the flexi-
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bility built into these systems (to allow
adjustment up or down in response to the degree
of attainment of the environmental goal),
significant changes in fee structures could be
much more easily made than altering mandated
control steps.
Depending upon the ultimate fate of the monies
collected under a charge system, revenue
addition is a concern. How easy would it be to
decrease the charge in response to a lessened
environmental problem or an overattainment of
goal were various programs or funds dependent
upon an anticipated revenue level?
Transfer payments are potentially a very sen-
sitive political issue. If the system employed
j.^6-!^!!^^—£°.mPensate f°r tne charges, total
regulatory costs are far greater for an econo-
mic incentives policy than for mandatory con-
trols. This destroys the theoretical benefit
of economic incentives options — lower cost.
If the system is designed to compensate for the
charges in some manner, the politically
sensitive issue of distribution of wealth among
the CFC users, industry or public, must be
addressed. Who pays, who gains and on what
basis?
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Economic Incentives Options
vi. Legal Problems
There are two types of legal concerns that must be
addressed. These are discussed in detail in 5-c below and in
Section III - Legal Considerations, so will only be touched on
here:
• It arguable whether the EPA has the authority
under current law to implement a marketable
permit system, depending upon how it were
designed. Additionally, administrative
agencies have no constitutional authority to
levy taxes.
• Proponents of economic incentives tend to
minimize the legal implications of first, the
proposed option designs and implementation
schemes, and second, of the anticipated
/
activities and responses of firms under a
charge system. However, it may not be legal
for firms to comply with some of the proposed
options.
To study the implications of economic incentives
options, EPA contracted with the Rand Corporation to analyze the
efficiency and impact of these options opposite traditional
command and control regulations if both forms were to be applied
to the goal of reducing CFC emissions. The balance of this
Appendix centers on our asssessment of the thoroughness and
validity of Rand's and EPA's (from the ANPR) assumptions,
analyses and conclusions for the potential use of economic
incentives regulatory options in the control of CFC emissions.
We have roughly grouped our comments into three areas.
Section 3 considers how some of the procedures used by Rand to
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estimate the costs of alternative regulatory policies may
influence the report's conclusions. Section 4 focuses on Rand's
and EPA's treatment of the economic incentive policy designs and
their implications. Section 5 deals with the implementation and
administrative issues associated with the use of incentive
options. Overlap in certain areas is unavoidable.
A preview of our comments is offered by three basic
propositions:
1. Rand's analysis of economic incentives regulatory
options is incomplete. Administrative costs of the policies are
not quantified and the analysis of control options is incomplete.
2. The Rand Report pays insufficient attention to legal
considerations, such as the danger that a permit system could be
used to attain monopoly power in the market for CFC.
3. As a consequence of EPA's definition of the scope of the
study, Rand limited its analysis to estimating the cost of
alternative modes of regulating CFC. By failing to address the
broader question of the net benefits that could be attained under
each policy option, the report fails to consider factors that can
have an important bearing on which policy alternative is
preferable from society's viewpoint.
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3. RAND'S ESTIMATING PROCEDURES
a. Data Uncertainties
There remains considerable uncertainty about the cost of
CFC regulation. As a result, the cost advantage of incentives
policies over direct controls could be greater or smaller than
estimated by Rand. As significant error in predicting compliance
costs could lead to (a) adoption of an inferior means of
regulating CFC and (b) a policy target that is unwarrantedly
stringent or lax.
A policy that restricts the use of CFCs must result in
either substitution by consumers of final products that make less
or no use of CFCs, or substitution by firms of other inputs for
some of the CFCs presently being used to produce final products.
In the absence of perfect substitutes for CFCs, these
substitutions will impose costs on consumers and firms.
Since perfect substitutes for CFCs do not exist, any
regulatory policy that leads to a less CFC-intensive production
technology will result in some increase in the real resource cost
of production. The size of the cost increase will depend loosely
on the ease of replacing CFCs with other inputs (a technological
issue) and the volume of output affected by the substitutions (a
matter of the size of the market traditionally involving use of
CFCs) . To estimate the costs imposed on firms by CFC
regulation, information is needed on the size of markets for
goods involving CFCs and the production cost of these goods by
alternative technologies using less CFCs.
These information requirements impose serious
difficulties. Historic data is limited and may not be very
accurate. Projecting future uses of CFCs involves further
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Economic Incentives Options
uncertainties. Continuing evolution of the uses for CFCs and the
technologies involved, adds further complication.
Rand has dealt with these uncertainties by attempting to
develop a working knowledge of the role played by CFCs in the
production of final products and, based largely on engineering
estimates, the scope and cost of possible substitutions for CFCs
in those production processes. These estimates, combined with
the assumption that firms will always seek to minimize their
production costs, provide the basis for Rand's estimation of the
compliance costs of each regulatory strategy.
However, considerable uncertainty remains about the true
compliance costs of CFC regulation. A key source of this
uncertainty is that Rand seems to have only limited knowledge of
the nature of end products dependent upon CFCs. A further source
of uncertainty is Rand's assumptions concerning substitutions
that can be made for CFCs.
The significance of these data uncertainties is that the
true compliance cost could be significantly higher or lower than
estimated by Rand. Hence, the cost advantage projected for
incentives policies could be either under- or over-estimated. If
incomplete information led to overlooking a direct control that
would substantially reduce CFC at a modest cost and could be
easily enforced, the compliance costs of direct controls would be
overestimated relative to an incentive system. On the other
hand, if the cost of reducing CFC use has a wider range across
user industries than estimated by Rand, the cost advantage of an
incentives policy would tend to be underestimated.
A significant error in estimating compliance costs can
have important effects on policy formulation. If the
implementation costs of taxation, marketable permits and direct
controls were the same, choice of the best policy alternative
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would depend simply on the ordering of policies by compliance
cost. Errors that did not affect the ordering would be
inconsequential. But if, for example, direct controls are
expected to be less costly to implement than a permit system, the
accuracy of compliance cost difference becomes important.
Once a form of regulation is selected, compliance costs
become relevant to the determination of the socially appropriate
reduction in CFC emissions (which should be the objective of
regulation). Consequently, although Rand focuses only on the
relative cost-effectiveness of the policy alternatives, the
accuracy of their cost estimates is also relevant to selecting
this appropriate degree of control. The potential optimal
curtailment of CFCs is inversely related to the potential cost to
society of reducing the uses of CFCs, so the larger the
compliance cost, the smaller the reduction in CFC use that the
regulatory policy would attempt to accomplish. This means that
an underestimate of compliance costs could lead to more stringent
regulation than would be socially desirable, and vice versa.
b. Discounting Procedures
The report measures the effectiveness of a regulatory
policy by its predicted curtailment of CFC production over the
period 1980 to 1990. Ignoring the effect of a policy on year-by-
year production (and thereby emissions) is justified in the
report by two arguments. First, the effect on the ozone layer is
relatively insensitive to different time profiles of the same
volume of cumulative emissions. Second, the time-lag between CFC
production and the full effect of emissions on the ozone layer is
long. Thus a policy that delays emissions within a decade
results in a relatively small delay before the full effect on the
ozone layer occurs. Since the report ignores the time profile of
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CFC reduction, all policies that produce the same cumulative
reduction over the decade beginning in 1980 are represented as
being of equal value to society.
This treatment of benefits is inconsistent with the way
costs are calculated in the report. The compliance costs
estimated for each year are discounted back to a base year and
represent the present value of all costs incurred in accom-
plishing the cumulative reduction in CFC production over the
decade. This discounting procedure recognizes that a real dollar
of goods is worth more today than tomorrow. Inconsistency arises
in the report's failure to discount the flow of benefits in a
similar way.
Although Rand suggests that the benefits from reduced
CFC emissions are relatively insensitive to their time profile,
that will not necessarily be so. Consider an extreme example,
for some stipulated cumulative CFC reduction over the period
1980-1990: all the reduction occurs in the first year under
policy A while all the reduction occurs in the tenth year under
policy B. The benefits from policy B will lag those from policy
A by 9 years. At the 11 percent rate of discount used by Rand
the present value of benefits produced by policy B will be
9
1/(1.11) , or about 40 percent of the value from policy A.
The report states that a constant tax rate over the
decade will produce a time profile of CFC use paralleling that
from direct controls. If the difference is negligible, the
failure to discount benefits does not interfere with a comparison
of the merits of the policies. But the report also considers a
tax that is initially set at a lower level and increased
uniformly over the decade, producing equivalent cumulative
reduction in CFC use. Failure to discount benefits introduces an
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Economic Incentives Options
error in comparing this policy to others. The policy is credited
with a lower present value of compliance costs, but the present
value of benefits also would be reduced by the delay.
c. Administrative Costs of Regulation
Public sector expenditures for developing, implementing
and enforcing regulation of CFCs are not included in Rand's esti-
mates of regulatory costs. Since these expenditures constitute
real resource costs, their omission tends to understate the real
cost to society of regulating CFCs. Because both the information
required to formulate a particular policy and the cost of en-
forcing it will be different for mandatory controls, taxation, or
a permit system, administrative expenses must be included to
correctly determine cost-effectiveness, as well as to assess
correctly the total cost of regulation.
Administrative expenses are difficult to estimate
because, to a considerable extent, they reflect discretionary
choices. The amount of information a regulatory authority elects
to acquire in the process of setting and enforcing policy will
affect both the cost and the quality of regulation. If there
were simple decision rules to determine the economically
efficient amount of information for a regulator to obtain, the
administrative costs of regulation could be estimated on that
basis. Since this is usually not the case, administrative costs
are difficult to anticipate.
But failure to take into account administative costs can
lead to two types of regulatory errors. First, if the selection
of a policy to regulate emissions is based exclusively on the
private sector compliance costs, the chosen policy may not be the
one minimizing the full cost of regulation — private and public
sector costs. Second, regulation which appears attractive when
only private sector costs are compared to benefits may be
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undesirable when the administrative costs of regulation are
added. This can mean either that no regulation would be
preferable or, when administrative costs rise with the stringency
of regulation, that the curb on emissions is tighter than, would
be in the public interest.
It is argued that a tax or a quota should be less costly
to administer than a system of direct controls. This implies
that Rand's omission of administrative expenses results in an
underestimate of the cost advantage of incentives policies.
However, there are myriad unanswered questions and concerns
relating to implementation and administrative issues for economic
incentives options [See section 6] . Design of these options to
accomodate these concerns undoubtedly will result in more complex
regulations than the theoretical ideal, leading to an increase in
development, implementation and enforcement costs. Costs could
even rise to the level of mandatory controls, depending upon the
complexity of the modifications required. Another consideration
is that in the case of CFCs, substantial information on which to
base mandatory controls already is available.
Enforcement costs can be avoided entirely at the risk of
substantial noncompliance with the regulations. Alternatively, a
regulatory agency can police the affected markets sufficiently to
insure that compliance is complete, resulting in substantial
enforcement costs. Actual enforcement costs will depend on the
ease of enforcing the selected mode of regulation and on the
degree of enforcement chosen.
The Rand Report implicitly assumes that enforcement of
each of the policy alternatives will be complete, and that
enforcement costs of incentives policies will be minor. It is
our view that Rand is somewhat glib in characterizing enforcement
costs of incentives policies as minor. Either a permit system or
taxation could create a substantial incentive to evade the
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regulation of CFC use, necessitating enforcement comparable to
that needed with mandatory controls. Additionally, as incentives
options become more complex (in order to address all the design
and implementation concerns), more enforcement will be needed.
An example would be the case of an incentives option with
exemptions.
Therefore, since the cost of enforcement may be substantial for
either incentive option, it certainly merits more careful
attention than Rand seems to have given it.
d. Impact of Uncertainty on Choice of Optimal Incentive
Design
Rand points out, that an important distinction between
quota and tax options results from the fact that there is some
uncertainty about the estimated demand schedules used to predict
the permit price or the requisite tax to achieve a given policy
goal. Under permits, the level of CFC use is known with
certainty, but the permit price that actually develops might
differ from the prediction; under taxes, the increase in CFC
price is known with certainty, but the reduction in CFC use that
occurs might differ from the prediction. Thus the earlier
discussed theoretical equivalence (same reduction in use at the
same cost) of the incentives policies is dependent upon perfect
information of CFC costs and demand. Since perfect information
is not available, the extent to which these are relative
uncertainties in the information on the demand for, and costs
(production and social) of, CFCs should dictate, at least in
part, a choice between incentives options. Consequently, a
choice between taxation and a permit system should depend in part
on whether the regulatory authority has a clearer notion of the
appropriate tax on CFCs or of the appropriate quantity.
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Rand's assessment of alternative methods for regulating
CFCs is limited to a consideration of the cost of obtaining a
designated reduction in CFCs under each policy. This, however,
is not a sufficient criterion to determine the best choice among
policy alternatives. If the degree to which it is socially
optimal to reduce CFC emissions is uncertain, the best mode of
regulation will not necessarily be the one that is most cost-
effective. As an example, if there is more uncertainty about the
correct tax level than the appropriate reduction in emissions —
but a permit system is felt to pose a danger of market concen-
trations — then the best solution might be direct controls, even
though theoretically more costly.
Last, significant uncertainty about the demand for CFC,
its production cost or the damage from CFC emissions can lead to
the public being worse off under any of the policy alternatives
than if CFCs had not been regulated.
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Economic Incentives Options
4. OPTION DESIGN IMPLICATIONS
a. Designs Should Reflect Different Potential Environmental
Impacts of Compounds
Different fluorocarbons have greatly different potential
stratospheric environmental impacts. Some (CFCs) are of high
concern; others (hydrogenated CFCs) of moderate to low concern;
and others (FCs containing no chlorine) of no concern. Economic
differences through a quota or fees system which penalizes least
the use of the compounds of lowest environmental concern. This
would focus emission reduction efforts on the compounds of
greatest risk, and encourage replacement of high risk CFCs, e.g.,
CFC-11 and CFC-12, with low risk substitutes, e.g., CFC-22 or
CFC-142b.
EPA's system of "permit pounds" is a step in the right
direction. However, as discussed in Appendix G. EPA has made
some errors in its system.
The concept of relative environmental risk could be
applied equally well to taxes (through setting different tax
rates by compound) or to marketable permits (through setting a
quota of the total permissible stratospheric chlorine burden from
CFCs and relating a permit unit to "ozone depletion potential"
rather than to pounds of CFC emissions). Under this scheme,
different compounds would have different permit values.
As an example, using our figures from Appendix G,
industry would have the choice of producing 34 pounds of CFC-22
or one pound of CFC-11, since both would account for equal units
of potential for ozone depletion. The net result would be both
more efficient regulation (as it would control directly the
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environmental risk factor) and cost-effective regulation (as it
would allow industry substantial flexibility in production and
use) .
b. Design Control Point - Production, Use or Emissions
There are a series of considerations relating to the
impact or control point of incentives options. Although EPA
discusses a number of the possibilities in the ANPR, neither
their identification nor analysis of the different approaches is
thorough. What is needed is an ordering of all the possibilities
with a discussion of the pros and cons of each. After the
initial questions of "What are we trying to control?" and "How
much control is needed?", are answered, a series of complex,
interrelated questions must be addressed. A representative
sampling of these and how they might be ordered follows:
• Should control.be imposed on users or producers?
a. If on users, should control be on CFC emissions or
CFC use?
i. If on emissions, what are the enforcement
problems?
ii. If on use, should all users be taxed the same
and have an equal opportunity to acquire
permits, or should taxes or permits vary by
application? Should there be exemptions for
certain uses (e.g., where no emission reduction
is possible or where no emissions occur) or for
certain users (e.g., small firms which would
otherwise be forced out of business)? What are
the problems associated with exemptions?
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b. If on producers, will there be legal problems?
What is the potential for restraint of trade?
• How should control be imposed?
a. Should permits initially be put up for bid or
allocated?
i. If put up for bid, who can bid and on how many?
ii. If allocated, on what basis? Who will be
eligible? What about new entries?
b. How should reclaimed material be treated?
• How would imports be handled?
a. If taxes, what would be the repercussions?
b. If permits, would imports have to fit into United
States permit quotas? If so, how?
EPA is proposing to use economic incentives concepts.
It is EPA's obligation to think them out and present proposals
which address these and related questions. EPA's approach to
date has been to ask industry to answer the questions rather than
EPA doing the necessary work to support its proposals.
In the ANPR, EPA proposes to regulate either the produc-
tion or the use of CFCs, not the emissions. However, regulation
of CFC use or production will not produce outcomes exactly equi-
valent to the direct regulation of emissions. And it is the
emission of CFCs which leads to the potential environmental
damage, not the production or use.
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Economic Incentives Options
When two products, one of which poses environmental
hazards, are unavoidably produced in fixed proportions, regula-
tion of the output of either product can be used to curtail
environmental damage. The choice between the hazardous product
itself or the product rigidly linked to it may not be important
unless the cost of enforcement differs.
If, however, the proportions in which the two products
are produced can be varied, a policy that regulates the harmful
product indirectly, by acting on the closely related product, can
lead to subtle inefficiencies because the relationship between
the two products is elastic. EPA fails to note this distinction.
The area requires further examination.
Further, a key advantage to regulating CFC emissions
directly — that could be lost with indirect regulation (taxes on
use or use permits) — is that under direct regulation of CFC
emissions, only emissions are penalized. CFC-using activities
which do not result in emissions, properly, are not penalized.
c. Transfer Payments
A critical concern with economic incentives options is
over the size, control and fate of the monies collected. For
simplicity, this problem can be approached three ways: i) ignore
compensations; ii) reduce the size of the transfer payment
(without undermining the economic incentives to reduce CFCs) ; or,
iii) compensate those hurt by the payments.
i. Uncompensated Transfer Payments
Rand estimates that transfer payments generated by
economic incentives options for even their moderate "benchmark"
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reduction in emissions will be approximately $1.5-1.7 billion, a
number many times in excess of the option's compliance costs. A
quote from the report succinctly sums up this problem.
"Under an uncompensated economic incentives policy,
cumulative transfer payments would be very large,
ranging upward from $1.5 billion for the least costly
benchmark-equivalent policy. For the firms that pay
them, uncompensated transfers dwarf the costs
of reducing emissions. On average, a firm's expenses
for transfers under an uncompensated benchmark-
equivalent policy are about fifteen times the costs of
actually . reducing emissions. For all but a few
CFC-using firms, the total expenses under uncompensated
economic incentives are greater than the compliance
costs under mandatory controls." [Rand, 1980, p. 18].
Other problems with uncompensated transfer dollars are
political. There is concern over the possibility of rate
manipulation and revenue addition [See section 2],
ii. Reduce Transfer Payments
Due to the potential problems with transfer payments,
Rand suggests a number of possibilities to reduce their impact.
An obvious solution would seem to be to exempt users where CFC
demand is relatively inelastic (because of use essentiality and
the unavailability of emission reduction options), e.g.,
polyurethane insulating foam. But once exemptions are allowed,
enforcement difficulties and costs increase markedly. For
enforcement and other reasons, Rand discards the exemption
approach.
1-29
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Economic Incentives Options
Instead, Rand suggests direct allocation of CFC use.
This approach involves giving an initial allocation of permits,
per period, to CFC users according to a regulatory formula,
rather than requiring that users initially purchase permits.
Even under this approach, however, the real cost of regulation is
likely to be unnecessarily high because the cost of administering
direct allocation of permits is likely to be considerably larger
than the cost of distributing permits by auction. Further
concerns are questions of allocation - what "regulatory formula"
and what basis would be used for distribution? What allowances
should be made for new uses or new users?
iii. Compensated Transfer Payments
Neither the benefits nor the beneficiaries of compen-
sation are made entirely clear by Rand or by EPA. A key concern
not addressed is that those who would benefit from compensation
are not necessarily those on whom the primary regulatory burden
would fall.
Throughout the study, it is assumed that demand for
final products using CFCs is perfectly price inelastic. If so,
user industries will be able to pass through to consumers any
increase in cost due to regulation, whether its source is higher
resource costs or transfer payments on taxes or permits. The
burden of adjustment, measured by potential reductions of real
income, would fall primarily on consumers of final products using
CFCs, and workers and stockholders in firms producing CFCs.
However, Rand focuses on compensation to user industries, as a
result of relaxing the assumption that final product demands are
perfectly inelastic. This leads one to consider the possibility
that it may not be possible to pass all cost increases through to
consumers.
1-30
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Economic Incentives Options
Of the policies proposed to nullify transfer payment
impact, the one least likely to increase regulatory compliance
costs would seem to be a free allocation of permits. Even this
approach, however, is likely to result in higher real cost of
regulation because of the cost of sorting our competing claims
and administering a direct allocation.
Each of the other combinations of incentives and
compensation considered by Rand appears to be capable of leading
to serious cost inefficiencies. Consider, for example, the
rebate scheme proposed in the report, which would involve
simultaneously subsidizing final goods that make use of CFCs
while taxing CFC use. If the demand for final products using
CFCs is at all responsive to price, a policy that simultaneously
taxes the input and subsidizes the output will result in a higher
real resource cost of curbing CFC emissions than a policy that
simply taxes the input.
In addition, if a firm knows compensation of payments
will be complete (i.e., all the emissions taxes or permit fees
paid will be returned to the firm), there will be no incentive
for firms to reduce their demand for CFCs. This can be seen by
noting that, under complete compensation, choice of less
CFC-intensive technology makes a firm worse off than making no
adaption to the charge. A firm that does not attempt to reduce
its exposure to the charge by reducing the use of CFC would not
be any worse off after regulation than prior to it, since the
firm would receive compensation exactly equal to its payments.
If on the other hand, it were to reduce its charge liability by
substituting other inputs for CFCs, it would be worse off. This
is because, although its reduced payments are compensated, the
rise in its cost of production resulting from reduced use of CFCs
would not be. If compensation for CFC payments is complete,
therefore, no cost-minimizing firm will reduce its use of CFCs.
1-31
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Economic Incentives Options
Although complete compensation is an extreme example,
the preceding analysis can be generalized in the form of two
propositions. First, the effectiveness of a charge to reduce
emissions will be limited under any scheme that makes the
transfer of governmental funds to a firm a positive function of
the firm's CFC charge liability. In addition, if a partial
compensation scheme leads to firms forming differing expectations
about the proportion of their payments that will be returned by
the compensatory policy, the CFC reduction that does occur will
not be accomplished at a minimum compliance cost.
Second, unless final product demand is completely
inelastic, any scheme linking compensation to the output level of
goods using CFCs will- result in higher than necessary compliance
costs.
Lastly, if one is going to compensate firms which would
be affected adversely by an incentives policy, there is no
obvious reason why compensation should not be made for compliance
costs as well.
To sum up concerns about transfer payment compensation
techniques, another quotation from the Rand Report is useful:
"The implementation issues associated with the design
of compensated economic incentives policies should not
be underestimated. Both the basis and the formulas for
compensation raise politically sensitive and
economically complex issues. They are politically
sensitive because of ther obvious and direct
implications for the distribution of wealth among the
CFC user and producer industries. They are economically
complex because it is no simple matter to devise speci-
fic rules that prevent distortions in the policy that
might thwart the economic incentives it is intended to
create." [Rand, 1980, p.239]
1-32
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Economic Incentives Options
d. Market Structure Effects of Regulatory Design
If markets are purely competitive, it should be possible
to establish a quota in the form of marketable permits that will
produce the same regulatory results as the imposition of a tax on
a pollutant. However, when the markets affected by regulation
are not purely competitive, the equivalence between taxation and
permits breaks down. Under this circumstance, a permit system
can have a variety of undesirable effects. As an example, when a
firm's purchase of permits is sufficiently large to affect the
price at which the permits are obtained, large firms will find it
profitable to engage in more costly substitutions for CFCs than
small firms. This would result in the compliance cost of
attaining any CFC abatement target being greater than it would be
when taxation is used.
The second broad problem of a permit system is that it
may unavoidably lead to a greater reduction in the use of CFCs
than would be socially desirable. This possibility arises under
a permit system because the requirement to possess permits to
produce (or use) CFCs could be exploited by firms to attain or
enhance monopoly power in their product markets.
As an example, assume the quantity of permits issued by
the government is equal to the socially optimal use of CFCs. If
socially optimal production is smaller than the output level that
would maximize industry profits, each firm will have a profit
incentive to produce up to the limit of its permits holdings,
regardless of the distribution of permits among producing firms.
In this situation, therefore, although the distribution of
permits probably will be of interest to each firm, it is of no
obvious importance from the perspective of efficient regulation.
1-33
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Economic Incentives Options
If on the other hand, the socially optimal production of
CFC were to exceed the aggregate output that maximized industry
profits, a potential would exist for a firm to profit from
hoarding some of the permits it acquired, rather than producing
up to the limit of its permit holdings. In effect, permits could
be used as a means of profitably restricting output, with the
result that CFC use would be reduced more than would be in the
public interest.
There are a number of devices that might be used to
prevent a permit system from being used to increase industry
concentration, but it is not obvious that any mechanism can be
completely effective without at the same time adding further to
the cost of regulation. Therefore, before adopting a permit
system to regulate CFCs, the ways in which the system might lead
to socially harmful industry concentration, and the steps that
might be taken to mitigate such developments, should be carefully
examined.
e. Risk Trade-offs
As with mandatory controls, economic incentives options
imposed only on CFCs would result in emission reduction activi-
ties (e.g., product or process substitution) that bring with them
other risks - to the worker, the consumer or the environment (See
Section V - Risks) . If the case made by Rand is correct that a
"moderate" economic incentives level will result in more
elimination of CFC emissions than mandatory controls, then the
risk "created" by incentives options likely will be greater than
that from mandatory controls. The degree of risk resulting from
the imposition of any regulatory option must be compared to the
risk the option is being employed to reduce.
1-34
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Economic Incentives Options
f. Diminishing Returns
From Rand's summary of the potential for, and costs of,
emission reduction under economic incentives options, it is clear
that successive price increments of the same amount yield even
smaller increments in emissions reduction. Further as the CFC
price rises, compliance costs rise far more rapidly than reduc-
tions in emissions. The same situation occurs under mandatory
controls — the first pounds of a pollutant reduced are the
cheapest.
What is worthy of comment is the steepness of the curve.
Clearly, there are practical economic limits for incentives
options. In addition, it should be noted that the steep rise in
compliance costs excludes transfer payments.
1-35
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Economic Incentives Options
5. OPTION IMPLEMENTATION AND ADMINISTRATION ISSUES
a. Uncertainty Concerns
The underlying uncertainty on regulatory costs and
benefits [See section 3] will lead regulated firms to recognize
the possibility that the initial policy may be subject to
significant changes to correct for regulatory error. This leads
to a second uncertainty issue.
One of the arguing points for economic incentives
options is their flexibility, i.e., they can be rapidly adjusted
in severity up or down to reflect a changing environmental risk
or degree of policy goal attainment. Unfortunately, this very
flexibility gives cause for concern.
If a tax or quota were adopted, there needs to be a
rationale for the level imposed and for future possible
adjustments. The rationale must be equally well understood by
the regulators and regulated industries alike. Industry needs to
know the parameters and logic of the system under which it must
work if it is to plan and respond satisfactorily to the
environmental objective. A control system should not be prone to
dramatic swings due to vulnerability to political pressure or
changing policymakers.
One of the attractions of command and control options is
that they generally are established only after fairly extensive
information exchanges, deliberations and challenge — with the
consequence that what ultimately is promulgated tends to remain
in place sufficiently long that operational and investment
decisions can be made with a reasonable expectation of payback.
1-36
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Economic Incentives Options
"In contrast, firms may perceive tax rates or quota
levels as highly variable, subject to regulatory whim or
political manipulation. If so, firms might be reluctant
to undertake long-term investments that would reduce
emissions for fear that future regulatory action would
make the investment obsolete or reduce its
cost-effectiveness. Thus, establishing and maintaining
long-range policy goals can contribute to the success of
an economic incentives policy strategy." [Rand, 1980,
p. 242].
The effect of uncertainty is also discussed in Section VII.
b. Mechanics of Implementation
Because there is little or no practical experience with
economic incentives regulatory options as designed by Rand, the
report left unanswered numerous "how to" questions. As noted
elsewhere, EPA has not answered any of the questions in its
economic incentives proposals in the ANPR. Again, preparation of
a grid would help identify the concerns which must be addressed
and aid the evaluation of the pros and cons of the alternative
solutions.
Some of the questions which need to be addressed are:
• Who would set the tax or control the permits?
• What would be the control mechanism? What records
and auditing would be required?
• When would levels be set? How would they be phased
in? How far in advance and for what duration would
levels be set for?
• What notification procedure would precede auctions
or changes in the levels of permits or taxes?
1-37
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Economic Incentives Options
• If permits were selected, what recourse would be
available to those missing the allocation or
auction, or for new entries?
c. Legal Issues (Also See Section III)
i. Taxes
It is clear that administrative agencies have no
constitutional authority to levy a tax. Any effort by the EPA to
impose a tax could be met with a successful constitutional
attack. Thus, if EPA decides a tax is the preferred method of
regulating CFCs, it will be necessary to go to Congress to secure
passage of a tax bill.
ii. Marketable Permits
The Rand Report and EPA in the ANPR set forth two
alternatives for distributing CFC permits. The first involves
EPA setting the total CFC emissions limit, and then granting
permits based on users' percentage of the total emissions prior
to EPA limitation. The second is to sell the permits at an
auction. There are different legal concerns with respect to the
two alternatives:
Allocation - This would require EPA to deter-
mine each user's relative market share and then
grant permits accordingly. Aside from the
antitrust implications of using market share,
and the natural reluctance of firms to release
such sensitive information, it is difficult to
see how EPA could reconcile the share numbers,
without accusations and perhaps challenges of
unfairness.
1-38
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Economic Incentives Options
Auction - It is possible that if EPA chose to
impose an auction system to control CFC pro-
duction, the Agency would be vulnerable to
challenge on the grounds that the system was in
effect a "tax" on the production of CFCs. As
noted earlier, EPA does not have the authority
to impose a tax.
Regardless of which implementation system were selected or the
associated legal questions, serious problems emerge from the
legal ramifications of how a marketable permit system would
operate in practice.
The Rand Report and EPA discuss the possibility of
futures markets developing for permits, or sales of permits
through a national securities exhange or through a commodities
market, and of Federal regulation of such markets. The more
sophisticated the trading in permits becomes, the more likely it
is that Federal securities laws will become involved. The
precise nature of this involvement, and the impact the
interaction between Federal securities and environmental laws
will have on the system, is a complex issue and requires further
examination.
Lastly, the Rand Report states that collusion among
firms and predatory behavior in the permit marketplace will not
be unacceptable because neither would diminish the emission-
reducing potential of a permit policy. Nevertheless, this
potential must be examined in depth because of antitrust
questions. A marketable permit system such as proposed by Rand
could be noncompetitive in nature. The pro-competitive policies
of the antitrust laws are important national objectives that
cannot reasonably be ignored by EPA. The impact to the proposed
permit system could be contrary to the policy objectives of the
antitrust laws.
1-39
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X. APPENDIX J
CHLOROFLUOROCARBON
PRODUCTION AND EMISSIONS
J-l
-------
CFC PRODUCTION AND EMMISSIONS
Table of Contents
Page
1. INTRODUCTION 3
2. CURRENT U.S. CFC PRODUCTION 4
3. PROJECTED GROWTH OF U.S. CFC PRODUCTION 6
4. WORLD CFC EMISSIONS AND GROWTH 8
5. U.S. SHARE OF WORLD CFC PRODUCTION 11
6. ESTIMATES SHOULD BE BASED ON CALCULATED 12
OZONE DEPLETION POTENTIAL FACTORS-PERMIT
POUNDS, NOT CFC POUNDS
7. SUMMARY 16
J-2
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CFC Production and Emissions
1. INTRODUCTION
Two of the Agency's stated major justifications for a
decision to regulate now are that: 1) world production and use
of CFCs have essentially offset the reduction created by the
U.S. aerosol use ban, and 2) estimates of future growth in world
production and use make the potential problem of ozone depletion
even more severe than the cited model calculations, because
these calculations are based on an assumption of constant
emissions at 1977 rates. Thus, careful examination of the
Agency's production and use estimates, both current and for
future years, is of great importance to the underlying question
of risk and the need for immediate regulation.
In the ensuing analysis and discussion we find the
Agency's estimates in the ANPR to be inconsistent with available
data and illogical opposite recent and projected trends. This
is particularly disconcerting in light of our efforts
[Du Pont, 1978; Masten, 1980] to provide thorough and
accurate data to the Agency and its contractors in hopes that
such cooperation would result in a reliable, shared data base on
which deliberations and decisions could be made.
It should be noted that a meaningful discussion of
EPA's treatment of current and projected production and emission
figures for CFCs in the U.S. and the world is difficult due to
the irreproducibility of EPA'S numbers. The sources referenced
in the ANPR offer either no numbers or substantially different
numbers than those used by EPA for the categories discussed.
1TheAgency issued a memo from Carroll Bastion to E. Douglas
Kenna on 12/11/80 which contained analyses of how EPA reached
some of its estimates, and which acknowledged numerous errors in
previously cited estimates. Receipt of this memo on 12/15/80
did not permit incorporation of analysis of its contents in
Du Pont's ANPR response. It will be responded to at a later
date, and this response should be considered part of Du Pont's
ANPR comments.
J-3
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CFC Production and Emissions
2. CURRENT U.S. CFC PRODUCTION
In the ANPR, it is stated:
"Production of CFCs in the United States is
expected to grow at a 7 percent annual rate [in
the absence of any further regulation] from 600
million pounds in 1980 to 1.2 billion pounds in
1990, according to the report on CFC control
written for EPA by the Rand Corporation."
The cited Rand Report provides the following estimates for
CFC production of CFC-11, 12, 22 and 113 (quantities in
106 Ib.) :
1976 1990
[Rand, 1980, Table 3.1] [Rand, 1980, Table 3.3]
Total Minus Total Minus
Total CFC-22 Total CFC-22
Production 891 721 1147 762
Sales for Non-
aerosol use* 474 357 957 692
*A term defined as production minus aerosol use and
"minus internal use, exports, packaging and tran-
sport emissions, and certain limited refrigeration
uses."
The first thing to be noted is that Rand makes no
estimates for 1980. Second, the estimates Rand does make (1976)
include the use of CFC-22 as an intermediate which, because it
is a non-emitting use, should be subtracted from all production
and emissions estimates.
J-4
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CFC Production and Emissions
Actual production of the five major CFCs in 1980 is
estimated by Du Pont to be approximately 755 million pounds,
excluding CFC-22 used as an intermediate. Over the last
three years Du Pont annually has analyzed data published by the
United States International Trade Commission for CFCs-11, 12 and
22, and supplemented these data with Du Font's estimates of
CFC-113 and 114 production. Table 1 below shows production for
the years 1977, 1978 and 1979 by product and by total.
TABLE 1
U.S. CFC PRODUCTION
(106 LB.)
Year CFC-11 CFC-12 CFC-22 CFC-113 CFC-114 TOTAL
25 830
29 806
18 755
1977
1978
1979
213
194
173
358
327
287
134
156
153
100
100
124
It is quite obvious from this data and preliminary
estimates for 1980 sales, that production of the five major CFCs
in 1980 will substantially exceed the 600 million pound figure
put forth by EPA.
2
CFC-11, 12, 22, 113 and 114.
production figures for CFC-22 in this Appendix
exclude CFC-22 use as an intermediate. We estimate this
use in 1979 was approximately 60 million pounds. There-
fore, total CFC production in 1979 was approximately 815
million pounds. This figure was used in Section II-CFC
Uses and Essentiality - as the basis for calculating the
approximate percentages of total CFC production by end
use application.
J-5
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CFC Production and Emissions
3. PROJECTED GROWTH OF U.S. CFC PRODUCTION
EPA's projection that U.S. CFC production will reach 1.2
billion pounds by 1990 seems questionable. Rand did estimate
1990 U.S. production at 1147 million pounds, but this must be
put into context. As noted in the previous section, the
estimate is overstated because it includes CFC-22 production
which is used as an intermediate, a non-emitting use.
Additionally, the situation at the time of Rand's work
(1978-1979) and the underlying assumptions made by Rand at that
time are quite different than today's realities.
Rand assumed in its base case that there would be no
further regulations and, implicitly, no threat of further
regulation. In reality, of course, the threat of regulation of
the non-aerosol uses of CFCs has been keenly felt over the last
few years and EPA's pronouncements over the past year have only
intensified this concern. Regardless of the level of regulatory
activity on CFCs by EPA, until such time as the validity of the
depletion theory is resolved, CFC-users will continue to be
highly uncertain over the future for CFCs. Such concern will
have a dampening effect on future growth -- users will be
reluctant to commit to new products or processes dependent upon
an unsure future availability of CFCs. Only a favorable
resolution of the theory, with an attendant removal of any
future regulatory threat would result in actual growth
approaching Rand's projections.
This uncertainty also affects the CFC producers to a
degree which further throws into question the appropriateness of
EPA using Rand's artificial base line estimate as a real world
forecast. Under the base line numbers, substantial production
capacity would have to be added for the U.S. production to reach
1.2 billion pounds of CFCs. But it is highly improbable that
J-6
-------
CFC Production and Emissions
business managers would make the significant capital investments
required to build new capacity (generally about $0.85 per pound
of annual capacity) due to the great uncertainty whether such
expansion could return its investment in the face of possible
further major CFC regulation. We are aware of no indications
that substantial additional CFC capacity has been initiated or
planned.
The combination of erroneous base figures for 1980 CFC
production, coupled with an unrealistic estimate of 1990
production given the current regulatory climate, makes the 7
percent growth rate projected by EPA unreasonable and
unsupportable.
J-7
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CFC Production and Emissions
4. WORLD CFC EMISSIONS AND GROWTH
EPA states in the ANPR:
"Total world emissions, in the absence of any
further regulation, are projected to grow at a 9
percent annual rate over the next decade, from 1.5
billion pounds in 1980 to 4.5 billion pounds in
1990, according to EPA analysis of data collected
for the Chemical Manufacturers Association."
There are several problems with this statement:
a) First, these numbers represent another example of
EPA's careless treatment and publication of numbers. If one
assumes that 1980 world emissions will total 1.5 billion pounds
and then projects a 9 percent annual growth for 10 years, the
result is 3.55 billion pounds, not 4.5 billion pounds.
[1.5 x (1.09)10) = 3.55]
b) Second, EPA alludes to an analysis of data provided by
the Chemical Manufacturers Association (CMA) to lend credence to
their figures. Table 2 on the next page shows the CMA data
[CMA, 1980b] for the years 1974-1979 for CFC-11 and 12, the
only CFCs consistently reported on by CMA.
J-8
-------
CFC Production and Emissions
YEAR
1974
1975
1976
1977
1978
1979
TABLE 2
CHEMICAL MANUFACTURERS' ASSOCIATION
WORLD PRODUCTION OF CFCS-11 and -12
(106 LB.)
CFC-11
833
714
772
732
708
666
CFC-12
TOTAL
1045
923
992
936
913
882
1878
1637
1764
1668
1621
1548
Compound Annual Rate: -3.8 percent
Du Font's estimate of world production of the five major CFCs is
shown below in Table 3.
TABLE 3
YEAR
1977
1978
1979
CFC-11
732
708
666
WORLD
CFC-12
936
913
882
CFC PRODUCTION
(106 LB.)
CFC-22
226
252
289
CFC-113
155
175
201
CFC-114
40
47
40
TOTAL
2089
2095
2078
Compound Annual Rate: -0.26 percent
J-9
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CFC Production and Emissions
It is difficult, if not impossible, to understand how
EPA could interpret the available data, which shows a declining
trend for world production, as supporting their claim of a 9
percent growth rate for the next decade.
c) Third, the European Economic Community (EEC) has
recently called for a 30 percent reduction of CFC use in
aerosols from 1976 levels by December 1981. EPA states in the
ANPR that EEC members accounted for 39 percent of the world
production of CFCs in 1977. Therefore, it seems even more
unlikely that world growth could approach the 9 percent level
claimed by EPA.
d) Fourth, similar to the U.S. situation, such growth
of world CFC production would require major capacity additions,
which, in turn, would require major new capital investments in
manufacturing facilities. Although other countries have not
taken the severe actions being pursued by EPA, bans or mandated
reductions in aerosol use of CFCs by some nations, coupled with
an EEC moratorium on new capacity for CFC-11 and 12, have
generated sufficient concern to make investments in major new
capacity prior to resolution of the science improbable.
J-10
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CFC Production and Emissions
5.
U.S. SHARE OF WORLD CFC PRODUCTION
In 1971, the U.S. share of world production of CFCs
was about 51.5 percent [IMOS, 1975] . Since that time, U.S.
share has steadily declined. Table 4 below (Du Pont estimates)
compares the U.S. production of CFCs to the world total,
illustrating the ongoing decline in U.S. share.
TABLE 4
U.S. SHARE OF WORLD CFC PRODUCTION
CFCs-11, 12, 22, 113, 114
(106 LB.)
YEAR
WORLD
PRODUCTION
U.S.
PRODUCTION
1977
1978
1979
2089
2095
2078
830
806
775
39.7
38.5
36.3
As discussed in detail in Section VI, further
regulation of U.S. production and use alone cannot solve the
problem, if it exists. In the ANPR, EPA's Table 3 graphically
illustrates that further unilateral action by the U.S. does not
significantly alter the total ozone depletion potential.
J-ll
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CFC Production and Emissions
6. ESTIMATES SHOULD BE BASED ON CALCULATED OZONE DEPLETION
POTENTIAL FACTORS - PERMIT POUNDS, NOT CFC POUNDS
In the ANPR, EPA discusses the depletion potential
factors for the different CFCs. (We provide our updated
methodology and results in Appendix G.) However, no effort has
been made by EPA to integrate this important concept into the
discussions of CFC production and emission growth. Table 5
shows the U.S. production of major CFCs for several recent years
adjusted for calculated ozone depletion potential. It is
significant that actual pounds have decreased at an annual rate
of roughly 5 percent but the rate of decline has been roughly
7.0 percent when the data is adjusted for the calculated
relative depletion potential.
Comparable analysis of the world production of CFCs is
shown in Table 6. The actual world pounds have declined at an
annual rate of roughly 0.3 percent but the relative depletion
potential adjusted pounds have declined at an annual rate of
approximately 2.1 percent.
J-12
-------
TABLE 5
U.S. CFC PRODUCTION (10 Lbs.)
ADJUSTED FOR CALCULATED RELATIVE OZONE DEPLETION POTENTIAL
(Normalized for CFC-11 = 1.0)
i
H-
U)
CFC
Actual
fc Lbs.
CFC-11 213
CFC-12 358
CFC-224 134
CFC-11 3 100
CFC-114 25
TOTAL 830
1977
Calculated
Relative Adjusted
Depletion Lbs.
Potential
1.00 213
0.84 301
0.03 4
0.82 82
0.61 15
615
Actual
Lbs .
194
327
156
100
29
806
Approximate Annual Growth Rates:
• Actual Pounds ~-5
• Calculated Ozone
Depletion Potential
Adjusted Pounds ~- 7
1978
Calculated
Relative Adjusted
Depletion Lbs.
Potential
1.00 194
0.84 275
0.03 5
0.82 82
0.61 18
574
percent
percent
1979
Calculated
Actual Relative Adjusted
Lbs. Depletion Lbs.
Potential
173 1.00 173
287 0.84 241
153 0.03 5
124 0.82 102 £
**i
18 0.61 11 °
»d
n
755 532 £
0
rt-
H-
o
3
0>
3
a
w
3
M-
CO
CO
»-••
O
3
Excluding CFC-22 used as Intermediate
-------
TABLE 6
WORLD CFC PRODUCTION UO Lbs.)
ADJUSTED FOR CALCULATED RELATIVE OZONE DEPLETION POTENTIAL
(Normalized for CFC-11 = 1.0)
CFC
Actual
# Lbs.
CFC-11 732
CFC- 12 936
CFC-225 226
CFC- 11 3 155
CFC-114 40
TOTAL 2089
1977
Calculated
Relative Adjusted
Depletion Lbs.
Potenti al
1.00 732
0.84 786
0.03 7
0.82 127
0.61 24
1676
1978
Actual
Lbs .
708
913
252
175
47
2095
Approximate Annual Growth Rates:
• Actual Pounds ~-.3
• Calculated Ozone
Depletion Potential
Adjusted Pounds ~- 2.
Calculated
Relative Adjusted
Depletion Lbs.
Potential
1.00 708
0.84 767
0.03 8
0.82 144
0.61 29
1656
percent
1 percent
1979
Calculated
Actual Relative Adjusted
Lbs. Depletion Lbs.
Potential
666 1.00 666
882 0.84 741
289 0.03 9
201 0.82 165 n
40 0.61 24 0
*d
ri
2078 1605 a
o
rt
H-
O
3
0)
QJ
W
3
H-
cn
CO
H-
0
en
Excluding CFC-22 used as Intermediate
-------
CFC Production and Emissions
Clearly, a production decrease of the CFCs of higher
calculated ozone depletion potential results in the total ozone
depletion potential adjusted pounds declining more sharply than
the decline in actual pounds. The regulatory initiatives
elsewhere in the world are focusing on CFC-11 and CFC-12 (the
very compounds with the greatest calculated potential for ozone
depletion) as aerosol propellants (e.g., the EEC 30 percent
cutback).t Therefore, actual future production of CFCs should
continue to overstate the potential for calculated future ozone
depletion. This important fact must be considered by EPA when
projecting future production and emission figures, since any
ozone depletion occurring will be proportional to the ozone
depletion potential adjusted pounds, not the actual pounds of
production or emissions. EPA should not use one set of numbers
(ozone depletion potential pounds or permit pounds) to make its
case in one argument but switch to a second set (actual pounds)
to make its case in another.
J-15
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CFC Production and Emissions
7. SUMMARY
In summary, EPA's analysis of production and emissions
is inaccurate/ misleading and unsubstantiated. The above com-
ments show that:
• 1980 U.S. CFC production (excluding CFC-22 used as
an intermediate) will approach 755 million pounds,
not 600 million pounds.
• It is very improbable that U.S. CFC production
would grow at 7 percent through 1990.
• It is unreasonable to project a 9 percent growth
rate for world CFC emissions.
• U.S. share of CFC production has been declining,
• The calculated potential for ozone depletion must
be considered when analyzing and projecting the
production and emissions of CFCs.
J-16
-------
X. APPENDIX K
INDUSTRY FUNDED FLUOROCARBON RESEARCH PROGRAM -
EFFECT OF CHLOROFLUOROCARBONS ON THE ATMOSPHERE
(PREPARED BY CHEMICAL MANUFACTURERS ASSOCIATION
FLUOROCARBON PROJECT PANEL)
Note: References cited in Appendix K are internal to this
appendix and are not necessarily listed in Section XI
"BIBLIOGRAPHY."
K-i
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CHEMICAL MANUFACTURERS ASSOCIATION
Fluorocarbon Research Program
Effect of Chlorofluorocarbons on the Atmosphere
Revision No. 14
The Fluorocarbon Research Program, sponsored and funded by
the industry is summarized in Revision No. 14, November 30, 1980.
Italics indicate developments since Revision No. 13.
For additional information, please contact the investigator
or CMA. Please note the new CMA address.
Sincerely,
^ C. Van Horn
/ 'Administrator
('/' Fluorocarbon Program
v Telephone: 202/887-1194
Attachment: Revision No. 14
November 30, 1980
K-ii
Formerly Manufacturing Chemists Association—Serving the Chemical Industry Since 1872.
2501 M Street, NW • Washington. DC 20037 • Telephone 202/887-1100 • Telex 89617 (CMA WSH)
-------
SUMMARY
Research Program on
EFFECT OF CHLOROFLUOROCARBONS ON THE ATMOSPHERE
Sponsored by: The Chlorofluorocarbon Industry
Prepared by: B. Peter Block
Hillel Magid
Richard B. Ward
Distributed by: Chemical Manufacturers Association
2501 M Street, N.W.
Washington, D. C. 20037
(Originally Issued: September 26, 1975)
Revision No. 14: November 30, 1980
K-iii
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TABLE OF CONTENTS
Page
Summary and Recommendations 1
The Industry-Sponsored Program 2
Assessment of Uncertainties 4
Goals of the Industry-Sponsored Program 5
Efforts to Resolve Current Uncertainties 7
Tables:
1 Chlorofluorocarbon Manufacturers Represented on
the CMA Technical Panel on Chlorofluorocarbon
Research 10
2 Chlorofluorocarbon Research Program - Financial
Summary 11
3 Chlorofluorocarbon Research Program - Types of
Research Activities, Summaries 12
A. Reaction Rate Constant Measurements 12
B. Source and Sink Studies 17
C. Laboratory Studies Related to Potential
Atmospheric Measurements 22
D. Tropospheric and Stratospheric Measure-
ments 30
E. Modeling 38
F. Other 41
G. Consultants 43
4A CMA Projects - Work Completed . 44
4B CMA Projects - Work in Progress 53
5 Publications from Work Supported by Chlorofluoro-
carbon Manufacturers 57
Index to Table 3 by Investigator and Project Number 73
K-iv
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SUMMARY
Research Program on
EFFECT OF CHLOROFLUOROCARBONS ON THE ATMOSPHERE
Sponsored by the Chlorofluorocarbon Industry
Administered by the Chemical Manufacturers Association
(Originally Issued: September 26, 1975)
Revision No. 14: November 30, 1980
This summary describes work supported by the manufacturers
of chlorofluorocarbons (CFCs, sometimes called fluorocarbons)
in an attempt to assess the possible impact of these chemicals
on the environment and, in particular, on the stratospheric
ozone layer.
Summary and Recommendations
In 1972 the CFC manufacturers began supporting a program to
investigate the effects of CFCs on the environment. This program
has been expanded greatly to help determine the extent, if any,
to which these compounds may affect the stratospheric ozone layer.
Industry and government-sponsored scientists working on the
halogen-ozone problem have cooperated effectively. Continuation
of this cooperation ie-essential, with special attention to
providing periodically updated summaries of research priorities,
programs, and results, together with critical analyses of the
reliability and significance of the data.
The programs now under way to develop methods for determin-
ing the ozone changes that are actually occurring (as opposed to
hypothetical or calculated ozone changes), to determine the
actual tropospheric lifetimes of CFCs 11 and 12 (now assumed to
K-l
-------
be infinite in most models), and to resolve important questions
about key stratospheric species—0-, CIO, total chlorine—will
lead to a much better understanding of the effect of the CFCs
on stratospheric ozone.
The industry position continues to be:
The ozone depletion theory warrants serious concern
and continuing investigation.
The international scientific consensus necessary to
resolve this issue must be based on convincing measure-
ments and evaluations, not theory.
Convincing experimental evidence can be obtained to
verify or disprove the theory quantitatively.
There is time to perform these necessary experiments
without significant risk to the health and welfare of
the population.
The Industry-Sponsored Program
In July of 1972, E. I. du Pont de Nemours & Company issued
to CFC manufacturers worldwide an invitation to a "Seminar on
the Ecology of Fluorocarbons." Its purpose was to establish a
technical program because, as stated in the invitation,
"Fluorocarbons are intentionally or accidentally
vented to the atmosphere worldwide at a rate
approaching one billion pounds per year. These
compounds may be either accumulating in the
atmosphere or returning to the surface, land or
sea, in the pure form or as decomposition prod-
ucts. Under any of these alternatives, it is
prudent that we investigate any effects which
the compounds may produce on plants or animals
now or in the future."
K-2
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Representatives of 15 companies attended the meeting,
agreed that such a program was important, and established and
funded a CFC research program under the administration of the
Chemical Manufacturers Association (CMA). Thus, in 1972, with
no evidence that CFCs could harm the environment, the producers
of these chemicals agreed that there was a need for more infor-
mation and proceeded to act.
The CFC producers supporting this program (see Table 1,
p. 10) represent almost the total free world production of CFCs.
The research is directed by the CMA Fluorocarbon Project Panel
with one member from each supporting company. This Panel meets
regularly to review progress on current research, evaluate new
proposals, and exchange data with contractors, with government
agencies, and with other scientists. A significant fraction of
the support for this program comes from European CFC producers,
and two meetings per year are held in Europe.
Publication of the Rowland-Molina hypothesis in 1974 iden-
tified a potentially serious problem, so the CMA research program
was expanded considerably. The CFC-ozone relationship attracted
the attention of many scientists in academic and government lab-
oratories, legislative and regulatory bodies, and the press.
CMA's program is concentrating on research most likely to answer
the critical question: to what extent will CFCs affect the
stratospheric ozone layer?
To strengthen the overall effort to find the answer, CMA
has attempted to coordinate its efforts with others working on the
same or related problems such as the Supersonic Transport and the
space shuttle. All of these problems concern the federal govern-
ment, and interactions with a number of agencies have been espe-
cially helpful in:
1. Taking advantage of the knowledge and experience
gained in the Climatic Impact Assessment Program;
2. Coordinating funding of programs addressing the
halogen-ozone problem;
3. Planning joint experiments with government research
groups; and
K-3
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4. Helping to set priorities for industry-sponsored
research.
About 355 research proposals have been reviewed to date,
and projects totaling about $9.5 million have been funded (see
Table 2, p. 11). Calendar 1981 commitments are expected to be
almost $2 million, and total expenditures through 1981 will be
over $11 million.
Assessment of Uncertainties
Two groups in the United States were charged during 1975
with looking exclusively at the scientific aspects of the halo-
carbon-ozone problem and making recommendations for further work.
In May 1975 the government's Interdepartmental Committee for
Atmospheric Sciences (ICAS) made recommendations for research and
monitoring programs. In July 1975 the Panel on Atmospheric Chem-
istry of the National Academy of Sciences (NAS) identified a
number of areas in which relevant data are nonexistent, frag-
mentary, or insufficient and in September 1976 issued a final
report containing recommendations for pertinent studies. Its
parent committee, the NAS Committee on Impacts of Stratospheric
Change, then recommended that up to two years be allowed before
a decision was made on the necessity for restrictive action.
The Clean Air Act Amendments of 1977 (U. S. Public Law 95-95)
established the U. S. Environmental Protection Agency (EPA) as the
agency responsible for assessing the probable effect of CFCs on
the ozone layer. Other U. S. agencies are given various responsi-
bilities in the scientific effort required to support any decisions,
and the EPA is required to rely on the NAS for advice on the status
of the science. In November 1979 the NAS Panel on Atmospheric
Chemistry and Transport issued its latest report on the status of
the CFC-Ozone theory.
Significant additions to pp. 4 - 9 since the last revision
are italicized.
K-4
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Goals of the Industry-Sponsored Program
The emphasis of the CMA-administered industry program has
been overwhelmingly in the major areas recommended for further
study by the NAS Panel and ICAS. The industry-sponsored program,
therefore, aims to fill in the most important gaps in existing
scientific knowledge. The only major area not in the CMA program
is acceleration of ozone monitoring, which can be accomplished
more appropriately by governmental and international agencies.
In addition, the CMA program has included work to correlate UV
radiation reaching the ground with ozone measurements and to
improve the statistical treatment of ozone data so that very
small abnormal changes can be detected in a much shorter period
of time than was previously believed possible.
The current CMA research program is consistent with the
needs and tasks identified recently by the NAS*:
Specific tasks include measurement of the wave-
length dependent quantum yields [photochemical
reaction rates] and branching ratios [distribu-
tion between alternative reaction products] of
the stratospheric photolysis of species such as
03, C10N02/ HOC1, and N03> [Page 45].
[Studies of] stratospheric chemical processes
[such as] those with negative activation energies
and incomprehensible A factors [currently unex-
plainable differences between theoretically and
experimentally derived mathematical expressions
for the reaction rates]. Reactions of H02 species
are a particular, but not the only, example of
this need. [Page 45].
*Panel on Stratospheric Chemistry and Transport, Committee
on Impacts of Stratospheric Change, National Research Council,
"Stratospheric Ozone Depletion by Halocarbons: Chemistry and
Transport", National Academy of Sciences, Washington, D. C.,
November, 1979. Added material is identified by square brackets
[ ], as are the pages in the reference where the needs and tasks
appear.
K-5
-------
Laboratory studies of the decomposition of [CFCs]
on desert sand should be designed to provide data
from which atmospheric lifetimes could be directly
calculated. [Page 72].
In several cases, simultaneous measurements of
photochemically related species (and perhaps
solar flux) are needed, ... [Page 100],
In particular, in the case of the anthropogenic
halocarbon compounds, the global spatial concen-
tration distribution and the temporal increase
need to be better determined. F-ll, F-12, and
CH^CCl-j are especially important. More F-21
measurements should be carried out. [Pages 133,
134].
A total chlorine concentration measurement would
be of great value. [Page 134].
Reduction of these ranges of uncertainty will
require more sophisticated and carefully ana-
lyzed 2-D and, ideally, 3-D models [Page 169],
The current CMA program also is consistent with the June
1978 recommendation of the Royal Society Study Group,* which
summarized their position as:
"The surface release of chlorofluoromethanes was
considered to be a potential, but so far unverified,
long-term hazard which requires considerable further
research. Particular attention must be paid to:
(a) the investigation of possible tropospheric
sink processes, since these can have a
major effect on predicted effects on strato-
spheric ozone,
*Royal Society Study Group, Final Report, June 28, 1978,
"Pollution in the Atmosphere - V. Problem Areas: Scientific
Priorities for Research."
K-6
-------
(b) the simultaneous measurement of key reactants,
transient intermediates and products in the
stratosphere in order to test the model hypoth-
esis and to direct future research, and
(c) the development of 2- and 3-dimensional models
to represent more realistically motions in the
atmosphere.
It was agreed that there is no need for hasty action and
that 3-4 years can be allowed for the research programmes
currently in train to produce their results."
Efforts to Resolve Current Uncertainties
There are presently several discrepancies and/or uncertain-
ties that the CMA program is trying to resolve. Its strato-
spheric measurement program includes the collection of more data
on total Cl, ClO, and HCl to determine the correctness of current
indications that their concentrations do not fit predicted pro-
files. The observation by others that high CIO concentrations
unexpectedly coexist with normal odd oxygen levels emphasizes
the need for more information on the concentration of chlorine
species. Simultaneous measurement of several species is neces-
sary to provide a rigorous test of the models, so the strato-
spheric measurement program is also aimed at simultaneous
measurement of important chemical species that are known or
believed to be present in the stratosphere.
In addition to in. situ stratospheric measurements during
balloon flights, the CMA program includes an effort to develop
ground-based monitoring techniques for some of the important
atmospheric species. HCl and HF now are routinely measured
from the ground at Jungfraujoch in Switzerland. Although a
ground-based method to monitor CIO has been developed, its
sensitivity is as. yet insufficient for accurate measurement
of ClO. This program is continuing, and it is expected that
the sensitivity of the method will be increased by about a
factor of 7 during 1980, permitting accurate, ground-based
measurements of this important stratospheric species.
K-7
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Another goal of the CMA program is to determine the tropo-
spheric lifetimes of certain CFCs. In 1977 the CMA initiated a
program to determine the tropospheric lifetimes of selected
compounds. Five stations have been set up, three in the northern
hemisphere (Lovelock and Simmonds, Rasmussen) and two in the
southern (Rasmussen), to measure the concentrations of CFCs 11 and
12 and other important species several times a day. Workup of the
analytical data, including incorporation of data on meteorological
conditions at each site, is being carried out under the direction
of CMA modeling contractors (Cunnold, Alyea, Prinn). This program
may require a period of three or more years to yield definitive
results.
The CMA program also seeks to measure rates for those reac-
tions for which the rates are not well established, measure the
ultraviolet and infrared spectra of compounds that may be present
in the stratosphere, and search for chemistry that has not yet
been included in present atmospheric models. Measurements made
thus far have demonstrated the significance of ClONO-, which was
not originally included in stratospheric models, and have pointed
to the probable importance of HOC1 in stratospheric chemistry.
The program also funds general studies of H02 chemistry, which
led to the revision of the rate constant for the reaction of H02
with NO and essentially eliminated nitrogen oxides as suspected
ozone depleters. Another study in progress is the investigation
of the formation of higher chlorine oxides.
Model evaluation and improvement is another facet of the CMA
program. One objective is to determine to what extent computer
models represent the "real world", and a second is to improve
models in such matters as the diurnal nature of solar radiation
and extension to two-dimensions. One value of two-dimensional
models is that they permit description of atmospheric species in
terms of both altitude and latitude and include seasonal variations,
facilitating comparison with measurements at a given location.
Statistical time series analysis is being used to detect
trends in ozone data that are small compared to observed natural
X-8
-------
variations. The method appears very sensitive and may be
capable of establishing a small ozone depletion over a long
period of time. The depletion calculated to date is larger
than the detection threshold as determined solely on a statis-
tical basis, but the extent to which other factors increase the
threshold is still uncertain. Ground-based and satellite data
are being analyzed for trends, and methods to assess the magni-
tude of long-term natural trends and instrument drift are being
investigated. This approach is especially attractive because
it seeks to answer directly the question of prime importance:
is stratospheric ozone depletion really occurring to the extent
predicted by the models?
More detail on the CMA program is given in Tables 3, 4A,
and 4B. Table 3 (p. 12} lists summaries of the projects by type
of research activity. Table 4A (p. 44) lists completed projects,
and Table 4B (p. 53) lists active projects in chronological
order of funding. Table 5 (p. 57) lists publications resulting
from industry-sponsored work. A document that relates the goals
of the individual industry-sponsored projects to the reduction
of uncertainties in the CFC-ozone question has been submitted to
EPA.*
In addition to the work supported by the CFC industry at
universities and other laboratories, there are studies underway
in the laboratories of individual member companies who have
scientists able to make significant contributions to the resolu-
tion of the problem. Three problems have received particular
attention by industry scientists: the identification and quanti-
fication of tropospheric sinks for CFCs, the application of
statistical methods to detect abnormal trends in stratospheric
ozone concentrations, and the evaluation and development of
modeling techniques.
*The Fluorocarbon Industry Research Program and Current
Uncertainties in the Ozone Depletion Theory, E. I. du Pont de
Nemours & Company, Inc., November, 1979.
K-9
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Table 1
CHLOROFLUOROCARBON MANUFACTURERS
represented on the
CMA TECHNICAL PANEL ON CHLOROFLUOROCARBON RESEARCH
Akzo Chemie bv (Holland)
Allied Chemical Corporation (U.S.)
Asahi Glass Co., Ltd. (Japan)
Australian Fluorine Chemicals Pty. Ltd. (Australia)
Daikin Kogyo Co., Ltd. (Japan)
E. I. du Pont de Nemours & Company, Inc. (U.S.)
Essex Chemical Corporation (Racon) (U.S.)
Du Pont Canada, Inc. (Canada)
Hoechst AG (West Germany)
Imperial Chemical Industries Limited (England)
I.S.C. Chemicals Ltd. (England)
Kaiser Aluminum & Chemical Corporation (U.S.)
Kali-Chemie Aktiengesellschaft (West Germany)
Mitsui Fluorochemicals Co. Ltd. (Japan)
Montedison S.p.A. (Italy)
Pennwalt Corporation (U.S.)
Rhdne-Poulenc Industries (France)
Showa Denko K. K. (Japan)
Ugine Kuhlmann, Produits Chimiques (France)
Union Carbide Corporation (U.S.)*
November 30, 1980
*Does not currently manufacture chlorofluorocarbons.
Supported the CMA program through June, 1977.
K-10
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Table 2
CHLOROFLUOROCARBON RESEARCH PROGRAM
Administered by
Chemical Manufacturers Association
Financial Summary
Type of Activity8
A. Reaction Rate Constant Measure-
ments
B. Source and Sink Studies
C. Laboratory Studies Related to
Potential Atmospheric Measurements
D. Tropospheric and Stratospheric
Measurements
E and F. Modeling and Other Projects
G. Consulting
SUBTOTAL
Administrative Expenses
TOTAL
Completed
Projects
693,796
1,825,967
1,033,082
140,403
$5,484,607
Active
Projects
Total
$ 494,016 $ 409,507 $ 903,523
1,297,343 410,091 1,707,434
427,347 1,121,143
1,249,906 3,075,873
978,594 2,011,676
42,869 183,272
$ 3,518,314 $ 9,002,921
509,714
$ 9,512,635
Individual projects are summarized in Table 4.
November 30, 1980
K-ll
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Table 3*
Chlorofluorocarbon Research Program
Types of Research Activities, Summaries
A. Reaction Rate Constant Measurements
Dr. J. W. BIRKS — University of Illinois — 75-1,
76-117A. Measurement of Reaction Rates Relevant to
the Fluorocarbon-Ozone Problem (completed).
Reaction rates were measured at various temperatures by a
discharge flow technique, and a quadrupole mass spectrometer
was used for detection of products. The reaction CIO + N02 +
M -»• C10N02 + M has the reaction rate 4.40 ± 0.66 x 10~33 exp[(1087
± 70)/T]cm6molec-2s-l for M = N2. No reaction of C10N02 with
NO, N02, 03, or HC1 was observed, indicating that these reac-
tions are unimportant as sinks for C10N02.
Reaction rates for CIO + 03 -*• OC10 + 02, CIO + 03 •»• C100 + 02,
and OC10 + 03 -»• 0103 + 02 rule out successive oxidation of
chlorine to perchloric acid based on the calculated photolysis
constant for OC10 of 7.6 x 10~2 s"1, but there is currently
disagreement on the accuracy of the calculated photolysis con-
stant.
The reaction CIO + 1^02 was not rapid enough to measure, with
no evidence for new products. The reaction Cl + ^02 •»• HC1 +•
H02 has a reaction rate between 10~^3 and 10~12 cm^molec^s"1.
The reaction Cl + ^©2 -" HC1 + ©2 (primarily, •*• HO + CIO to a
minor extent) is fast. The reaction CIO + S02 + 02 + C100 +
303 is slow.
Rate measurements on NO + 03, 0 + C10N02/ and BrO + N02 have
been studied. A 15% higher activation energy for NO + 03 •*•
N02 + 02 has been measured. Four-center reactions o-f C10C1
with Cl, 0, N, or CIO were studied by molecular beam mass
spectrometry, with reaction at the 0 atom in C10C1 indicated
in each case.
Dr. J. W. BIRKS — University of Colorado — 77-192, 78-
244, 79-276, 80-321, 80-329. Studies of Homogeneous and
Heterogeneous Reactions of Importance in the Stratosphere.
The studies that were made at the University of Illinois (75-1
and 76-117A, p. 12, and 76-117B, p. 17) are being continued.
*Significant additions since the last revision are italicized.
K-12
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Table 3 (continued)
The rate constant for the reaction CIO + H02 •* HOC1 + 02 was
found to be independent of pressure over the range 2-6 torr,
the result being k^ = (4.5 ± 0.9) x 10~12 cm3molec"ls"1. An
upper limit of 2% for the branching ratio to the alternative
products of this reaction, HC1 + 03, was established by attempt-
ing to detect ozone as a reaction product. The effect of 02
or N2 in the presence of He or Ar on the C10+ mass spectrometer
ion current at room temperature and at 245°K is also being
studied. A value for the reaction rate for 2H02 •* H202 + 02 has
been obtained, agreeing with previous measurements (3 to 4 x
10-12 cm3molec""ls~l) . The temperature dependence will be exam-
ined.
The rate constants for the reaction of HO with HOC1 and with
H02N02 will be measured using a flash photolysis-resonance fluo-
rescence technique. A quadrupole mass spectrometer operating
in the positive ion mode will be used for detection in these
reactions. The technique of negative ion mass spectrometry will
be developed for determining products and measuring the rate
constants for the following reactions: HO + H02> CIO + H02/ ClOO
+ NO, and OC100 + NO. In addition the flash photolysis products
from HOC1, ClOO, and OC100 are to be examined. The nature of
these products and the quantum efficiency with which these species
photolyze are potentially important factors in the calculation
of the ozone depletion estimate in the presence of odd chlorine.
Dr. C. J. HOWARD — National Oceanic and Atmospheric
Administration, Boulder — 76-100. Laser Magnetic
Resonance Study of H02 Chemistry (completed).
H02 reactions of stratospheric importance are being measured
using a laser magnetic resonance technique. The rate con-
stant for the reaction H02 + N02 + M f HOON02 + M is 1.5 to
2.0 x 10*31 cm6molec-2s-l. The major pathway is the production
of peroxynitric acid, a species not previously considered in
the models.
The rate constant for the reaction H02 + NO •* N02 + OH is 8 ± 2
x iQ-12 cmSmolec-is"1 at room temperature, a value about 30
times faster than the previously accepted value. The tempera-
ture dependence of this reaction has been measured.
The rate constant for the reaction between H02 and 03 is 1.4 x
10~14 exp(-580/T) cm3molec-ls-l.
The reactions of HO and H02 with ^05 appear to be very slow
and consequently not important in the atmosphere.
Dr. C. J. HOWARD — National Oceanic and Atmospheric
Administration, Boulder - 77-223. Study of CIO Chemistry
by Laser Magnetic Resonance (completed).
The rate constant for the reaction H02 + CIO •+• HOC1 + 02 is
3.3 x 10-11 exp(-850/T) + 4.5 x lO'*2lT/300)-3.7 cm3molec-ls-l
K-13
-------
Table 3 (continued)
over the temperature range 235-393°K. Thus the reaction has
a negative activation energy, indicating the possibility of
an intermediate complex. A search is in progress for 03, a
product of the alternate channel H02 + CIO •* HC1 + 03, which
would act as an odd oxygen source (cf. 79-289, p. 14).
Dr. C. J. HOWARD — National Oceanic and Atmospheric
Administration, Boulder — 79-289. Kinetic Studies
of Stratospheric Chlorine Chemistry. •
A system suitable for determining the products of many signifi
cant atmospheric reactions using tunable infrared diode laser
detection has been built.
A new method for accurately measuring U^O in the atmosphere
using a tunable diode laser has been developed. A flow system
using LMR detection has been built for measuring the rate con-
stants of important reactions at pressures and temperatures
corresponding to those actually present in the stratosphere.
Dr. M. J. KURYLO — National Bureau of Standards —
78-233. Rates of Reaction of Cl Atoms with the Primary
Products of Alkane Photooxidation (completed) .
Flash photolysis resonance fluorescence (FPRF) has been used
to establish an upper limit rate constant for Cl + OCS (1 x
10~13 cm^molec-is-l (220-3238K) ) . The reaction rate for Cl +
H2CO has been confirmed as (1.09 ± 0.4) x 10~10 exp[-(131 ±
98)/T] cm3molec-lsec-l. The rate for OH + CH3CC13 is (5.41 ±
1.84) x 10-12 exp[-(1813 ± 95) /T] cm^molec-ls-1. This lower
rate suggests higher tropospheric OH concentration. An upper
limit of. < 3 x 10~16 cm3molec-1s~1 for the reaction CH3 + 02
•* OH + H2CO at 368 °K is based on failure to detect either product.
The temperature-dependent rate for the ozone formation reaction
0 + 02 + M (M = N2, 02, Ar) has been measured, providing the
first detailed analysis for M = N2 and p2, and indicating a
weaker temperature dependence than previously assumed for 02.
The recommended value for ozone formation in air [1.07 x 1Q-35
exp(525 ± 60/T) cm6molec~2s-1] is similar to the current NASA
recommendation. Studies of atmospheric quenching of 02 (^A, V
> 0) indicate that vibrational quenching dominates over any
possible reactivity of this species in the stratosphere.
Dr. M. J. KURYLO — National Bureau of Standards — 80-307.
Reactions within the HOX Cycle.
Flash photolysis resonance fluorescence will be used to measure
rate constants for the reactions R0% + E02» BO + HO^HO^t o.nd SO
+ H202.
K-14
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Table 3 (continued)
Dr. J. N. PITTS, JR. — University of California at
Riverside — 74-2. Atmospheric Reactions of Fluoro-
carbons (completed).
Reaction rate constants have been measured for the reactions
of O^D) with CFCs 11, 12, 22, 113, and 114, and of OH with
CFCs 11, 12, and 22. The results indicate that in the strato-
sphere the reaction of O(!D) atoms with CFCs 11 and 12 is
secondary to photolysis, whereas the reaction of OH with CFC
22 is much more important than photolysis. The photooxidation
products of 11, 12, and 22 at 184.9 nm, i.e., COFCl and COF2
as appropriate, are also observed to be the products for reac-
tion with 0(lD).
Dr. J. N. PITTS, JR. — University of California at
Riverside — 77-190. Atmospheric Chemistry of Peroxy-
nitric Acid (completed).
The HOoN02 cross sections vary smoothly from 1.6 x lO'l? cm2
molec-iat 190 nm to ^ 2 x 10-20 cm2molec-l at 330 nm. The
infrared cross sections for the 802.7 and 1303.9 cm'l Q
branches of HOgN02 at 0.06 cm-1 resolution are 2.1 x 10-19
and 1.8 x 10"18 cm2molec-l, respectively.
Dr. A. R. RAVISHANKARA — Georgia Institute of
Technology — 80-295. A Study of the Reaction
of OH with CIO.
The rate constant for the overall reaction OH + CIO -»• Products
and for the branch forming HC1 + ©2 as products will be
determined in a discharge flow system. Microwave interfer-
ometry, a novel technique, will be used in determining the
concentration of HC1.
Dr. F. STUHL — University of Bochum — 77-170. Deter-
mination of the Photodissociation Process and Absorption
Cross Section of FC-11 and 12 in the Near UV (completed).
The absorption spectra of some chlorine containing methanes
(CC14, CHC13, CH2C12, CFC 13, and CFC 31) and ethanes (CFC
113, CFC 114, CFC 115, CFC 133a, and CFC 142b) and also of
N20 were determined at wavelengths around 220 nm. Some of
these spectra were obtained at both 298 and 2088K. A chemical
method was used to determine the absorption cross section
of CFC 11 at 253.7 nm and the absorption properties at wave-
lengths greater than 280 nm. It is concluded from these
experiments that the tropospheric decay rate of CFC 11 is
smaller than 10"10 s"l for homogeneous gas phase photolysis.
K-15
-------
Table 3 (continued)
Dr. G. A. TAKACS — Rochester Institute of Technology
— 77-196. Photoabsorption Cross Sections for Compounds
of Atmospheric Interest (completed).
Ultraviolet-visible absorption spectra have been measured and
solar photodissociation rates have been calculated for S02C12,
CC13N02, CF3NOC1, SOC12, S02F2, S02C1F, CH3S02C1, and CC13SC1.
A maximum photoabsorption cross section, which indicates a
long stratospheric lifetime, has been established for HCIC^.
Attempts to measure photoabsorption spectra for gaseous
ONO(S02)OH and ONO(S02)C1 were unsuccessful. Photolysis of
CFC 11 and CC14 in the presence of solid NaCl with wavelengths
longer than 300 nm results in maximums of 2.3 x 10"** and 2.4 x
10~* molec, respectively, photodissociating per incident photon
on the NaCl.
Dr. B. A. THRUSH — University of Cambridge — 75-58,
75-5811. Reactions of the H02 Radical Studied by Laser
Magnetic Resonance (completed).
The rate coefficient of the reaction 0 + H02 has been measured
for the first time. The value found, 3.5 ± 1.0 x 10-H cm3
molec-is"1 at 293°K, improves the fit of the calculated OH
profile with Anderson's recent measurements. The rate coeffi-
cient of the reaction OH + H02 has been measured based on
direct measurement of H02 and found to be 5.1 ± 1.6 x 10"H
cm3molec-ls-l at 293°K.
Dr. J. WIESENFELD — Cornell University — 76-128,
77-220. Photochemistry of Small Chlorinated Molecules
(completed).
The photochemistry of chlorine nitrate was studied by deter-
mining the yields of Cl and ClO from the flash photolysis of
C10N02. The rate of reaction between 0 and ClON02 has been
measured and is in good agreement with the literature value.
Dr. R. ZELLNER — University of Goettingen — 77-195.
Experimental Investigation of the Branching Ratio in
the O(!D) + H20 Reaction (completed).
The branching ratio in the reaction O^D) + H20 -»• 2 HO (1) and
•*• H2 + 02 .(I1) has been determined at 298°K from direct measure-
ments of HO and H2 to be 0.01 (k^/lci') (+0.005, -0.01). The
main conclusions to be drawn from this result are:
1. Reaction 1' is not an important source of H2 in the
upper stratosphere and mesosphere.
2. The reduction of mesospheric HOX through the occurrence
of reaction 1' is not large enough to account for dis-
crepancies in calculated and measured 03 concentrations.
K-16
-------
Table 3 (continued)
B. Source and Sink Studies
Dr. P. AUSLOOS — National Bureau of Standards —
77-186, 78-254. Follow up for Photodecomposition
of Chloromethanes Absorbed on Silica Surfaces (com-
pleted) .
The decomposition of CF2C12, CFC13, CH3C1, CC14, CH3CCl3,
and CH2CC12 on Tunisian sand at dilute concentrations (100
ppb - 100 ppm) has been investigated in both the presence
and the absence of light and/or moisture. Experiments with
13CCl4, 13CFCl3, and 13CF2C12 in the presence of oxygen show
that one molecule of 13cc>2 is produced per halomethane molecule
destroyed on the surface. For CH3CC13, surface destruction
leads to CH2CC12 rather than C02-
Under all conditions relative stabilities were as follows
CF2C12 > CFC13 > CC14 > CH3CC13 . Both with and without light
the rate of surf ace- induced destruction decreases rapidly with
increasing moisture content. When the chlorofluoromethanes
were exposed to sand with a moisture content in equilibrium
with laboratory air (35% humidity at 20 °C) , no decomposition
was observed. However, a sudden reduction in moisture con-
tent by 40% or more leads to a measurable destruction rate
for CC14 and
Dr. J. W. BIRKS — University of Illinois — 76-117B.
Studies of Heterogeneous Reactions (completed) .
Potentially important heterogeneous reactions were studied.
H.SO./H.O
The value of for the reaction C10N02 — — - — =-» HOCl + HON02
lies in the range 2 x 10~4 to 10"3.
Dr. M. J. CAMPBELL — Washington State University —
75-53. Chlorofluoromethane Destruction by Natural
lonization (completed) .
Laboratory measurements at high irradiation levels show large
rate constants for removal of CC14 and CFC 11. The rate con-
stant for CFC 12 is much smaller. The significance of these
results with respect to atmosphere sinks for the CFCs is
questionable.
Drs. D. M. CUNNOLD, F. N. ALYEA, and R. G. PRINN —
CAP Associates — 77-213, 78-251, 79-281, 80-323.
Coordination and Analysis of Data for the Atmospheric
Lifetime Experiment (ALE) .
The tabulated data from the five automated long-term ground
measurement stations tcf. 79-280 (Lovelock and Simmonds,
p. 19) and 79-279 and 79-263 (Rasmussen, p. 21)] are being
completed, archived, checked statistically to aid in evaluat-
ing the performance of the network, and analyzed at least
annually for trends and approximate global concentrations .
Where possible, lifetime estimates will be calculated along
with their confidence ranges.
K-17
-------
Table 3 (continued)
The 8-box tropospheric model (see Cunnold, et al., 78-252,
p. 38) has been utilized to calculate that the average trend
for CFC 11 from the five monitoring stations should be repre-
sentative of the global trend with an accuracy of at least
0.5%/yr. The 8-box model will be used to prepare other esti-
mates for the sensitivity of the ALE. Recommendations for
calibration and data reporting in ALE have been made.
Measurement precision is good for the data processed up to
June 1980. The measurement time sequence is not yet sufficient
for accurate lifetime calculations. Preliminary indications
are that CFC 11 may have a lifetime about half that expected
from stratospheric photolysis alone, but with 2 a error limits
of 7 years to infinity. Seasonal variations that correlate well
with air motions between the hemispheres are observed at all
stations.
Dr. R. J. DONOVAN — University of Edinburgh — 79-286.
Reaction of CIO with OH: A Potential Sink for C10X.
i
A laboratory investigation, using flash photolysis, will be made
of the CIO/OH reaction. Temperature and pressure dependence
and the nature of the reaction products will be determined to
elucidate further the mechanism of the reaction.
Dr. M. KAUFMAN — Emory University — 76-126, 77-197.
Studies of Compounds of Sulfur, Oxygen, and Chlorine
(completed).
The three body recombination rate constant for Cl and S02 at
2958K has been found to be 1.3 x 10~33 cm6molec~2s~1 with Ar,
2.3 x ID'33 cm^molec~2s~l with N2, and 19 x 10~33 cm6molec~2g-l
with S02. At 281°K the first and third values become 2.9 x
10~33 and 20 x 10~33, respectively. Ultraviolet cross sections
of S02C12 and HOS02C1 have been determined, and the incorpora-
tion of 36cl into sulfate-type aerosol particles has been
studied. Surface effects appear to have dominated the latter
experiment.
When OCS is added to a Cl/Cl2/Ar mixture at room temperature,
SCI"1" and SC1$ ions are detected mass spectrometrically. The
rate constant for the reaction Cl 4- OCS -»• SCI + CO is less
than 10~16 cm3molec~1s~1 at 296°K.
Dr. F. KORTE — Technical University of Munich —
77-194. Photodegradation of Chlorofluoromethanes
in the Troposphere (completed).
The photodegradation of CFC 11 and CFC 12 on silica gel and
on Mecca sand was studied with the aid of 14C-labelled com-
pounds. Whereas in the dark no change was determined with
silica gel, there was significant decomposition on the sand
with formation of 14C02 (up to 50%) . Irradiation with UV
K-18
-------
Table 3 (continued)
U>290 nm) led to 1-5% decomposition of the CPCs on silica
gel also with formation of ^CC^. Irradiation with UV was
not observed to increase the decomposition rate on sand.
The results suggest that decomposition takes place at active
sites on the surface.
Dr. M. J. KURYLO — National Bureau of Standards —
78-233. Rates of Reaction of Cl Atoms with the Primary
Products of Alkane Photooxidation (completed).
See Table 3, Section A (p. 14).
Dr. J. E. LOVELOCK — University of Reading — 75-67,
77-144. Unidentified Factors in the Fluorocarbon-Ozone
Problem (completed).
Coarse Saharan surface dust showed an unusual degree of re-
tention for CFC 11 and CC14. Investigations were made on the
relationship ,between photochemically produced atmospheric
peroxy compounds (e.g., peroxyacetyl nitrate) and the inci-
dence of skin carcinoma.
Observations on dissolved gases in the ocean were made during
the April 1977 voyage of RRS Challenger. Concentrations of
N2O in ocean and atmosphere confirmed earlier estimates of
N20 flux from the ocean.
Dr. J. E. LOVELOCK and P. G. SIMMONDS — Private —
77-193, 78-243, 79-280, 80-324. Operation of Stations in
Adrigole and Barbados for the Atmospheric Lifetime
Experiment.
Automated long-term ground measurement stations are being
operated in Adrigole (continuing the data base already col-
lected there) and in Barbados. Hewlett-Packard electron-
capture gas chromatographs are being used to collect data
for CFCs 11, 12, and 113, CH3CC13, CC14, and N20, which are
processed, tabulated, and forwarded to CAP Associates for
analysis.
Both stations are operating well with data being processed
from March 3, 1978 (Adrigole) and July 12, 1978 (Barbados).
Battery back-up protection has been installed at both stations
to minimize problems from power interruptions. Several de-
tails that are important to the continuous operation of
remote stations have been identified, and maintenance pro-
cedures are being modified appropriately. Adrigole data are
affected more by air pollution events than the other remote
stations, and techniques to handle such events are being
developed. Barbados data show the expected small variability.
K-19
-------
Table 3 (continued)
Dr. L. R. MARTIN - Aerospace Corp. — 75-81, 75-8111.
Laboratory Investigation of the Heterogeneous Inter-
action of Cl and CIO with H2S04 (completed).
A flowing afterglow apparatus was used to measure the rate of
the heterogeneous reactions of Cl and CIO with sulfuric acid,
simulating the stratospheric aerosol. The reaction rate of
Cl is too slow for its reaction to constitute a significant
sink, although rates were markedly increased by the presence
of certain metal salts in the sulfuric acid. Even at strato-
spheric temperatures the HC1 formed goes into the vapor phase.
The for CIO on H2S04/H20 substrates is 1 x 10~3 at room
temperature. These, the first examples of heterogeneous
reactions with stratospheric aerosol, are not in any models.
Dr. V. A. MOHNEN — State University of New York, Albany
— 75-64. Ion Molecule Reactions Involving Fluoro-
carbons (completed).
Ion molecule reactions between the equilibrium ion distribu-
tion formed in pure air-like gas mixtures and CFC 12 were
studied. From these investigations it was concluded that:
(1) stable CFC 12 attachments to ions ("cluster formation")
of the form H+-(H20)n, 02--(H20)n, cb3-.(H20)n, and C04~'
(H20)n do not occur; (2) dissociative charge transfer reac-
tions between H+-(H20)n and CFC 12 are not observed for all
n >2; (3) approximate rate constants for dissociative charge
transfer reactions between CFC 12 and 05~-H20 and CFC 12 and
C03~ are 3 x 10~12 cm3s~1 and <2 x KT13^cm3s~1, respectively;
(4) knowledge of time integrated rate constants for atmos-
pheric negative ions is necessary before the importance of
ion reactions with CFCs can be estimated, but the likelihood
of substantial importance is small.
Dr. L. F. PHILLIPS — University of Canterbury (NZ) —
78-241. Determination of Atomic Oxygen Yields in the
Photolysis of HOC1 and C100 (completed).
The photolysis was studied by looking for prompt 0 atoms
by observation of resonance fluorescence on a nanosecond time
scale. Detection limits for ground-state oxygen atoms pro-
duced by photolysis of N02 were established.
Gaseous mixtures containing EOC1 were photolyaed with UV radia-
tion at 237 nm from a nitrogen laser to determine whether the
SOCl -»• HCl + 0 reaction path occurred. Because the signal to
noise ratio was too low, attempts to measure oxygen atoms by
resonance fluorescence gave inconclusive results. Recommenda-
tions were made for improving the sensitivity of the detection
method in future studies.
K-20
-------
Table 3 (continued)
Dr. J. N. PITTS, JR. — University of California at
Riverside — 75-12. Monitoring and Atmospheric Reac-
tions of Fluorocarbons (completed).
CFCs 11 and 12 are photochemically stable in simulated sun-
light, even when irradiated for several weeks. Plant tissues
did not absorb measurable quantities of CFCs 11, 12, or 22,
and no adverse effects could be measured. CFCs penetrate into
the soil atmosphere, and concentrations change in direct
relationship with changes in concentration in the atmosphere
above ground.
Dr. R. A. RASMUSSEN — Washington State University —
75-71. Measurement of Fluorocarbon Content of "Antique"
Air Samples (completed).
A sensitive method for the determination of low parts per
trillion analysis of CFCs 11 and 12 in small-volume air
samples in containers was developed and applied to a wide
variety of vessels believed to contain antique air. All
samples analyzed showed varying levels of CFCs. Contamina-
tion during handling is not a problem, so that either CFCs
were present in nature prior to 1930 or the samples were con-
taminated by leakage during storage.
Dr. R. A. RASMUSSEN — Rasmussen Associates — 75-84.
Collection and Analysis of Antarctic Ice Cores (com-
pleted) .
The concentration of halocarbons in air obtained from Antarctic
snow shows no enrichment in samples obtained from the Ross ice
shelf (mainly -30°F), whereas there is enrichment in samples
obtained from the South Pole (-50 to -60°F).
Dr. R. A. RASMUSSEN — Private — 76-140. Lower Strato-
spheric Measurement of Non-methane Hydrocarbons (completed)
Ethane, ethylene, and acetylene are found in the upper tropo-
sphere and lower stratosphere at concentrations of 40-820 ppt.
Total concentrations of the three species range from 1085 ppt
(NH troposphere) to 323 ppt (SH stratosphere).
Dr. R. A. RASMUSSEN — Oregon Graduate Center —
77-201, 78-248, 78-263, 79-279, 80-325. Operation of
Stations in American Samoa, Cape Meares, Oregon, and
Tasmania for the Atmospheric Lifetime Experiment.
Automated long-term ground measurement stations are being oper-
ated in American Samoa and Tasmania as detailed in 77-193
(Lovelock and Simmonds, p. 19). Data have been processed from
May, 1978, (Tasmania) and June, 1978, (American Samoa) up to
June, 1980.
K-21
-------
Table 3 (continued)
The fifth ALE station at Cape Meares, Oregon, became opera-
tional early in 1980 and is now contributing measurement data
routinely to the ALE network.
Dr. R. A. RASMUSSEN — Oregon Graduate Center —
77-215. Kilauea Volcanic Emissions — Halocarbon
Measurements (completed) .
Electron capture gas chromatograph analyses were made on
fumerolic emissions from two vents on Kilauea at the site
of the September, 1977 lava flow. Some 20 halocarbons were
observed and compared with local control samples. CFCs 11
and 12, CC14, and 0130:13 were not significantly different
from controls. Peaks tentatively identified as ^0 and
methyl halides showed elevated concentrations versus controls,
The presence of ^0 was confirmed by GC-MS.
Dr. C. SANDORFY — University of Montreal — 73-2.
Spectroscopy and Photochemical Changes of Fluoro-
carbons (completed) .
The vacuum ultraviolet and photoelectron spectra of CFCs were
measured. The photochemical vulnerability of these molecules
was predicted from their spectra.
R. E. SHAMEL — A. D. Little, Inc. — 79-275. Analysis
of Release of FC-11 from Rigid Plastic Foam Products in
the U. S. (completed).
The lifetime for CFC-11 emissions from rigid foam is much longer
than previously assumed and will not be a problem for the ALE
lifetime calculations.
Drs. P. G. SIMMONDS and J. E. LOVELOCK — Private —
79-269. Determination of Tropospheric Halocarbons
and Their Relative Importance.
See Table 3, Section C (p. 27).
C. Laboratory Studies Related to Potential Atmospheric Measure-
ments
Dr. J. W. BIRKS; Drs. C. J. HOWARD and F. C. FEHSENFELD
— University of Colorado; National Oceanic and Atmos-
pheric Administration, Boulder — 77-222. Development
of a Technique for Measuring the Total Chlorine Content
in Air.
The goal of this project is to develop an analytical instru-
ment for measuring the total chlorine content of whole air.
In principle a gas stream will be passed through a discharge
plasma, and chlorine emission lines in the vacuum UV region
K-22
-------
Table 3 (continued)
will be used to determine chlorine content. The equipment
consists of a UV monochromator, discharge source, and resonance
fluorescence detector.
The chlorine signal response has been investigated for a number
of different chlorine-containing compounds, and the linearity
of the total chlorine signal is under investigation.
Dr. H. L. BUIJS — Bomem, Inc. — 75-90. Construction
of a Fourier Transform Spectrometer (completed).
A spectrometer with a projected resolution of 0.02 cm~l was
constructed for use in the simultaneous determination of
C10N02 and either HC1 or HF, or of HC1 and HF. See Table 3,
Section D (p. 31).
Dr. H. L. BUIJS — Bomera, Inc. — 77-168. Measurement
of Halogen Compounds for Determination of Total Chlorine
and Total Fluorine in the Stratosphere Using Long-Path
Inteferometric Spectroscopy (completed).
A library study has shown that there are very few published
experimental data of sufficient resolution and quality for
the interpretation of solar IR spectra.
Dr. H. L. BUIJS — Bomem, Inc. — 77-221. Measurement
of Infrared Spectra of Selected Stable Molecules.
Fourier transform infrared spectra of methyl chloride in the
3.3 um region and of phosgene, carbonyl chlorofluoride, and
carbonyl fluoride in the 1.3 ym to 5.6 ym region have been
recorded at 0.01 cm~l resolution both at room temperature and
at stratospheric temperature (^240°K). The low-resolution
spectrum of methyl chloroform from about 2.1 ym to 5.6 ym
showed no useful features for detection of this species in the
atmosphere.
Dr. J. A. COXON — Dalhousie University — 78-255, 80-315.
The A2IIj_ "-X2!^ Band System of CIO: Absolute Absorption
Cross Sections at High Resolution for Bands of Stratos-
pheric Interest.
Equipment and facilities for spectroscopic work on the CIO
radical have been assembled. CIO has been generated in a
fast flow system from the reaction Cl + OC10 -»• 2C10. Both
35C10 and 37do will be investigated, particularly at X>290 nm.
Preliminary absorption traces of the A2IIi-X2IIi band system of
CIO have now been recorded at high resolution. Several bands,
11-0 to 4-0 in the ^3/2 subsystem, have been identified. The
absorption intensity of these bands is high. Even from this
preliminary work it is possible to establish an important new
K-23
-------
Table 3 (continued)
result: the width of individual lines in a vibrational band
appears to be greater than previous estimates made from photo-
graphic plates. Systematic measurements of CIO absorption
intensities (especially for the bands of stratospheric inter-
est) and the calculation of absolute absorption cross sections
are in progress. These data would assist continuous monitoring
of CIO from high altitude platforms.
Dr. D. D. DAVIS — University of Maryland — 74-10.
Laboratory Determination of the Sensitivity of Laser-
Induced Fluorescence for the Detection of CIO under
Atmospheric Conditions (completed).
Ground-state stationary CIO concentrations of about 1012
cm~3 were scanned at several electronic absorption wave-
length regions with a tunable UV laser. Laser-induced
fluorescence proved to be unusable for measuring CIO.
Dr. D. D. DAVIS —University of Maryland/Georgia
Institute of Technology — 75-73. Laboratory Measure-
ment of Spectroscopic Absorption Cross Sections of
CIO (completed).
A frequency doubled tunable dye laser with a band width of
0.0015 nm was used to measure the absorption cross sections
of CIO as a function of wave length for the A^Hj/2 9-0
band. There was overall lack of resolution in the data,
and an unassigned peak was observed at 283.06 nm. Simulated
spectra indicated that a baseline resolved spectrum is not
feasible, that the unassigned peak could be a 3^C10 absorp-
tion, and that the 35C10 line width is somewhat wider than
reported by Coxon and Ramsay. The real cross section
attributable to 35C10 at 282.94 nm (the largest peak in the
spectrum) is calculated to be CJR19>5 = 1.04 x 10~16 cm2.
Dr. D. D. DAVIS — University of Maryland/Georgia
Institute of Technology — 75-87. Development of
Instrument for Stratospheric OH Measurement by Laser-
Induced Fluorescence (completed).
A miniaturized dye laser module for balloon flights has been
built and tested.
Dr. A. E. J. EGGLETON — Atomic Energy Research Estab-
lishment, Harwell — 76-116. Total Chlorine Measure-
ments in the Troposphere and Stratosphere (completed).
The feasibility of measuring total chlorine and fluorine in
the atmosphere by neutron activation and y photon activation,
respectively, after collection of reactive species and par-
ticulate material on filters and collection of gaseous
compounds on activated charcoal was studied. The proposed
K-24
-------
Table 3 (continued)
method proved unsuitable for the determination of total
chlorine and fluorine contained in unreactive organic com-
pounds due to a combination of insufficiently low halogen
blank values in the best activated charcoal prepared and to
inadequate adsorptive capacity for the more volatile organic
compounds .
Dr. C. J. HOWARD — National Oceanic and Atmospheric
Administration, Boulder — 75-47. Laboratory Deter-
mination of the Feasibility of Laser Magnetic Resonance
for CIO Detection and Reaction Studies (completed) .
It has been demonstrated that CIO can be detected by laser
magnetic resonance with a sensitivity of about 10^-0 molec
cm~3. Current maximum model predictions are about 10 8
molec cm~3, and measurements have approached 10^ molec cm" 3
at 30 km.
Dr. C. J. HOWARD — National Oceanic and Atmospheric
Administration, Boulder — 80-299. Infrared Spectro-
scopy of Atmospheric Species .
This measurement program is to provide accurately calibrated
high-resolution infrared spectra of shorter lived atmospheric
species for the identification and quantification of these
constituents in the stratosphere. A Fourier transform infrared
spectrometer is to be obtained. The first species to be studied
is peroxynitric acid. (This project is dependent on the ac-
quisition of appropriate cofunding.)
Dr. H. D. KNAUTH — University of Kiel — 77-171.
Laboratory Study of the UV and IR Spectra of HOC1 ,
HOON02/ and HC104 in the Temperature Range of the
Stratosphere (completed) .
It was not possible to obtain partial pressures of HO2N02
greater than 0.1 torr in the N205/H202 system in Pyrex
vessels. The spectrum for gaseous HOC1 was derived from
extinction measurements on the C12/H20 system at 333°C
for different values of the equilibrium constant for the
reaction H20 + C^O ->• 2HOC1. The results are not in com-
plete agreement with those of Timmons (76-129, p. 28), so
additional work on the absorption centered around 300 nm
is required.
Dr. H. D. KNAUTH — University of Kiel — 77-224.
Laboratory Study for Determination of the Equilibrium
Constant of the Reaction C^O + H2O •*• 2HOC1 and the
UV Spectrum of HOC1 (completed) .
The gas phase system C^O + H20 = 2HOC1 has been investi-
gated by UV from 200 to 500 nm at 333°K. Isobestic points
were found at 214, 233, 335, and 380 nm. The equilibrium
K-25
-------
Table 3 (continued)
constant 0.132 ± 0.008 and HOC1 cross sections were
derived from absorbance measurements of the mixtures at
equilibrium. The resulting HOC1 spectrum shows absorption
bands with peaks at 240 and 310 nm. Very clean C120/H20/
HOC1 mixtures proved to be remarkably stable. Thermal
decomposition produced C12 with intermediate formation of
C102. The absorption cross sections of C120, C102, and
C12 were determined separately at 333°K.
Dr. J. E. LOVELOCK — Private — 76-120. The Electron
Capture Detector as a Reference Standard for Analysis
of Atmospheric Halocarbons (completed).
A theoretical model of the operation of the electron capture
detector was developed. Application to the procedure used
at the Adrigole station and on the RV Shackleton (1971-2)
indicate that measurements at these bases are within 3% of
theoretical predictions for CCl^ and CFC 11. This evaluation
was extended to CH3CC13 measurements.
Dr. J. E. LOVELOCK — Private — 78-226, 78-264, 80-293.
Development of Primary Fluorocarbon Standards.
An exponential dilution technique, using a converted barn as
the dilution chamber, has been developed to provide primary
standards for halocarbon concentration measurements.
During what had been expected to be the final phase of measure-
ments on CFC-11 and CFC-12, measurements outside the previously
accepted error limits were obtained. A review of the experimental
procedures to identify hitherto undetected sources of system-
atic error has been made. None was found with the possible
exception of water contamination of fluorocarbon samples during
transfer. Final measurements are now expected to be completed
before the end of the year.
Dr. K. MOE —- Private ~ 78-235. Effect of Aerosol
Scattering on Ozone Measurements with the Dobson
Spectrophotometer (completed).
The NCAR UV double monochromator (UVDM) and associated com-
puter programs have been shown to be capable of ozone
measurements of hitherto unobtainable accuracy, while
simultaneously measuring aerosol optical depth as a func-
tion of wavelength in the region of strong ozone absorption.
An ozone value of 0.328 + 0.006 cm was obtained at 10:00 h
MST for June 8, 1978 compared with a corrected Dobson measure-
ment of 0.340 cm at 12:05 h MST.
The increasing number of UVDMs being deployed could provide
accurate ozone data to resolve the discrepancy between pre-
dictions of ozone decrease from photochemical models and
Dobson measurements, which show no decrease or increase.
K-26
-------
Table 3 (continued)
Dr. D. G. MURCRAY — University of Denver ~ 75-92,
77-152, 78-265. Laboratory Measurement of High
Resolution Infrared Spectra of Chlorine-Containing
Molecules of Stratospheric Interest.
Laboratory measurements of the high resolution infrared
spectra of chlorine-containing molecules are being made.
Statistical-band-model analyses and integrated intensity
measurements for the 10.8 ym band of CFC 12 and 11.8 ym
band of CFC 11 have been published. The spectrum of H202
has been measured. A compendium of laboratory IR spectra
(resolution 0.04-0.06 cm~l) has been prepared. A list of
compounds measured as well as detailed spectra are available
to investigators upon request to CMA, attention J. C. Van
Horn.
Dr. R. W. NICHOLLS — York University — 75-11 and
75-11-11. Experimental and Theoretical Studies on
the UV Spectrum of CIO with Stratospheric Applications.
Absolute absorption coefficients and cross sections have been
measured for all bands and the photodissociation continuum of
the V"=0 progression for CIO. The very complicated emission
spectrum that has been excited over the wavelength range
2500-4500 & in discharges through C1O2 and C^O is currently
undergoing measurement, identification, and analysis. Com-
puter-based synthetic spectra of various CIO bands have been
calculated. Current work, which emphasizes the (2,0), (3,0),
and (4,0) bands, should be of immediate diagnostic applica-
tion to ground-based and balloon-based stratospheric spec-
troscopic observations.
Dr. R. W. NICHOLLS — York University ~ 75-30b.
Laboratory Studies of the Infrared Vibration-Rotation
Spectrum of CIO (completed).
Work in this area was suspended to allow greater effort in
the UV measurements (75-11).
Dr. R. A. RASMUSSEN — Private — 76-142, 78-247.
Interlaboratory Comparison of Fluorocarbon Measure-
ments (completed) .
A second round of identical samples of rural air has been
circulated blind to participating laboratories for analysis
for CFCs 11 and 12, CHC13, CH3CC13, CC14, and N20. Overall
the results obtained showed a spread similar to that ob-
tained in the 1976 NASA workshop. However/as in 1976, there
was excellent agreement between Rasmussen and Lovelock, who
use two different methods of calibration. A third round of
K-27
-------
Table 3 (continued)
samples was analyzed by 19 laboratories. Good agreement
(±5%) was obtained by the S laboratories using common primary
standards, but the other 14 laboratories showed much larger
variations, with mean values considerably lower than those of
the 5 laboratories.
Drs. P. G. SIMMONDS and J. E. LOVELOCK — Private —
79-269. Determination of Tropospheric Halocarbons
and Their Relative Importance.
New methods are to be sought for the improved measurement of
halocarbons that are not presently determined with sufficient
sensitivity by EC/GC. Techniques will evaluate enhancement
of EC sensitivity by cryotrapping, selective adsorbents, the
use of "doped" carrier gas, and chemical conversion. The
first priority is to improve routine monitoring of CH3C1.
New techniques such as the electrolytic conductivity detector
(which could also provide the basis of a total chlorine monitor)
and the photoionization detector will also be evaluated. It
is hoped that these new techniques will permit future routine
monitoring of a wider range of both natural and anthropogenic
halocarbons.
Laboratory development experiments on the doping and cryogenic/
adsorbent techniques for methyl chloride continue to make good
progress. Attempts to increase detection sensitivity by chem-
ical conversion of methyl chloride to methyl iodide have so far
proved unsuccessful. A preliminary evaluation of the photo-
ionization detector, using a borrowed instrument, showed this
method of detection to be unpromising, and a new instrument will
therefore not be purchased.
Dr. R. K. SKOGERBOE — Colorado State University —
77-206. Development of a Measurement System for the
Determination of Total Chlorine in Air (completed).
The technique involves two flame reactions. The first, in a
H2~rich flame, forms HCl, which is treated with indium to yield
InCl. The InCl is then excited in an air-rich flame and detected
photometrically. Blind analyses of calibration samples proved
that the sensitivity of the technique was not sufficient to be
of value for stratospheric measurements. However, it is hoped
that the system can be put to use in tropospheric monitoring.
Dr. D. H. STEDMAN — University of Michigan — 74-7.
Atmospheric Determination of CIO Concentration: A
Feasibility Study (completed).
Laboratory studies have demonstrated the feasibility for
detecting stratospheric CIO by chemical conversion to Cl
(by reaction with NO) accompanied by vacuum ultraviolet
resonance fluorescence. In-flight use of this technique
is being supported by NASA.
K-20
-------
Table 3 (continued)
Dr. D. H. STEDMAN — University of Michigan - 76-132.
Absolute Calibration of Fluorocarbon Measurements
(completed).
A feed-back flow system for the calibration of CFC samples
has been built.
Dr. D. H. STEDMAN — University of Michigan — 77-151.
Generation and Exchange of Calibrated Samples of
Fluorocarbons (completed).
Work on this project was stopped because of feasibility
problems.
Dr. R. B. TIMMONS ~ Catholic University — 76-129.
Photochemical and Chemical Kinetics Measurements of
Stratospheric Importance with Respect to the Fluoro-
carbon Issue (completed).
HOC1 is a possible stratospheric sink the magnitude of which
would depend on the absorption cross section. Earlier
spectral measurements were inaccurate. Pure HOC1 cannot be
prepared, for an equilibrium mixture of C^O and HOC1 exists,
The equilibrium constant for this reaction is Kp = 0.8.
This value and the UV absorption cross sections of C^O have
been used to determine the UV absorption cross sections of
HOC1 between 200-330 nm. The 230-240 nm peak was lower than
previously measured, and no peak was found at 320 nm.
Dr. R. B. TIMMONS — University of Texas, Arlington —
77-214, 78-258. Photochemical and Chemical Kinetics
Measurements of Stratospheric Importance with Respect
to the Fluorocarbon Issue.
The UV absorption cross sections of HOC1 between 200-330 nm
over longer pathlengths are being determined under condi-
tions such that interference by C120 is minimal, i.e., low
C120 concentration and excess H20. An induction period for
the increase in UV absorption at 320 nm is observed, sug-
gesting that the 320 nm absorption may be due to more than
one species.
The equilibrium constant for the C120 +• H20 reaction appears
to be essentially temperature independent over the tempera-
ture range 25 to 57°C.
Work is in progress using a quadrupole mass spectrometer
toward the direct determination of the concentration of
HOC1 and any other interfering species, thus making the
measurement of the UV absorption cross section more accurate.
K-29
-------
Table 3 (continued}
Dr. R. J. SAYKALLY — University of California,
Berkeley — 80-300. Near- and Far-Infrared Spectro-
scopy.
This project seeks to develop far-infrared laser electric
resonance as a technique for detection and measurement of
transient species, with parallel work- in tunable F-center
laser spectroscopy. Species chosen for the studies are
HOCl, BOy, OH, and CH^O. The methods have potential appli-
cations in both laboratory kinetics and stratospheric measure-
ments.
Drs. W. A. TRAUB and K. V. CHANCE — Smithsonian
Astrophysical Observatory at Harvard University
— 80-318. Far-Infrared Laboratory Spectroscopy
of Halogen-Containing Molecules.
Laboratory spectra of SCI, HOCl, and CION02 will be studied at
a resolution of about 0.03 cm~* in the region 70 to 250 cm~l,
in order to establish the positions,~ strengths, and pressure
broadening effects of air on the lines and bands. This work
is done in support of an ongoing balloon measurement program.
D. Tropospheric and Stratospheric Measurements
Dr. J. E. BECKMAN — Queen Mary College, London —
79-282. Airborne Millimeter-Wave Determination of
CIO.
Airborne observations of CIO using a 241 GHz receiver will be
made. This equipment will be flown "piggyback" on a NASA
aircraft (C141) flight scheduled for late October 1980.
Drs. A. BONETTI and B. CARLI; Dr. J. E. HARRIES ~
University of Florence, Consiglio Nazionale delle
Ricerche, Istituto di Ricerca sulle Onde Elettro-
magnetiche, Italy; National Physical Laboratory,
U. K. — 76-137, 80-297. Submillimeter-Infrared
Balloon Experiment.
Vertical distributions and diurnal variability of H20, 03,
N02, HN03, HC1, CFCs 11 and 12, CIO, C10N02, and other
molecules are being determined using the 9 to 15 micron infra-
red region and submillimeter wavelengths from 200 to 1000
microns. Data from the October 1978 flight have been reduced
for CFCs 11 and 12, 03, and HN03-
Laboratory measurements of the rotational spectra of molecular
species relevant to stratospheric chemistry and photochemistry
will be carried out in the spectral interval 5 to 80 cm~l with
possible extension to 120 cm-1 with a resolution of 0.0023 cm~l
up to 40 cm-1 and with a resolving power of 1,210^ beyond 40 cm-1,
The spectra will be produced through the same Submillimeter
Polarising Interferometer employed in the stratospheric flights.
K-30
-------
Table 3 (continued)
Dr. F. BRUNER — Urbino University — 78-256. Deter-
mination of F-21 and Other Halocarbons in the Tropos-
phere (completed).
Two analytical methods for the quantitative determination of
atmospheric CFC-21 at 1-50 ppt concentration have been set up
based on GC separation followed, respectively, by EC and MS.
In both methods the permeation tube technique has been adopted
as the primary quantitative standard.
A series of samples have been collected from rural and indus-
trial areas in Italy and over the Red Sea and the Indian Ocean.
Concentrations of CFC-21 ranged from a few ppt to as great as
40-50 ppt.
Dr. H. L. BUIJS - Bomem, Inc. — 75-90, 75-98. Measure-
ment of HC1 and HF in the Stratosphere by Fourier
Transform Spectroscopy (completed).
Balloon flights to Alaska (May 1976) and New Mexico (September
1976 and March 1977) have provided profiles for HF and HC1
concentrations. The HC1 profile (volume mixing ratio), but
not the HF profile, appears to show a maximum at 23-25 km,
where the volume mixing ratios are 8 x 10~10 (HCl) and 10~10
(HF). The HCl value is similar to values obtained by other
investigators.
Upper limits on the concentrations of C2Hg and CH3C1 are < 0.6
x 10~9 and £ 1 x 10~9 (mole fraction), respectively.
See Table 3, Section C (p. 23 ).
Dr. H. L. BUIJS — Bomem, Inc. — 77-156. Operational
Costing for Flights Planned in 1977.
HCl and HF profiles were recorded by infrared techniques from
a balloon launched in New Mexico on October 27. 1978. The
HCl mixing ratio increased from about 2 x 10~1" at 20 km to
about 1 x 10~9 at 35 km. Similar values for HF are about 3 x
10-11 and 3 x 10~10, respectively. The shape of the curve of
HF/HCl vs. altitude is in reasonable agreement with that of
Farmer and Raper (1977) over the altitude interval 17-27 km
but does not agree with the profile calculated from models by
Sze (1978).
Additional balloon flights are planned for simultaneous measure-
ment of HCl, HF, and/or ClON02.
K-31
-------
Table 3 (continued)
Dr. D. H. EHHALT — Nuclear Research Establishment
Juelich — 76-145. Electron Spin Resonance Detection
of Stratospheric Radicals (completed).
Under a program supported by the German Government's Depart-
ment of Research and Technology a cryogenic sample was
collected at 30.5 km at 1600-1700 hr (conditions of relatively
low radical concentration) during Murcray's March 1977 balloon
flight. The frozen sample was analyzed by ESR, showing the
following concentrations. N02: 3.5 x 108; H02: 8.5 x 10°
molec cm"3; CIO: not detected.
Dr. P. A. EKSTROM ~ Battelle Memorial Institute, Pacific
Northwest Laboratories — 75-27. Ground-Based Millimeter-
Wavelength Observations of Stratospheric CIO (completed).
About 500,000 data points were obtained in the microwave
spectra near 93 GHz with the Kitt Peak radiotelescope. Ex-
cessive noise made interpretation difficult, but base-line
corrected spectra suggested an upper limit on CIO of one
hundred times model predictions.
Dr. A. GIRARD — Office National d1Etudes et de
Recherches Aerospatiales, France — 75-88. Measure-
ment of HC1, HF, CIO, etc., in the Stratosphere by
High Resolution Infrared Spectroscopy (completed).
Vertical profiles of HC1, NO2, H20, and CH4 between 26 and
35 km have been deduced from two balloon-borne grating
spectrometer experiments. There is a hint of a decrease
in HC1 mixing ratio at the upper limit of the October 1977
experiment. Laboratory infrared spectra have been obtained
for C1N03, N02, HN03, and HCHO. The method of infrared
limb sun pointing was found to be inadequate for the detec-
tion of CIO in the atmosphere.
Drs. A. GOLDMAN and A. BARBE — University of Denver;
University of Reims, France — 80-322. Collaborative
Studies on Atmospheric Spectroscopy.
Atmospheric species such as 03, 3Cl, HF, NO 2, NO, N 20 ,
OCS, etc., are to be identified and quantified by their infra-
red absorption spectra. The work will cover a wide range of
laboratory, ground-based, and theoretical studies and utilize
the complementary skills and established collaboration between
Denver and Reims.
K-32
-------
Table 3 (continued)
Dr. P. JOUVE ~ University of Reims, France — 79-290.
Measurement of the Vertical Distribution of HC1, 03, and
HCHO and the Ratio HF/HCl.
Ground-baaed measurements of HCl, HF> and other important species
will be made using high resolution infrared spectroscopy. These
measurements will be made during 1981 from an observatory in
Haute Province, France, by a team from Jouve's group at the ONES
Laboratory located in Reims.
Dr. J. E. LOVELOCK — University of Reading, Private
— 73-1, 74-3, 75-67, 77-144. Fluorocarbons in the
Environment (completed).
The electron capture gas chromatograph (ECGC) has been
developed and applied to the measurement of several halocar-
bons in the lower stratosphere and troposphere, particularly
over Europe and the Atlantic Ocean. In 1976 levels of CFC
11 were about 130 ppt (U. K.) and 80 ppt (Southern Hemi-
sphere) . CHoCl, with the ocean and smouldering vegetation
as identified sources, was at about 10~9 v/v in the Northern
Hemisphere but was found to be higher over the southern
African continent (2.2 x 10~9 v/v in Kenya) (cf. Rasmussen,
77-181, p. 35) • CC14 and CH3(^13 were also unexpectedly
high. Portable monitoring equipment has been provided and
put to use in South Africa and Australia. The levels of
CH3CC13 found in the Southern Hemisphere (50 ppt) appeared
higher than expected from release and tropospheric lifetime
estimates. Northern Hemisphere values were about 100 ppt.
Measurements of CFC 11 in the atmosphere and ocean were made •
during the April 1977 voyage of RRS Challenger in the north-'
east Atlantic Ocean. Average air concentrations of 155 ppt
were observed for CFC 11, and it was present at saturation
quantities down to depths of 500 m.
See Rasmussen 76-142, p. 27.
Dr. D. G. MURCRAY — University of Denver — 75-13,
76-101, 76-135, 77-166. The Measurement of the
Stratospheric Distribution of Fluorocarbons and
Other Constituents of Interest in the Possible
Effect of Chlorine Pollutants on the Ozone Layer.
Measurement of stratospheric distribution by balloon-borne,
high-resolution, infrared absorption measurement at large
solar zenith angles has been achieved using a specially
constructed grating spectrometer. The distributions for
CFCs 11 and 12 and CC14 obtained showed a concentration
increase of about 2.5, with a rather wide range of uncer-
tainty, from 1968 to 1975 for CFCs 11 and 12. Subsequent
flights also yielded HC1 and HN03 profiles. A preliminary
value of ^2 ppbv for the concentration of ClONO^ at 26 km
has been calculated. The upper limit for H202 is 1 ppbv
at 20 km.
K-33
-------
Table 3 (continued)
An October 1978 balloon flight with an interferometer system
instead of a grating system was successful and recorded
through sunset with the last record obtained at solar zenith
angle >95°. A strong absorption at 1283 cm'1 is due to CF4
with an estimated mixing ratio of 75 pptv at 25 km. The
C10N02 mixing ratio is 0.8 pptv from 24 km to 32 km, then
falling to 0.4 ppbv at 33.5 km. Several features coincide
with some of the HOC1 lines, but the agreement appears
fortuitous, and no features can be assigned with certainty
to HOC1. The upper limit for H202 is 0.5 ppbv at 20 km and
for COF2 is 0.4 ppbv at 25 km.
Dr. D. G. MURCRAY ~ University of Denver — 77-211.
Acquisition of an On-Board Digital Recording System
(completed).
The balloon-borne interferometer system has been improved by
incorporating into it on-board recording capability. Advan-
tages are two-fold: a back-up is provided in case the
telemetry system malfunctions, and it becomes possible to
operate under atmospheric wind conditions that might
carry the balloon out of telemetry range. The system was
used for a balloon flight October 28, 1978. Analysis of
the recorded data indicates the unit meets design objectives.
Dr. D. G. MURCRAY — University of Denver — 78-228.
Detection of Selected Molecules by Ground-Based
Solar Spectroscopy (completed).
Solar spectra were examined with a resolution of 0.01 cm~l.
An atlas of the 775-950 cm~l and 1050-1300 cm~l regions has
been prepared.
A workshop on solar spectroscopy was held at the National
Bureau of Standards, March 26, 1980.
Drs. D. G. MURCRAY and H. K. ROSCOE — University of
Denver; Oxford University, England — 77-219. Strato-
spheric HC1 Measurements Conducted as a Piggy-Back to
Murcray's Flight.
Because the vibration problem with the solar-absorption
pressure modulator radiometer used for the HCl measurements
could not be reasonably solved, this project was cancelled.
Drs. D. G. MURCRAY and H. K. ROSCOE — University of
Denver; Oxford University, England — 80-328. An Inter-
comparison of Measurements of Stratospheric HCl.
A simultaneous measurement of the HCl profile in the strato-
sphere will be made on a balloon flight. Muraray will utilise
a high resolution IR interferometer, and Roaaoe will uae a
pressure modulated radiometer.
K-34
-------
Table 3 (continued)
Dr. R. A. RASMUSSEN — Washington State University —
75-2, 75-59. Fluorocarbon Research (completed).
An attempt was made to obtain halocarbon concentration
measurements as far into the stratosphere as could be
reached by an available commercial aircraft. A small port-
able gas chromatograph was used for on-board measurements,
and cannister samples were collected for subsequent detailed
halocarbon analysis on the ground. One phase of the study
consisted of samples collected over a wide area of the
Pacific Northwest, a second of samples collected frequently
to the maximum attainable altitude over Alaska. The halo-
carbon concentrations are either constant or decrease very
slowly with altitude in the tropopause, decrease rapidly in
the tropopause from the tropospheric concentration to an
average value identifiable with the stratosphere, and do
not show a clear pattern of concentration gradients above
the tropopause.
A trans-Pacific flight from 80°N to 60°S has been completed,
and the air samples collected have been analyzed for halo-
carbons. Most of the samples were collected at 39,000 to
43,000 ft. CFC 12 concentrations are about 10% higher in
the north than in the south at ground level, and the differ-
ence is apparently greater for CFC 11.
Dr. R. A. RASMUSSEN — Private — 77-181. Measurement
of the Concentration of Methyl Chloride in Air in
Kenya (completed).
Air samples were obtained at ground level and by aircraft
in Kenya and over the Indian Ocean. Analyses showed CH3C1
at 600-700 ppt over Kenya, rising to 900-2000 ppm in areas
where slash burning was being conducted (cf. Lovelock,
77-144, p. 33). Boundary layer analyses over the Indian
Ocean were 750-880 ppm. N20 levels were 324-378 ppb.
Other analyses showed CFC 12, 235-246 ppt; CFC 11, 137-
143 ppt? CH3CC13, 74-96 ppt; and CC14, 120-135 ppt. Com-
parison with previous data showed interhemispheric differ-
ences for the above five species.
Dr. R. A. RASMUSSEN — Oregon Graduate Center —
78-260. Identification of FC-21 in the Atmosphere
(completed).
Measurements of CFC 21 in Tasmania, at the South Pole, and
in "clean" air from Cape Meares, OR, show concentrations
of 0.05-0.6 ppt, compared with concentrations of 2 ppt at
Harwell, U. K. GC/MS identification confirms CFC 21,
distinguishing CFC 21 from CI^I. CFC 21 samples do not
increase in CFC 21 content on storage, nor is CFC 21 pro-
duced from fluoroplastics examined, nor is CFC 21 observable
in CFC 11 or CFC 12 standards. CFC 21 is highly variable,
and more measurements are needed.
K-35
-------
Table 3 (continued)
Dr. R. A. RASMUSSEN — Private ~ 80-308. F-22 Measure-
ments in the Atmosphere.
The concentration of CFC-22 is being measured in approximately
76 air samples collected since April 1978 by the ALE network
with supplemental samples from late 1976. The data will be
used to determine the rate of increase of CFC-22 over the
past three years.
Dr. B. A RIDLEY — York University — 76-102A,
76-102B. Measurement of Fluorocarbons and Related
Chlorocarbons in the Stratosphere by Collection
and Analysis (completed).
Series of evacuated stainless steel spheres were used to
obtain samples of stratospheric air at various altitudes
up to 39 km from three balloon flights. Some problems
were encountered in the absolute calibration of the
electron capture gas chromatograph, but the results are
consistent with a stratospheric photolysis sink for CFC
11 and 12 and N20.
Drs. P. M. SOLOMON and R. L. deZAFRA — State
- University of New York, Stony Brook — 76-130, 77-
225, 79-278, 80-316. Millimeter Wave Observations
of Chlorofluoromethane Byproducts in the Strato-
sphere.
This study is directed toward the development of a ground-
based method for continuous determination of CIO. One of
the millimeter wave observing systems is based on a 3-nm
maser, a unique instrument that is the most sensitive
detector in the world in the 83-94 GHz range.
A 256-channel radio frequency spectrometer has been built
and tested for tha analysis and identification of the weak
pressure-broadened 93 GHz signal from stratospheric ClO.
An upper limit of 1.5 ppb CIO was measured with the 130 GHz
receiver. In a joint effort with Bell Laboratories CIO has
been detected at 201 GHz at an observatory near Amherst,
Massachusetts.
In early 1980 the daily variability in the total CIO column
was about a factor of 2, which is not predicted by the models.
The average total CIO column was about a factor of 2 lower than
model predictions. These measurements also indicate that the
CIO in the lower stratosphere is less than the model profile,
indicating that the OR concentration is also lower than calcu-
lated. These results imply a lower ozone depletion than now
estimated.
K-36
-------
Table 3 (continued)
Dr. 0. C. TAYLOR — University of California at
Riverside — 73-3, 74-2. Monitoring and Atmos-
pheric Reactions of Fluorocarbons (completed).
An electron capture gas chromatograph was used to measure
the concentrations of CFCs 11 and 12 in the troposphere
over southern California and in the lower stratosphere over
New Mexico and Colorado. The tropospheric concentrations
were found to vary from day to day as climatic conditions
affected dispersion and dilution. Concentration decreased
with increasing altitude in the lower stratosphere.
Dr. R. A. YOUNG - Xonics, Inc. ~ 75-50, 75-86.
Development of an Instrument to Measure, 0, CIO,
03, and Total Cl in the Stratosphere (completed).
A preliminary evaluation of resonance fluorescence for the
stratospheric measurement of CIO and total chlorine was
made during the September 1975 STRATCOM balloon flight.
This work and subsequent laboratory work indicated that
alternative methods for these measurements hold greater
near-term promise.
Dr. R. ZANDER — University of Liege — 76-141, 78-232.
Ground-based Infrared Measurements.
The 7.5-meter focal length double-pass infrared spectrometer
at the Jungfraujoch International Scientific Station (alti-
tude 3580 meters) is being used to monitor atmospheric
column densities of HF, HC1, and CI^Cl in the 2-5 micron
range. Resolution of the instrument is about 0.02 cm~l.
The equipment will also be modified to cover the 8-13 micron
region to permit monitoring of HN03, CFCs 11 and 12, CCl^
CIO, and C10N02.
Results indicate a steady increase of about 10% per year in
HF content in the stratosphere, whereas there is no clear
trend in the average column density of HCl.
Average column mixing ratios of 1.5 ± 0.6 x 10~9 for CH3C1
in June 1979 and an upper limit of 1.5 ± 0.5 x 10~10 for
C10N02 were measured. Cloud cover limited winter measurements
K-37
-------
Table 3 (continued)
E. Modeling
Dr. G. BRASSEUR — Institut d'Aeronomie Spatiale,
Belgium — 80-320. Modeling of the CFC Effect on
the Ozone Layer.
A 2-D model will be developed in which the chemistry ia coupled
with dynamics and temperature distribution. A 1-D model will
be used for studying new chemistry. Special emphasis will be
given to comparison between observed and computed distributions
of trace species (^z°> CFC-11, CFC-12, CS4t ClOt ....) and
studies of simultaneous perturbations («.g.t CFCs and C0%) in-
cluding thermal and dynamical feedbacks on perturbation calcu-
lations.
Drs. D. M. CUNNOLD, F. N. ALYEA, and R. G. PRINN —
CAP Associates — 75-24, 76-122, 77-199, 78-252, 79-281,
80-323. Meteorological and Multi-Dimensional Model-
ing Considerations Relating to Atmospheric Effects
of Halocarbons.
Studies to assess the accuracy and shortcomings of the 1-D
model used to estimate ozone depletion indicated that a
tropospheric lifetime for CFCs 11 and 12 as short as 10
years was not inconsistent with atmospheric measurements.
Thus, ozone depletion estimates might be considerably less
than present estimates. The great variability of strato-
spheric measurements indicates that simultaneous measure-
ments for many important stratospheric species are needed
and that seasonal dependence of species must be considered.
The neglect of dynamical feedback processes in the radiative
models used to calculate warming (greenhouse effect) limits
the value of calculated effects. Preliminary calculations
have been made including feedback effects due to inclusion
of the hydrological cycle and circulatory effects. Pre-
liminary results indicate that inclusion of the hydrological
cycle would strongly counteract the greenhouse effect, where-
as circulatory changes would slightly increase it.
Because it has been shown that meteorological conditions can
cause variations in both tropospheric and lower stratospheric
fluorocarbon measurements in Alaska, temporal and latitudinal
variability of fluorocarbon concentration has been estimated
with the use of an 8-box model of the troposphere, and the
results related to the sensitivity of trend detection in the
Atmospheric Lifetime Experiment (cf. 79-281, p. 17) and to
previous interhemispheric observations.
A preliminary estimate was made for the lifetime of a tropo-
spheric sink due to photodecomposition of CFCs on sand. The
sink would imply a lifetime of 30 years if 40% of the CFCs
were destroyed over the Sahara Desert.
K-38
-------
Table 3 (continued)
A methodology was developed for determining the lifetime of
tropospheric sinks of CFCs by daily monitoring. This
methodology is being implemented under 79-279, 79-280 and
79-281 (pp. 21, 19, and 17, respectively).
The surface temperature increase resulting from atmospheric
CFC mixing ratios increasing to 2 ppbv has been reestimated
at 0.2 ± 0.5°K (95% confidence limits). The significance of
its impact is thus extremely uncertain and is only one of a
number of factors that could induce climatic change.
Dr. N. D. SZE — Environmental Research and Tech-
nology, Inc. — 75-32, 76-115. Model Analysis of
The Fluorocarbon Problem (completed).
A one-dimensional model has been used to evaluate the role
of stratospheric water in the NOX and C1X cycles, the rela-
tionship of eddy diffusion coefficient and CFC lifetime,
the use of CFC measurements to calculate lifetime, and the
effect of chlorine nitrate. The importance of OH concen-
tration on calculated ozone depletion was shown, and key
reactions were identified. Analyses showed 10-20 year
tropospheric lifetimes were not inconsistent with measure-
ments and helped to define quantitatively the uncertainties
associated with ozone depletion calculations.
Inclusion of multiple scattering in the model had a negligi-
ble effect on the ozone depletion estimates. The modeled
ozone profile above 40 km is a factor of 2-3 lower than
recent measurements. Calculated CIO profiles are a factor
of 2-4 too low at 28-35 km when compared with Anderson's
CIO data.
A diurnal model has been developed that is capable of cal-
culating stratospheric concentration profiles of any HOX,
C10X, or Ox species.
Dr. N. D. SZE — Atmospheric & Environmental Research
Inc. ~ 77-173, 78-234, 79-273, 80-311. Theoretical Models
of Stratospheric Chemistry, Perturbations, and Trace
Gas Measurements (continuation of 76-115).
Iterative procedures, which lower the computer time by a
factor of 3 for the diurnal model, have been developed.
The modeled HF data and HF/HC1 ratio are at least a factor
of 2 higher than the measured values. A possible explana-
tion is that OH is less than model predictions, thus
indicating a greater reservoir of inactive chlorine. If
the rate of formation of OC100 is sufficiently rapid, it
can constitute a "holding tank" for active chlorine.
Theoretical calculations indicate that the possibility of
a 20-year tropospheric sink due to adsorption of CFCs 11
and 12 on desert sand with subsequent photodecomposition
by sunlight cannot be ruled out.
K-39
-------
Table 3 (continued)
Incorporating new rate constants for the reactions H02 +
NO -»• NO + N02 and H02 + 03 -»• HO + 202 raises calculated
steady state ozone reduction to a level that should be
detectable within 6-8 years using an 18-station network
of ozone monitoring stations.
It has been shown that if 10% of the reaction between H02
and CIO proceeds by the product channel HC1 +03 the ozone
depletion estimate can be lowered by a factor of at least 2.
Preliminary work on 2-D models has utilized a simplified
compartmental approach. Spatial inhomogeneity of effects
is predicted. A full 2-D model has been developed in a joint
effort with the U. S. Air Force.
Preliminary indications are that if the downward eddy dif-
fusion coefficient is larger than the upward eddy diffusion
coefficient, then the calculated ozone reduction due to
release of CFCs would be reduced. Also, a preliminary analy-
sis shows that the total ozone column is sensitive to the
eddy diffusion coefficient. This could have a potential
feedback effect on the ozone depletion estimate if the eddy
diffusion coefficient changes with changes in ozone.
Studies on the effect of coupling the perturbations to the
atmosphere due to increased concentrations of CO and CH4 and
increased use of fertilizer show that the net perturbation
of ozone may be significantly less than for CFCs alone. In
particular, it has been shown that coupling the effects due
to increasing C02 resulting from greater use of fossil fuel
and CFC emissions results in a lower value for the ozone
depletion estimate.
The effect of anthropogenic and natural emissions of organic
bromine compounds has been considered in the model and found
to have a minimal effect on the ozone depletion estimate.
The potential importance of 02(1Ag) reactions has been shown.
Introduction of this chemistry along with the measured
02 (^-Ag) profile into the model could enhance the 0-03 ratio
and magnify existing discrepancies between measured and
modeled profiles.
Current values of photodissociation cross sections for H02N02
indicate that its reaction with HO could result in a reduction
of the ozone depletion estimates and in better agreement between
measured and calculated profiles for many atmospheric species.
Measurement of C2H6 and C2H2 can be used to infer local con-
centrations of HO and Cl, a further check on observed and cal-
culated profiles.
Using current values for the rate constants for the reactions of
HO with SO2, B^OS, and OH lowers ozone depletion estimates by
about a factor of 2.
K-40
-------
Table 3 (continued)
F. Other
Dr. M. J. BAILEY — University of Maryland — 80-317
Uncertainties and Benefit-Cost Analysis of CFC Control.
A recently concluded, EPA-funded analysis of the potential costs
and benefits of CFC control is being expanded and further re-
fined. The new study takes into account recent revisions in
atmospheric models and projected future changes in atmospheric
composition. Although the range of possible outcomes is broad,
indications for the most likely case are that the benefits of
unregulated fluorocarbon use will outweigh any of their harmful
effects.
Dr. D. BERGER — Temple University — 75-62. Ground-
Level Monitoring of Ultraviolet Solar Radiation (com-
pleted) .
The monitoring of solar ultraviolet radiation, which was
initiated by the Climatic Impact Assessment Program (CIAP)
and subsequently funded for one year by CMA, is now being
supported by NOAA.
Drs. E. PARZEN and M. PAGANO — Frontier Science and
Technology Research Foundation, Inc. — 76-106. Total
World Ozone Level: Statistical Analysis (completed).
Ozone column measurements from at least 20 stations have
been evaluated statistically to detect trends in recorded
ozone concentrations and to establish the limits of detec-
tion for such trends. Time series analysis has been shown
to be substantially more sensitive in detecting non-random
ozone changes than the estimates of such sensitivity made
by the Federal Task Force on Inadvertent Modifications of
the Stratosphere (IMOS) in 1975. Analysis of ozone data
from 9 stations shows that no detectable abnormal trend in
the ozone data has occurred over the last 6 years. The
absence of detectable trends provides an upper limit for
actual depletion and a test of model predictions.
If sufficient sensitivity is achieved, this technique will
enable an effective early warning system for ozone deple-
tion to be established.
Drs. G. C. TIAO and G. REINSEL — University of
Wisconsin — 78-250, 80-304. Statistical Analysis
of World-wide Stratospheric Ozone Data for the Detec-
tion of Trend.
The ground-based and satellite ozone data are being obtained
and prepared in a form suitable for computer analysis. Analysis
of long-term ozone data from 36 ground-based stations shows an
average increase of 0.3% ± 1.4% for the period 1970-1978. The
NAS report indicates that the ozone should have decreased by
K-41
-------
Table 3 (continued)
1.5% ± 1.1% during that same period. The difference between
these two studies is statistically significant. Ground-based
data are currently being compared with satellite ozone data in
order to assess the magnitude of errors due to instrument drift
and non-uniform positioning of ground-based ozone-measuring
stations. In addition, efforts to correlate long-term meteoro-
logical variables with ozone data, in order to assess whether
there are long-term cycles in the ozone data, are in progress.
Dr. G. S. WATSON — Princeton University — 78-257.
Statistical Investigations of the CFM Problem.
Available data on ozone and related variables are being
studied in an attempt to understand the natural variation
of ozone in space and time. Theoretical models for ozone
trends and their predictions are being checked against
observed ozone as a function of time and position. An
effective "early warning" system will then be designed.
Preliminary analysis of Umkehr data from 32-50 km, where maximum
ozone depletion is predicted, has shown a slight increase in
ozone. The models predict a 5% decrease.
K-42
-------
Table 3 (continued)
G. Consultants
1. Under Contract
Dr. J. G. Anderson
Dr. D. R. Herschbach
Dr. I. C. Hisatsune
Dr. L. E. Snyder
Dr. R. T. Watson
Harvard
University
Dr. A. W. Castleman, Jr. University of
Colorado
Harvard
University
Pennsylvania
State Univer-
sity
University of
Illinois
Jet Propulsion
Laboratory
Stratospheric
Measurements
Heterogeneous
Chemistry
Homogeneous
Chemistry,
Kinetics, and
Spectroscopy
Molecular
Spectroscopy
and Chemical
Kinetics
Millimeter Wave-
length Spectros-
copy
Chemical Kinetics
and Photochemistry
2. Without Compensation
Dr. F. C. Fehsenfeld
Dr. E. E. Ferguson
NOAA Environ- Reactions of
mental Research Charged Species
Laboratories
November 30, 1980
K-43
-------
Table 4A
Research Funded by the Chlorofluorocarbon Industry
and
Administered by the Chemical Manufacturers Association
WORK COMPLETED
Program
Investigation of spectroscopy
of and photochemical changes
in fluorocarbons
Monitoring of fluorocarbons in
the atmosphere and simula-
tion of atmospheric reactions
of fluorocarbons^
Measurement of fluorocarbons in
the atmosphere0
Laboratory investigation of the
feasibility of measuring CIO
in the atmosphere by the
chemical conversion-resonance
fluorescence detection method
Laboratory determination of
sensitivity of laser-induced
fluorescence for the detec-
tion of CIO under atmospheric
conditions
Continuation of 73-3b
Continuation of 73-lb
Investigation of ion-molecule
reactions involving chloro-
fluorocarbons
Development of an instrument
to measure 0, CIO, 03, and
total Cl in the stratos-
phere15
Investigator Organization
Sandorfy U. of Montreal
Taylor
Lovelock
Stedman
Davis
Pitts
Lovelock
Mohnen
Young
U. of Calif.
Riverside
' U. of Reading
U. of Michigan
U. of Maryland
U. of Calif.-
Riverside
U. of Reading
SUNY-Albany
Xonics, Inc.
Proposal Completion
Number Date
73-2
73-3
73-1
74-7
74-2
75-50
10/11/74
10/16/74
10/27/74
2/28/75
74-10 5/31/75
12/31/75
74-3 12/31/75
75-64 4/1/76
4/7/76
(continued)
K-44
-------
Table 4A (continued)
Program
Measurement of fluorocarbons and
related chlorocarbons In the
stratosphere and upper tropos-
phere^5
Continuation of 74-2
Investigation of the destruction
of chlorofluoromethanes by
naturally occurring ions
Ground-based millimeter wave-
length observations of
stratospheric CIO
Laboratory and theoretical
studies of the ultraviolet
and visible electronic
spectra of C10D
Modeling of the fluorocarbon-
ozone system^
Critique of models used to
estimate chlorofluorocarbon
effects on ozoneb
Studies of reactions of HO2
by laser magnetic resonance
Continuation of 75-50
Measurement of stratospheric
distribution of fluoro-
carbons and related species
by infrared absorption
spectroscopyb
Measurement of reaction rates
relevant to the fluoro-
carbon-ozone problem"
Measurement of OH in the
stratosphere by laser
induced fluorescence
Investigator
Rasmussen
Organization
Proposal Completion
Number Date
Pitts
Campbell
Ekstrom
Nicholls
Sze
Cunnold,
Alyea,
Prinn
Thrush
Young
Murcray
Birks
Davis
Washington State U. 75-2
U. of Calif.- 75-12
Riverside
Washington State U. 75-53
Battelle Northwest 75-27
York U.
ERT, Inc.
CAP Associates
U. of Cambridge
Xonics, Inc.
U. of Denver
U. of Illinois
U. of Maryland
75-11
75-32
75-24
75-1
75-87
4/15/76
4/15/76
4/23/76
5/24/76
6/14/76
8/18/76
9/10/76
75-58 11/8/76
75-86 11/15/76
75-13 1/24/77
2/4/77
2/23/77
(continued)
K-45
-------
Table 4A (continued)
Program
Exploration for unidentified
factors in the fluorocarbon-
ozone problem^
Laboratory studies of the
infrared vibration-rotation
spectrum of CIO
Absolute calibration of fluoro-
carbon measurements
Collection and analysis of
Antarctic ice cores
The electron capture detector
as a reference standard in
the analysis of atmospheric
halocarbons
Laboratory measurement of
spectroscopic absorption
cross sections of CIO
Measurement of fluorocarfaon
content of "antique" air
samples
Measurement of HC1 and HF in
the stratosphere by Fourier
transform spectroscopyb
Continuation of program for
ground level monitoring of
ultraviolet solar radiation
Continuation of 75-lb
Studies of heterogeneous
reactions^3
Meteorological and multi-
dimensional modeling con-
siderations relating to
atmospheric effects of
halocarbons'3
Climatic effects of fluoro-
carbonsb
Investigator Organization
Lovelock Private
Proposal Completion
Number Date
Nicholls
Stedman
Lovelock
Davis
Buijs
Berger
Birks
Birks
Cunnold,
Alyea,
Prinn
Cunnold,
Alyea,
Prinn
75-67
York U.
U. of Michigan
Rasmussen Rasmussen Assoc.
Private
U. of Maryland
75-73
Bomem, Inc.
Temple U.
U. of Illinois
U. of Illinois
CAP Associates
75-98
75-62
CAP Associates
3/10/77
75-30b 3/25/77
76-132 4/1/77
75-84 4/19/77
76-120 5/3/77
5/12/77.
Rasmussen Washington State U. 75-71 9/2/77
9/26/77
10/20/7;
76-117A 12/12/77
76-117B 12/12/7:"
76-122 12/12/73.
76-122S 12/12/77
(continued*
K-46
-------
Table 4A (continued)
Program
Electron spin resonance detec-
tion of stratospheric radicals
Measurement of the concentration
of methyl chloride in air in
Kenya
Continuation of 75-67b
Kilauea volcanic emissions—
halocarbon measurement
Laboratory determination of the
feasibility of laser mag-
netic resonance for CIO
detection and reaction
studies
Photochemical and chemical
kinetic measurements of
stratospheric importance with
respect to the fluorocarbon
issue**
Laboratory measurement of high
resolution infrared spectra
of chlorine-containing
molecules of stratospheric
interest13
Reactions of the HO2 radical
studied by laser magnetic
resonance
Construction of Fourier-
transform spectrometer
Interlaboratory comparisons of
fluorocarbon measurements^
Generation and exchange of
calibrated samples of fluoro-
carbons
Laboratory investigation of the
heterogeneous interaction of
Cl and CIO with H2S04b
Investigator Organization'
a
Ehhalt
Lovelock
Rasmussen
Howard
Timmons
Murcray
Thrush
Buijs
Stedman
Martin
Nuclear Research
Establishment -
Juelich
Rasmussen Private
Private
Oregon Graduate
Center
NOAA-Boulder
Catholic U.
U. of Denver
U. of Cambridge
Bomem, Inc.
Rasmussen Private
U. of Michigan
Aerospace Corp.
Proposal Completion
Number Date
76-145 12/12/77
77-181 12/12/77
77-144 12/23/77
77-215 12/27/77
75-47
75-92
75-81
1/10/78
76-129 1/16/78
2/10/78
75-58 II 3/2/78
75-90 3/8/78
76-142 3/8/78
77-151 3/10/78
3/27/78
(continued)
K-47
-------
Table 4A (continued)
Program
Continuation of 75-32b
Studies of compounds of sulfur,
Investigator
Sze
Kaufman
Organization3
ERT, Inc.
Emory ,U.
Proposal
Number
76-115
76-126
Completion
Date
3/28/78
5/24/78
oxygen, and chlorine^
Total world ozone level:
statistical analysis
Stratospheric measurement of
CIO and OH
Laboratory study of the UV and
IR spectra of HOC1, HOON02,
and HCIO^ in the temperature
range of the stratosphere
Photochemistry of small
chlorinated molecules*3
Continuation of 75-2
Atmospheric chemistry of
peroxynitric acid
Continuation of 75-81
Ground-based infrared measure-
ments*3
Measurements of HC1, HF, CIO,
etc., in the stratosphere
by high resolution infrared
spectroscopy
Coordination and analysis of
data for atmospheric life-
time experiment"
Measurement of fluorocarbons
and related chlorocarbons
in the stratosphere by
collection and analysis
Continuation of 76-122b
Parzen,
Pagano
Murcray
Knauth
Rasmussen
Pitts
Martin
Zander
Girard
Cunnold,
Alyea,
Prinn
Ridley
Cunnold,
Alyea,
Prinn
Frontier Science
and Technology
Research Founda-
tion, Inc.
U. of Denver
U. of Kiel
Wiesenfeld Cornell U.
Washington State U.
U. of Calif.-
Riverside
Aerospace Corp.
U. of Liege
ONERA-France
CAP Associates
York U.
CAP Associates
76-106
76-135
75-88
77-213
76-102
77-199
5/25/78
5/30/78
77-171 6/14/78
76-128 7/5/78
75-59 8/10/78
77-190
75-81 II 12/6/78
76-141 12/11/78
1/2/79
2/13/79
2/26/79,
2/26/79
(continued),.
K-48
-------
Table 4A (continued)
Program
a
Operation of stations at
Adrigole and Barbados for
atmospheric lifetime experi-
mentb
Operation of stations in
American Samoa and Tasmania
for atmospheric lifetime
experiment^5
Development of primary fluoro-
carbon standards
Experimental investigation of
the branching ratio in the
O(!D) + H20 reaction
Acquisition of on-board
digital recording system
Theoretical models of strato-
spheric chemistry, per-
turbations , and trace gas
measurement a*5
Determination of the photo-
dissociation process and
absorption cross section
of FC-11 and 12 in the
near UV
Continuation of 76-129^
Total chlorine measurements
in the troposphere and
stratosphere
Millimeter wave observations
of chlorofluoromethane
byproducts in the strato-
sphere'3
Continuation of 76-126
Photoabsorption cross
sections for compounds of
atmospheric interest
Investigator Organization
Lovelock, Private
Simmonds
Rasmussen Oregon Graduate
Lovelock
Zellner
Murcray
Sze
Stuhl
Timmons
Eggleton
Solomon,
deZafra
Kaufman
Takacs
Private
U. of Denver
AER, Inc.
U. of Bochum
U. of Texas-
Arlington
AERE Harwell
Proposal Completion
Number Date
77-193 2/28/79
77-201 3/29/79
78-226 4/2/79
U. of Goettingen 77-195 4/12/79
77-211 4/12/79
77-173 4/17/79
77-170 5/3/79
77-214
76-116
6/15/79
7/6/79
SUNY Stony Brook 76-130 7/6/79
Emory U. 77-197 7/6/79
Rochester Inat. 77-196 7/24/79
Technol.
(continued)
K-49
-------
Table 4A (continued)
Program
Lower stratospheric measurement
of non-methane hydrocarbons
Laboratory study for deter-
mination of the equilibrium
constant of the reaction
C120 + H20 - 2 HOC1 and the
UV spectrum of HOC1
Effect of aerosol scattering on
ozone measurements with the
Dobson spectrophotometer
Continuation of 75-92b
Studies of homogeneous and
heterogeneous reactions of
importance to the strato-
sphere'5
Photodegradation of chloro-
fluoromethane in the
troposphere
Follow-up for photodecomposi-
tion of chloromethanes
absorbed on silica sur-
faces15
Continuation of 77-213°
Continuation of 77-199b
Continuation of 76-128
Measurement of halogen com-
pounds for determination of
total chlorine and total
fluorine in the stratosphere
using long-path interfero-
metric spectroscopy
Investigator Organization
Rasmussen Private
a
Knauth
Moe
Murcray
Birks
Korte
Ausloos
Cunnold,
Alyea,
Prinn
Cunnold,
Alyea,
Prinn
Wiesenfeld
Buijs
U. of Kiel
Private
U. of Denver
U. of Colorado
U. of Munich
NBS
CAP Associates
CAP Associates
Cornell
Bomem, Inc.
Proposal Completion
Number Date
76-140 7/30/79
77-224 8/9/79
78-235
77-152
77-192
77-194
77-186
78-251
78-252
77-220
77-168
9/12/79
10/17/79
11/8/79
11/16/79
11/28/75
12/17/79
1/18/80
2/1/80
2/4/80
(continued,
-------
Table 4A (continued)
Program
Determination of a measurement
system for the determination
of total chlorine in air
Identification of FC 21 in the
atmosphere
Continuation of 76-130b
Continuation of 77-193b
Continuation of 77-192b
Laser magnetic resonance study
of HO- chemistry
Study of CIO chemistry by laser
magnetic resonance
Continuation of 77-201b
Development and implementation
of a simplified multidimen-
sion model for stratospheric
chemistry perturbations,
radiation feedback and trace
gas measurement1*
Continuation of 77-1A2
Detection of selected mole-
cules by ground-based
solar spectroscopy
Analysis of Release of FC-11
from Rigid Plastic Foam
Products in the U. S.
The exponential dilution
chamber for the calibration
of instruments and the
preparation of standards13
Investigator Organization
Skogerboe Colorado State U.
Rasmussen
Solomon,
deZafra
Lovelock,
Simmonds
Birks
Howard
Howard
Sze
Murcray
Shamel
Lovelock
Oregon Graduate
Center
SUNY Stony Brook
Private
U. of Colorado
NOAA-Boulder
NOAA-Boulder
Rasmussen Oregon Graduate
Center
AER, Inc.
Rasmussen Oregon Graduate
Center
U. of Denver
A.D.Little, Inc.
Private
Proposal Completion
Number Date
77-206 2/4/80
78-260 2/5/80
77-225 2/13/80
78-243 2/18/80
78-244 2/20/80
76-100 3/12/80
77-223 3/12/80
78-248 4/24/80
78-234 5/14/80
78-247
78-228
79-275
78-264
5/28/80
5/29/80
5/29/80
7/9/80
(continued)
K-51
-------
Table 4A (continued)
Program
Rates of reaction of Cl atoms
with the primary products of
alkane photooxldatlon
Determination of FC-21 and other
halocarbons In the troposphere
Determination of atomic oxygen
yields In the photolysis of
HOC1 and C100
Submillimeter-infrared balloon
experiment^5
Effectiveness of various un-
treated sand surfaces bringing
about the oxidation of CCl^,
CFC13, and CF2C12
The A2IIi + X2JIi Band System
of ClOb
Investigator Organization
Kurylo NBS
Bruner
Phillips
Bonetti,
Car11,
Harries
Ausloos
Urbino U.
U. of Canterbury
(N.Z.)
CNR - IROE
(Florence, Italy),
National Physi-
cal Laboratory
U. K.
NBS
Proposal Completion
Number Date
________ i
78-233 9/4/80
78-256 9/23/80
78-241 9/30/80
76-137 11/6/80
78-254
Coxon
Dalhousie U.
78-255
a. Abbreviated affiliations are expanded under study descriptions in Table 3.
b. Work continued in a follow-on contract.
c. Final report accepted by the Panel.
November 30, 1980
K-52
-------
Table 4B
Research Funded by the Chlorofluorocarbon Industry
and
Administered by the Chemical Manufacturers Association
WORK IN PROGRESS
Program
Continuation of 75-13
Continuation of 75-11
Operational costs for flights
planned in 1977
Laboratory measurment of
infrared spectra of
selected stable molecules
Development of technique for
measuring total chlorine
content of air
Simultaneous balloon flight
with J. G. Anderson
Continuation of 76-141
Absorption measurements of
HOC1 and related mole-
cules
Statistical analysis of
worldwide stratospheric
ozone data for the
detection of trends0
Continuation of 78-234c
Statistical investigations
of the CFM problem
Continuation of 77-152
Continuation of 78-244c
Investigator Organization
Murcray U. of Denver
Nicholls York U.
Buijs Bomem, Inc.
Proposal Contract
Number
Date
Buijs
Howard,
Birks,
Fehsenfeld
Murcray
Zander
Timmons
Tiao, Box
Sze
Watson
Murcray
Birks
76-101 4/6/76
75-11 II 8/18/76
77-156 6/9/77
U. of Liege
U. of Texas-
Arlington
U. of
Wisconsin
AER, Inc. 79-273
Princeton U. 78-257
U. of Denver 78-265
U. of Colorado 79-276
Contract
Period
10 b
12 mo.
12 mo.b
12 mo.b
Bomem, Inc. 77-221 2/24/78 14 mo.1
NOAA-Boulder/ 77-222 3/27/78 12 mo.
U. of Colorado
U. of Denver 77-166 4/27/78 9 mo.
78-232 6/28/78 12 mo.
78-258 1/12/79 12 mo.1
78-250 4/4/79 18 mo.
7/26/79 12 mo.
8/2/79 24 mo.
8/23/79 12 mo.1
9/1/79
12 mo.
(continued)
K-53
-------
Table 4B (continued)
Program
a
Proposal Contract Contract
Investigator Organization Number
Date
Measurement of the Vertical
Distribution of HC1, 03,
and ECHO and the ratio
HF/HC1
Jouve
U. of Reims
79-290
Period
Combination and continuation
of 78-251 and 78-252C
Determination of tropospherlc
halocarbons and their
relative importance
Continuation of 78-243c
Operation of Fifth ALE
Station, Cape Mearea, ORC
Continuation of 78-248c
Continuation of 77-225c
Reaction of CIO with OH
Kinetic Studies of Strato-
spheric Chlorine Chem-
istry
Reaction of OH with CIO
Continuation of 78-264
Airborne millimeter wave
determination of CIO
Uncertainties and benefit-
cost analysis of CFC
control
Continuation of 79-273
Continuation of 79-278
Cunnold ,
Alyea,
Prinn
Simmonds ,
Lovelock
Simmonds
Rasmussen
Rasmus sen
Solomon,
deZafra
Donovan
Howard
Ravishankara
Lovelock
Beckman
Bailey
Sze
Solomon,
deZafra
CAP Assoc.
Private
Private
Oregon Grad-
uate Center
Oregon Grad-
uate Center
SUNY Stony
Brook
U. of
Edinburgh
NOAA-Boulder
Georgia Tech.
Private
Queen Mary
College,
London
U. of
Maryland
AER, Inc.
SUNY Stony
Brook
79-281
79-269
79-280
78-263
79-279
79-278
79-286
79-289
80-295
80-293
79-282
80-317
80-311
80-316
11/16/79
11/19/79
11/20/79
11/21/79
11/21/79
1/3/80
2/20/80
4/20/80
5/23/80
6/9/80
6/24/80
8/7/80
8/11/80
8/19/80
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
6 mo.
6 mo.
Open
12 mo.
12 mo.
b
b
b
b
b
9/18/80 12 mo.
(continued)
K-54
-------
Program
Table 4B (continued)
Proposal Contract Contract
Investigator Organization Number Date Period
F-22 measurements in the
atmosphere
Continuation of 78-250
Continuation of 79-276
Continuation of 78-255
Far-infrared laboratory
spectroscopy of halogen-
containing molecules
Continuation of 79-281
Continuation of 76-137
Infrared spectroscopy of
atmospheric species
Near- and Far- Infrared
Spectroscopy
Reactions within the HOX
cycle
Modeling of the CFC effect
on the ozone layer
Collaborative studies on
atmospheric spectroscopy
Continuation of 79-280
Continuation of 78-263
and 79-279
An inter comparison of
measurements of strato-
Rasmussen
Reinsel ,
Tiao
Birks
Coxon
Traub ,
Chance
Cunnold ,
Alyea,
Prinn
Bonetti
Howard
Saykally
Kurylo
Brasseur
Goldman,
Barbe
Simmonds
Rasmus sen
Murcray ,
Roscoe
Private
U, of
Wisconsin
U. of Colorado
Dalhousie U.
Smithsonian
Astrophysical
Observatory
at Harvard
CAP Assoc.
U. of Florence
NOAA-Boulder
U. of
California
NBS
Institut
d ' Aeronomie
Spatiale,
Belgium
U. of Denver/
U. of Reims
Private
Oregon Gradu-
ate Center
U. of Denver,
Oxford U.
80-308
80-304
80-321
80-315
80-318
80-323
80-297
80-299
80-300
80-307
80-320
80-322
80-324
80-325
80-328
9/26/80
10/13/80
10/21/80
10/23/80
10/31/80
11/18/80
Pending
Pending
Pending
Pending
Pending
Pending
Pending
Pending
Pending
6 mo.
15 mo.
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
24 mo.
12 mo.
12 mo.
12 mo.
12 mo.
12 mo.
Open
spheric HC1
(continued)
K-55
-------
Table 4B (continued)
Proposal Contract Contract
Program ' Investigator Organization Number Date Period
Continuation of 79-276 Birks U. of Colorado 80-329 Pending 12 mo.
a. Abbreviated affiliations are expanded under study descriptions in Table 3.
b. Contract extended.
c. Work continued in a follow-on contract.
d. Dependent on appropriate cofunding.
November 30, 1980
K-56
-------
Table 5
PUBLICATIONS FROM WORK SUPPORTED BY CHLOROFLUOROCARBON MANUFACTURERS
Alexander Grant & Company
1. Environmental Analysis of Fluorocarbons FC-11, FC-12, and FC-22,
February 5, 1976.
2. Environmental Analysis of Fluorocarbons FC-11, FC-12, and FC-22—
Manufacturing Chemists Association, July 8, 1977.
3. 1977 World Production and Sales of Fluorocarbons FC-11 and FC-12,
June 26, 1978.
4. 1978 World Production and Sales of Fluorocarbons FC-11 and FC-12,
July 24, 1979.
Allied Chemical Corporation
1. Statistical Modeling of Total Ozone Measurements with an Example
Using Data from Arosa, Switzerland, W. J. Hill and P. N. Sheldon,
Geophys. ReB. Lett., 21 (12), 541-4 (1975).
•I^MM^^te^^^M^H^Mi^^^^nM^B^^MB^BMM^^^^^ ^QM
2. Analyzing Worldwide Total Ozone for Trends, W. J. Hill, P. N.
Sheldon, and J. J. Tiede, Geophys. Res. Lett., £(1), 21-4 (1977).
3. Quantifying the Threshold of Stratospheric Ozone Trend Detection
Using Time Series Analysis, P. N. Sheldon, J.J. Tiede, and W. J.
Hill, Proc. Fifth Conf. Probability Statistics (Am. Meterol.
Soc.), 234-9 (1977).
4. Ozone Trend Detectability: Update and Discussion, J.J. Tiede,
P. N. Sheldon, and W. J. Hill, Atmos. Environ., 13(7), 999-1003
(1979).
P. Ausloos, National Bureau of Standards
1. Decomposition of N20 Over Particulate Matter, R. E. Rebbert and
P.A., Geophys. Res. Lett., J5 (9), 761-4 (1978).
J. W. Birks, University of Colorado (Formerly University of Illinois)
1. Four-Center Reactions Involving Dichlorine Monoxide, J.W.B., B.
Shoemaker, T.J. Leek, and D.M. Hinton, draft ms.
2. Studies of Reactions of Importance in the Stratosphere. I. Reaction
of Nitric Oxide With Ozone, J.W.B., B.Shoemaker, T.J. Leek, and
D.M. Hinton, J. Chem. Phys., 65 (12), 5181-5 (1976) (12/15/76).
I^^MM^^^M^BM^MM^^B^^^^H^^M^M^ ^^^%
(continued)
K-57
-------
Table 5 (continued)
J. W. Birks, University of Colorado (Continued)
3. Studies of Reactions of Importance in the Stratosphere. II. Re-
actions Involving Chlorine Nitrate and Chlorine Dioxide, J.W.B.,
B. Shoemaker, T.J. Leek, R.M. Borders, and L.J. Hart, J. Chem.
Phva.. 66 (10), 4591-9 (1977) (5/15/77).
4. Studies of Reactions of Importance in the Stratosphere. III.
Rate Constant and Products of the Reaction Between ClO and H02
Radicals at 298 K, T.J. Leek, J-E.L. Cook, and J.W.B., J. Chem.
Phys., 72 (4), 2364-73 (1980).
5. Studies of Reactions of Importance in the Stratosphere. IV. Rate
Constant for the Reaction Cl+HOCl •» HCl+ClO over the Temperature
Range 243-265 K, J-E.L. Cook, C.A. Ennis, T.J. Leek, and J.W.B.,
draft ms.
A. Bonetti, University of Florence
1. New Measurements of Stratospheric Composition Using Submilli-
metre and Infrared Emission Spectroscopy, M.J... Bangham, A.B.,
R.H. Bradsell, B. Carli, J.E. Harries, F. Mencaraglia, D.G.
Moss, S. Pollitt, E. Rossi, and N. R. Swann, draft ms.
F. Bruner, University of Urbino
1. A Calibration Method for the GC Analysis of Halocarbons in
Atmospheric Samples Using Permeation Tubes and BCD, G.
Crescentini, F. Mangani, A.R. Mastrogiacomo, and F.B., draft ms.
2. Occurrence of F21 (CHCljF) in the Troposphere, G. Crescentini
and F. B., draft ms.
H. L. Buijs, Bomem, Inc.
1. Simultaneous Measurement of the Volume Mixing Ratios of HC1 and
HP in the Stratosphere, H.L.B., G.L. Vail, G. Tremblay, and
D.J.W. Kendall, Geophys. Rea. Lett., 2. W' 205-8 (1980).
M. J. Campbell, Washington State University
1. Halocarbon Decomposition by Natural lonization, M.J.C., Geophys.
Res. Lett., 3 (11), 661-4 (1976).
^•— «•>
2. Reply to comments by F.C. Fehsenfeld and D.L. Albritton on
preceding paper [Geophys. Res. Lett., £(1), 61-3 (1979], M.J.C.,
Geophys. Res. Lett., 1 (1), 64 (1977).
(continued)
K-58
-------
Table 5 (Continued)
Chemical Manufacturers Association
1. World Production and Release of Chlorofluorocarbons 11 and 12
Through 1978, August 6, 1979.
2. World Production and Release of Chlorofluorocarbons 11 and 12
Through 1979, May 23, 1980.
M.A.A. Clyne, Queen Mary College (London)
1. Reaction Kinetics Involving Ground X2II and Excited A2E+ Hydroxy
Radicals. Part 1. Quenching Kinetics of OH A2Z+ and Rate
Constants for Reactions of OH X2II with CH3CCl3 and CO, M.A.A.C.
and P.M. Holt, J. Chem. Soc. Faraday Trans. 2, 75 (3) 569-81
(1979). —
2. Reaction Kinetics Involving Ground X2II and Excited A2!* Hydroxy
Radicals. Part 2. Rate Constants for Reactions of OH X2II with
Halogenomethanes and Halogenoethanes, M.A.A.C. and P.M. Holt,
J. Chem. Soc. Faraday Trans. 2, 75 (3), 582-91 (1979).
3. Kinetic Studies of Free Radical Reactions by Mass Spectrometry.
I. The Reactions SO + N02 and CIO + NO, M.A.A.C. and A.J.
MacRobert, Int. J. Chem. Kinet., 12 (2), 79-96 (1980).
R. A. Cox, AERE Harwell (England)
1. Kinetics of Chlorine Oxide Radicals Using Modulated Photolysis.
Part 2. ClO and C100 Radical Kinetics in the Photolysis of
Cl2 + 02 + N2 Mixtures, R.A.C, R.G. Derwent, A.E.J. Eggleton,
and H.J. Reid, J. Chem. Soc. Faraday Trans. 1, 75 (7), 1648-66
(1979).
P.M. Cunnold, F.N. Alyea, R.G. Prinn, Massachusetts Institute of
Technology and Georgia Institute of Technology
1. The Impact of Stratospheric Variability on Measurement Programs
for Minor Constituents, R.G.P., F.N.A., and D.M.C., Bull. Am.
Meteorol. Soc., 57 (6), 686-94 (1976)
2. Meteorological Control of Lower Stratospheric Minor Species
Variations: An Observational Example, F.N.A. and D.M.C., Atmos.
Environ., 12, (6-7), 1075-80 (1978).
3. Meterorological Constraints on Tropospheric Halocarbon and
Nitrous Oxide Destructions by Siliceous Land Surfaces, F.N.A.,
D.M.C., and R.G.P., Atmos. Environ, !£ (6-7), 1009-11 (1978).
4. A Methodology for Determining the Atmospheric Lifetime of Fluro-
carbons, D.M.C., F.N.A., and R.G.P., J. Geophys. Res., 83 (C 11),
5493-5500 (1978). ~*
(continued)
K-59
-------
Table 5 (Continued)
P.M. Cunnold, F.N. Alyeaf R.G. Prinn, Massachusetts Institute of
Technology and Georgia Institute of Technology (continued)
5. Uncertainties in Feedbacks in Simple Climate Models and Their
Influence on Prediction of the Climatic Impact of Fluorocarbons,
R.G.P., F.N.A., C.A. Cardelino, and D.M.C, draft ms.
6. Comment on "Measurement of CCl^F and CC14 at Harwell over the
Period January 1975-November 1977," D.M.C., F.N.A., and R.G.P.,
Atmos. Environ., 14(5), 617-18 (1980).
D. D. Davis, Georgia Institute of Technology (Formerly University of
Maryland).
1. A Temperature Dependent Kinetics Study of the Reaction of OH
with CHsCl, CH2C12, CHCla, and CK^Er, D.D.D., G. Machado,
B. Conaway, Y. Oh, and R. Watson, J. Chem. Phys., 65 (4),
1268-74 (1976) (8/15/76). *~*
2. A Temperature Dependent Kinetics Study of the Reaction of OH
with CH2C1F, CHC12F, CHC1F2, CH3CCl3, CH3CF2C1, and CF2C1CFC12,
R. T. Watson, G. Machado, B. Conaway, S. Wagner, and D.D.D.,
J. Phys. Chem., 81 (3), 256-62 (1977) (2/10/77).
2 2
3. High Resolution Absorption Cross Sections for the A n-X II Sys-
tem of CIO, P. H. Wine, A. R. Ravishankara, D. L. Philen, D.D.D.,
and R. T. Watson, Chem. Phys. Lett., 50 (1), 101-6 (1977)
(8/15/77). ~~
E. I. du Pont de Nemours & Company, Inc.
1. Atmospheric Stability of Fluoroalkanes - Implications for Ozone
Depletion, R. L. McCarthy and J. P. Jesson, Symposium on Fluo-
rine Chemistry, Kyoto, Japan, August 26, 1976.
2. Measurement of the Reaction Rate of CFC13 with Atmosphere-Like
Ions, R. G. Hirsch, Atmos. Environ., 10 (9), 703-5 (1976).
Comment. F. C. Fehsenfeld, D. L. Albritton, et al., Ibid., 11
(3), 283-4 (1977). Reply, R.G.H., 284-5.
3. Laboratory Microwave Spectrum of C10N02 and Evidence for the
Existence of C10NO, R. D. Suenram, D. R. Johnson, L. C. Glasgow,
and P. Z. Meakin, Geophys. Res. Lett., 3 (10), 611-14 (1976),
^ (12) , 758 (1976) . """
4. The Fluorocarbon-Ozone Theory. I. Production and Release,
World Production and Release of CC13F and CC12F2 (Fluorocarbons
11 and 12) through 1975, R. L. McCarthy, F. A. Bower, and J. P.
Jesson, Atmos. Environ., 11 (6), 491-7 (1977).
(continued)
K-60
-------
Table 5 (continued)
E. I. du Pont de Nemours & Company, Inc. (continued)
5. The Fluorocarbon-Ozone Theory. II. Tropospheric Lifetime, An
Experimental Estimate of the Tropospheric Lifetime of CC13F,
J. P. Jesson, P. Meakin, and L. C. Glasgow, Atmos. Environ.,
11 (6), 499-508 (1977).
Photodecomposition of Chloromethanes Adsorbed on Silica Surfaces,
P. Ausloos, R. E. Rebbert, and L. C. Glasgow, J. Res. Nat. Bur.
Stand., A, 82 (1), 1-8 (1977) (7-S/-/77).
7. A One-Dimensional Model of ATmospheric Transport and Photochem-
istry, P. Meakin, C. Miller, R. G. E. Franks, and J. P. Jesson,
draft ms.
8. World Production and Release of Chlorofluorocarbons 11 and 12
Through 1976, Anon., draft ms., July 15, 1977.
9. The Stratospheric Abundance of Peroxynitric Acid, J. P. Jesson,
L. C. Glasgow, D. L. Filkin, and C. Miller, Geopnys. Res. Lett.,
JL (11), 513-16 (1977).
10. World Production and Release of Chlorofluorocarbons 11 and 12
Through 1977, Anon., draft ms., July 17, 1978.
11. The Fluorocarbon-Ozone Theory. III. 'Fluorocarbon Mixing and
Photolysis. The Effects of Eddy Diffusion and Tropospheric
Lifetime on C13F and CC12F2 Tropospheric Mixing Ratios, P.
Meakin, P. S. Gumerman, L. C. Glasgow, and J. P. Jesson, Atmos.
Environ., I2_ (6-7) , 1271-85 (1978).
12. The Fluorocarbon-Ozone Theory. IV. Fluorocarbon Mixing and
Photolysis. The Effects of Eddy Diffusion and Tropospheric
Lifetime on Stratospheric Odd Chlorine Mixing Ratios, L. C.
Glasgow, P. S. Gumerman, P. Meakin, and J. P. Jesson, Atmos.
Environ., 12, (11), 2159-72 (1978).
13. The Fluorocarbon-Ozone Theory. V. One-dimensional Modeling
of the Atmosphere, C. Miller, P. Meakin, R. G. E. Franks, and
J. P. Jesson, Atmos. Environ., ,12. (12) 2481-2500 (1978) .
14. The Fluorocarbon-Ozone Theory. VI. Atmospheric Modeling—
Calculation of the Diurnal Steady State, C. Miller, D. L.
Filkin, and J. P. Jesson, Atmos. Environ., 13 (3), 381-94
(1979).
15. Extended Theory of Tandem Electron Capture Detectors, J. D. Lee
and R. G. Hirsch, Atmos. Environ., 13. (9), 1305-9 (1979).
16. The Stratospheric Abundance of Hypochlorous Acid (HOC1), L. C.
Glasgow, J. P. Jesson, D. L. Filkin, and C. Miller, Planet.
Space Sci., 27 (8), 1047-54 (1979).
^••^Mi
(continued)
1C-61
-------
Table 5 (continued)
E. I. du Pont de Nemours & Company, Inc. (continued)
17. Temperature Dependent Absorption Cross-Sections for Formaldehyde
(CH20): The Effect of Formaldehyde on Stratospheric Chlorine
Chemistry, A. M. Bass, L. C. Glasgow, C. Miller, J. P. Jesson,
and D. L. Filkin, Planet. Space Sci., 2^ (7), 675-9 (1980).
18. The Fluorocarbon-Ozone Theory. VII. One Dimensional Modeling.
An Assessment of Anthropogenic Perturbations, C. Miller, J. M.
Steed, D. L. Filkin, and J. P. Jesson, Atmos. Environ., in
press.
19. Two-Dimensional Model Calculations of Stratospheric HC1 and CIO,
J. M. Steed, C. Miller, D. L. Filkin, and J. P. Jesson, Nature,
in press.
20. Time Series Search for Trend in Total Ozone Measurements, D. S.
St. John, draft ms.
J. E. Harries, National Physical Laboratory, U. K.
1. See 1 under Bonetti.
Hoechst AG
1. Global Distribution of Fluorocarbons, 0. Klais and H. J. Fink,
Ber. Bunsenges. Phys. Chem., 8J. (11), 1147-50 (1978).
2. Heterogeneous Photolysis of Fluorocarbons Adsorbed on Artificial
and Natural Dusts and Sand Samples, 0. Klais and M. F. Feser,
Hoechst Internal Report, 1978.
C. J. Howard, NOAA Boulder
1. Kinetics of the Reaction of H02 with N02, C.J.H., J. Chem. Phys.,
£7 (11), 5258-63 (1977).
2. Kinetics of the Reaction of HO? with NO, C.J.H. and K. M.
Evenson, Geophys. Res. Lett., J^ (10) 437-40 (1977).
3. Temperature Dependence of the Reaction H02 + NO •* OH + N02,
C.J.H., J. Chem. Phys., 71_ (6) , -2352-9 (1979).
4. Temperature Dependence of the Reaction of CIO and HO2 Radicals,
R. M. Stimpfle, R. A. Perry, and C.J.H., J. Chem. Phya., 71
(12) , 5183-90 (1979) . ~~
(continued)
K-62
-------
Table 5 (continued)
C. J. Howard, NOAA Boulder (continued)
5. Kinetics of the Reaction of HO2 with Ozone, M. S. Zahniser and
C.J.H., J. Chem. Phys., TQ (4), 1620-6 (1980).
6. Yields of H02 in the Reaction of Hydrogen Atoms with Ozone,
C.J.H. and B. J. Finlayson-Pitts, J. Chem. Phys., 72 (6),
3842-3 (1980). -"*•
7. Kinetic Study of the Equilibrium H02 + NO = HO + N02 and the
Thermochemistry of H02> C.J.H., J. Am. Chem. Soc., 102 (23),
6937-41 (1980). ~~~*
8. Tunable Diode Laser Measurement of Nitrous Oxide in Air, P. S.
Connell, R. A. Perry, and C.J.H., Geophys. Res. Lett., in
press.
9. Laser Magnetic Spectroscopy of CIO and Kinetic Studies of the
Reactions of CIO with NO and N02, Y. P. Lee, R. M. Stimpfle,
R. A. Perry, J. A. Mucha, K. M. Evenson, D. A. Jennings, and
C.J.H., draft ms.
M. Kaufman, Emory University
1. Rate Constant of the Reaction between Chlorine Atoms and Sulfur
Dioxide and Its Significance for Stratospheric Chlorine Chem-
istry, L. W. Strattan, R. E. Eibling, and M. K., Atmos. Environ.,
13 (1), 175-7 (1979).
H. D. Knauth, University of Kiel
1. Equilibrium Constant of the Gas Reaction C120 + H2O = 2HOC1
and the Ultraviolet Spectrum of HOCl, H.D.K., H. Alberti, and
H. Clausen, J. Phys. Chem., JQ (12), 1604-12 (1979).
F. Korte, Technical University of Munich
1. Mineralization of Chlorofluorocarbons in the Sunlight of the
Troposphere, S. Gaeb, J. Schmitzer, H. W. Thamm, and F.K.,
Angew. Chem. Int. Ed. Engl., 17_ (5) , 366 (1978).
2. Heterogeneous Photodecomposition of Fluorochlorocarbons under
Simulated Tropospheric Conditions, S. Gaeb and F.K., Ber.
Bunsenges. Phys. Chem., 82, (11), 1151-3 (1978).
3. Degradation of CC12F2: Formation of C02 upon Adsorption on
Mecca Sand, M. Bahadir, S. Gaeb, J. Schmitzer, and F.K.,
Chemosphere, 7 (12), 941-2 (1978).
•^^^••^^^•^M^HMMH^M^B^^BM ^^^
(continued)
K-63
-------
Table 5 (continued)
F. Korte, Technical University of Munich (continued)
14
4. Mineralisation of CC12F2 Catalyzed by Active Surfaces,
M. Bahadir, S. Gaeb, J. Schmitzer, and F.K., Z. Naturforach. B,
,34 (6), 822-6 (1979).
5. Mineralization of CCl4 and CC12F2 on Solid Surfaces, Z.
Naturforsch. B, £5, (8), 946-52 (1980).
M. J. Kuryloj National Bureau of Standards
i. Rate Constant Measurements for the Reaction Cl + CH20 •* HCl +
CHO. Implications Regarding the Removal of Stratospheric
Chlorine, P. C. Anderson and M.J.K., J. Phys. Chem., j 3. (16),
2055-7 (1979).
2. A Flash Photolysis Resonance Fluorescence Investigation of the
Reaction OH + CH3CC13 + H20 + CH2CC13, M.J.K., P. C. Anderson,
and 0. Klais, Geophys. Res. Lett., .6. (10), 760-2 (1979).
3. An Upper Limit for the Rate Constant of the Bimolecular Reaction
CH3 + 02 * HO + H2CO at 368K, 0. Klais,. P. C. Anderson, A. H-
Laufer, and M. J. K., Chem. Phys. Lett., 66 (3), 598-601 (1979).
4. Rate Constant Determinations for the Reaction of Hydroxyl
Radicals with Methyl Chloroform: A Review of Recent Studies
and Their Effect on the Calculation of Tropospheric OH, M.J.K.,
P. C. Anderson, and 0. Klais, draft ms.
5. A Reinvestigation of the Temperature Dependence of the Rate Con-
stant for the Reaction 0+02+M+03+M (for M « 02/ »2, and
Ar) by the Flash Photolysis Resonance Fluorescence Technique,
0. Klais, P. C. Anderson, and M.J.K., Int. J. Chem. Kinet.,
1^ (7) , 469-90 (1980).
6. Atmospheric Quenching of Vibrationally Excited 02<1A) » 0. Klais,
A. H. Laufer, andM.J.K., J. Chem. Phys., j73^ (6) , 2696-9 (1980).
J. E. Lovelock, University of Reading
1. Atmospheric Halocarbons and Stratospheric Ozone, J.E.L., Nature,
^52, 292-4 (1974) (11/22/74).
2. Long-range Transport of Photochemical Ozone in Northwestern
Europe, R. A. Cox, A. E. J. Eggleton, R. G. Derwent, J.E.L.,
and D. H. Pack, Nature, 255, 118-21 (1975) (5/8/75).
3. Natural Halocarbons in the Air and Sea, J.E.L., Nature, 256,
193-4 (1975) (7/17/75). ~*~
(continued)
K-64
-------
Table 5 (continued)
J. E. Lovelock, University of Reading (continued)
4. Photochemical Oxidation of Halocarbons in the Troposphere,
R. A. Cox, R. P. Derwent, A. E. J. Eggleton, and J.E.L.,
Atmos. Environ., l^ (4), 305-8 (1976).
5. Halocarbon Behavior from a Long Time Series, D. H. Pack, J.E.L.,
G. Cotton, and C. Curthoys, Atmos. Environ., 11 (4), 329-44
(1977).
6. The Electron Capture Detector Theory and Practice, J.E.L.,
J. Chromatogr., 99, 3-12 (1974).
7. Methyl Chloroform in the Troposphere as an Indicator of OH
Radical Abundance, J.E.L., Nature, 267, 32 (1977).
8. Fluorotrichloromethane and Tetrachloromethane Data in the British
Isles 1970-1975, J.E.L. and D. H. Pack, Health Saf. Lab. Environ.
Q. - U. S. Energy Res. Dev. Adm., (April), 3-20 (1976).
9. Electron-Capture Detector: Theory and Practice. II. J.E.L.
and A. J. Watson, J. Chromatogr., JJ58, 123-38 (1978).
L. R. Martin and H. S. Judeikis, Aerospace Corporation
1. Measurement of Chlorine Atom Diffusion, H.S.J. and M. Wun,
J. Chem. Phys., 68. (9), 4123-7 (1978) (5/1/78).
2. Chlorine Atom and ClO Wall Reaction Products, L.R.M., A. G. Wren,
and M. Wun, Int. J. Chem. Kinet., j.^ (5), 543-57 (1979).
3. Surface Reactions of Chlorine Molecules and Atoms with Water and
Sulfuric Acid at Low Temperatures, A. G. Wren, R. W. Phillips,
and L. U. Tolentino, J. Colloid Interface Sci., 70 (3), 544-57
(1979). "*~
4. Heterogeneous Reactions of Cl and CIO in the Stratosphere, L.R.M.,
H.S.J., and M. Wun, J. Geophys. Res., ^ (CIO), 5511-18 (1980).
K. Moe
1. Simultaneous Measurements of Total Ozone and Aerosol Extinction,
K.M., L. Muth, and P. Crooimans, ms. for presentation at Inter-
national Ozone Symposium, Boulder, Colo., 1980.
(continued)
K-6S
-------
Table 5 (continued)
D. G. Murcray, University of Denver
1. Simultaneous Stratospheric Measurements of Pluorocarbons and
Odd Nitrogen Compounds, W. J. Williams, J. J. Rosters, :
A. Goldman, and D.G.M., draft ms.
2. Statistical-Band-Model Analysis and Integrated Intensity for
the 10.8 ym Band of CF2C12/ A. Goldman, F. S. Bonomo, and D.G.M.,
Geophys. Res. Lett., 3 (6), 308-12 (1976).
^^^^^^^••^^^^•^^••^^•••^••••^^MH^Mfl^^^B ^^f+
3. Measurements of Stratospheric Fluorocarbon Distribution Using
Infrared Techniques, W. J. Williams, J. J. Rosters, A. Goldman,
and D.G.M., Geophys. Res. Lett., 3. (7), 379-82 (1976).
4. Measurement of Stratospheric Mixing Ratio Altitude Profile of
HC1 Using Infrared Absorption Techniques, W. J. Williams, J. J.
Rosters, A. Goldman, and D.G.M., Geophys. Res. Lett., 3 (7),
383-5 (1976). *~
5. Statistical Band Model Analysis and Integrated Intensity for
the 11.8 urn Band of CFC13, A. Goldman, F. S. Bonomo, and D.G.M.,
Appl. Opt., IS, (10), 2305-7 (1976).
6. Upper Limit for Stratospheric C10N02 from Balloon-Borne Infrared
Measurements, D.G.M., A. Goldman, W. J. Williams, F. H. Murcray,
F. S. Bonomo, C. M. Bradford, G. R. Cook, P. L. Hanst, and
M. J. Molina, Geophys. Res. Lett., 4 (6), 227-30 (1977).
^M^H^MM^^MMNMMM^^HIMHM^M^H^^MM^M #^^
7. Identification of the V3 Vibration-Rotation Band of CF4 in
Balloon-Borne Infrared Solar Spectra, A. Goldman, D.G.M., F. J.
Murcray, G. R. Cook, J. W. Van Allen, F. S. Bonomo, and R. D.
Blatherwick, Geophys. Res. Lett., J5_ (7), 609-12 (1979).
8. Stratospheric Distribution of Chlorine Nitrate, D.G.M., A.
Goldman, F. H. Murcray, F. J. Murcray, and W. J. Williams,
Geophys. Res. Lett., 6^ (11), 857-9 (1979).
R. W. Nicholls, York University
1. The Absorption Cross Sections and f-Values for the v" = 0
Progression of Bands and Associated Continuum for the CIO
(A2IIi •*• X2IIi) System, M. Mandelman and R.W.N., J. Quant.
Spectrosc. Radiat. Transfer, 17 (4), 483-91 (19777"!
M. Pagano and E. Parzen, State University of New York at Buffalo
1. Statistical Time Series Analysis of Worldwide Total Ozone for
Trends, E.P., M.P., and H. J. Newton, draft ms.
(continued)
K-66
-------
Table 5 (continued)
J. N. Pitts, Jr., and 0. C. Taylor, University of California
at Riverside"
1. Fluorocarbons in the Los Angeles Basin, N. E. Hester, E. R.
Stephens, and O.C.T., J. Air Pollut. Control Assoc., 24 (6),
519-5 (1974). "*-*
2. Relative Rate Constants for the Reaction of 0( D) Atoms with
Fluorocarbons and N20, J.N.P., H. L. Sandoval, and R. Atkinson,
Chem. Phys. Lett., 29^ (1) , 31-4 (1974) (11/1/74).
3. Reactions of Electronically Excited 0( D) Atoms with Fluoro-
carbons, H. L. Sandoval, R. Atkinson, and J.N.P., J. Photochem.,
£ (4), 325-7 (1974).
4. Tropospheric and Stratospheric Chemical Sinks for Commercial
Fluorocarbons, J.N.P. and R. Atkinson, Trans. Amer. Geophys.
Union, 55L (12) , 1153 (1974).
5. Mechanisms of Photochemical Air Pollution, J.N.P. and B. J.
Finlayson, Angew. Chem. Int. Ed. Engl., 14 (1), 1-15 (1975).
6. Fluorocarbon Air Pollutants. II. N. E. Hester, E. R. Stephens,
and O.C.T., Atmos. Environ., A (6^7), 603-6 (1975).
7. Fluorocarbon Air Pollutants, Measurements in Lower Stratosphere,
N. E. Hester, E. R. Stephens, and O.C.T., Environ. Sci. Technol.,
^ (9), 875-6 (1975).
8. The Photostability of Fluorocarbons, S. Japar, J.N.P., and
A. M. Winer, draft ms.
9. Background and Vertical Atmospheric Measurements of Fluorocarbon-
11 and Fluorocarbon-12 over Southern California, L. Zafonte,
N. E. Hester, E. R. Stephens, and O.C.T., Atmos. Environ., 9,
1007-9 (1975). **
10. Rate Constants for the Reaction of OH Radicals with CHF2C1,
CF2C12, CFC13, and H2 Over the Temperature Range 297-434K,
R. Atkinson, D. A. Hansen, and J.N.P., J. Chem. Phys., 63 (5),
1703-6 (1975) (9/1/75).
11. Tropospheric and Stratospheric Sinks for Halocarbons: Photo-
oxidation, 0(1D) Atom and OH Radical Reactions, R. Atkinson,
G. M. Brewer, J.N.P., and H. L. Sandoval, J. Geophys. Res.,
^(33), 5765-70 (1976) (11/20/76).
12. Fluorocarbon Air Pollutants. III. Fluorocarbon Measurements in
the Lower Stratosphere, N. E. Hester, E. R. Stephens,and O.C.T.,
draft ms.
(continued)
K-67
-------
Table 5 (continued)
J. N. Pitts, Jr., and 0. C. Taylor, University of California
at Riverside (continued)
13. Ultraviolet and Infrared Absorption Cross Sections of Gas
Phase H02N02/ R. A. Graham, A. M. Winer, and J.N.P., Geophys.
Res. Lett., 5 (11), 909-11 (1978).
^^^••M^^^M^M^M^H^BM ^M^
R. A. Rasmussen, Oregon Graduate Center (Formerly Washington State
University)
1. Halocarbon Measurements in the Alaskan Troposphere and Lower
Stratosphere, E. Robinson, R.A.R., J. Krasnec, D. Pierotti, and
M. Jakubovic, Atmos. Environ. , 11^ (3), 215-23 (1977).
2. Detailed Halocarbon Measurements Across the Alaskan Tropopause,
E. Robinson, R.A.R., J. Krasnec, D. Pierotti, and M. Jakubovic,
Geophys. Res. Lett., £ (6), 323-6 (1976).
3. Global and Regional N20 Measurements, R.A.R. and D. Pierotti,
Pure Appl. Geophys., 116 (2-3), 405-13 (1978).
4. Interlaboratory Comparison of Atmospheric Nitrous Oxide Measure-
ments, R.A.R. and D. Pierotti, Geophys. Res. Lett., 5 (5),
353-5 (1978). ***
5. Interlaboratory Comparison of Fluorocarbon Measurements, R.A.R.,
Atmos. Environ. , JL2. (12) , 2505-8 (1978) .
6. Nitrous Oxide Measurements in the Eastern Tropical Pacific
Ocean, D. Pierotti and R.A.R., draft ms.
7. F-ll and N20 in the North American Troposphere and Lower Strato-
sphere, W. D. Saunders, E. Robinson, D. R. Cronn, R.A.R., and
D. Pierotti, Water Air Soil Pollut., JLO. (4), 421-39 (1978).
8. The Sahara as a Possible Sink for Trace Gases, 0. Pierotti,
L. E. Rasmussen, and R.A.R., Geophys. Res. Lett., 5 (12), 1001-4
(1978). "**
9. Concentration Distribution of Methyl Chloride in the Atmosphere,
R.A.R., L. E. Rasmussen, M. A. K. Khalil, and R. W. Dalluge,
J. Geophys. Res., in press.
10. Measurements of CHFC12 (Freon 21) in Background Tropospheric
Air, S. A. Penkett, N. J. D. Prosser, R.A.R., and M. A. K.
Khalil, Nature, J86., 793-5 (1980) (8/21/80).
11. Methyl Chloroform (C^CC^) : Accumulation in the Earth's Atmos-
phere, M. A. K. Khalil and R.A.R., draft ms.
(continued)
K-68
-------
Table 5 (continued)
R. A. Rasmussen, Oregon Graduate Center (Formerly Washington State
University) (continued)
12. Atmospheric Halocarbons: Measurements and Analyses of Selected
Trace Gases, R.A.R. and M. A. K. Khalil, ms. for presentation
at NATO Advanced Study Institute, October, 1979.
13. CHC1F2 (F-22) in the Earth's Atmosphere, R.A.R., M. A. K. Khalil,
S. A. Penkett, and N. J. D. Prosser, Geophys. Res. Lett., 7 (10),
809-12 (1980). ••*'
14. Atmospheric Trace Gases in Antarctica, R.A.R., M. A. K. Khalil,
and R. W. Dalluge, Science. in press.
15. Sources of Atmospheric Trace Gases in the Southern Hemisphere,
M. A. K. Khalil and R.A.R., Atmos. Environ., in press.
16. Interlaboratory Comparison of Fluorocarbons 11, 12, Methyl
Chloroform, and Nitrous Oxide Measurements, R.A.R. and M. A. K.
Khalil, Atmos. Environ., in press.
17. Atmospheric Measurements of CF4 and Other Fluorocarbons Contain-
ing the CF3 Group, S. A. Penkett, N. J. D. Prosser, R.A.R.,
and M. A. K. Khalil, J. Geophys. Res., in press.
18. Atmospheric Trace Gases Over China, R.A.R., M. A. K. Khalil, and
J. S. Chang, draft ms.
C. Sandorfy, University of Montreal
1. Vacuum Ultraviolet and Photoelectron Spectra of Fluorochloro
Derivatives of Methane, J. Doucet, P. Sauvageau, and C.S.,
J. Chem. Phys., 58 (9), 3708-16 (1973) (5/1/73).
^^^•^^•^•^•^^^••^^^^••^^"•"•^ ^^M^
2. Vacuum Ultraviolet Absorption Spectra of Fluoromethanes, P.
Sauvageau, R. Gilbert, P. P. Berlow, and C.S., J. Chem. Phys.,
59 (2) 762-5 (1973) (7/15/73).
3. Vacuum Ultraviolet Absorption Spectra of Chlorofluoromethanes
from 120 to 65 nm, R. Gilbert, P. Sauvageau, and C.S., J. Chem.
Phys., 60 (12), 4820-4 (1974) (6/15/74).
4. Vacuum Ultraviolet and Photoelectron Spectra of Fluoroethanes,
P. Sauvageau. J. Doucet, R. Gilbert, and C.S., J. Chem. Phys.,
61 (1), 391-5 (1974) (7/1/74).
5. On the Hydrogen Bond Breaking Ability of Fluorocarbons Contain-
ing Higher Halogens, T. DiPaolo and C.S., Can. J. Chem., 52 (21),
3612-22 (1974). ""*"
(continued)
K-69
-------
Table 5 (continued)
C. Sandorfy, University of Montreal (continued)
6. Fluorocarbon Anaesthetics Break Hydrogen Bonds, T. DiPaolo and
C.S., Nature, ^252., 471 (1974) (12/6/74).
7. Photoelectron and Par-Ultraviolet Absorption Spectra of Chloro-
fluoro-Derivatives of Ethane, J. Doucet, P. Sauvageau, and C.S.,
J. Chem. Phys., $2. (2), 355-9 (1975) (1/15/75).
8. Photoelectron and Par-Ultraviolet Spectra of CF3Br, CP2BrCl,
and CF2Br2, J. Doucet, R. Gilbert, P. Sauvageau, and C.S.,
J. Chem. Phys., _62. (2), 366-9 (1975) (1/15/75).
9. Photoelectron and Vacuum Ultraviolet Spectra of a Series of
Fluoroethers, A. H. Hardin and C.S., J. Fluorine Chem., 5 (5),
435-42 (1975). "*"
10. Ultraviolet Absorption of Fluorocarbons, a Review, C.S., Atmos.
Environ., JL£ (5), 343-51 (1976).
P. M. Solomon and R. L. deZafra, State University of New York at
Stony Brook
1. Chlorine Oxide in the Stratospheric Ozone Layer: Ground-Based
Detection and Measurement, A. Parrish, R. L. deZ., P.M.S.,
J. W. Barrett, and E. R. Carlson, draft ms.
D. H. Stedman, University of Michigan
1. Measurement Techniques for the Ozone Layer, D.H.S., Res./Dev.,
January^ 1976, pp. 22-4, 26.
F. Stuhl, University of Bochum
1. The Ultraviolet Absorption of Some Halogenated Methanes and
Ethanes of Atmospheric Interest, C. Hubrich and F.S., J. Photo-
chem., 12^ (2) ,- 93-107 (1980).
N. D. Sze, Atmospheric & Environmental Research (Formerly Environmental
Research & Technology, Inc.)
1. Measurement of Fluorocarbons 11 and 12 and Model Validation:
An Assessment, N.D.S. and M. F. Wu, Atmos. Environ., 10 (12),
1117-25 (1976). •*"
(continued)
K-70
-------
Table 5 (continued)
N. D. Sze, Atmospheric & Environmental Research (Formerly Environmental
Research & Technology, Inc.(continued)
2. Heterogeneous Photodecomposition of Halogenated Compounds in
the Troposphere, T. Y. Kong and N.D.S., EOS Trans. Am. Geophys.
Union, J50. (8), 811 (1978).
3. Stratospheric Fluorine: A Comparison Between Theory and Measure-
ments, N.D.S., Geophys. Res. Lett.,^(9), 781-3 (1978).
4. Is CS2 a Precursor for Atmospheric COS? N.D.S. and M. K. W. Ko,
Nature, 2J7JB, 731-2 (1979).
5. Stratospheric Sulfur Cycle: A Theoretical Model, N.D.S. and
M. K. W. Ko, draft ms.
6. CS2 and COS in the Stratospheric Sulfur Budget, N.D.S. and
M. K. W. Ko, Nature, ^280, 308-10 (1979).
7. Coupled Effects of Atmospheric N20 and 03 on the Earth's Climate,
W. C. Wang and N.D.S., Nature, 23,6, 589-90 (1980).
8. Could the Reaction of H02N02 with HO be a Sink for Stratospheric
Odd Hydrogen?, M. K. W. Ko and N.D.S., draft ms.
9. Atmospheric Ozone: Comparison of Observations with Two-Dimen-
sional Model Calculation, M. K. W. Ko, M. Livshits, and N.D.S.,
draft ms.
G. A. Takacs, Rochester Institute of Technology
1. Heats of Formation and Bond Dissociation Energies of Some Simple
Sulfur- and Halogen-Containing Molecules, G.A.T., J. Chem. Eng.
Data, 23^ (2) , 174-5 (1978).
2. Atmospheric Photodissociation Lifetimes for Nitromethane, Methyl
Nitrite, and Methyl Nitrate, W. D. Taylor, T. D. Allston, M. J.
Moscato, G. B. Fazekas, R. Kozlowski, and G.A.T., draft ms.
3. Laboratory Investigations Concerning Atmospheric Chlorine, M. J.
McClements, W. D. Taylor, M. C. Withiam, T. D. Allston,
G. Fazekas, and -G.A.T., draft ms.
B. A. Thrush, University of Cambridge
1. The Rates of Reaction of H02 with HO and 02 Studied by Laser
Magnetic Resonance, J. P. Burrows, G. W. Harris, and B.A.T.,
Nature, 267^, 233-4 (1977).
(continued)
K-71
-------
Table 5 (continued)
G. C. Tiao and G. Reinael, University of Wisconsin
1. Statistical Analysis of Stratospheric Ozone Data for the
Detection of Trend, G.R., G.C.T., M. N. Wang, R. Lewis,
and D. Nychka, Atmos. Environ., in press.
R. P. Wayne, University of Oxford
1. Relative Rate Constants for the Reactions of 0( D) Atoms with
Fluorocarbons and with NoO, R. G. Green and R.P.W., J. Photo-
chem., 6u (5), 371-4 (1977).
2. Vacuum Ultra-violet Absorption Spectra of Halogenated Methanes
and Ethanes, R. G. Green and R.P.W., J. Photochem., 6 (5),
375-7 (1977). *•
November 30, 1980
K-72
-------
Index to Table 3 by Investigator and Project Number
Investigator
Alyea
Project Number*
Ausloos
Bailey
Barbe
Beckman
Berger
Birks
Bonetti
Brasseur
Bruner
Buijs
Carli
Campbell
Chance
Coxon
II
Cunnold
75-24
76-122
77-199
77-213
78-251
78-252
79-281
80-323
77-186
78-254
80-317
80-322
79-282
75-62
75-1
76-117A
76-117B
77-192
77-222
78-244
79-276
80-321
80-329
76-137
80-297
80-320
78-256
75-90
75-98
77-156
77-168
77-221
76-137
75-53
80-318
78-255
80-315
75-24
76-122
77-199
(O
(c)
(c)
(c)
(c)
(c)
(0
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(0
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
38
38
38
17
17
38
17,38
17,38
17
17
41
32
30
41
12
12
17
12
22
12
12
12
12
30
30
38
31
23,31
31
31
23
23
30
17
30
23
23
38
38
38
(continued)
K-73
-------
Index to Table 3 by Investigator and Project Number
(continued)
Investigator
Cunnold
Project Number*
Davis
deZafra
n
Donovan
Eggleton
Ehhalt
Ekstrom
Fehsenfeld
Girard
Goldman
Harries
Howard
n
n
n
ii
Jouve
Kaufman
n
Knauth
Korte
Kurylo
n
Lovelock
77-213
78-251
78-252
79-281
80-323
74-10
75-73
75-87
76-130
77-225
79-278
80-316
79-286
76-116
76-145
75-27
77-222
75-88
80-322
76-137
75-47
76-100
77-222
77-223
79-289
80-299
79-290
76-126
77-197
77-171
77-224
77-194
78-233
80-307
73-1
74-3
75-67
76-120
77-144
77-193
(0
(c)
(c)
(0
(c)
(0
(0
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
17
17
38
17,38
17,38
24
24
24
36
36
36
36
18
24
32
32
22
32
32
30
25
13
22
13
14
25
33
18
18
25
25
18
14,19
14
32
32
19,33
26
19,33
19
(continued)
K-74
-------
Index to Table 3 by Investigator and Project Number
(continued)
Investigator
Lovelock
Project Number*
Martin
Moe
Mohnen
Murcray
Nicholls
Pagano
Parzen
Phillips
Pitts
Prinn
n
78-226
78-243
78-264
79-269
79-280
80-293
80-324
75-81
75-81-11
78-235
75-64
75-13
75-92
76-101
76-135
77-152
77-166
77-211
77-219
78-228
78-265
80-328
75-11
75-11-11
75-30b
76-106
76-106
78-241
74-2
75-12
77-190
75-24
76-122
77-199
77-213
78-251
78-252
79-281
80-323
(0
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(0
(c)
(c)
(c)
(c)
(c)
(0
(c)
(0
(c)
(c)
(c)
(c)
(c)
27
34
27
27
27
41
41
20
15
21
15
38
38
38
17
17
38
17,38
17,38
(continued)
K-75
-------
Index to Table 3 by Investigator and Project Number
(continued)
Investigator
Rasmussen
it
Project Number*
Ravishankara
Reinsel
n
Ridley
Roscoe
n
Sandorfy
Saykally
Shame1
Simmonds
Skogerboe
Solomon
Stedman
Stuhl
75-2
75-59
75-71
75-84
76-140
76-142
77-181
77-201
77-215
78-247
78-248
78-260
78-263
79-279
80-308
80-325
80-295
78-250
80-304
76-102A
76-102B
77-219
80-328
73-2
80-300
79-275
77-193
78-243
79-269
79-280
80-324
77-206
76-130
77-225
79-278
80-316
74-7
76-132
77-151
77-170
(c)
(C)
(C)
(C)
(C)
(C)
(0
(C)
(C)
(C)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
Page
35
35
21
21
21
27
35
21
22
27
21
35
21
21
36
21
15
41
41
36
36
34
34
22
30
22
19
19
22,28
19
19
28
36
36
36
36
28
29
29
15
(continued)
K-76
-------
Indtx to Table 3 by Investigator and Project Number
(continued)
Investigator
Project Number*
Sze
n
M
n
n
n
Takacs
Taylor
n
Thrush
M
Tiao
n
Timmons
n
n
Traub
Watson
Wiesenfeld
n
Young
n
Zander
n
Zellner
75-32
76-115
77-173
78-234
79-273
80-311
77-196
73-3
74-2
75-58
75-58-11
78-250
80-304
76-129
77-214
78-258
80-318
78-257
76-128
77-220
75-50
75-86
76-141
78-232
77-195
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
(c)
39
39
39
39
39
39
16
37
37
16
16
41
41
29
29
29
30
42
16
16
37
37
37
37
16
*(c) indicates completed project
K-77
-------
X. APPENDIX L
UNCERTAINTIES - CHLOROFLUOROCARBON EFFECTS
AND STRATOSPHERIC OZONE
(SRI REPORT)
L-l
-------
Uncertainties
The following Appendix is taken from a report [SRI,
1980] of a March, 1980 workshop run by SRI International for the
EPA. The workshop was sponsored by EPA to evaluate "...the
critical issues that are hindering EPA's ability to make a fully
supportable decision on further CFC regulations." The principle
findings of the workshop are summarized in the report's Table 2
(attached) . The full report also is included as part of the
Du Pont submission.
L-2
-------
TABLE 2. IMPORTANT ISSUES IN CHLOROFLUOROCARBON EFFECTS AND OZONE DEPLETION
Importance3
Areac
Issue or Uncertainty0
Researchable?
Time (years)6
High
Releases
Identify what chemicals are likely to deplete ozone
or affect near-surface temperatures, and thus should
be assessed as to their current and future releases.
Describe how patterns of technological innovation
will change the need for CFCs and related sub-
stances and create new policy options not currently
under consideration for CFC control.
Improve accuracy of projections of future U.S.
emissions by CFCs, by source, under the assumption
of no further regulatory interventions.
Yes
Yes, with
difficulty
Yes
2-5
High
Transport
and
Chemistry
Validate models of ozone depletion against measure-
ments, with calibration as required; may be direct
measurement of ozone or measurements of ratios of
species.
Yes
High
Climate
Describe spatial and temporal variations in tem-
perature, precipitation, cloudiness, and evapo-
transpiration, leading to description of changes
in soil moisture.
Estimate synergistic effects of CFCs with CO2 on
temperature change, because increments are more
likely to be adverse if baseline is significantly
disturbed.
Yes
10
Yes, but not
under EPA
program
2-5
f
i
CO
-------
TABLE 2. (Continued)
Importance5
Arear
Issue or Uncertainty0
Researenable?*^ Time (years)6
High
Health
Integrate by epidemiology the form of the relation-
ship of melanoma incidence and mortality of ultra-
violet exposures over the range possible from CFC
releases.
Yes
2-5
High
Biology/
Ecology
Obtain and evaluate available data on the patterns Yes
of habits and habitats of aquatic species that
determine their exposure and susceptibility to
ultraviolet light.
Determine and explain the differences between Yes
laboratory and field susceptibility to ultra-
violet radiation of selected crops and aquatic
species.
Determine the environmental and health consequences Yes
of proposed substitutes for CFCs.
1-2
High
Economics
f
i
Develop a combined scientific and ethical basis
for setting discount rates for estimates of
future control costs and benefits, including
different rates for costs and benefits if
necessary.
Determine the social value placed on the respon-
sibility to future generations and the way to
treat potential catastrophic effects.
Describe the proper way to evaluate the signifi-
cance of changes (such as a large change in
average atmospheric ozone content) never before
experienced, and how society should respond
to them.
Yes
Yes
No
-------
TABLE 2. (Continued)
Importance0
Areab
Issue or Uncertainty0
Researchable?^ Time (years)6
Moderate
Releases
Improve estimates of current and future release Yes
rates outside the United States under the assump-
tion of no further regulations.
Determine what U.S. government policy will be on No
other issues, such as solvent use of non-CFCs.
Estimate the worldwide elasticity of demand to Yes
CFC prices so that the response of industry to
various policy interventions can be understood
better.
Determine release rates of other pollutants that Yes
either deplete ozone or affect the transport and
chemistry of ozone-depletors.
1-2
2-5
Moderate
Transport
and
Chemistry
tr"
I
Ul
Model and measure how CFCs selectively change the Yes
temporal and spatial variations in ozone concen-
trations: Are variations damped or accentuated?
Determine the influence of other man-made and Yes
natural emissions on the effectiveness of
CFC ozone depletion.
Set upper bounds on the effectiveness of possible Yes
tropospheric processes that destroy or entrap CFCs
and thus reduce their flux to the stratosphere.
Investigate the adequacies of one-dimensional and Yes
multi-dimensional models in describing average and
spatially resolved ozone depletion.
5-10
1-3
5-10
-------
TABLE 2. (Continued)
Importance5
Areab
Issue or Uncertainty0
Researchable?d Time (years)6
Moderate
Climate
Identify additional chemical species that can Yes
significantly affect the global temperature
balance and estimate their effects.
Refine our understanding of the global feedback Yes
parameter that accounts for water vapor in the
atmosphere, albedo of clouds and surface, vertical
temperature profile and so on to determine the
temperature change equivalent to a given heat input
change.
Improve knowledge of temperature changes in the Yes
stratosphere and consequences on weather.
5-10
lYbderate
Health
Develop a biological model (experimental animal
study) for examining the melanoma dose-response
relationship, and explore the theoretical biology
implied.
Investigate the dependence of non-melanoma and
especially melanoma cancer incidence on dose-rate,
especially for very high short-term exposures.
Determine whether an average increase in UV will
push the natural variations in UV over a biological
stability level for melanoma.
Separate the effects of UV irradiation from other
causative factors, especially for melanoma.
Establish and explain the relationship of non-
melancrna skin cancer incidence to ultraviolet
exposures over the range possible from CFC
releases.
Yes
Yes
Not in rea-
sonable time
Yes
Yes
5-10
10
2-5
2-5
-------
TABLE 2. (Continued)
Importance0
Area1
Issue or Uncertainty0
Researchable?d Time (years)6
Moderate
Health
Determine the population distribution of UV doses Yes
by geography, time, and demographic characteristics.
Describe the likely human behavioral response to Yes
increased levels of UV and (possibly) temperature.
Moderate
Biology/
Ecology
Describe the variability of chlorophyll (a) dis-
tribution in natural waters and its effect on the
penetration of UV with depth.
Determine the significance of shifts in ecological
community structure to the welfare and stability
of the human environment.
Estimate the susceptibility of sensitive environ-
ments (e.g., desert, tundra) to UV increase in com-
parison with more robust environments.
Investigate the dependence of biological and ecolo-
.gical effects on UV dose rates, especially to under-
stand the significance of experiments performed at
high rates.
Determine sensitivity of specific economically
important crops to UV in the laboratory and in
the field.
Determine sensitivity of specific crops to
temperature changes.
Determine sensitivity of specific aquatic
organisms to UV.
Yes
Not in rea-
sonable time
Yes
Yes
Yes
Yes
Yes
1-2
2-5
-
8
-------
TABLE 2. (Concluded)
Importance3
Moderate
Areab
Biology/
Ecology
Issue or Uncertainty0
Investigate the UV action spectra for selected
biological effects.
Researchable?°
Yes
Time
3
(years)6
Determine likely adaptation of important
species to increased UV.
Yes
10
Moderate
Economics
Describe what kinds of control decisions are,
in practical terms, irreversible, and the
social consequences of making erroneous ones.
o
Develop methods for achieving equity given a
distribution of costs and benefits to
various parties, nationally or worldwide,
over time.
Predict social behavior in response to the
adverse consequences of UV and temperature
change: Will society adapt to minimize their
severity?
Probably not
No
Yes
10
aAn integrated subjective assessment of the importance of resolving the issue for decisions on CFC control.
Both importance within the area of study and importance of the area to the.decision are included. No significance
is implied by the order within importance categories.
klhe issues are roughly sorted by the area of study, but many are transdisciplinary.
°These descriptions are necessarily brief and may omit important subleties. See also Section 5.
"•This judgment depends both on the length of time required for meaningful progress and the likelihood of acceptance of the
findings.
=oeRange of time required to make significant progress in resolving the issue or reducing the uncertainty.
• i
sr
H-
3
rt
«•
CO
-------
Bibliography
XI. BIBLIOGRAPHY
Page
A. Bibliography to All Sections Except Effects
Appendix F XI-2
[includes numbered references* 1-156]
B. Bibliography to Effects Appendix F-l XI-20
(Urbach - Skin Cancer)
[includes numbered references* 157-169]
C. Bibliography to Effects Appendix F-2 XI-45
(Klein - UV-B Measurement)
[includes numbered references* 170-175]
D. Bibliography to Effects Appendix F-3 XI-46
(Biggs - Crops)
[includes numbered references* 176-184]
E. Bibliography to Effects Appendix F-4 . XI-47
(Damkaer - Marine)
[includes numbered references* 185-191]
* Copies of numbered references only appear in the following
Bibliography Volumes:
References 1-43 are contained in Volume 4
References 44-115 are contained in Volume 5
References 116-159 are contained in Volume 6
References 160-191 are contained in Volume 7
XI-1
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XI. BIBLIOGRAPHY
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176 Biggs, R. H. and Kossuth, S. V. (1978). Impact of solar UV-B
radiation on crop productivity, Final report of UV-B biological
and climate effects research. Terrestrial. FY 77. Univ.
Florida, Gainesville, Ft.
177 Biggs, R. H., Sisson, W. T., and Caldwell, M. M. (1975). Response
of higher terrestrial plants to elevated UV-B irradiance. In;
Nachtwey, D. S., Caldwell, M. M., and Biggs, R. H. (eds).
Impacts of climatic change on the biosphere, CIAP Monograph 5,
Part 1: Ultraviolet radiation effects. U.S. Dept. Trans.,
Springfield, VA, pp. 4-34 to 4-50.
178 Caldwell, M. M. (1977). The effects of solar UV-B radiation
(280-315 nm) on higher plants: Implications of stratospheric
ozone reduction. In: Castellani, A. (ed). Research in
photobiology. Plenum Publishing Corp., New York, pp. 597-607.
179 Duncan, W. G. (1971). Leaf angles, leaf area, and canopy
photosynthesis. Crop Science 11, 482-485.
Evans, L. T. (ed) (1975). Crop Physiology. Cambridge Univ. Press,
pp. 374.
180 Kossuth, S. V. and Biggs, R. H. (1978). Sunburned blueberries.
Fla. State Hort. Soc. Proc. 91» 173-175.
131 Lindoo, S. J., Seeley, S. B.., and Caldwell, M. M. (1979). Effects
of ultraviolet-B radiation stress on the abscisic acid status o'
Rumex patientia leaves. Physiol. Plant. 45, 67-72.
182 Loomis, R. S., Rabbinge, R., and Ng, E. (1979). Explanatory models
in crop physiology. Ann. Rev. PI. Physiol. 30, 339-367.
NAS - National Academy of Sciences - (1979). Report of the Committe
on Impacts of Stratospheric Change, ij^ "Protection Against
Depletion of Stratospheric Ozone by Chlorofluorocarbons."
December, Washington, D.C.
Ormond, P., Hammer, A., Krizek, D. T., Tibbitts, T. W., McFarlane,
J. C., and Langhans, R. W. (1980). Base-line growth studies of
"First Lady" marigolds in controlled environments. J. Am. Soc.
Hort. Sci. 105, 632-638.
184 Robberecht, R. and Caldwell, M. M. (1978). Leaf epidermal
transmittance of ultraviolet radiation and its implication for
plant sensitivity to ultraviolet-radiation induced injury.
Oecologia 3_2, 277-287.
Xl-46
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Bibliography
E. Bibliography to Effects Appendix F-4 (Damkaer - Marine).
185 .Damkaer, D. M., Dey, D. B., Heron, G. A., and Prentice, E. F.
(1980) . Effects of UV-B radiation on near-surface
zooplankton of Puget Sound. Oecologia, 44, 149-158.
186 Hunter, J. R., Taylor, J. H., and Moser, H. G. (1979). Effect of
ultraviolet irradiation on eggs and larvae of the northern
anchovy, Eugraulis mordax, and the Pacific mackerel, Scomber
japonicus^during the embryonic stage. Photochemistry and
Photobiology, 29, 325-338.
187 Jitts, H. R., Morel, A. ,! and Saijo, Y. (1976). The relation of
oceanic primary production to available photosynthetic
irradiance. Aust. J.. Mar. Freshwater Res., 27, 441-454.
188 Karanas, J. J., Van Dyke, H., and Worrest, R. C. (1979).
Midultraviolet (UV-B) sensitivity of Acartia clausii
Giesbrecht (Copepoda) . Limnol. Oceanogr., 24 (6) , 1104-1116.
189 Lorenzen, C. J. (1979). Ultraviolet radiation and phytoplankton
photosynthesis. Limnol. Oceanogr., ^_4_(6) , 1117-1120.
190 Nachtwey, D. S. (1976) . Potential effects on aquatic ecosystems
of increased UV-B radiation. Proceedings of the Fourth
Conference on the Climatic Impact Assessment Program, Hard,
T. M. and Broderick, A. J., eds., pp. 79-86.
DOT-TST-OTS-75-38, U.S. Department of Transportation,
Washington, D.C.
NAS-National Academy of Sciences-(1979). Report of the Committee
on Impacts of Stratospheric Change in_ "Protection against
depletion of stratospheric ozone by chlorofluorocarbons.
Washington, D.C.
191 Thomson, B. E. , Worrest, R. C., and Van Dyke, H. (1980). The
growth repsonse of an estuarine diatom (Melpsira nummuloides
[Dillw.] Ag.) to UV-B (290-320 nm) radiation.Estuaries,
3(1), 69-72.
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