JOURNAL OF AEROSOL MEDICINE

Volume 8, Supplement 1,1995

Mary Ann Liebert, Inc., Publishers

CFCs, their Replacements,

and the Ozone Layer
TIM J NOAKES

ICI Klea
PO Box 13
The Heath
Runcorn
Cheshire WA74QF, UK

ABSTRACT

Chlorofluorocarbons (CFCs) have become widely used in a variety of applications, ranging

from aerosols to refrigeration, through their unique combination of the properties of non-
flammability and general inertness. However, their chemical stability, which makes CFCs relatively
safe and non-toxic, is also responsible for their potential to damage the environment. From 1974
opinion developed that CFCs might indirectly affect the stratospheric 'ozone layer' through their
ability to transport halogens, particularly chlorine, to this level. By the mid 1980s a consensus
emerged that atmospheric CFCs could contribute significantly to ozone depletion and an annual
thinning (a 'hole') in the ozone layer over the Antarctic was reported. Some of the atmospheric
chemistry which is believed to occur, and some of the measurements made on the ozone 'layer' are
reviewed together with the environmental regulatory actions that have been taken. These are
leading to a controlled rapid phase out of a number of industrial chemicals, including CFCs.
The pharmaceutical industry uses significant quantities of CFCs as propellants in metered dose
inhalers (MDIs). Two suitable alternative molecules, the hydrofluoroalkanes (HFAs) HFA134a
and HFA227, which have the required properties but are not ozone depleting, are introduced.

INTRODUCTION

Between 1960 and 1975 CFCs became an essential part of the mechanics that underpinned
our modern society. Though often incorrectly portrayed as purely aerosol propellants, they were, in
fact, indispensable in a wide range of applications, covering refrigeration, foam blowing, aerosols
(including MDIs), and specialist cleaning solvents.
This was due to the unique combination of a group of properties found in CFCs.
Whilst these properties in themselves are not unique, they are rarely all found combined in a single
molecule. These properties are:
(1) Low boiling points (ranging from + 24°C [CFC11] to -40°C [CFC115]).
(2) Non-flammability.
(3) Inertness in storage.
(4) No toxicological effects.
KEYWORDS: CFC, HFA, ozone chemistry, ozone depletion, ozone 'hole'.

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 By 1974 worldwide production of the main CFCs (11 and 12) was approximately 800,000
tonsper annum. However, a number of groups, including the producer industries, were becoming
concerned as to the fate of these very stable compounds in the environment. A study
commissioned by a group of producers, and later reviewed by the Manufacturing Chemists
Association (1977), was used in a subsequent paper published by Molina and Rowland (1974)
which made some very disturbing assertions as to their possible fate.

THE PROBLEM

The Rowland and Molina hypothesis (Molina and Rowland, 1974) proposed that the
stability of certain classes of halocarbon could, indirectly, pose a threat to the environment.
It suggested that if a halocarbon was both volatile and chemically inert in the lower atmosphere
then it would, in time, reach the stratosphere through the processes of atmospheric mixing.
There, under the impact of energetic ultra-violet (UV) radiation, it would decompose to produce
free radical species which could interfere with the complex balance of the creation and destruction
of stratospheric ozone.
It is now known that stratospheric chemistry, including the creation and destruction of ozone
and its perturbation by other materials, is extremely complex, with several hundred chemical
reactions having been identified (Proceedings of the 4th CIAP, 1975). The essentials of this
chemistry, and the Rowland and Molina proposal, can be reduced to a few key processes.
First, there is what might be described as the 'benign' stratospheric ozone cycle:
hv
1. o2 ->20«
2. 0» + 02->03
hv
3. o3-> O» + 02
4. 03 + 0» .>202
In reaction 1, oxygen is dissociated into two oxygen radicals by absorption of hard
(180-240 nm) UV radiation (hv). The two atoms then can separately react with more oxygen to
form ozone (as shown in reaction 2) or possibly undergo reaction with ozone to produce oxygen as
shown in reaction 4. The ozone formed then absorbs UV radiation in the frequency range
210-310 nm (UV-B) leading to its decomposition back into oxygen and oxygen radicals (as shown in
reaction 3), the reverse, in fact, of reaction 2. Thus, this scheme provides a basic explanation of the
UV absorption characteristics of ozone, and an understanding that it is naturally destroyed as a
fundamental part of that absorption process.
There is, however, a second class of process that interferes with the effectiveness of the
'benign' process described above. This 'parasitic' process can be simplified as follows:
5. 03 + X».>XO» + 02
6. XO». + 03-.>202 + X»
7. X» + X» <.-> X2
As can be seen from the above reactions, ozone is destroyed without the absorption of any
UV in the process. Furthermore, the reactions are catalytic in the general radical species X« where,
depending upon its lifetime, one atom can partake in many thousands of such reactive cycles
repeatedly passing through reactions 5 and 6 before it is destroyed.
X» can be a wide range of chemical species. For example, naturally occurring hydroxyl
radicals derived from water, and nitrosyl radicals from atmospheric nitrogen dioxide both behave in
this way. In addition, most of the halogens (chlorine, bromine, iodine) can also contribute to this
class of reactions. There are many natural routes by which these elements reach the stratosphere
(eg methyl bromide from seaweed) and the two schemes together can be considered as a simple
description of the stratospheric status quo prior to man's contributions.
However, the advent of man-made halocarbons (some particularly stable chlorinated
solvents, CFCs, hydrochlorofluorocarbons [HCFCs] and halon fire extinguishants) has potentially
added a perturbing element to the ozone .creation and destruction balance. Rowland and Molina

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proposed that the additional burden of these materials and their decomposition products in the
stratosphere could lead to significant extra destruction of stratospheric ozone. As shown in
reaction 3, stratospheric ozone absorbs, in its own destruction, short wavelength UV radiation
thereby presenting a screen to these frequencies. An increase at ground level in UV-B could have a
number of undesirable consequences both to numerous biological systems and also directly to man
(such as an increase in the incidence of cataracts and malignant melanoma).
In 1974 this was only an hypothesis, with little direct evidence. Over the next ten years or so
scientific opinion was divided, as an increasing body of evidence either supported or contradicted
man-made halocarbons as being significant contributors to ozone depletion.

THE ANTARCTIC OZONE 'HOLE'

In 1985 the British Antarctic Survey, which had been monitoring the levels of polar
stratospheric ozone over a 30 yearperiod, published results (Farman et al., 1985) which indicated
that since 1970 there was a significant, unexpected and increasing level of polar ozone depletion
during the Antarctic spring. Ozone levels then returned to normal later in the year, providing hard
evidence to support what had previously been a largely theoretical argument. Following this
discovery, repeated measurements have shown that the peaks of depletion tend to be increasing
year on year. This 'hole' has subsequently been shown to be readily formed because of certain
circumstances which are unique to the Antarctic: a stable vortex in the Polar atmosphere, a cold
land-mass and formation of high polar stratospheric clouds.
However, measurements were now also being made on stratospheric ozone levels over
temperate latitudes, and much more limited and temporary seasonal depletions were being
reported in a number of locations including over Northern temperate latitudes. A number of
natural events were also having an effect on ozone levels which were contributing to further
depletions.
Particularly significant was the ejection into the upper atmosphere of large amounts of dust
by the eruption of Mount Pinatubo in July 1991. It has been shown that much of the upper
atmosphere chemistry was occurring heterogeneously on the surface of such particles (hence the
importance of the polar stratospheric clouds mentioned above), including the ozone depleting
chemistry previously described. Thus, such a rapid increase in the amount of dust led to further
fluctuations in the amount of recorded ozone depletion.

REGULATION

Although some regulation of CFC production had occurred in the USA shortly after the
proposal of Rowland and Molina, regulatory momentum began to steadily develop with the results
of both practical and theoretical research into the potential effects of CFCs plus improved
atmospheric measurements. This led to the signing, in 1985, of the Vienna Convention. Following
this Convention, and further evidence of ozone depletion from sources such as the British Antarctic
Survey, a protocol to the Convention, the Montreal Protocol, which specified control of CFCs, was
signed in September 1987 (Montreal Protocol, 1987).
As more evidence confirming the contribution to depletion accumulated, there were calls
for an acceleration to phase-out schedules from a number of groups including producer industries.
This was taken into account in the amended and shortened phase-out timetables. The current
situation is for a 100% phase out of all uses of CFCs on January 1st 1995 in the European Union,
with a similar phase out 1 year later in the rest of the industrialised world. The sole exception to
this timetable is for CFC propellants in MDIs to allow for the lengthened time-scales in the
development of suitable alternatives.

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 INDUSTRIAL RESPONSE

The traditional CFC user industries responded in a variety of ways to this proposed
phase out:
(1) To seek an alternative liquefied gas propellant system which had some of the key
properties of CFCs but was flammable (butane, propane). Much domestic aerosol production has
been converted to these propellants.
(2) To use transitional liquefied gases which had all the properties of CFCs but a lower
ozone depletion potential. These are the HCFCs with applications such as solvents, refrigeration
and industrial aerosols. These are now also under phase out.
(3) To seek alternative technology not involving the use of liquefied gases (eg alternative
spraying systems).
(4) To seek a replacement for CFCs which had all of the key properties, but was not ozone
depleting. HFAs were viewed as the most promising option, although it soon became apparent that
they would only be used in applications where all the key properties were required, such as
specialist aerosols (including MDIs), air conditioning and refrigeration.
THE HYDROFLUOROALKANES

Currently 6 HFAs have been developed by the chemical industry which, either singly or in
blends, deliver all of the properties of CFCs for most applications. The key differences are:
(1) There is no high boiling point (bp) HFA yet available.
(2) They do not cause any ozone depletion.
(3) They are significantly harder to make.
Of these, two are under development by the pharmaceutical industry as future
MDI propellants. They are 1,1,1,2 tetrafluoroethane (HFA134a, bp -26.2°C) and 1,1,1,2,
3,3,3 heptafluoropropane (HFA227ea [referrred to as HFA227 by the pharmaceutical industry],
bp -17°C).
HFA134a is mainly produced for use as a refrigerant, and is manufactured on a larger scale
than all the other HFAs. The amount required as a pharmaceutical grade for use in MDIs is only a
small proportion of this total. In contrast, the majority of HFA227 production will be for use as an
MDI propellant with only a small proportion being for other industrial uses.
Thus, the manufacturing approach for these two HFAs will be quite different. An HFA134a
producer will need to adopt all the practices necessary to comply with the rigorous requirements of
the pharmaceutical industry encapsulated in Good Manufacturing Practice (GMP). Production of a
pharmaceutical grade of HFA134a will therefore require these to be applied to what is, in essence, a
sidestream of a continuous bulk commodity chemicals process.
In contrast, because HFA227 will be primarily produced for the pharmaceutical industry,
the process will be structured at the outset to comply with these requirements. However, the
absence of a large volume industrial production base load, coupled with other factors such as the
degree of fluorination, will result in a potentially more costly propellant. Thus the strategic
manufacturing approach to these two HFAs will be quite different.
CONCLUSION

There is significant consensus that CFC phase out is essential to protect the ozone layer and
from this consensus a number of regulatory decisions, starting with the Vienna Convention in 1985,
are leading to a controlled rapid phase out of a number of industrial chemicals including CFCs.
Two CFC replacement propellants, HFA134a and HFA227, are currently being evaluated.
In both cases, the pharmaceutical grade propellants that will emerge at the end of the development
programmes will be the most thoroughly tested and tightly controlled propellants produced to date.
Between them, they will provide the foundation for MDI production into the 21st century.

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 REFERENCES

FARMAN, J. C, GARDINER, B. G., SHANKLIN, J. D. (1985). Large Losses of Total Ozone in

Antarctica Reveal Serious CIOx/NOx Interaction. Nature 325,207-210.
MANUFACTURING CHEMISTS ASSOCIATION. (1977). Effect of Fluorocarbons on the
Atmosphere: Summary of Fluorocarbons Research Programme. Revision 6, March 31,1977.
MOLINA, M. J. and ROWLAND, F. S. (1974). Stratospheric sink for chlorofluoromethanes:
chlorine atom catalysed destruction of ozone. Nature, 249,810-812.
MONTREAL PROTOCOL. (1987). Montreal Protocol on Substances that Deplete the Ozone
Layer. Sept 16 1987,26 1LM 1541.
PROCEEDINGS OF THE 4TH CIAP (Climatic Impact Assessment Programme)
CONFERENCE. (1975). DOT-TSC-OST-75-38.

Address reprint requests to:

Dr Tim J Noakes
ICI Klea
PO Box 13
The Heath
Runcorn
Cheshire
WA7 4QF
UK

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