Vol. 1, No.

5 GEOPHYSICAL R•SHARCH LETTERS September 1974

ESTIMATES OF POSSIBLE FUTURE OZONE REDUCTIONS

FROM
CONTINUED
USEOFFLUORO-CHLORO-METHANES
(CF2C12,
CFC13)
P. J. Crutzen
(1)
National
Center
forAtmospheric
Research
(2)
Boulder, Colorado 80303, U.S.A.
and

Aeronomy Laboratory, NOAA

Boulder, Colorado 80302, U.S.A.

Abstract. In agreement with arguments put of chlorine compounds in the stratosphere is too
forward by Molina and Rowland (1974) it is con- low, at least judging from a reported upper limit
cluded that very large reductions in ozone con- of HC1 of 0.18 x lOTM in the lower stratosphere
centrations above about 30 km m•y result from (Farmer, 1974). However,other chlorine gases
the continued use of fluoro-chloro-methanes may be more abundant than HC1, so that a defini-
(CF•Cl• andCFCl•)• whichare dissociatedby tive assessment of the effect of C1 and ClO on
ult•aviolet radiation in the stratosphere and ozone must wait until more observations become
mesosphere, thereby giving rise to ozone- available. Our knowledge of the natural cycles
attacking C1 and ClO. Below about 30 km the of chlorine compounds in the atmosphere is very
reductions in ozone are much smaller and even a incomplete, especially with regard to their
slight increase in ozone concentrations may transport into the stratosphere. Chlorine com-
result. The total column abundance of ozone in pounds are injected into the stratosphere by
the atmosphere is, however, reduced by about volcanic eruptions, mainly as HC1 (Stolarski
logo, assumingthat the present rate of produc- and Cicerone, 1974). The average rate of vol-
tion of CF2Cl
2 andCFCl
3 remains
unaltered. canicinjectionsof chlorineinto_theatmosphere
Chapman
(1930)
proposed
thatozone
isproduced
has2be_e
• estimated
tobeabout
lO'[molecules
in theupper
atmosphere
bythereactions. am s (Ryan
andMukh.
erjee,1973),of which
only a fraction would reach the stratosphere.
J1 This rate of injection is so low that we may
R1 02 + h• . , 20 k < 240nm exclude a decisive influence from volcanic

R2 activity on the ozone layer. Another possibility

0 + 02 +M . . 03 +M is the releaseof gaseous
HC1whenHoSO
4 is added
and destroyed by
to sea salt particles (Eriksson, 194•). Lacking
good knowledge of the removal of HC1 by rainout
and washout processes in the troposphere, it is
R3 03 + h• , 0 + 02 k < 1140nm not possible to assess even approximately the
possible supply of natural chlorine with this
R4 0 + 03 --• 202 mechanism to the,stratosphere. Whether or not
the natural flux of chlorine compounds is sig-
Additional ozone reducing reactions are, how-
nificant, it has been pointed out by Molina and
ever, more important, especially those involving
Rowland(1974) that the input of ch10r'i'nein the
NOandNO
2 as catalysts(Crutzen•
1970) form of industrial fluoro-chloro-methanes into
the stratosphere is very significant. Fluoro-
R5 NO+ 03 --- NO
2 + 02 chloro-methanes, mainly CF2'2
C1 and CFC13 , are
-12 used in refrigerators and as propellant gases
R6 NO2+ 0 ; NO+ 02 k6=
9.2x10 in aerosol cans. Probably being inert in the
cm3s1 lower atmosphere, these gases are destroyed
mainly by ultraviolet radiation in the stratos-
phere.
The possible role of C1 and ClO as important
ozone destroying catalysts in the natural strato-
sphere has been proposed recently by Stolarski R7a CF2Cl
2 + h• --• CF2C1
+ Cl k < 230nm
and Cicerone (1974). On the other hand• Wofsy
and McElroy (1974) and Crutzen (1974) find such R7b CFCl
3 + h• , CFCl
2 + Cl k < 230nm
a role not likely• mainly because the abundance

(1) On leave from the Meteorology Department, followed by additional reactions yielding C1
University of Stockholm, Sweden. (and ClO), which destroy ozone catalytically by
the pair of reactions .
(2) The National Center for Atmospheric
Research is sponsored by the National Science -ll
Foundation. R8 Cl + 03 --• ClO+ 02 k8 = 1.7x lO
Copyright 1974 by the American Geophysical Union. cm
3 s-1
205
206 Crutzen' Possible Future Ozone Reductions

-11 -11

R9 ClO+ 0 --• C1+ 02 k9 = 5.3 x 10 R14 C1+ H2 - ; HCi+ H k14' 5.65x10

cm
3 s-1 exp 57 cm 3s
Molina and Rowland (1974) indicated that this HCi• which does not attack O_ is converted back
source of C1 and ClO is so large that ozone is intoC1(andClO)through
th•reactions
likely to be reduced substantially in the future
if the productionof CF2C12andCFCi_will not
be reduced. It is the purposeof th{s article
R15HC1
+HO--- C1+H20k15
=2.1xlO
-12
to give quantitative estimates of ozone des-
tructions resulting from the continued use of
these species.
catalytic
The efficiency
chain can be appreciated
of the C1-ClO
from the
R16HC1
+0 --- C1+ HO k16= 1.88x10
-11
fact that the reaction coefficient of reaction
R9 is almost six times larger than that of
reaction R6. The net ozone destroying effect R17HC1
+h• • H+C1 k • 2200•
of both catalytic cycles can be evaluated from
the last two terms of the equation: These reactions and their rate coefficients have
been reviewed recently by Watson (unpublished
d manuscript• 1974). The absorption cross sec-
d--•
(03)= 2J1(02)
+ Transport-
2k4(0)(03) tions of CF C1 and CFCi• have been measuredby
Molinaand•ow•and (unpublished
manuscript•
1974).
(1) Additionallossreactions
of C1andClOvia re-
which expresses the rate of change of ozone con- actions
OCiO•with
0• HO
ClOH• an2•
C1NO• NO•
NOp
C1NOpand
•aybeleading
todue
neglected
to the instability of thes• products in sunlight.
centration. Thesymbols
with the parenthe•õs It should also be noted that almost all fluorine
denote the concentrations• in particles cm •
of the indicated species. The mathematical for- produced from CFTC1 and CFC1 will end up as
mulation of the contriMution to ozone changes HF•which•
as HC• •oesnotr•act withozone.
resulting from the transport of ozone follows The future steady state distribution of
from the discussion later in this paper. There CF•C12•CFCi• HCi• Ci• ClO•andHF• as well as
are several other reactions affecting chlorine th• ozonere•uctions•are estimated
with the aid
compounds which must be considered. The of a one-dimensional photochemical model in
reaction which the vertical transfer of matter is des-
cribed with the aid of the eddy diffusion con-
RiO C lO + NO
---• C1 +NO2 cept• so that• for instance in the case of HCi•
we will write

klo = 18x
. 10-11
d__
dt
(XCl)-- 0 = (Cl)
together with reaction R8 forms a catalytic
pair of reactionsconvertingNOto N02•thereby
enhancing the effect of the NO-NO_ catalytic
tk12(CH4
)+k13
(H02)+
k14(H2)
t
-a(HCl)
I !kls(HO
a)+
k16(i
i+J17
I
cycle. If the concentrations
of •10 are suf-
ficiently large• it is important to include the
effect of reaction RiO in the ratio x . (s)
In the above expression (M) denotes the con-
+ (ø) (2) centration of air molecules• z denotes the
height (15-95 km) and K the vertical eddy dif-
fusion coefficient. Th• values of K are not
well known and the calculations haveZtherefore
where
from
Jll reaction
the
is the photodissociation
rate of NO
2 been performed adopting two different .•ets-1 of
2
eddy diffusion coefficients (unit: cm s ):
Rll NO
2 + h• -- NO+ 0 k •<400nm.

The loss processes of C1 and ClO• leading to

I
IKK==104{exp
10
4 0.13(z-50)}
z
z
15km•
50km• zz_<50
<_95km
km
(C•.r,,u.
tze.n• 1974)
HCi• which must be included are-
x = •04
z
15 km • z _• 20 km
-11
x = 104
4 ---
R12 C1+ CH HC1+ CH
exp
3 k12= 5xlO
cm
3s
II z

KZ, = 105
exp lz-20
t 20 km _< z •

30 km• z •
30 km

50 km
z- 50
Kz = 105 50 km• z • 95 km
exp 1•.9
-10
R13 C1 + HO
2 --- The latter choice of K gives the best agreement
HC1+ 02 k13= 10 between theoretical an• observed distributions
1
cm
3s- (assumed) of CH
4 andH2 (Ehhaltet al.• 1974).
 Crutzen' Possible Future Ozone Reductions 207

It is possible to write equations like (3) in CF Cl_ and CFCl_ is converted to HF, it is
ß 2 •
and boundary conditions in discrete form as a possible to calculate the vertical distribution
set of linear algebraic equations which may be of HF accordingly. It now remains to calculate
solved by matrix inversion technique. Due to •he distributions of C10x (= C1 + C10) and HC1.
the interaction of the chemical species an We write:
iterative'procedure is necessary.

are
In the present study the chlorine
considered in addition
reactions
to the set of re- •--(c•o
dt x) =(•c•)(•(•o) +•(o) +
actions considered in a previous study (Crutzen,
1974). The solar zenith angle was kept fixed
at 4•.
The distribution of the halogen compounds is
solved in the following manner. First• the
vertical distributionsat CF2C12
andCFC13
are C1 and ClO satisfy closely the steady state
calculated,adopting,e.g. for CF2C12,
the upper equation
boundary condition'
(C•) k•0(•0)+k•(0)
-•z(•)•• ((%%))
(•) "= J?a(CF•C•)•(•)
and
(CZ0x)
=ks(0•)
+kz0(•0)
+k•(0) (S)
where H is chosen equal to 5 kin. The above
relation equatesthe upwardflux of CF2C12 (•c•) = (c:) - (c•o•) . (9)
through the upper boundary to its estimated
total destruction rates above 95 kin. The lower
Inserting expressions (8) and (9) into (7)we
boundary
formulated
condition
as'
(at z = 15kin)for CF2C12
is obtain a linear equation in C10x ß The condi-
tions for C10x at both the upper and lower
boundaries are obtained by considering that
- K(M)•d((CF2C12))
z (M) =1.5x1072s-1.(5)
cm approximately

(clo•)
This equationequatesthe upwardflux of CF2C12
at the lower boundary to its present rate of
Fd(ClO
x) = • Fd(CIX
) (lO)
manufacturing (Molina and Rowland, 1974). Simi-
lar equations as (4) and (5) can be written to where
Fd(ClOx)
andFd(CIX
) express
the downward
fluxes of C10x and CIX. It• therefore• follows
express
the boundary
conditions
for CFC13. that at the boundaries
Assuming that heterogeneous processes are unim-
portant, the total mixing ratio of C1 and F
atoms should be independent of altitude in the (ii)
well mi•ed 15-95 km region. Defining
• (•) •
z (•) = ,(clo•)
(CLX) = (C1) + (ClO) + (HC1), we find therefore:
where
already, = Fd(C1X)/(C1X
) hasbeencalcu-
lated. Finally, the concentration of HCl, Cl
(SIX)
(•)
+'3 (c•c•)
(•)
+ 2 (c•c•)
(•)
= constant
ß
(6) and C10 are obtained with the aid of equations
(9) and (8).
,

Assuming that the mixing ratio of CIX is

very low (taken to be zero) at the lower boun- The results of the calculations are given
dary, it is now easy to calculate from equation in Tables I and II for the two choices of eddy
(6) the vertical distribution of CIX at all diffusion coefficients I and II. The first
levels. Assuming that almost all F contained column in each table gives the calculated ozone

TABLE I. Calculated ozone concentrations in the unpolluted stratosphere, percentage changes

of ozone
concentrations
dueto CF2C12
andt
CFC13,andcorresponding
mixingratios
andconcentrations
of CF2C12,
CFC13,
ClO
x, HC1,HF,C1,NO,andNO
2. Thenumbers
5.0(11) shouldbe read as 5 x 101•.

Alt.
ic•sc•s)(c•c•) (clo•) (•c•) (•)
(•m)(o•) •o•) (•) (•) (•) (•) • (c•) (•o) (•oa)
50 6.6(10) -6 - - :•.o(-:•o) •.2(-9) •.•(-9) •.9(•) •.o(7) 3.•(•)
45 3.0(11) -23 - - •.•(-•0) •.0(-9) •.3(-9) 7.2(•) •.6(8) 7.•(6)
40 1.i(i2) -42 - - •.2(-9) •.•(-9) •.•(-9) •.7(•) 6.•(8) •.8(8)
35 2.2(12) -27 4.7(-11) •.2(-9) 3.9(-9) k.2(-9) 2.5(5) •.0(9)
30 3.5(12) -8.• k.k(-lO) 7.k•-12)6.2(-lO) 3.8(-9) 3.k(-9) 1.1(5) 1.3(9) 2.7(9)
25 4.4(i2) +•.5 1.2(-9) 1.•(-10) 1.8(-10) 2.3(-9) 1.8(-9) 3.9(k) 1.1(9) 2.2(9)
2o 3.i(i2) +6.5 1.7(-9) 3.6(-10) 1.2(-11) 8.7(-10)6.2(-10) 9.1(3) 1.2(9) 1.6(9)
i5 5.0(ii) - •.9(-9) k.9(-•o) .... 3.•(8) •.•(7)
208 Crutzen' Possible Future Ozone Reductions

TABLE II. Quantities as in Table I, calculated with set II of the eddy diffusion coefficients.

5o - -
45 2.8(11) -11 1.6(-11) 1.3(-10) 2.9(-9) 2.•(-9) 2.8(•) •.3(8) 2.1(7)
8.0(8)
3• 2.2(Z2) -•3.• •.7(-•o) 3.•(-•2) •.N(-•o) 2.2(-9) 2.o(-9) 9.•(•) 9.9(8) •.•(9)
$o
2• •.0(•2) -k k.9(-lo) 8.8(-•) 1.k(-lo) •.7(-9) 1.3(-9) 3.•(k) •.2(9) 3.0(9)
20 k.l(12) -2.• 7.7(-•0) 2.3(-•0) 1.•(-•) 8.7(-•0)6.2(-•0) 9.9(3) l.k(9) 2.2(9)
- ....

distribution at someselected le•Is in.an •'without:d'elay,•'•

as 'it• is ½oncei•bte•that •in
atmosphere not polluted by CF2 C12 and CFC13 . dustrial and cosmetic practices may lead to
The remaining columns give respectively the per- important reductions in ozone, the full effect
centage reductions in ozone concentrations of which may be felt first after 50-100 years
by coming generations.
resultingfromtheuseof CF2C12
andCFC13,
as
well as the calculated mixing ratio and concen-
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-.

(1974) find an approximately twofold excess of Ryan, J. A. and N. R. Mukherjee, Estimate of

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the background concentration of C1 compounds in chemistry,
C_an.
J. Chem.,
52, 1582,1974.
the stratosphere, it is yet not possible to
assess reliably the influence of natural and
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however, an urgent need to study this subject accepted August 12, 1974.)