CHAPTER 13

Ozone Depletion Potentials,

Global Warming Potentials,
and Future Chlorine/Bromine Loading

Lead Authors:
S. Solomon
D. Wuebbles

Co-authors:
I. Isaksen
J. Kiehl
M. Lal
P. Simon
N.-D. Sze

Contributors:
D. Albritton
C. Bruhl
P. Connell
J.S. Daniel
D. Fisher
D. Hufford
C. Granier
S.C. Liu
K. P atten
V. Ramaswamy
K. Shine
S. P innock
G. V isconti
D. Weisenstein
T.M.L. Wigley
 CHAPTER13
OZO N E D EPLETION POTENTIA LS , G LOBA L WA RMING POTE NTIA LS,
A ND FUTU R E C H LO R I N E/ B R O M I N E LOAD I N G
C ontents

SCIENTIFIC SUMMARY . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . .. 1 3 . 1

1 3 . 1 INTRODUCTION . . . . . . .
. . ........... .. ................. ....... ........... ............. ... ...... ...... ......... ... ... .. . . . . . . . . .. .. ................. ....... . 13.3

1 3 . 2 ATMOSPHERIC LIFETIMES AND RESPONS E TIMES .

................. ................ . ................. . ...... .......... . . . . . . . 1 3 .4

1 3 . 3 CVBr LOADING AND SCENARIOS FOR CFC S UBSTITUTES ........... .......... . .. ..................... . ...... ......... . . . 1 3 .7
1 3 . 3 . 1 Equivalent Tropospheric Chlorine Loading .................................... .. ........ . . .. . . .
.... ...... .. ........... . . . .... ... . . 1 3 .7
1 3 . 3.2 Equivalent Effective Stratospheric Chlorine . . . .
.... ................ ... ....... ......... ... ........ .... ................. . . . . .. . . .. 13. 1 1

1 3 .4 OZONE DEPLETION POTENTIALS . .

...... ........ ...... .......... .. . . .. .......... ..... .. . . .. . . . . . . . .
. .. . . ... ... .. . ......... ....... ... .. . . . 13.12
1 3 .4. 1 Introduction .
............. .................... . . .,. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 3 . 1 2
1 3 .4.2 Relative Effectiveness of Halogens i n Ozone Destruction . . .
......... .. ... ........ .. . .. . . . . .. . ....... ................. . . 13.13
1 3 .4.2. 1 Fluorine . . . .
..... ........... ....... . ............................. . . . . . . . .
.. ........ ...... . .. ...... .. .. .. ...... . .............. ... .. . . . . 13.13
1 3.4.2.2 B romine . . . . .
.... .... ................. .. .... ........................ . ... ....... . . . .. . .
........ ...... ....... .......................... . 13. 14
1 3 .4.2.3 Iodine . . .. . .... ..................... ...... ........................ .... ........ . .. . . . . .
... .. . .... ... .......... ............. ... ........ . . . 1 3 . 15
1 3 .4.3 Breakdown Products of HCFCs and HFCs . . . . .
.................. .. ........ .. . ............. ........ ... ....... ................ . . . . 13.16
1 3 .4.4 Model-Calculated and Semi-Empirical S teady-State ODPs .. . .......... . .. ...... .. . .
. .. ............. ... . . ........... . . 13.16
1 3 .4.5 Time-Dependent Effects . . . . . . . .. . .. . . . . . .... ............. .. ...... ............... ......... .. . .. . ... ............. .......... . .. ... ............ 13.18

1 3 .5 GLOBAL WARMING POTENTIALS . . .

....... ....... ..... ....................... ........ . ... . . ... .. ... .. . .
.. .. .............................. 1 3 . 20
1 3 .5 . 1 Introduction .
... ......... .. ......... .. .
................ .......................................... . ..... ........................ ........... .... . . . . . 1 3 .20
1 3 .5 . 2 Radiative Forcing Indices . .. ........ ... .. .
........................ ...................... .. . . .
. ......... ...... .................. .. .. .. .. . . . . 1 3.21
1 3 .5 .2. 1 Formulation .
.......... ...... .............................................. . . . . . . .. . . . .
. ..... .. ............... ..................... . 1 3.21
1 3 .5 .2.2 S ensitivity to the State o f the Atmosphere . . .
....... ..... .. ..... .. ......... . . .. . ..
..... ... ......................... 1 3 .23
1 3 . 5 . 3 Direct GWPs . . . .
..... .... ....... .............. ........................... ...... ........ .. .. . . . .. . .. ....... .. . .. .
... .... .. .......... . . . .......... . 1 3 . 24
1 3 .5 .4 Indirect Effects .. .. .
.... ...... ... . .. . .
........ .......... ................................ ........... ...... ... . . . . . ... .
.......... .................. 1 3 .26
1 3 . 5 .4. 1 General Characteristics . .
.......................... ............. ..................... ........ .. ... .......... ............. . . . . 1 3 .26
1 3 .5 .4.2 Indirect Effects upon the GWP of CH4 .
... ........................................................................ 1 3 .27
1 3 .5.4.3 Net Global Warming Potentials for Halocarbons .......... ...... . .. .. .
.. . ..................................... 13.29

REFERENCES ........................................................................................................................................................ 1 3 .32

 OOPs, GWPs and C I-Br LOADING

SCI ENTIF I C SUMMARY

S cientific indices representing the relative effects of different gases upon ozone depletion and climate forcing are
presented. Several scenarios for future chlorine/bromine loading are described that are aimed at implementation of the
Copenhagen Amendments of the Montreal Protocol and the consideration of possible further options. Ozone Depletion
Potentials (ODPs) and Global Warming Potentials (GWPs) are evaluated with improved models and input data, and
their sensitivities to uncertainties are considered in greater detail than in previous assessments. Major new findings are
as follows:

Peak levels of ozone-depleting compounds are expected at stratospheric altitudes in the late 1 990s. Because
current emission estimates suggest that the tropospheric chlorine/bromine loading will peak in 1994, further re­
ductions in emissions would not significantly affect the timing or magnitude of the peak stratospheric halogen
loading expected later this decade (i.e., about 3-5 years after the tropospheric peak) .

Approaches to lowering stratospheric chlorine and bromine abundances are l imited. Further controls on ozone­
depleting substances would be unlikely to change the timing or the magnitude of the peak stratospheric
halocarbon abundances and hence peak ozone loss. However, there are four approaches that would steepen the
initial fall from the peak halocarbon levels in the early decades of the next century:

(i) If emissions of methyl bromide from agricultural, structural, and industrial activities were to be eliminated
in the year 200 1 , then the integrated effective future chlorine loading above the 1 980 level (which is related
to the cumulative future loss of ozone) is predicted to be 1 3% less over the next 50 years relative to full
compliance with the Amendments and Adjustments to the Protocol.

(ii) If emissions of hydrochlorofluorocarbons (HCFCs) were to be totally eliminated by the year 2004, then the
integrated effective future chlorine loading above the 1 980 level is predicted to be 5% less over the next 50
years relative to full compliance with the Amendments and Adjustments to the Protocol.

(iii) If halons presently contained in existing equipment were never released to the atmosphere, then the inte­
grated effective future chlorine loading above the 1 980 level is predicted to be 1 0% less over the next 50
years relative to full compliance with the Amendments and Adjustments to the Protocol.

(iv) If chlorofluorocarbons (CFCs) presently contained in existing equipment were never released to the atmo­
sphere, then the integrated effective future chlorine loading above the 1 980 level is predicted to be 3% less
over the next 50 years relative to full compliance with the Amendments and Adjustments to the Protocol.

Failure to adhere to the international agreements will delay recovery of the ozone layer. If there were to be
additional production of CFCs at, for example, 20% of 1992 levels for each year through 2002 and ramped to zero
by 2005 (beyond that allowed for countries operating under Article 5 of the Montreal Protocol), then the integrat­
ed effective future chlorine loading above the 1980 level is predicted to be 9% more over the next 50 years relative
to full compliance with the Amendments and Adjustments to the Protocol.

Production of CF3 from dissociation of CFCs, HCFCs, and hydrofluorocarbons ( HFCs) is highly unlikely to
affect ozone. ODPs of HFCs containing the CF3 group (such as HFC- 1 34a, HFC-23, and HFC- 1 25) are highly
likely to be less than 0.00 1 , and the contribution of the CF3 group to the ODPs of HCFCs (e.g., from HCFC- 1 23)
and CFCs is believed to be negligible.

1 3. 1
O O Ps, GWPs and C I-Br LOAD I N G

ODPsfor several new compounds such a s HCFC-225ca, HCFC-225cb, and CF3l have been evaluated using both
semi-empirical and modeling approaches, and estimated to be 0.03 or less.

Both the direct and indirect components of the G WP of methane have been estimated using model calculations.
Methane's influence on the hydroxyl radical and the resulting effect on the methane response time lead to substan­
tially longer response times for decay of emissions than OH removal alone, thereby increasing the GWP. In
addition, indirect effects including production of tropospheric ozone and stratospheric water vapor were consid­
ered and are estimated to range from about 15 to 45% of the total GWP (direct plus indirect) for methane.

GWPs including indirect effects of ozone depletion have been estimated for a variety of halocarbons ( CFCs,
halons, HCFCs, etc.), clarifying the relative radiative roles of diff erent classes of ozone-depleting compounds.
The net GWPs of halocarbons depend strongly upon the effectiveness of each compound for ozone destruction;
the halons are highly likely to have negative net GWPs, while those of the CFCs are likely to be positive over both
20- and 1 00-year time horizons.

GWPs are not very sensitive to likely future changes in C02 abundances or major climate variables. Increasing
C02 abundances (from about 360 ppmv currently to 650 ppmv by the end of the 22nd century) could produce
20% larger GWPs for time horizons of the order of centuries. Future changes in clouds and water vapor are
unlikely to significantly affect GWPs for most species.

•
GWPs for 16 new chemical species have been calculated, bringing the number now available to 38. The new
species are largely HFCs, which are being manufactured as substitutes for the CFCs, and the very long-lived fully
fluorinated compounds, SF6 and the perfluorocarbons.

13. 2
 OOPs, GWPs and C I- B r LOAD I N G

13 .1 INTRODUCTION al. , 1 992). Their primary purpose is for comparison of

relative impacts of different gases upon ozone (e. g., for
Numerical indices representing the relative im­
evaluating the relative effects of choices among different
pacts of emissions of various chemical compounds upon
CFC substitutes upon ozone) . As in prior analyses, the
ozone depletion or global radiative forcing can be useful
ODP for each substance presented herein is based on the
for both scientific and policy analyses. Prominent
mass emitted into the atmosphere, and not on the total
among these are the concepts of Chlorine/Bromine
amount used. In some cases (such as emissions of
Loading, steady-state and time-dependent Ozone Deple­
CH3Br in soil fumigant applications) not all of the com­
tion Potentials (ODPs) , and Global Warming Potentials
pound used may be emitted into the global atmosphere
(GWPs), which form the focus of this chapter. Detailed
(see Chapter 1 0) . Steady-state ODPs represent the cu­
descriptions of the formulations of these indices are pro­
mulative effect on ozone over an infinite time scale (also
vided later. Here we briefly review the broad definitions
referred to here as "time horizon") . Time-dependent
of these concepts and cite some of their uses and limita­
ODPs describe the temporal evolution of this ozone im­
tions:
pact over specific time horizons (WMO, 1 990, 1 992;
Solomon and Albritton, 1 992; see Section 1 3 .4.5). At­
Chlori n e/ B romine Loading
mospheric models and semi-empirical methods have
Chlorine/bromine loading represents the amount been used in combination to best quantify these relative
of total chlorine and bromine in the troposphere or indices (Solomon et al. , 1 992; WMO, 1 992). As a rela­
stratosphere. Stratospheric chlorine/bromine loading tive measure, ODPs are subject to fewer uncertainties
depends upon the surface emissions of gases such as than estimates of the absolute percentage ozone deple­
chlorofluorocarbons (CFCs), hydrochlorofluorocarbons tion, particularly when only the ODP differences among
(HCFCs), and halons (which are based in large part upon various chlorinated gases are considered. Models used
industrial estimates of usage) and upon knowledge of the to evaluate ODPs now include better representations of
reactivity and hence the atmospheric lifetimes and midlatitude and polar vortex heterogeneous chemistry
chemical roles of those and related compounds. Recent processes than those used earlier. Comparisons of mod­
depletions in stratospheric ozone in Antarctica and in the el and semi-empirical methods reduce the uncertainties
Arctic have been linked to anthropogenic halocarbon in ODPs. However, evaluations of ODPs are still subject
emissions (see Chapter 3), and the weight of evidence to uncertainties in atmospheric lifetimes and in the un­
suggests that ozone depletions in midlatitudes are also derstanding of stratospheric chemical and dynamical
related to the emissions of these compounds (see WMO, processes. The recent re-evaluation of the chemical rate
1 992 and Chapter 4 of this document). Thus, the chlo­ and products for the reaction of BrO + H02 and resulting
rine/bromine loading is a key indicator of past and future effects on ODPs for bromocarbons provide a graphic ex­
changes in ozone. However, it should be recognized that ample of potential impacts of such uncertainties (see
chlorine/bromine loading is a measure only of changes Section 1 3 .4). Like chlorine/bromine loading, ODPs do
in halogen content. It does not account for additional not include other processes (such as changes in C02 and
factors that could also affect the time-dependent changes hence stratospheric temperatures) that could affect the
in atmospheric ozone or the linearity of their relationship future impacts of different gases upon ozone.
to chlorine/bromine loading (e. g. , carbon dioxide trends
that can also affect stratospheric temperatures). Global Warming Potentials

Global Warming Potentials provide a simple rep­

Ozone Depletion Potentials
resentation of the relative radiative forcing resulting
Ozone Depletion Potentials (ODPs) provide a rel­ from a unit mass emission of a greenhouse gas compared
ative measure of the expected impact on ozone per unit to a reference compound. Because of its central role in
mass emission of a gas as compared to that expected concerns about climate change, carbon dioxide has gen­
from the same mass emission of CFC- 1 1 integrated over erally been used as the reference gas. However, because
time (Wuebbles, 1 983 ; WMO, 1 990, 1 992; S olomon et of the complexities and uncertainties associated with the

13.3
OOPs , GWPs and C I- B r LOAD ING

carbon cycle, extensive effort has been put into evaluat­ long-lived perfluorocarbons and SF6, are also included
ing the effects on GWPs from uncertainties in the because of their potential roles as greenhouse gases and
time-dependent uptake of carbon dioxide emissions. As because some have been suggested as CFC and halon
described in Chapter 4 of IPCC (1 994), calculations replacements.
made with climate models indicate that, for well-mixed After emission into the current or proj ected atmo­
greenhouse gases at least, the relationship between sphere, the time scale for removal (i.e., the time interval
changes in the globally integrated adjusted radiative required for a pulse emission to decay to 1 /e of its initial
forcing at the tropopause and global-mean surface tem­ perturbed value) of most ozone-depleting and green­
perature changes is independent of the gas causing the house gases reflects the ratio of total atmospheric burden
forcing. Furthermore, similar studies indicate that, to to integrated global loss rate. As such, the total lifetime
first order, this "climate sensitivity" is relatively insensi­ must take into account all of the processes determining
tive to the type of forcing agent (e.g. , changes in the the removal of a gas from the atmosphere, including
atmospheric concentration of a well-mixed greenhouse photochemical losses within the troposphere and strato­
gas such as C02, or changes in the solar radiation reach­ sphere (typically due to photodissociation or reaction
ing the atmosphere). GWPs have a number of important with OH), heterogeneous removal processes, and perma­
limitations. The GWP concept is difficult to apply to nent removal following uptake by the land or ocean. In a
gases that are very unevenly distributed and to aerosols few cases, the time scale for removal of a gas from the
(see, e.g. , Wang et al. , 1 991, 1 993). For example, rela­ atmosphere cannot be simply characterized or is depen­
tively short-lived pollutants such as the nitrogen oxides dent upon the perturbation and/or the background
and the volatile organic compounds (precursors of atmosphere and other sources; in those cases (chiefly
ozone, which is a greenhouse gas) vary markedly from C02 and CH4) we refer to removal of a pulse as the re­
region to region within a hemisphere and their chemical sponse time or decay response.
impacts are highly variable and nonlinearly dependent Alternatively, atmospheric lifetimes can be de­
upon concentrations. Further, the indices and the esti­ fined by knowledge of global source strengths together
mated uncertainties are intended to reflect global with the corresponding mean atmospheric concentra­
averages only, and do not account for regional effects. tions and trends, but these are usually more difficult to
They do not include climatic or biospheric feedbacks, define accurately. The atmospheric lifetime may be a
nor do they consider any environmental impacts other function of time, due to changing photochemistry asso­
than those related to climate. The direct GWPs for a ciated, for example, with ozone depletion or temperature
number of infrared-absorbing greenhouse gases have trends, but these effects are likely to be small for at least
been analyzed in this report, with a particular emphasis the next several decades and will not be considered here.
on a wide range of possible substitutes for halocarbons. The total lifetimes of two major industrially pro­
The evaluation of effects on other greenhouse gases re­ duced halocarbons, CFC- 1 1 and CH3 CCl3, have been
sulting from chemical interactions (termed indirect reviewed and re-evaluated in a recent assessment (Kaye
effects) has been more controversial. Underlying as­ et al., 1 994 ). The empirically derived lifetime for CFC- 1 1
sumptions and uncertainties associated with both direct determined in that study is 50 (±5) years (as compared to
and indirect GWPs are discussed briefly in Section 1 3 . 5 . 55 years in the previous WMO [1 992] assessment) . As
in previous assessments, the lifetimes presented here are
not based solely upon model calculations, but use infor­
13.2 ATM OS P HERIC LI FETIM ES AND
mation from measurements to better constrain the
RESPONSE TIM ES
lifetimes of these and other gases. The lifetime of CFC-
Atmospheric lifetimes or response times are used 1 1 is used here to normalize lifetimes for other gases
in the calculation of both ODPs and GWPs. The list of destroyed by photolysis in the stratosphere (based upon
compounds considered in this assessment is an extension scaling to the ratios of the lifetimes of each gas com­
of those in WMO (1 992), primarily reflecting the con­ pared to that of CFC- 1 1 obtained in the models
sideration of additional possible replacements for CFCs discussed in Kaye et al., 1 994) . This approach could be
and halons. Additional compounds, such as the unusually limited by the fact that different gases are destroyed in

1 3. 4
 -�-

O OPs, GWPs and C I- B r LOAD ING

different regions of the stratosphere depending upon the discussed in IPCC ( 1 990) and IPCC ( 1 992) as an indirect
wavelength dependence of their absorption cross sec­ effect on OH concentrations, and thus is not new. It aris­
tions (weakening the linearity of their comparison to es through the fact that small changes in OH due to
CFC- 1 1 ) , particularly if stratospheric mixing is not rapid addition of a small pulse of CH4 slightly affect the rate of
(see Plumb and Ko, 1 992). Depending on absolute cali­ decay of the much larger amount of CH4 in the back­
bration factors used by different research groups, Kaye ground atmosphere, thereby influencing the net removal
et al. ( 1 994) derived a total lifetime for CH3CC13 of ei­ of the added pulse. It is critical to note that the exact
ther 5 . 7 (±0.3) years for 1 990 or 5 . 1 (±0.3) years, value of the CH4 pulse response time depends upon a
respectively (see Prinn et al., 1 992), compared to 6. 1 number of key factors, including the absolute amount of
years in the earlier WMO ( 1 992) assessment. B ecause CH4, size of the pulse, etc., making its interpretation
of the current uncertainties in absolute calibration, we complex and case-dependent. Here we consider small
use a lifetime for CH3CC13 of 5 .4 years with an uncer­ perturbations to the present atmosphere, and base the
tainty range of 0.6 years in this report. From this total definition of the methane pulse response time to be used
atmospheric lifetime, together with the evaluated loss in calculation of the GWP upon the detailed explanation
lifetimes of CH3CC13 due to the ocean (about 85 years, of the effect as presented in Prather ( 1 994) and in Chap­
with an uncertainty range from 50 years to infinity; see ter 2 of IPCC ( 1 994) .
Butler et al. , 1 991) and stratospheric processes (40 ± 1 0 Table 1 3 - 1 shows the recommended total atmo­
years), a tropospheric lifetime for reaction with O H of spheric lifetimes for all of the compounds considered
6.6 years can be inferred (±25% ). The lifetimes of other here except methyl bromide (the reader is referred to
key gases destroyed by OH (i. e. , CH4, HCFCs, and Chapter 1 0 for a detailed discussion of the lifetime of
hydrofluorocarbons [HFCs]) can then be inferred rela­ this important gas). The response time of methane is
tive to that of methyl chloroform (see, e.g., Prather and also indicated. The lifetimes for many compounds have
Spivakovsky, 1 990) with far greater accuracy than would been modified relative to values used in WMO ( 1 992;
be possible from a priori calculations of the complete Table 6-2). The estimates for the lifetimes of many of
tropospheric OH distribution. We note that a few of the the gases destroyed primarily by reaction with tropo­
newest CFC substitutes (namely, the HFCs -236fa, spheric OH (e.g., HCFC-22, HCFC- 1 4lb, HCFC- 1 42b,
-245ca, and -43- lOmee) have larger uncertainties in life­ etc.) are about 1 5% shorter than in WMO ( 1 992), due
times since fewer kinetic studies of their chemistry have mainly to recent studies suggesting a shorter lifetime for
been reported to date. It is likely that methane is also CH3CC13 based upon improved calibration methods and
destroyed in part by uptake to soil (IPCC, 1 992), but this upon an oceanic sink (Butler et al., 1 99 1 ) . Similarly, the
process is believed to be relatively slow and makes a estimates for the lifetimes of gases destroyed mainly by
small contribution to the total lifetime. Possible soil photolysis in the stratosphere (e.g., CFC- 12, CFC- 1 1 3,
sinks are not considered for any other species. H- 1 30 1 ) are about 1 0% shorter than in IPCC ( 1 992) due
The special aspects of the lifetime of methane and to a shorter estimated lifetime for CFC- 1 1 and related
the response time of a pulse added to the atmosphere species. Lifetime estimates of a few other gases have
were defined in Chapter 2 of IPCC ( 1 994 ), based largely also changed due to improvements in the understanding
upon Prather ( 1 994) . Those definitions are also em­ of their specific photochemistry (e.g., note that the life­
ployed here. Small changes in CH4 concentrations can time for CFC- 1 1 5 is now estimated to be about 1 700
significantly affect the atmospheric OH concentration, years, as compared to about 500 years in earlier assess­
rendering the response time for the decay of the added ments) . Fully fluorinated species such as SF6, CF4, and
gas substantially longer than that of the ensemble (i.e., CzF6 have extremely long atmospheric lifetimes, sug­
longer than the nominal 1 0-yr lifetime for the bulk con­ gesting that significant production and emissions of
centration of atmospheric C� in the current atmosphere). these greenhouse gases could have substantial effects on
This is due to the nonlinear chemistry associated with radiative forcing over long time scales. In contrast,
relaxation of the coupled OH-CO-CH4 system (see CF3I, which is being considered for use as a fire extin­
Prather, 1 994; Lelieveld et al. , 1 99 3 ; and Chapter 2 of guishant and other applications, has an atmospheric
IPCC [ 1 994] for further details). This effect was also lifetime of less than 2 days.

13.5
O O Ps, GWPs and C I- B r LOADING

Table 13-1. Lifetimes and response times recommended for OD P and GWP calculations.

Gas Lifetime or Response Reference

Time (yrs)
CFC- 1 1 50 (±5) 2
CFC- 1 2 1 02 3
CFC- 1 3 640 1
CFC- 1 1 3 85 3
CFC- 1 1 4 300 1
CFC- 1 1 5 1 700 1
CCl4 42 3
OI 3 CCl 3 5 .4 (±0.4) 2
CHCl 3 0.55 4
0I 2Cl 2 0.4 1 4
HCFC-22 13 . 3 4
HCFC- 1 23 1 .4 4
HCFC- 1 24 5.9 4
HCFC- 14lb 9.4 4
HCFC- 142b 1 9.5 4
HCFC-225ca 2.5 4
HCFC-225cb 6.6 4
OI 3Br 1 .3 Chapter 1 0
CF3 Br (H- 1 30 1 ) 65 3
CF2C1Br (H- 1 2 1 1 ) 20 3
HFC-23 250 10
HFC-32 6.0 4
HFC- 1 25 36 4
HFC- 1 34 1 1 .9 5
HFC- 1 34a 14 4
HFC- 143 3.5 11
HFC- 1 43a 55 4
HFC- 1 52a 1 .5 4
HFC-227ea 41 9
HFC-236fa 250 7
HFC-245ca 7 6
HFC-43-lOmee 20.8 7
HFOC- 1 25E 82 6
HFOC- 1 34E 8 6
SF6 3200 1
CF4 50000 1
C 2F 6 1 0000 1
C 6f 14 3200 1
C 5F 1 2 4 1 00 1
c-C4F 8 3200 1
CF3 I <0.005 8
N 20 1 20 3
OI 4 (pulse response) 14.5 ± 2.5 12

13.6
 O O Ps, GWPs and C I-Br LOAD ING

Table 13-1. N otes.

1. Ravishankara et a!. ( 1 993).

2. Prather, private communication 1 99 3 , based on NASA CFC report (Kaye et al., 1 994) and other
considerations as described in text.
3. Average of reporting models in NASA CFC report (Kaye et al., 1 994). Scaled to CFC- 1 1 lifetime.
4. Average of JPL 92-20 and IUPAC ( 1 992) with 277 K rate constants for OH+halocarbon scaled against
OH+CH 3CCl3 and lifetime of tropospheric CH3CC13 of 6.6 yr. Stratospheric lifetime from WMO ( 1 992).
5. DeMore et al. (1993 ) . Used 277 K OH rate constant ratios with respect to CH3CCl3, scaled to tropospheric
lifetime of 6.6 yr for CH3CC13.
6. Cooper et al. ( 1 992) . Lifetime values are estimates .
7. W. DeMore (personal communication, 1994) with 277 K rate constants for OH+halocarbon scaled against
OH+CH 3CCl3 and lifetime of tropospheric CH3CCl3 of 6.6 yr.
8. Solomon et a!. ( 1 994).
9. Briihl, personal communication based on data for the reaction rate constant with OH provided by Hoescht
Chemicals, 199 3 ; Zhang et al. (1994) and Nelson et al. (1993) with 277 K rate constants for OH+halocarbon
scaled against OH + CH3CC13 and lifetime of tropospheric CH3CC13 of 6.6 yr.
10. Schmoltner et al. (1993) with 277 K rate constants for OH+halocarbon scaled against OH+CH 3CCl3 and
lifetime of tropospheric CH 3CC13 of 6.6 yr.
1 1. Barry et al. (1994) with 277 K rate constants for OH+halocarbon scaled against OH+CH3CCl3 and lifetime of
tropospheric CH3CCl3 of 6.6 yr.
1 2. Prather (1994) and Chapter 2 of IPCC (1994) .

The basis for the recommended lifetimes is de­ provides the input needed to evaluate past trends. The
scribed within the Table and its footnotes . These values longest and most complete record of CFC emissions is
are used for all calculations presented in this chapter. contained in the industry-sponsored "Production, Sales
and Atmospheric Release of Fluorocarbons" report
(AFEAS, 1 99 3 ) . This report contains estimates of pro­
13.3 C H LO R IN E/ B RO M IN E LOAD IN G AND
duction in countries not covered in the industry survey.
SC ENA R I OS FOR C FC SUBSTITUTES
Recently, with declining global production in response
13.3.1 Eq uivalent Tropospheric Ch lorine to the Montreal Protocol, the fractional contribution to
Load ing the total of this "unreported" production, a portion of
which is in developing (Article 5) countries, has amount­
For the purposes o f this report, a detailed assess­ ed to about 25 % . Estimates of unreported production
ment of those sources of tropospheric chlorine and based on matching observed and calculated trends in the
bromine loading relevant to stratospheric ozone destruc­ relevant trace gases are consistent with AFEAS esti­
tion was carried out. The approach taken is similar to mates (see, e. g. , the detailed analysis in Cunnold et al. ,
that of Prather and Watson ( 1 990) and previous assess­ 1 994).
ment reports (WMO, 1 992). This analysis is more Expected uses and the corresponding release times
complete in that it includes a description of the time for each of the gases are considered, in order to more
delay between consumption and emission of the ozone­ accurately determine yearly emission amounts (AFEAS ,
depleting substances. The time delays are based upon 1 99 3 ; Fisher and Midgley, 1 99 3 ; Gamlen et al., 1 986;
uses (e.g. , refrigeration, solvents, etc.). The procedure is McCarthy et al., 1 977; McCulloch, 1 992; Midgley,
also discussed in Daniel et al. ( 1 994). The best under­ 1 989; Midgley and Fisher, 1993). Possible time-depen­
standing of the past history of emissions of fourteen of dent changes in release times (e. g. , for improved
the most important halocarbons, together with current technologies) are not considered. For methyl bromide, a
estimates of the lifetimes of these gases (Table 1 3 - 1 ) budget of natural and anthropogenic sources based upon

13. 7
 O OPs, GWPs and C I- B r LOADING

Chapter 1 0 is adopted. Anthropogenic sources of methyl suggest that the adopted value of a of 40 is likely to be a
· bromide are assumed to be zero before 193 1 . A constant low estimate. A higher value of a would increase the
anthropogenic emission is assumed from 1 93 1 to 1 994 contributions of methyl bromide and the halons. The
of 73 ktonnes/year (see Chapter 10). As noted in Chap­ adopted methyl bromide lifetime of 1 .3 years includes an
ter 1 0, it is possible that decreases in methyl bromide ocean sink. If loss to the ocean were to be slower, the
emissions associated with the declining use of gasoline lifetime would be longer and the anthropogenic methyl
additives could have offset some of the known increases bromide contribution would be larger. On the other
in agricultural use of this compound during the 1 970s hand, a faster ocean sink would decrease the contribu­
and 1 980s. However, precise information is not avail­ tion. Similarly, a decrease (increase) in the fractional
able. Although this assumption will affect the calculated emission of methyl bromide used for agricultural pur­
historical contribution of methyl bromide to equivalent poses would decrease (increase) the calculated
chlorine loading, because of the short lifetime of methyl contribution from that source. The budget of methyl
bromide, it has very little effect on projected contribu­ bromide and its uncertainties are discussed in detail in
tions. Anthropogenic emission of methyl bromide does Chapter 10 of this assessment.
not equal production, and this difference is explicitly Chlorinated solvents such as CH2Cl2, C2Cl4, and
considered in all calculations of methyl bromide's atmo­ C2HCl3 were not explicitly considered in this analysis.
spheric loading and their impacts presented in this B ased upon emission estimates, WMO ( 1 992) suggests
chapter. that these species are present at about the 35, 32, and 1
The calculated contributions of methyl bromide pptv levels, respectively, within the current troposphere.
and other bromocarbons to equivalent chlorine loading Wang et al. ( 1 994) present observations of C2Cl4 show­
are more uncertain than that of other compounds. For ing average abundances of only 7 pptv. The lifetimes of
the purpose of comparing the roles of chlorine- and bro­ these gases may be long enough to allow a fraction to
mine-containing gases once they reach the stratosphere, reach the stratosphere and thereby contribute to strato­
it is assumed that each bromine atom is 40 times more spheric chlorine loading. Schauffler et al. ( 1 993) report
damaging to ozone than chlorine (see Section 1 3 .4), al­ tropospheric measurements of CH2Cl2 of about 30 pptv
lowing evaluation of an "equivalent tropospheric in 1 992 and report direct measurements of this gas near
chlorine" that includes an estimate of the net ozone im­ the tropical tropopause of about 1 5 pptv, suggesting
pact of bromocarbons. The enhanced effectiveness of substantial transport to the stratosphere. While the abun­
bromine (hereafter referred to as a) depends in principle dances of these gases are presently small, increasing use
upon the amount of active chlorine present, making it a would increase the abundances. At a growth rate of, for
time-dependent quantity. However, in the next few de­ example, 3 %/year, CH2Cl2 and C2HCl3 could reach
cades (i.e., until about 2020), the chlorine content of the abundances ofO. l ppbv in 36 and 1 5 6 years, respectively.
stratosphere is expected to change relatively little, mak­ Thus, while these relatively short-lived gases probably
ing a essentially constant during this period. Towards contribute little to contemporary stratospheric chlorine
the middle and latter parts of the twenty-first century, loading, there is observational evidence of significant
decreases in chlorine abundances will likely lead to in­ transport to the stratosphere for some species, and con­
creases in the value of a, at least in polar regions. This tinued growth would lead to a greater contribution to
follows from the fact that the reaction of ClO with itself stratospheric chlorine loading. On the other hand, a re­
represents an important ozone loss process in the Antarc­ cent survey (P. Midgley, personal communication)
tic (and Arctic) that is dependent upon the square of the indicates that industrial emissions of these gases in the
stratospheric chlorine abundance, while the reaction of U . S ., Europe, and Japan have steadily decreased since
ClO with BrO is linearly dependent upon the strato­ 1 984, so that current emissions are more likely to be de­
spheric chlorine abundance. Thus, as chlorine abundances creasing than increasing.
decline, the reaction of ClO with BrO will become more Water-soluble emissions such as sea salt or volca­
important relative to ClO + ClO. This and other consid­ nic HCl are effectively removed in clouds and rain (see,
erations discussed in Section 1 3 .4 (particularly the role e. g., Tabazadeh and Turco, 1 993) and do not represent
of the H02 + BrO reaction in the lower stratosphere) significant sources of stratospheric chlorine. Short-lived

13.8
 OOPs, GWPs and C I-Br LOADING

bromocarbons such as bromoform were also not consid­ HCFC and H F C Mixing Ratio s for Case A
ered here. 1000
Equivalent chlorine loading was evaluated for
eight cases to demonstrate impacts of various assump­
HFC-134a
tions for future use of ozone-depleting substances. A / '
/
complete description of the scenarios is provided in Ta­
/
'
ble 1 3-2. Global compliance to the Copenhagen '
agreements is represented by case A. Estimates of future
HCFC- 22
......... ./"\. '
>
emissions of hydrochlorofluorocarbons (HCFCs) and +- ...-·- ·-.). '
hydrofluorocarbons (HFCs) are based on a detailed anal­
a.
a. "\ ·�.. '
ysis of projected global demand for each gas carried out V HCFC-124 \ '-HCFC- '-'
by the U.S. Environmental Protection Agency (EPA) to -\ '\. 142b
2030 (D. Hufford, personal communication, 1 993). Es­
;' "l \
timates beyond 2030 will depend on agreements for /� cFC-
123 \
·� '­

HCFC use in developing countries; no attempt is made I

to account for potential use and emissions beyond 2030.
0. I L...L.J.
. ..II
.L..J.
:.....L. ..J .I..L
...J_J... ..J... L. ...J.
...L.li.....L. ....I ...
L....uo�...
..J_ ...... ....�....�

Such use would increase the HCFC equivalent chlorine 1975 2000 2025 2050 2075 2100
loading. Figure 1 3- 1 shows calculated tropospheric con­
Year
centrations of HCFCs and HFC- 1 34a based on the EPA
analysis.
A complete phase-out of HCFCs after 2030 is as­ Figure 13- 1. Calculated abundances of hydrofluo­
rocarbons and hydrochlorofluorocarbons for case A.
sumed, after which time a 2.5%/year increase in
HFC- 1 34a is adopted (intended to represent not only
HFC- 1 34a itself but the combined impact of a class of The bottom panel of Figure 1 3-2 shows the contri­
hydrofluorocarbons that could be used as HCFC substi­ butions of the various gases considered here to the
tutes after 2030) . These are important only insofar as equivalent tropospheric chlorine versus time for case A.
their radiative forcing is concerned, since they do not It shows that anthropogenic sources of chlorine and bro­
significantly deplete stratospheric ozone (see Section mine are believed to have contributed much of the
1 3 .4). The use of shorter-lived or less infrared active equivalent chlorine in today's troposphere. Direct mea­
gases could reduce the estimated radiative forcing from surements of chlorinated and brominated source gases
such compounds. Figure 1 3 - 1 shows a steep increase in have been obtained near the inflow region at the tropical
the projected HFC concentrations in the latter part of the tropopause on recent aircraft missions (Schauffler et al. ,
twenty-first century; the effect of such increases on radi­ 1 993). These reveal abundances of halocarbon source
ative forcing is discussed further in Chapter 8 . gases very close to those shown in Figure 1 3-2 for 1 992.
Cases B through G demonstrate impacts relative to Further, concurrent measurements on-board the same
case A of continued CFC production outside internation­ aircraft confirm that HCl emitted at low altitudes from
al agreements, an accelerated HCFC phaseout, a methyl volcanoes, oceans, and other sources makes a very small
bromide phaseout or a 2 %/year increase in industrial contribution to the total chlorine injected in the tropical
methyl bromide use, and complete recapture (as opposed stratospheric inflow region (less than 0. 1 ppbv; Schauf­
to recycling) of halons, CFCs- 1 1 , - 1 2, and - 1 1 3 banked fler et al. , 1 993). Figure 1 3-2 also shows that equivalent
in existing equipment (i. e. , refrigeration, air-condition­ chlorine is expected to maximize in the troposphere in
ing, fire extinguishants). Recapture illustrates the impact 1 994 under current agreements, and would return to lev­
of potential use of non-ozone depleting substitutes that els near those believed to be present when Antarctic
could reduce future emissions of these compounds. Case ozone depletion first became statistically significant
H is presented in order to compare the current (Copen­ compared to variability (i. e. , near 1 980) around the mid­
hagen) agreements to the earlier London Amendments. dle of the twenty-first century if the emissions
corresponding to case A are adopted. Since equivalent

13.9
O O Ps , GWPs and C I- B r LOAD ING

Table 13-2. Scenarios for future ch lorine and bromine loading.

Case Description

Case A Global Compliance to Montreal Protocol as Amended and Adjusted in

Copenhagen (Protocol) : CFCs, carbon tetrachloride, and methyl
chloroform phased out in developed countries by 1 996. Consumption
in 1 992 for Article 5 countries is assumed to be 5% of 1 992 global
production, growing to 1 0 % of 1 992 global production by 1 996,
constant to 2002, and a linear decline to zero by 2006. HCFC
emissions based on U . S . EPA analysis as described in the test, and are
consistent with limits under the Protocol. The halons in existing
equipment (the "bank") as derived from McCulloch, 1 992, are emitted
in equal amounts over the period 1 993 - 2000 for halon- 1 2 1 1 and the
period 1 993-20 1 0 for halon- 1 30 1 . Methyl bromide emissions are
assumed constant over the period 1 994 - 2 1 00.
Case B Production and Consumption Outside Protocol: Assumes continued
production of CFC and carbon tetrachloride production at a rate equal
to about 20% of 1 992 global production through 2002 and then a
linear decrease to zero by 2006. All other emissions as in case A.
Case C Destruction of Halon B ank: Assumes all halons contained in existing
equipment are completely recovered after 1994. All other emissions as
in case A.
Case D HCFC Early Phase-Out: Assumes that HCFC emissions cease on a
global basis in 2004. All other emissions as in case A.
Case E Methyl Bromide Increase: Assumes a 2%/year increase in agricultural
emissions of methyl bromide until global agricultural emissions reach
a maximum value three times that of the present. All other emissions
as in case A.
Case F Methyl Bromide Phase-Out: Assumes a 1 00% phase-out in all
anthropogenic sources of methyl bromide emission except biomass
burning (see Chapter 1 0) by 200 1 . All other emissions as in case A.
Case G Destruction of CFC Bank: Assumes that all banked CFC- 1 1 and CFC -
1 2 in hermetically sealed and non-hermetically sealed refrigeration
categories are completely recovered in 1995 and hence never released
to the atmosphere. All banked CFC- 1 1 3 is also assumed to be
completely recovered. All other emissions as in case A.
Case H London Amendments: Global compliance with the 1 990 London
Amendments to the Montreal Protocol rather than the 1992
Copenhagen Amendments.

13. 10
 OOPs , GWPs and C I- B r LOA DING

Equivalent Effective Stratospheric Chlorine especially in the key region below about 25 km. Com­
Case A pounds that dissociate less readily within the stratosphere
3500 r-----.
than others deliver less reactive chlorine, thereby de­
3000 creasing their effectiveness from that indicated by their
tropospheric loading. Examples of this behavior include
2500
HCFC-22 and HCFC- 1 42b. Observations show that
> 2000 about 65 % of the input of these gases to the stratosphere
a.
a. remains undissociated by the time they exit the strato­
1500
sphere (see Solomon et al. , 1 992), substantially reducing
1000 their impact on stratospheric ozone as compared to gases
such as CC14, which undergo nearly complete dissocia­
tion while in the stratosphere. Here we evaluate the
0 �-�--��--���--�- chlorine release in the lower stratosphere (below 25 km),
1940 1960 19 80 2000 2020 2040 2060 2080 2100
Year since this is the region where most of the column-inte­
grated ozone loss in the present atmosphere is observed
to take place (WMO, 1 992 and Chapter 1 of this docu­
Tropospheric Chlorine Loading ment). The dissociation of many key compounds
Case A relative to a reference gas (CFC- 1 1 ) in the lower strato­
5000
4500
sphere has been evaluated by Solomon et al. ( 1 992) and
by Daniel et al. ( 1 994) using both observations and model
4000
calculations and is used here to define the equivalent effec­
3500
tive stratospheric chlorine (EESC). In addition, a 3-year
>
..... 3000
a. lag between tropospheric emission of halocarbons and
a. 2500
stratospheric ozone impact is assumed, based in part on
2000
tracer studies (e.g., Pollock et al. , 1 992) . Using these
1500
CH3 8r- natural
factors together with the estimate of a of 40 as discussed
1000 above, we define an "equivalent effective stratospheric
500 CH3CI chlorine" abundance that characterizes the impact of
0 �-�-�--L-�--�----�� each source gas upon lower stratospheric ozone (similar
1940 1960 1980 2000 2020 2040 2060 2080 2100
to the "free halogen" defined in WMO, 1 992). This def­
Year
inition is the same as that used for time-dependent ODPs
discussed in Section 1 3 .4.5.
Figure 13-2. Contributions of various gases to the
The top panel of Figure 1 3-2 displays cumulative
equivalent tropospheric (bottom ) and stratospheric
(top) chlorine versus time for case A. equivalent effective stratospheric chlorine for case A.
Curves are lowered compared to tropospheric chlorine
loading due to incomplete dissociation of the com­
tropospheric chlorine loading is expected to maximize in pounds. Peak chlorine loading occurs in 1 997 as
1 994, further controls would not reduce peak concentra­ determined by the peak tropospheric loading that oc­
tions provided that global emissions continue to follow curred three years earlier (bottom panel), suggesting that
the requirements of the Protocol and its Amendments . the maximum risk of ozone depletion has been deter­
However, consumption outside current Protocol agree­ mined by emissions occurring prior to 1 995, assuming
ments could increase the concentration. case A emissions.
Figure 1 3-3 shows the equivalent effective strato­
13 .3.2 Equivalent Effective Stratospheric
spheric chlorine represented by case A (Copenhagen
Chlori n e
Amendments) compared to the provisions of the original
Tropospheric chlorine loading alone does not de­ 1 987 Montreal Protocol. The figure also illustrates what
termine the impact of a compound upon ozone loss, could have happened with no international agreements

13.11
O O Ps, GWPs and C I-Br LOAD ING

Equivalent Effective Stratospheric Chlorine for that year a reasonable proxy for the point where, all
15000 other things being equal, ozone depletion is likely to
1
No cease. For case A, for example, that point in time (re­
Protocol / ferred to here as x) is expected to be reached in 2045 .
I
12000
I Table 1 3-3 presents the corresponding years for the other
I scenarios considered here. For evaluating cumulative
long-term ecological impacts due to ozone depletion, it
9000
I I Montreal may also be useful to consider a similar integral begin­
> I Protocol
.... / / ning not in 1 995 but in 1 980 (thus integrating over the
.I
a. /
a. 6000 / / entire period when ozone depletion has been observed).
.I /
/ / A similar definition was used in WMO ( 1 992), except
"/
/ that tropospheric values in 1 985 were chosen as the ref­
/'
3000 / erence point below which ozone depletion was assumed
/
/ to cease, and the integral was performed from that point
/

onwards rather than from 1 995 onwards. Table 1 3-3

0
compares the percent differences from the base case A
1950 1975 2000 2025 2050 2075 2100
for each scenario for the following quantities: a) inte­
Year
grated equivalent effective stratospheric chlorine
loading from 1 995 until year x (the point when EESC
Figure 13-3. Estimated equivalent effective strato­
drops below 1 980 levels) and b) integrated equivalent ef­
spheric chlorine represented by case A (Copenhagen
Amendments) compared to the provisions of the fective stratospheric chlorine loading from 1 980 until
origi nal 1987 Montreal Protocol , and a case with no year x. Positive values denote integrated EESC levels
i nternational ag reements on ozone-depleti ng gas­ that exceed the base case, while negative values indicate
es (where a 3%/year i ncrease in global e missions integrated EESC levels below the base Copenhagen sce­
of CFCs and m ethyl chloroform was assumed, less nario. The magnitudes of natural sources of chlorine and
than known trends up to that time) .
bromine (e. g., from CH3Cl and CH3Br) do not influence
these calculations, provided that they are not changing
on ozone-depleting gases (where a 3%/year increase in with time.
global emissions of CFCs and methyl chloroform was
assumed, less than known trends up to that time). The
13.4 OZO N E D EPLETION POTENTIA LS
figure shows that without international agreements,
equivalent effective stratospheric chlorine would likely
13.4.1 Introduction
reach values about twice as large as today's levels by
2030 and about three times today's levels by about 2050. Understanding of atmospheric chemical processes
Even with the provisions of the original Montreal Proto­ and the representation of these processes in models of
col, equivalent effective stratospheric chlorine would be global atmospheric chemistry and physics have im­
likely to double by about the year 2060. Instead, under proved since the WMO ( 1 992) assessment. In particular,
the current provisions, the stratospheric abundances of prior modeling analyses of ODPs were based largely on
ozone-depleting gases are expected to begin to decrease calculations including only gas phase chemistry, al­
within a few years. though a few calculations were carried out that included
One important measure of future ozone loss is the some of the chemistry occurring on background sulfuric
time integrated equivalent effective chlorine (pptv-year) acid aerosols. Some of the models used in the analysis
to be expected from January 1 , 1 995, through the time presented here include representations of polar vortex
when ozone depletion is likely to cease (i. e. , the integrat­ processes (albeit in highly parameterized fashions) as
ed future ozone loss) . Ozone depletion first became well as most effects of heterogeneous chemistry on
observable in a statistically significant sense in about background sulfuric acid (but not volcanic) aerosols.
1 980, making the return to equivalent effective chlorine The models still tend to underestimate the absolute

13. 1 2
 O O Ps, GWPs and C I-Br LOADING

Table 13-3. Resu lts of scenario calculations: integrated E ESC differences (from case A) and the year
when EESC drops below 1980 levels.

Scenario Year (x) when EESC is Percent difference in Percent difference in

X X
expected to drop below
fEESCdt from fEESCdt from
1980 value
1995 1980
case A. case A.
A - Copenhagen 2045 0.0 0.0
B - Production outside of 2048 +9 +7
Protocol
C - Destruction of halon 2043 -10 -7
bank
D - HCFC early phase-out 2044 -5 -4
E - Methyl bromide 2057 +11 +9
mcrease
F - Methyl bromide 2040 -13 -10
phase-out
G - Destruction of CFC 2044 -3 -2
bank
H - London Amendments 2055 +38 +30

ozone losses in the lowest part of the stratosphere (see to chlorine for ozone loss, which is critical for the ODPs
Chapter 6); these limitations can affect ODPs, especially of the halons and CH3Br.
those for bromocarbons. The semi-empirical approach
developed by Solomon et a!. ( 1 992) implicitly accounts 13.4.2.1 FLUORINE

for observed ozone destruction profiles both inside and

It has long been assumed that atomic fluorine re­
outside of the polar vortices that are believed to reflect
leased from chlorofluorocarbons would be tied up in the
heterogeneous processes. While the semi-empirical ap­
form of HF and therefore unable to participate in catalyt­
proach is based upon limited data at low latitudes and
ic cycles that significantly deplete ozone. For example,
high altitudes (above about 25 km), these limitations oc­
Stolarski and Rundel ( 1 975) concluded that the catalytic
cur in regions that are believed to make relatively small
efficiency for ozone depletion by fluorine atoms is less
contributions to the globally averaged ozone loss and
than 1 0- 4 that of chlorine in the altitude range from 25 to
hence to the ODP. Based upon these improvements in
50 km. While recent estimates of the equilibrium con­
understanding, we did not explicitly evaluate chlorine
stant, Keq, for F + Oz � FOz published in JPL ( 1 992)
loading potentials (a simpler but less complete index) in
suggest that FOz could have an appreciable thermal dis­
this report (see WMO, 1 992).
sociation lifetime of the order of 1 day or longer in the
stratosphere, it is unlikely that FOx compounds can lead
13.4.2 Relative Effectiveness of Halogens i n
to significant ozone loss, as discussed in Chapter 12.
Ozone Destruction
Direct observations of HF and fluorine source gases
A range of molecules are being considered as sub­ (e. g. , Zander et al. , 1 992) support the view that there are
stitutes for the chlorofluorocarbons and halons. S ome of no large unrecognized reservoirs for fluorine. As in pre­
these are non-halogenated compounds that result in no vious reports, we assume here that atomic fluorine and
ozone loss, but others contain iodine or fluorine and related species do not cause significant ozone depletion.
could in principle deplete stratospheric ozone. It is also In contrast to atomic fluorine, FO, and FOz, it has,
of interest to review the effectiveness of bromine relative however, recently been suggested (Li and Francisco,

13. 13
O O Ps , GWPs and C I-Br LOA DI N G

1 991; Biggs e t al. , 1 993) that the CF30x group could be 50

stable enough to undergo catalytic cycles that deplete 38° N, Winter
ozone at a significant rate before being decomposed to 45

less stable products that form HF. It has also been sug­ E
-"
40
gested that the FC(O)Ox group could undergo similar
Q)
"0
chemistry (see Chapter 1 2). These free radical groups .2
35
are produced upon decomposition of a number of HFCs +-

<i:
and HCFCs, and even a few CFCs. Notably, it was sug­ 2! 30 Cl
0
gested that such processes could compromise the use of E
.,.
0
HFC- l 34a as a substitute that does not damage the .... 25
a.
ozone layer. Briefly, the key chemical reactions are: a.
<!
20
CF3CFH2 (HFC- 1 34a) + OH (multi-step) --7
CF3 + other products ( 1 3- 1 )

CF3 + 0 2 + M --7 CF302 ( 1 3-2)

CF302 + 03 --7 CF30 + 2 02 ( 1 3-3)

Figure 13-4. Calculated effectiveness of C F3, bro­
CF30 + 03 --7 CF302 + 02 ( 1 3-4) mine, and iodine in ozone destruction at midlatitudes
relative to chlorine (based on resu lts from Garcia­
The last two reactions constitute a catalytic cycle analo­ Solomon model as discussed in text) .
gous to the OH and H02 reactions with ozone, and could
in principle be an effective ozone loss cycle in the lower
1 000 times less effective than chlorine for ozone de­
stratosphere. The key factors in terminating this catalyt­
struction at 20 krn in midlatitudes. While higher local
ic chain are reactions that can break down the CF3 group,
values might be obtained in polar winter (where NO
forming either stable products or products that rapidly
abundances are very small), the impacts of CF3-related
decompose to produce HF. Two such reactions have
reactions on the globally averaged ODPs of CF3-con­
been identified:
taining chlorofluorocarbons (such as CF3Cl) and
CF30 + NO --7 CF20 + FNO ( 1 3-5) hydrochlorofluorocarbons (such as CF3CHCl2) are be­
lieved to be negligible, and the ODPs of HFCs such as
CF30 + CH4 --7 CF30H + CH3 ( 1 3-6) HFC- 1 34a and HFC-23 are highly likely to be less than
l x l 0- 3 based upon current kinetic data (Ravishankara et
Chapter 12 discusses recent measurements of these and
al. , 1 994) .
other relevant kinetic rate constants in considerable de­
tail. Direct laboratory measurements coupled with
13.4.2.2 BROMINE
model calculations have shown that the chain-terminat­
ing reactions above are sufficiently fast, and the chain­ The chemistry of atmospheric bromine is dis­
propagating reactions sufficiently slow, that the Ozone cussed further in Chapter 10. The understanding of the
Depletion Potentials relating to the presence of a CF3 relative roles of bromine and chlorine in depleting ozone
group are essentially negligible. Recently, Ravishankara was discussed by Solomon et al. ( 1 992), who noted that
et al. ( 1 994) and Ko et al. ( 1 994a) have examined the in situ and remote sensing measurements of ClO, BrO,
implications of these processes for the effectiveness of and OClO strongly suggest that bromine is about 40
CF3 radical groups for ozone loss relative to chlorine. times more efficient than chlorine for Antarctic ozone
Figure 1 3-4 shows the calculated efficiency of CF3 as loss. Assuming that the rate-limiting steps for ozone loss
compared to chlorine from the Garcia-Solomon model in the Antarctic are the reactions ClO + ClO and CIO +
used in the study of Ravishankara et al. for midlatitudes BrO, the value of a for Antarctic ozone loss can be de­
in winter. The figure illustrates that current laboratory rived as follows :
measurements imply that the CF3 group is at most about

13. 14
 O O Ps , GWPs and C I-Br LOAD I NG

2k(BrO)(C10) I ( Bry ) illustrates that model calculations o f the O D P for bro­

a
2k(C10)(C10) + 2k(BrO)(ClO) I (Ch) mine-bearing compounds are likely to be quite sensitive
to the altitude profile of ozone destruction. Since
( 1 3-7) present models tend to underestimate the observed
ozone losses in the lowest part of the stratosphere (see
where the denominator represents the rate of ozone loss
Chapter 6), where bromine is particularly efficient for
due to chlorine compounds per atom of chlorine avail­
ozone loss, this figure implies that the model-derived
able (i. e. , Cl released from all source gases, denoted here
globally averaged values of a (weighted by the ozone
as Cly ) and the numerator represents the rate of ozone
loss distribution) will also be underestimates assuming
loss due to bromine compounds per atom of bromine
present photochemical schemes.
available (Bry ) . Since the reaction ClO + ClO is believed
Bromine's effectiveness for ozone loss in the low­
to account for about 7 5 % of the Antarctic ozone loss
er stratosphere is related to the fact that a large fraction
while ClO + BrO accounts for about 25 % (see Solomon
of the available Bry resides in the ozone-depleting forms
et al. , 1 992 and references therein) and Cly is about 2.5
of Br and BrO. In contrast, only a very small fraction of
ppbv while Bry is about 15 pptv in this region, the value
available Cly resides in Cl and ClO except in the special
of a for Antarctic ozone loss is about 40. S alawitch et al.
case of polar regions. Thus, since all halogen atoms are
( 1 990, 1 993) pointed out that the lower absolute abun­
very reactive (e. g. , with atomic oxygen, H02, and each
dances of ClO observed in the Arctic as compared to
other), bromine chemistry's effectiveness relative to
Antarctica implies that bromine will be more effective
chlorine will generally be driven by the fact that the BrOI
for ozone loss there (i. e. , ClO + BrO will be more impor­
Br y ratio is on the order of 50- 1 00 times larger than the
tant compared to ClO + ClO).
ClOICl y ratio in the lower stratosphere outside of polar
Recent laboratory studies have confirmed and ex­
regions. This in tum implies that the value of a is not
panded understanding of the important role of bromine.
very sensitive to which reactions are the dominant rate­
Poulet et al. ( 1 992) have shown that the kinetic rate con­
limiting steps in ozone destruction, at least for current
stant for the reaction of BrO + H02 is about six times
photochemical schemes (e.g. , ClO + BrO, H02 + BrO,
faster than previously believed at room temperature; this
H02 + ClO, etc.).
has been confirmed by the measurements of Bridier et
al. ( 1 993). As noted in WMO ( 1 992), the importance of 13.4.2.3 IODINE
bromine for ozone loss could be substantially dimin­
ished if as much as 1 0 % of the reaction between BrO + The ability of reservoir molecules to sequester
H02 were to yield HBr at the rate indicated by Poulet et halogen radicals and thereby reduce their impact on
al. ( 1 992), while it would be enhanced if less than a few ozone is inversely related to the size of the halogen atom.
percent HBr is produced. The latter appears to be true Thus fluorine rapidly forms HF, while chlorine forms
based upon the study of Mellouki et al. ( 1 994), who HCl and ClON02. The bromine reservoirs (HBr and
showed that the yield of HBr from this reaction is likely BrON02) are weakly bound, making BrO and Br effec­
to be below 0. 1 % even at stratospheric temperatures tive ozone-destroying species as shown above. Iodine
based on new measurements and thermochemical data, a reservoirs such as HI, ION02, and others are known to
result consistent with modeling studies of the BrO gradi­ be very readily dissociated by photolysis or reaction
ent (Garcia and Solomon, 1 994). Figure 1 3-4 shows the with OH, rendering any iodine that reaches the strato­
calculated effectiveness of bromine for ozone destruc­ sphere at least as effective as bromine for ozone loss and
tion relative to chlorine based upon the above very probably much more so. However, iodine source
photochemistry from the model of Garcia and Solomon gases are very short-lived because of the relatively weak
( 1 994) . The figure suggests that bromine is roughly 1 00 carbon-iodine bond. If the iodine source gases are short­
times more effective in the region of peak observed lived enough, then anthropogenic releases (particularly
ozone loss (near 20 km). Very similar results have also at the surface at midlatitudes) may not reach the strato­
been calculated with the Lawrence Livermore National sphere in abundances sufficient to result in significant
Laboratory (LLNL) two-dimensional model. The figure ozone loss. In this case, compounds such as CF3I could
represent useful substitutes for the halons.

13. 15
OOPs, GWPs and C I- B r LOAD ING

The chemistry of iodine in the troposphere was been focused on the carbonyl and PAN-like compounds.
discussed in detail by Chameides and Davis ( 1 980). Re­ The chemistry of these intermediates is discussed in de­
cent!y, Solomon et a!. ( 1 994a, b) have considered the tail in Chapter 1 2, where it is shown that photolysis and
impact of iodine on stratospheric ozone compared to heterogeneous removal (in clouds and rain) likely makes
chlorine, based mainly on the iodine photochemistry the tropospheric abundances of these intermediates too
considered in the kinetic evaluation of Atkinson et al. small to affect ODPs or GWPs.
( 1 992). Solomon et al. ( 1 994a, b) showed that current On the other hand, Kindler et al. ( 1 994) showed
photochemical schemes imply that iodine is at least as that the stratospheric lifetime of the phosgene (COC12)
effective as bromine for ozone destruction based upon produced by the dissociation of such compounds as CC14
the measured rate for H02 + IO (shown in Figure 1 3-4 as and CH3CCI3 is long enough to imply a reduction of per­
Iodine [minimum]) . In addition, Solomon et al. ( 1 994b) haps 1 0- 1 5 % in the ODPs for CC4 and CH3CCl3.
emphasized that several key chemical processes relating Similarly, fluorophosgene (COFCl) is a product of the
to iodine-catalyzed ozone destruction have not yet been degradation of HCFC- 1 4 1 b. The lifetime of this species
quantified in laboratory studies, notably IO + ClO and is also believed to be rather long in the stratosphere, sug­
IO + BrO. If these reactions were to take place relatively gesting a similar reduction in the ODP of HCFC- 1 4 l b.
rapidly, iodine could be as much as 2000 times more ef­ These chemical processes have not been included in the
fective than chlorine for ozone destruction near 20 km ODP estimates discussed below.
(denoted as Iodine [max] in Figure 1 3-4). This proposed
chemistry does not significantly change the value of a, 13.4.4 Model-Calculated and Semi-Empirical
for the reasons discussed above. In combination with Steady-State OOPs
anthropogenic trends in ClO and BrO, as little as 1 pptv
Model-derived ODPs have been determined for a
of iodine in the lower stratosphere due to the very large
range of compounds using the two-dimensional models
natural sources of compounds such as methyl iodide
at LLNL (D. Wuebbles and K. Patten), Atmospheric and
could be significant for lower stratospheric ozone loss
Environmental Research, Inc. (AER; D. Weisenstein and
(Solomon et al. , 1 994b ). These considerations are taken
M. Ko), and Universita' Degli Studi-L' Aquila (G. Vis­
into account in the estimate of the ODP for CF3I present­
conti and G. Pitari). In addition, the ODPs of some
ed in Solomon et al. ( 1 994a) and later in this chapter. In
bromocarbons were evaluated in the Oslo model (I. Isak­
spite of these large efficiencies, the very short lifetime of
sen et al.) and some HCFCs were considered in the
CF3I (less than 2 days; see Solomon et al. , 1 994a) results
Indian Institute of Technology (IIT)/Delhi one-dimen­
in an estimated upper limit for the steady-state ODP for
sional model (M. Lal et al. ) . The National Oceanic and
surface emissions of this compound of only 0.008. Oth­
Atmospheric Administration/National Center for Atmo­
er iodine-bearing compounds, such as C2F5 I, would
spheric Research (NOAA/NCAR) two-dimensional
likely have similar ODPs.
model was used to analyze the ODPs for HFC- 1 34a,
HFC-23, HFC- 1 25, and CF3I (Ravishankara et al. , 1 994;
13.4.3 Breakdown Products of HCFCs and
Solomon et al. , 1 994a) . Each of these models used up­
HFCs
dated kinetics (based primarily on JPL, 1 992), with the
In the calculation of the ODPs for HCFCs present­ exception that the L' Aquila results do not include the
ed here, it is assumed that chlorine atoms will be new BrO + H02 rate. These models also account for the
promptly released (and hence able to participate in effects of heterogeneous chemistry on background
ozone destruction) once the parent molecule is broken stratospheric sulfate aerosols and most include a repre­
down. Concern has been raised that the ODPs of some sentation of polar vortex processes. The ODPs presented
HCFCs could be enhanced if the tropospheric break­ in Table 1 3-4 use results from the models normalized to
down products contain chlorine and have atmospheric the atmospheric lifetimes in Table 1 3- 1 . They agreed to
lifetimes comparable to or longer than the precursor within 10% in most cases and within 30% in all cases
HCFC (WMO, 1 990, 1 992) and thus potentially be examined; the results from reporting models were aver­
transported to the stratosphere. Particular attention has aged. In the AER 2-D model (D. Weisenstein, private

13. 16
 OOPs, GWPs and CI- B r LOADING

Ta ble 13-4. Steady-state O O Ps derived from 2- D models and from the semi-empirical approach.
O O Ps are normal ized based on recommended atmospheric l ifetimes in Section 1 3. 2 .

Trace Gas Model-Derived ODP Semi-Empirical ODP

CFC- 1 1 1 .0 1 .0
CFC- 1 2 0.82 0.9
CFC- 1 1 3 0.90 0.9
CFC- 1 1 4 0.85
CFC- 1 1 5 0.40
co 4 1 .20
GI 3CC1 3 0. 1 2 0. 1 2
HCFC-22 0.04 0.05
HCFC- 1 23 0.0 14 0.02
HCFC- 1 24 0.03
HCFC- 1 4 l b 0. 1 0 0. 1
HCFC- 1 42b 0.05 0.066
HCFC-225ca 0.02 0.025
HCFC-225cb 0.02 0.03

HFC- 1 34a < 1 .5xl0 - 5 <5xl0-4

HFC-23 <4xl 0- 4
HFC- 1 25 < 3xl0- 5

GI 3Br ( 1 .3 yr lifetime) 0.64 0.57

CF3Br (H- 1 30 1 ) 12 13
CF2C 1Br (H- 1 2 1 1 ) 5.1 5

CF3I <0.008

GI 3C l 0.02

communication, 1 993), the derived ODP for CH3Br in­ Ions shown in Table 1 3-4 are slightly smaller than in the
creased by 3 3 % due to the change from the old to the WMO ( 1 992) assessment, probably because of changes
new kinetic rate constant for the reaction between BrO in atmospheric lifetimes and the consideration of polar
and H02, illustrating the key role of this reaction as dis­ processes.
cussed above. The factors influencing the ODP for As discussed in WMO ( 1 992), Solomon et al.
CH3Br and their possible uncertainties are discussed fur­ ( 1 992) have formulated a semi-empirical approach for
ther in Chapter 1 0 . The best estimate of the lifetime for determining ODPs based mainly upon observations rath­
CH3Br is about 1 .3 years as discussed in Chapter 1 0, er than models . These semi-empirical ODPs have been
rather than the value of 2 years used in the WMO ( 1 992) updated using the atmospheric lifetimes discussed in
report. Thus, the increased chemical effectiveness of Section 1 3 . 2, along with some updates in the observed
bromine for ozone loss is approximately cancelled by fractional dissociation of halocarbons in the stratosphere
the decreased lifetime in deriving an ODP for CH3Br. (Daniel et al. , 1 994). Table 1 3 -4 gives the semi-empiri­
Model-derived ODPs for the long-lived CFCs and ha- cal steady-state ODPs based on this analysis. The

13. 1 7
OO Ps, GWPs and CI- B r LOADING

effectiveness o f bromine relative t o chlorine for ozone and 'tcFC- 1 1 indicate the molecular weights and atmo­
loss in this analysis was assumed to be 40; as indicated in spheric lifetimes of species x and CFC- 1 1 , respectively,
Section 1 3 .4, this value is likely to be too low in the re­ while nx is the number of chlorine or bromine atoms in
gion where bromine emissions are most effective in the molecule (and note that CFC- 1 1 contains 3 chlorine
destroying ozone at midlatitudes, suggesting that the atoms per molecule) . Also, ts is the time required for a
semi-empirical ODPs for CH3Br and the halons may be molecule to be transported from the surface to the region
underestimated. A value of a of 80 is plausible in the of the stratosphere in question, and t is time. In the fol­
lower stratosphere (see Chapter 1 0 and Garcia and So­ lowing figures, the time refers to the time since reaching
lomon, 1 994), and would approximately double the the lower stratosphere at middle-to-high latitudes (which
ODPs of these compounds. is believed to be on the order of three years). In princi­
ple, the above equation should be integrated over the
13.4.5 Time- Dependent Effects entire stratosphere in order to derive the globally aver­
aged time-dependent ODP. In practice, however, the
While steady-state Ozone Depletion Potentials de­
ozone column depletion observed in the current atmo­
scribe the integrated impact of emission of a halocarbon
sphere is dominated by the region below 25 km. Further,
upon the ozone layer compared to CFC- 1 1 , it is also of
mixing processes imply compact linear correlations be­
interest to consider the time dependence of these effects
tween many of the long-lived halocarbon source gases in
(WMO, 1 990, 1 992; S olomon and Albritton, 1 992).
this region (Plumb and Ko, 1 992), making the term in
Time-dependent ODPs can be used to provide insight
brackets, { Fx/FcFC- 1 1 } , very nearly a constant over
into the effect of a mix of compounds upon the short­
broad regions of the lower stratosphere (see Daniel et al. ,
term future of the ozone layer (e.g. , the next few decades,
1 994).
when peak chlorine and bromine loading are expected to
Using the above equation, together with the re­
occur), while steady-state ODPs indicate integrated ef­
vised lifetimes of Table 1 3- 1 , updated values of { Fxl
fects over longer time scales. We describe below in more
FcFC- 1 1 } where available from Daniel et al. ( 1 994) , and
detail than in previous reports the physical processes that
a value of a of 40 for bromocarbons and 2000 for io­
control the expected time dependence of ODPs for vari­
docarbons, semi-empirical time-dependent ODPs were
ous chemicals. We then present updated time-dependent
deduced. In addition, the instantaneous (i. e. , not inte­
Ozone Depletion Potentials for several molecules of in­
grated) relative ozone loss was also considered. Figure
terest based upon new kinetic information and lifetimes
1 3-5 shows instantaneous time-dependent relative ozone
as discussed in this report.
loss rates (compared to CFC- 1 1 ) for several molecules
A simple semi-empirical framework for under­
of interest here. The time axis on the figure refers to the
standing the physical reasons for time-dependence of
time since reaching the stratosphere, not the total time
ODPs was presented by Solomon and Albritton ( 1 992),
(which is about 3-5 years longer; see Pollock et al. ,
who showed that the following equation can be used to
1 992). The instantaneous ozone loss rates relative to
approximate the time-dependent ODP at any point in the
CFC- 1 1 for the first few years are determined largely by
stratosphere:
the values of a for bromocarbons or iodocarbons and by
t the values of { Fx/FcFC- 1 d and nx for chlorocarbons.

}
-(t-t, )I rx dt
Je
ODPx ( t ) = { Fx
FCFC-11
.
Mc
Mx
FC-11 nx
.

3
. a . .-t"-
, -----
J e-(t-t, )l rcFC-t l dt
Over longer time scales, the short-lived compounds are
removed from the atmosphere, and the slope of their de­
cay depends upon the relative values of 'tx and 'tCFC- 1 1 ·
t, Note, for example, that HCFC- 1 4 l b (which contains 2
( 1 3-8) chlorine atoms) initially destroys roughly 2/3 as much
ozone as CFC- 1 1 . It has a lifetime of about 10 years, and
The term in brackets, { Fx/FcFC- 1 1 } , denotes the fraction therefore its instantaneous ozone loss drops to very
of the halocarbon species, x, injected into the stratosphere small values within a few decades. The ozone-depleting
that has been dissociated compared to that of CFC- 1 1 effects of pulsed injections of compounds with shorter
(obtained from measurements of both). Mx, McFC- 1 1 , 'tx, lifetimes ( such as HCFC- 1 23) decay much faster. A

13. 18
 OOPs, GWPs and CI- B r LOADING

steady-state values. The steady-state ODP for HCFC-

I 1 23 therefore asymptotes to a value below 0.02 in about
"'
"' I
o _ I 1 00 years. A calculation of the time-dependent ODPs
_j _ /
Cll I � C FS,- 1 1 3
for CH3Br using the Oslo model gave values of 5 .6, 2.3,
c U
O l.L
C H 3 Br and 1 .5 for time scales of 1 0, 20, and 30 years, respec­
ou - - - _\__ _ _ _ _ _ _ ... ... --" tively, very similar to the semi-empirical values shown in
"'
:::l
� ... _
Figure 1 3-6. In the above calculations, a lifetime of 2.0
0
a.> . �
C +-
(])

.I
__: � - � \ H C FC - 1 4 1 b years was used for CH3Br. The ODPs for this gas would
0 0 ·, - ......._ �
� a;
E o:::
"'
\ \ '-' ··.
H C FC - 1 2 3 \ '\
be about 30% smaller over long time scales if a lifetime
of 1 .3 years was employed.
c .0 1 \ '•\ Figure 1 3-6 includes an upper-limit estimate of the
' FC - 2 2
\� time-dependent ODP for surface releases of CF3I, based
on the framework described in Solomon et al. ( 1 994a) .
The calculated upper limit to the ODP for this gas is
Ti m e ( ye a r s )
about 0.08 in the first five years and asymptotes to a
value below 0.0 1 in about 1 00 years.
Figure 13-5. I nstantaneous time-dependent rela­
Although the ODP concept has primarily been ap­
tive ozone loss rates (compared to C FC-11) for
several compounds of i nterest. Note that the x-axis plied to the relative effects of halocarbons on
refers to the time si nce reaching the stratosphere, stratospheric ozone, there have also been several recent
not the total time. attempts to determine ODPs for emissions of other
gases. For example, Ko et al. ( 1 994b) have evaluated an
ODP for chlorine emitted directly into the stratosphere
compound with a lifetime longer than that of CFC- 1 1
from launch of the U.S. Space Shuttle. They derive a
(such as CFC- 1 1 3) has an impact on the ozone layer rel­
time-dependent ODP that is quite large initially (but is
ative to CFC- 1 1 that grows for time scales longer than
also dependent on the definition of what constitutes a
the 50-year lifetime of CFC- 1 1 , because of the decay of
mass emission, the choice being emission of HCl only or
the reference gas. The behavior of CH 3Br is qualitative­
ly similar to that of HCFC- 1 23 , but it has a very large
initial ozone impact because of the value of a, making its
1 00
relative ozone loss in the first few years close to 10 times
that of CFC- 1 1 (approximately a/3) .
0
The time-dependent Ozone Depletion Potentials
...... - ·· - · · -··-
+-
c
are simply the time integrals of the instantaneous relative
ozone loss rates shown in Figure 1 3-5. These are illus­
Q)
+-
0
a..
c"H; Br --
C F2 C!Br
--- �z..:..:
trated in Figure 1 3-6. Note, for example, the growth of c -
�� - - - - - - - - - - - -
0 � · -
--
CFC-1 1 3
....... ,

. .. -. . 7
Q; - --...
....-....-... ...�.�
.
the ODP for CFC- 1 1 3 for time scales longer than about --
--- H C FC - 1 41 b
-
1 00 years, at which time more CFC- 1 1 3 remains to de­
0.
(]) .I ..... -...;;.: ......._ -
..._ ...._ · --... : •• ....- .._ - - _H C FC - 2 2
- - -
0
....... ....... .
stroy ozone than the reference gas, CFC- 1 1 . The Q) C F I ...... " ' :-::.:.: : -
3
time-dependent ODP for a very short-lived gas such as
c
0
N
0
.0 1
... __ _ Hcr.c-=i23
- - -
HCFC- 1 23 has large values for the first five years. How­
H C FC - 225ca
ever, by the end of the first five years, HCFC- 1 23 is
destroying very little ozone (Figure 1 3-5), because it has .00 1
I 10 1 00 1000
been nearly completely removed from the atmosphere. T i m e ( yea r s )
The reference gas, CFC- 1 1 , is continuing to destroy
ozone, so that the cumulative value of the denominator
Figure 13-6. Ti me-dependent Ozone Depletion
in Equation 1 3- 8 continues to increase. It is this slow Potentials for several compounds of i nterest. Note
increase in the denominator that controls when the ODPs that the x-axis refers to the time since reach ing the
for short-lived gases such as HCFC- 1 23 reach their stratosphere, not the total time.

13. 19
 O O Ps, GWPs and CI- B r LOADING

the total fuel load). The effect from the Space Shuttle Factor 1: The strength with which a given species
decays quite rapidly due to removal of the emitted HCl absorbs longwave radiation and the spectra/ location of
from the stratosphere. its absorbing wavelengths. Chemical species differ
Since the ozone layer is believed to respond rela­ markedly in their abilities to absorb longwave radiation.
tively rapidly to changes in chlorine and/or bromine Overlaps of the absorption spectra of various chemical
loading (time scale of about 3-5 years or less), time­ species with one another (especially H20, C02, and, to a
dependent Ozone Depletion Potentials provide an appro­ lesser extent, 03) are important factors. In addition,
priate measure of the expected ozone response to while the absorption of infrared radiation by many
changing inputs of source gases relative to the reference greenhouse gases varies linearly with their concentra­
molecule. On the other hand, steady-state Ozone Deple­ tion, a few important ones display nonlinear behavior
tion Potentials may be applicable to evaluation of (e. g. , C02, Cf4, and N20) . For those gases, the relative
associated long-term biological impacts, where the eco­ radiative forcing will depend upon concentration and
system response may take place over many decades of hence upon the scenario adopted for the future trace-gas
exposure to changes in ultraviolet radiation resulting atmospheric abundances. A key factor in the greenhouse
from ozone changes. role of a given species is the location of its absorption
spectrum relative to the region in the absorption of atmo­
spheric water vapor through which most outgoing
13 .5 GLO BAL WARM I N G POTENTIALS
planetary thermal radiation escapes to space. Conse­
quently, other things being equal, chemical species that
13 .5.1 I ntroduction
have strong absorption band strengths in the relatively
This section addresses the numerical indices that weak water-vapor "window" are more important green­
•
can be used to provide a simple representation of the rel­ house gases than those that do not. This is illustrated in
ative contribution of an atmospheric trace gas to Figure 1 3-7, which shows how the instantaneous radia-
greenhouse warming, drawing heavily on the informa­
tion in the earlier ozone assessments (WMO, 1 990,
1 992), the climate-system reports of the Intergovern­
10 -1 °
mental Panel on Climate Change (IPCC, 1 990, 1 992,
1 994), and recent journal publications. The major objec­ I
Cl lo- l l C 2 F6
tive of the text that follows is to update the information � - ·-.
(\j ' , L i f e t i me � I O , OO O y r
on radiative forcing indices. To this end, we describe the 'E lo-1 2 '·
calculations of the indices contained herein, discuss the 3 '
�
\ \
sensitivity of the results to some of the specifications and Cl
10- 13
·a
c:
\ \
\
assumptions, and present the resulting numerical indices \
and their uncertainties.
t£ l o- 1 4
\
\
\
\
�
As in the case of ODPs, calculating the relative al­ ·.;:::
. !2 lo -1 5
- �,- - \ C 02
teration in radiative forcing due to the change in
"0
\ - -r- - -
c£ 1 \
greenhouse gas A compared to that due to a change in 10- 1 6
I \ H FC - 1 34 0
* H C F C -2 25co \ \ � 1 4 yr
greenhouse gas B can be evaluated more accurately than "'-' 2 . 5 yr
� 7 1 \
the absolute climate response due a change in a single .E 1 0- 1
c: \ \
I
greenhouse gas alone. In the following, we briefly dis­ � \
10-18
cuss some key factors that contribute to GWPs. £ 10 1 00 1000

Common to all greenhouse gases are three major T i m e ( yr )

factors - two technical and one user-oriented - that de­
termine the relative contribution of a greenhouse gas to Figure 13-7. I nstantaneous radiative forcing
radiative forcing and hence are the primary input in the (W m -2 kg - 1 ) versus tim e after release for several
formulation, calculation, and use of radiative forcing different greenhouse gases. The C02 decay re­
sponse function is based u pon the Bern carbon
indices:
cycle model with fixed C02 concentrations.

13.20
 O O Ps, GWPs and CI- B r LOADING

tive forcings due to the pulse emission of one kilogram

of various long-lived gases with differing absorption
properties change as the concentrations decay away in
F
··
·· •

c2 ·s . . . · · · · · ·
· · ·
time after they have become well mixed (e. g. , about a · · ·

1 0000
.......·
· ·

L ifetime � I O,OOO yr
· · ·
year after injection into the atmosphere). The relevant .9
· · ·

point here is on the left-hand scale at t I, namely, that c .

Q)
=

0
..... . , H F C - 1 34a
' ' ..._ J1CFC-225ca -..... . "' 1 4 r
- · -..
the radiative forcing of an equal emission of the various
0... Y
gases can differ by as much as four orders of magnitude. Ol 1 000 .... .... � 2 . 5 yr '·
'
c ',
'
', .
,
Laboratory studies of molecular radiative properties are .E
'­
....
....
a .... ....
a key source of the basic information needed in the cal­ .... ....
3 ....
.... ....
culation of radiative forcing indices. The status of such a 1 00 .... ....
.0 ....
spectroscopic data of greenhouse gases is discussed in ....
0 ....

detail in Chapter 8 and in Chapter 4 of IPCC ( 1 994) . 0

Factor 2 . The lifetime of the given species i n the

atmosphere. Greenhouse gases differ markedly in how 10 1 00 1 000
long they reside in the atmosphere once emitted. Clear­ Ti m e H o r izo n ( y r )
ly, greenhouse gases that persist in the atmosphere for a
long time are more important, other things being equal,
Figure 13-8. Global Warming Potentials (GWPs)
in radiative forcing than those that are shorter-lived. for a range of g reen house gases with differing l ife­
This point is also illustrated in Figure 1 3- 8 . As shown, ti mes, using C02 as the reference gas.
the initial dominance of the radiative forcing at early
times can be overwhelmed by the lifetime factor at later
lived, gas like N20; however, in the longer term, the re­
times.
verse is true. Methane is a key greenhouse gas discussed
The relative roles of the strength of radiative ab­
extensively below; its integrated radiative forcing would
sorption and lifetimes on GWPs, as shown in Figures
lie below that of N20 and reach a plateau more quickly
1 3-7 and 1 3-8, parallel those of chemical effectiveness
because of its shorter lifetime.
and lifetimes on ODPs, as illustrated in Figures 1 3-5 and
The spread of numerical values of the radiative
1 3-6.
forcing indices reported in Section 1 3.5.2 below largely
Factor 3. The time period over which the radiative
reflects the influence of these three major factors. In ad­
effects of the species are to be considered. Since many
dition to these direct radiative effects, some chemical
of the responses of the Earth' s climate to changes in radi­
species also have indirect effects on radiative forcing
ative forcing are long (e.g. , the centennial-scale warming
that arise largely from atmospheric chemical processes.
of the oceans), it is the cumulative radiative forcing of a
For example, important products of the oxidative remov­
greenhouse gas, rather than its instantaneous value, that
al of CH4 are water vapor in the stratosphere and ozone
is of primary importance to crafting a relevant radiative
in the troposphere, both of which are greenhouse gases.
forcing index. As a consequence, such indices involve
These are discussed in Section 1 3 .5 .4.
an integral over time. Rodhe ( 1 990) has noted that the
choice of time interval can be compared to cumulative­
13.5.2 Radiative Forci ng Indices
dosage effects in radiology. IPCC ( 1990, 1 992) used
integration time horizons of 20, 1 00, and 500 years in 13.5.2.1 FoRMULATION
calculating the indices. Figure 1 3-8 shows the integrals
of the decay functions in Figure 1 3-7 for a wide range of The primary radiative forcing indices used in sci­
time horizons. It illustrates the need for the user of the entific and policy assessments are the Global Warming
radiative forcing indices to select the time period of con­ Potential (GWP) and Absolute Global Warming Poten­
sideration. A strongly absorbing, but short-lived, gas tial (AGWP) . Other possible formulations are described
like HCFC-225ca will contribute more radiative forcing and contrasted with those in IPCC ( 1 994).
in the short term than a weaker-absorbing, but longer-

13.21
OOPs, GWPs and CI- B r LOA D I N G

Global Warming Potential trace gases and is not well described by a single lifetime
(Moore and Braswell, 1 994). Wuebbles et al. ( 1 994b)
Based on the major factors summarized above, the
and Wigley ( 1 993) have also noted the importance of un­
relative potential of a specified emission of a greenhouse
certainties in the carbon cycle for calculations of GWPs
gas to contribute to a change in future radiative forcing,
when COz is used as the reference. Furthermore, COz is
i. e. , its GWP, has been expressed as the time-integrated
also recirculated among these reservoirs at an exchange
radiative forcing from the instantaneous release of 1 kg
rate that is poorly known at present, and it appears that
of a trace gas expressed relative to that of 1 kg of a refer­
the budget of COz is difficult to balance with current
ence gas (IPCC, 1 990) :
information. As a result, when COz is used as the refer­
ence gas, the numerical values of the GWPs of all
H
f,T a, · [ x( t) ] dt
greenhouse gases are apt to change in the future (perhaps

GWP(x) J=0'""
TH.,--- - ( 1 3-9)
substantially) simply because research will improve the
Jo a, · [ r(t) ] dt
= --

understanding of the removal processes of C02. While

recognizing these issues, Caldeira and Kasting ( 1 993)
discuss feedback mechanisms that tend to offset some of
these uncertainties for GWP calculations.
where TH is the time horizon over which the calculation
is considered; ax is the climate-related radiative forcing
Absolute Global Warming Potential
due to a unit increase in atmospheric concentration of the
gas in question; [x(t)] is the time-decaying abundance of Wigley ( 1 99 3 ; 1 994a, b) has emphasized the un­
a pulse of injected gas ; and the corresponding quantities certainty in accurately defining the denominator for
for the reference gas are in the denominator. The adjust­ GWP calculations if C02 is used as the reference mole­
ed radiative forcings per kg, a, are derived from infrared cule, and suggested the use of "Absolute" or AGWPs
radiative transfer models and are assumed to be indepen­ given simply by the integrated radiative forcing of the
dent of time. The sensitivity of these factors to some gas in question:
climate variables (H20, clouds) is discussed later. As
noted above, ar is a function of time when future changes
in C02 are considered. Time-dependent changes in ax or
AGWP(x) · [x(t)] dt W yr
· · kg 1
-
. m -2
lifetimes are not explicitly considered here. The trace
=

0
gas amounts, [x(t)] and [r(t) ] , remaining after time t are
( 1 3- 1 0)
based upon the atmospheric lifetime or response time of
the gas in question and the reference gas, respectively.
The advantage of this formulation is that the index is
The reference gas has been taken generally to be
specific only to the gas in question. An important disad­
COz, since this allows a comparison of the radiative
vantage is that the absolute value of radiative forcing
forcing role of the emission of the gas in question to that
depends upon many factors that are poorly known, such
of the dominant greenhouse gas that is emitted as a result
as the distributions and radiative properties of clouds
of human activities, hence of the broadest interest to pol­
(e.g. , Cess et al. , 1 993).
icy considerations. However, the atmospheric residence
B ased upon the recommendation of the co-authors
time of COz is among the most uncertain of the major
of Chapter 1 from IPCC ( 1 994), we use the results from
greenhouse gases. Carbon dioxide added to the atmo­
the carbon cycle model of Siegenthaler and co-workers
sphere decays in a highly complex fashion, showing an
("Bern" model) for the decay response of COz for the
initial fast decay over the first 1 0 years or so, followed by
GWP calculations presented here. The fast initial (first
a more gradual decay over the next 1 00 years or so, and a
several decades) decay of added C02 calculated in cur­
very slow decline over the thousand-year time scale,
rent carbon cycle models reflects rapid uptake by the
mainly reflecting transfer processes in the biosphere,
biosphere and is believed to be an important improve­
ocean, and deep ocean sediments, respectively. Because
ment compared to that used in IPCC ( 1 990, 1 992). This
of these different time constants, the removal of COz
change in decay decreases the integrated radiative fore-
from the atmosphere is quite different from that of other

13. 22
 O OPs, GWPs and CI-Br LOADING

ing of C02 and thereby acts to increase the estimated would yield GWP values that are smaller by 1 5 % or less.
GWPs of all gases (see IPCC, 1 994). We present AG­ The decreases in the radiative forcing per molecule due
WPs for C02 needed for conversion of the results to to the increasing C02 atmospheric abundance appear to
other units and other C02 decay functions (e. g. , to show be opposite in sign to those due to the changed C02 de­
the impact of the choice of the denominator on GWP cay response (see Caldeira and Kasting, 1 993, and
values). Wigley, 1 994a) .
IPCC ( 1 994) and this report also considered the
13.5.2.2 SENSITIVITY TO THE STATE OF THE ATMOSPHERE possible evolution of the radiative forcing of CH4 and
NzO and the interplay between the spectral overlap of
To provide realistic evaluations of GWPs for spec­
these two gases using the IS92a scenario published in the
ified time horizons and estimate their uncertainties,
Annex of IPCC ( 1 992). If the calculations were made
future changes in the radiative properties of the atmo­
with the IS92a CH4 and NzO scenarios rather than with
sphere must be considered. Some of these changes to the
the constant current values, the direct GWPs of CH4
present state can be estimated based upon scenarios
would decrease by 2 to 3%, and the 20-, 1 00-, and 500-yr
(e. g. , C02 concentrations), while others are dependent
GWPs of NzO would decrease by 5, 10, and 1 5 % , re­
upon the evolution of the entire climate system and are
spectively. The impact of the adopted future scenarios
poorly known (e.g. , clouds and water vapor) . In IPCC
for COz, CH4, and NzO on the radiative forcing of other
( 1 990), the composition of the background atmosphere
trace species was not considered.
used in the GWP calculations was the present-day abun­
dances of COz, CH4, and nitrous oxide (NzO), which
Water Vapor
were assumed constant into the future. However, likely
changes in COz, CH4, or N20 concentrations will lead to While it is likely that water vapor will change in a
future changes in the radiative forcing per molecule of future climate state, the effect of such changes upon the
those gases (and perhaps others whose spectral bands direct GWPs of the great maj ority of molecules of inter­
overlap with them), as noted previously. The radiative est here is expected to be quite small. For example, the
properties of C02 are particularly sensitive to changes in model of Clerbaux et al. ( 1 993) was used to test the sen­
concentration, since the large optical depth of C02 in the sitivity of the direct GWP for CH4 to changes in water
current atmosphere makes its radiative forcing depend vapor. Even for changes as large as 30% in water vapor
logarithmically on concentration (see WMO, 1 992 and concentration, the calculated GWP of CH4 changed by
Chapter 8 of this document). Thus, the forcing for a par­ only a few percent (C. Granier, personal communication,
ticular incremental change of C02 will become smaller 1 993). For many other gases whose radiative impact
in the future, when the atmosphere is expected to contain occurs largely in the region where water vapor's absorp­
a larger concentration of the gas. In the case of CH4 and tion is relatively weak, similar or smaller effects are likely.
N20, there is a square-root dependence of the forcing on
their respective concentrations (IPCC, 1 990) ; hence, just Clouds
as for C02, the forcings due to a specified increment in
Clouds composed of water drops or ice crystals
either gas are expected to become smaller for future sce­
possess absorption bands in virtually the entire terrestri­
narios. For the other trace gases considered here, the
al infrared spectrum. By virtue of this property, they
present and likely future values are such that the direct
modulate considerably the infrared radiation escaping to
radiative forcing is linear with respect to their concentra­
space from the Earth' s surface and atmosphere. Since
tions and hence is independent of the scenario.
cloud tops generally have lower temperatures than the
IPCC ( 1 994) showed in detail that the dependence
Earth' s surface and the lower part of the atmosphere,
of the AGWP of C02 upon choice of future atmospheric
they reduce the outgoing infrared radiation. This reduc­
C02 concentrations is not a highly sensitive one. A con­
tion depends mainly on cloud height and optical depth.
stant atmosphere at pre-industrial values (280 ppmv)
The higher the cloud, the lower is its temperature and the
would yield values different by less than about 20% for
greater its reduction in infrared emission. On the other
all time horizons. Similarly, the increasing C02 concen­
hand, higher clouds (in particular, high ice clouds) tend
trations in a future scenario stabilizing at 650 ppmv

1 3.23
OOPs, GWPs and CI- B r LOA DI N G

to have low water content and limited optical depths. reference noted above and (ii) improved values for atmo­
Such clouds are partially transparent, which reduces the spheric lifetimes.
infrared trapping effect. Several new gases proposed as CFC and halon
The absorption bands of several trace gases over­ substitutes are considered here for the first time, such as
lap significantly with the spectral features of water drops HCFC-225ca, HCFC-225cb, HFC-227ea, and CF3I.
and ice crystals, particularly in the "window" region. Table 1 3-5 also includes for the first time a full evalua­
Owing to the relatively strong absorption properties of tion of the GWPs of several fully fluorinated species,
clouds, the absolute radiative forcing of many trace mol­ namely SF6, CF4, C2F6, and C6F1 4· SF6 is used mainly
ecules is diminished in the presence of clouds. However, as a heat transfer fluid for electrical equipment (Ko et al. ,
it is important to note that the impact of changes in 1 993), while CF4 and C2F6 are believed to be produced
clouds upon GWPs depends upon the difference be­ mainly as accidental by-products of aluminum manufac­
tween the change in radiative forcing of the gas ture. C6F1 4 and other perfluoroalkanes have been
considered and that of the reference gas, not the absolute proposed as potential CFC substitutes. The very long
change in radiative forcing of the gas alone. IPCC lifetimes of the perfluorinated gases (Ravishankara et
( 1 994) shows that the model calculations of Granier and al. , 1 993) lead to large GWPs over long time scales.
co-workers suggest that the presence or absence of The uncertainty in the GWP of any trace gas other
clouds results in changes of the relative radiative forc­ than C02 depends upon the uncertainties in the AGWP
ings of the molecules considered here of at most about of C02 and the AGWP of the gas itself. The uncertain­
1 2% . Thus, uncertainties in future cloud cover due to ties in the relative values of AGWPs for various gases
climate change are unlikely to substantially impact GWP depends upon the uncertainty in relative radiative forc­
calculations. ing per molecule (estimated to be about 25 % for most
gases, as shown in Chapter 8) and on the uncertainty in
13 .5.3 Direct GWPs the lifetimes of the trace gas considered (which are likely
to be accurate to about 10% for CFC- 1 1 and CH 3CCl3
New direct GWPs of many gases were calculated
and perhaps 20-30% for other gases derived from them) .
for IPCC ( 1 994) and for this report with the radiative
Combining these dominant uncertainties (in quadrature)
transfer models developed at the National Center for At­
suggests uncertainties in the direct AGWPs for nearly all
mospheric Research - NCAR (Briegleb, 1 992; Clerbaux
of the trace gases considered in Table 1 3-5 of less than
et al. , 1 993), Lawrence Livermore National Laboratory
±35 % . Uncertainties in the AGWPs for C02 depend
- LLNL (Wuebbles et al. , 1 994a, b), the Max Planck In­
upon uncertainties in the carbon cycle (see Chapter 1 of
stitut flir Chemie - Mainz (C. Briihl et al. , 1 993 ; Roehl et
IPCC, 1 994) and on the future scenario for C02. The
al. , 1 994), the Indian Institute of Technology (Lal and
effect of the latter uncertainty is likely to be relatively
Holt, 1 99 1 , updated in 1 993 ), and the University of Oslo
small, as shown in Chapter 5 of iPCC ( 1 994) .
(Fuglestvedt et al. , 1 994). The radiative forcing a-factors
The reference gas for the GWPs in Table 1 3-5 is
adopted are those given in Chapter 8 of this report and in
the C02 decay response from the "Bern" carbon cycle
IPCC ( 1 994 ). Some of these values are apt to be amend­
model (Chapter 1 of IPCC, 1 994). The GWPs calcula­
ed in the near future (see Chapter 4 of IPCC, 1 994).
tions were carried out with background atmospheric
Table 1 3-5 presents a composite summary of those re­
trace gas concentrations held fixed at 354 ppmv.
sults. In addition, it presents results from the studies of
The direct GWPs given in Table 1 3-5 can be readi­
Ko et al. ( 1 993) and Stordal et al. (personal communica­
ly converted to other frameworks such as AGWPs,
tion, 1 994) for SF6, and from Solomon et al. ( l 994a) for
GWPs for a changing atmosphere, and GWPs using as
CF3I. With the exception of CF3I, all of the molecules
reference either a specific carbon cycle model or the
considered have lifetimes in excess of several months
three-parameter fit employed in IPCC ( 1 990, 1 992).
and thus can be considered reasonably well-mixed; only
Table 1 3 -6 presents the relevant factors to carry out such
an upper limit rather than a value is presented for CF3I.
conversions:
For those species addressed in IPCC ( 1 992), a majority
To convert to AGWP units, the numbers in Table
of the GWP values are larger, typically by 1 0-30%.
1 3-5 should be multiplied by the AGWP for the
These changes are largely due to (i) changes in the C02

13. 24
 OOPs, GWPs and CI- B r LOADING

Table 13-5. G lobal Warmi n g Potentials (mass basis), referenced to the AGWP for the adopted carbon
cycle model C02 decay response and future C02 atmospheric concentrations held constant at cur­
rent levels. Only di rect effects are considered, except for methane.

Global Warming Potential

S p ecies Chemical
(Time Horizon)
Formula
20 years 100 years 500 years
CF Cs
CFC- 1 1 CFCl 3 5000 4000 1400
CFC- 12 CF z O z 7900 8500 4200
CFC- 1 3 CClF3 8 100 1 1700 13600
CFC- 1 13 Cz F 3 0 3 5000 5000 2300
CFC- 1 14 Cz F 4 0 2 6900 9300 8300
CFC- 1 15 Cz F s O 6200 9300 13000

H C F Cs, etc.
Carbon tetrachloride CCl 4 2000 1400 500

Methyl chloroform rn 3 co 3 360 1 10 35

HCFC-22 (ttt) CF z HCl 4300 1700 520

HCFC- 14 1b (ttt) Cz FH 3 o 2 1800 630 200
HCFC- 142b (ttt) Cz F z H 0 4200 2000 630
3
HCFC- 123 (tt) Cz F 3 HClz 300 93 29
HCFC- 124 (tt) Cz F 4 HCl 1500 480 150
HCFC-225ca Ctt) c3 F 5 HC1z 550 170 52
HCFC-225cb Ctt) C3 F s HClz 1700 530 170

Bromocarbons
H- 130 1 CF 3Br 6200 5600 2200
O ther
HFC-23 (t) CHF3 9200 12 100 9900
HFC-32 (ttt) Oi z F z 1800 580 180
HFC-43- 10mee (t) C4H zF w 3300 1600 520
HFC- 125 (tt) C2HFs 4800 3200 1 100
HFC- 134 (t) CHF2CHF2 3 100 1200 370
HFC- 134a (ttt) rn 2FCF3 3300 1300 420
HFC- 152a ( tt) CzH 4F 2 460 140 44
HFC- 143 (t) CHF2CH 2F 950 290 90
HFC- 1 4 3 a (tt) CF 3CH 3 5200 4400 1600
• HFC-227ea (t) C3HF7 4500 3300 1 100
HFC-23 6fa (t) C3H 2F 6 6 100 8000 6600
HFC-245ca (t) C3H 3 F s 1900 6 10 190
Chloroform (tt) CHCl3 15 5 1
Methylene chloride (tt) rn 2c1 2 28 9 3

Sulfur hexafluoride SF 6 16500 24900 3 6500

Perfl uoromethane CF 4 4 100 6300 9800

Perfluoroethane Cz F 6 8200 12500 19 100
Perfluorocyclo-butane c-C 4F g 6000 9 100 13300

Perfluorohexane C 6F l 4 4500 6800 9900

Methane * rn 4 62 ± 20 24.5 ± 7.5 7.5 ± 2.5
Nitrous oxide N20 290 320 180
Trifluoroiodo-methane CF 3I < 5 << 1 <<< 1

* Includes direct and indirect components (see Section 1 3 .5 .4.2).

(ttt) Indicates HFC/HCFCs in production now and likely to be widely used (see Chapter 4 of IPCC, 1994).
(tt) Indicates HFC/HCFCs in production now for specialized end use (see Chapter 4 of IPCC, 1994) .
(t) Indicates HFC/HCFCs under consideration for specialized end use (see Chapter 4 of IPCC, 1994).

13.25
OOPs, GWPs and C I- B r LOADING

*
Table 13-6. Absolute GWPs (AGWPs) (W m-2 yr ppmv- 1 ).

C ase Time Horizon

20 year 100 year 500 year

C0 2 , Bern Carbon Cycle Model, fixed C0 2 (354 ppmv) 0.235 0.768 2.459

C0 2 , Bern Carbon Cycle Model, S650 scenario 0.225 0.702 2. 1 79

C0 2 , Wigley Carbon Cycle Model, S650 scenario 0.248 0.722 1 .957

C0 2 , Enting Carbon Cycle Model, S650 scenario 0.228 0.693 2.288

C0 2, LLNL Carbon Cycle Model, S450 scenario 0.247 0.821 2.823

C0 2, LLNL Carbon Cycle Model, S 650 scenario 0.246 0.790 2.477

C0 2, LLNL Carbon Cycle Model, S750 scenario 0.247 0.784 2.472

C0 2-like gas, IPCC ( 1 990) decay function, fixed C02 (354 ppmv) 0.267 0.964 2.848
*Multiply these numbers by 1 .29 1 x 1 0- 1 3 to convert from per ppmv to per kg.

adopted Bern carbon cycle model, fixed C02 (354 tions. When the full interactive chemistry of the atmo­
ppmv) scenario (i. e. , Line 1 in Table 1 3-6) and sphere is considered, a very large number of possible
multiplied by 1 .29 1 x 1 0- 1 3 to convert the AGWP indirect effects can be identified (ranging from the pro­
of C02 from per ppmv to per kg. duction of stratospheric water vapor as an indirect effect
To convert to GWP units using one of the other of H2 inj ections to changes in the HCl/ClO ratio and
indicated carbon cycle models and/or trace-gas fu­ hence in ozone depletion resulting from CH4 inj ections).
ture scenarios, the numbers in Table 1 3-5 should The effects arising from such processes are diffi­
be multiplied by the AGWP for the adopted B ern cult to quantify in detail (see Chapter 2 of iPCC, 1 994),
carbon cycle model, fixed C02 (354 ppmv) sce­ but many are highly likely to represent only small pertur­
nario (Line 1) and divided by the AGWP value in bations to the direct GWP and to global radiative
Table 1 3-6 for the carbon cycle model and/or sce­ forcing. As noted above for ODPs, recent work has
nario in question. shown that the production of products such as fluoro­
To convert to GWPs that are based on the same and chlorophosgene and organic nitrates from the break­
reference as was used in IPCC ( 1 990, 1 992), the down of CFCs and HCFCs is unlikely to represent a
numbers in Table 1 3-5 should be multiplied by the substantial indirect effect on the GWPs of those species,
AGWP for the adopted Bern carbon cycle model, due to the rapid removal of these water-soluble products
fixed C02 (354 ppmv) scenario (Line 1 ) and divid­ in clouds and rain (see Chapter 1 2 and Kindler et al. ,
ed by the AGWP value in Table 1 3-6 for the 1 994). Similarly, the addition o f HCFCs and HFCs to
C02-like gas, IPCC ( 1 990) decay function, fixed the atmosphere can, in principle, affect the oxidizing ca­
C02 (354 ppmv) (i. e. , last line in Table 1 3-6). pacity of the lower atmosphere and hence their lifetimes,
but the effect is completely negligible for reasonable
13 .5.4 Indirect Effects abundances of these trace gases.
Table 1 3-7 summarizes some key stratospheric
13.5.4. 1 GENERAL CHARACTERISTICS
and tropospheric chemical processes that do represent
In addition to the direct forcing caused by injec­ important indirect effects for GWP estimates . The cur­
tion of infrared-absorbing gases to the atmosphere, some rent state of understanding of these processes is
compounds can also modify the radiative balance examined in detail in Chapters 2 and 5 of IPCC ( 1 994).
through indirect effects relating to chemical transforma- It is particularly difficult to calculate GWPs of short-

13. 26
 O O Ps, GWPs and C I- B r LOA D I N G

Table 13-7. I mportant i n di rect effects o n GWPs.

Sign of Effect
Species Indirect Effect on GWP

OI 4 Changes in response times due to changes in tropospheric OH +

Production of tropospheric 0 3 +
Production of stratospheric H20 +
Production of C02 (for certain sources) +

CFCs, HCFCs, Depletion of stratospheric 0 3 -

Bromocarbons Increase in tropospheric OH due to enhanced UV -

co Production of tropospheric 0 3 +
Changes in response times due to changes in tropospheric OH +
Production of tropospheric C0 2 +

NOx Production of tropospheric 0 3 +

NMHCs Production of tropospheric 0 3 +

Production of tropospheric C0 2 +

lived gases with localized sources, such as NOx and non­ spatial distributions of the aerosols (see Chapter 3 of
methane hydrocarbons. Further, lack of detailed IPCC, 1 994) . For the first time, an estimate of the effects
knowledge of the distributions of these and other key tro­ from depletion of ozone on halocarbon GWPs is also
pospheric gases complicates calculations of indirect presented in this chapter, drawing upon (i) the extensive
effects relating to tropospheric ozone production (see discussion on ODPs and photochemical considerations
Chapters 5 and 7). It is, however, important to recognize behind them in S ection 1 3 .4, (ii) the discussion of the
that ozone processes in the upper troposphere are more relationship between radiative forcing due to ozone
effective for radiative forcing than those near the surface change and climate sensitivity in Chapter 8, and (iii) the
(see Chapter 8), emphasizing chemical processes occur­ available scientific literature.
ring in the free troposphere.
We present here the indirect GWP effect of tropo­ 13.5.4.2 INDIRECT EFFECTS UPON THE GWP OF CH4

spheric ozone production only for CH4. Additional

Recent research studies of the indirect effects on
GWP quantification (e. g. , for tropospheric ozone precur­
the GWP of methane include those of Hauglustaine et al.
sors such as CO, non-methane hydrocarbons (NMHCs),
( 1 994a, b), Lelieve1d and Crutzen ( 1 992), Lelieveld et
and NOx) must await further study of the model inter­
al. , ( 1 993), and Bruhl ( 1 993). In this report, we consider
comparisons described in Chapter 2 of IPCC ( 1 994) and
those results together with inputs from Chapters 2 and 4
improved field, laboratory, and theoretical characteriza­
of iPCC ( 1 994). The relative radiative forcing for meth­
tion of the processes involved in tropospheric ozone
ane itself compared to C02 on a per-molecule basis is
production. Reliable radiative forcing indices for gases
given in Table 4.2a of IPCC ( 1 994) and is used here.
that form atmospheric aerosols (e.g. , sulfur dioxide,
Eight multi-dimensional models were used to study the
S02) cannot currently be formulated meaningfully,
chemical response of the atmosphere to a 20% increase
chiefly because of the lack of understanding of many of
in methane, as discussed in Section 2.9 of IPCC ( 1 994).
the processes involved (e. g. , composition of the aerosols,
The calculated range of ozone increases from the full set
radiative properties, etc.) and because of uncertainties
of tropospheric models considered in that study provides
regarding the climate response to the inhomogeneous
insight regarding the likely range in ozone production.

13. 2 7
O O Ps, GWPs and CI-Br LOADING

Uncertainties i n these calculations include those related coal mines and natural gas. Thus, the indirect effect of
to the NOx distributions employed in the various models, C02 production does not apply to much of the CH4 in­
formulation of transport processes, and other factors dis­ ventory, and is not included in the table below (in
cussed in detail in Chapter 2 of IPCC ( 1 994). The contrast to IPCC ( 1 990), where this effect was included) .
estimated uncertainty in the indirect GWP for CH4 from As in Table 1 3-5 , the GWPs were calculated rela­
tropospheric ozone production given below is based tive to the C02 decay response of the Bern carbon cycle
upon the calculated mid-to-upper tropospheric ozone re­ model with a constant current C02 and CH4 atmosphere.
sponse of the models to the prescribed methane Table 1 3-8 summarizes the composite result for methane
perturbation at northern midlatitudes and consideration GWPs, its uncertainty, and considers the breakdown of
of the current inadequacies in the understanding of many the effects among various contributing factors. The
relevant atmospheric processes. The calculated ozone ranges in CH4 GWPs shown in Table 1 3-8 reflect the
changes from the model simulations derived for a 20% uncertainties in response time, lifetime, and indirect ef­
increase in methane imply an indirect effect that is about fects, as discussed below. We assume a lifetime of
25 ± 1 5 % of the direct effect of methane (or 1 9 ± 1 2% of methane in the background atmosphere of l 0 ± 2 years
the total), using the infrared radiative code of the LLNL (which is consistent with the budget given in IPCC,
model. A similar number is estimated in Chapter 4 of 1 994). However, the response time of an added pulse is
IPCC ( 1 994). This upper end of this range is close to assumed to be much longer ( 1 2- 1 7 years based upon
that presented in IPCC ( 1 990) . Chapter 2 of IPCC, 1 994). The total GWPs reported in
Release of C� leads to increased stratospheric IPCC ( 1 990) including indirect effects are within the
water vapor through photochemical oxidation; estimates ranges shown in Table 1 3-8. The longer response time
of this indirect effect range are on the order of 5 % or less adopted here for methane perturbations is responsible
of the direct effect of methane (4% of the total) based on for a large part of the change in methane GWP values
the discussion in Chapter 4 of iPCC ( 1 994) ; current re­ compared to the nominal values including direct effects
sults from the LLNL, NCAR, and Mainz radiative/ only in the IPCC ( 1 992) report (although the fact that
photochemical two-dimensional models; and the pub­ indirect effects were likely to be comparable to the direct
lished literature (e. g. , Lelieveld and Crutzen, 1 992; effect was noted) . This change is based entirely on the
Lelieveld et al. , 1 99 3 ; Briihl, 1 99 3 ; Hauglustaine et al. , analysis presented in Chapter 2 of iPCC ( 1 994) used to
1 994a, b). We adopt 5% of the direct effect in the table define the methane response time for this report (see
below, which is smaller than the value quoted in IPCC Prather, 1 994) . The decay response has been thoroughly
( 1 990). tested only for small perturbations around a background
Each injected molecule of CH4 ultimately forms state and continuing input flux approximately represen­
C02, representing an additional indirect effect that tative of today's atmosphere. It would be different if, for
would increase the GWPs by approximately 3 for all example, large changes in methane emissions were to
time horizons (see IPCC, 1 990) . However, as noted by occur in the near future. It is also believed to be sensitive
Lelieveld and Crutzen ( 1 992), this indirect effect is un­ to other chemical factors such as the sources of carbon
like! y to apply to biogenic production of CH4 from most monoxide. The GWP determined in this manner is sim­
sources (e.g. , from rice paddies), since the ultimate ilarly valid for relatively small perturbations, e.g. , those
source of the carbon emitted as CH4 in this case is C02, that would be required to stabilize concentrations at cur­
implying no net gain of carbon dioxide. While non-bio­ rent levels rather than continuing the small trend (order
genic methane sources such as mining operations do 1 %/year) observed in the past decade (see Chapter 2).
lead indirectly to a net production of C02, this methane However, the GWP shown in Table 1 3-8 cannot be used
is often included in national carbon production inven­ to estimate the radiative forcing that occurred since pre­
tories. In this case, consideration of C02 production in industrial times, when methane concentrations more
the GWP could lead to "double-counting," depending than doubled.
upon how the GWPs and inventories are combined. As
shown in IPCC ( 1 994), most human sources of methane
are biogenic, with another large fraction being due to

13.28
 O O Ps, GWPs and CI- B r LOADING

Table 13-8. Total GWP for CH4 , incl uding indirect effects, referenced to the AGWP computed fo � the
co2 decay response of the Bern carbon cycle model and future C02 atmosphenc _ concentrations
held constant at current levels.

GWP Time Horizon

20 year 100 year 500 year

Total CH4 GWP, including indirect effects and 1 2- 1 7 year 42-8 2 1 7-32 5- 1 0
response time

Fraction of total GWP due to tropospheric 0 3 change 1 9 ± 1 2% 19 ± 1 2% 19 ± 1 2%

Fraction of total GWP due to stratospheric H 20 change 4% 4% 4%

13.5.4.3 NET GLOBAL WARMING POTENTIALS FOR ( 1 993). Daniel et al. ( 1 994) have considered the indirect
HALOCARBONS effects of ozone depletion in analyses of the GWPs for
halocarbons. They concluded that the indirect effect var­
Chlorofluorocarbons effectively absorb infrared
ies greatly for different kinds of halocarbons (e. g. ,
radiation and have been estimated to have accounted for
halons, CFCs, HCFCs), a result that will be discussed
as much as about 25% of the anthropogenic direct radia­
further below.
tive forcing of the Earth's climate system over the period
Several recent studies have addressed the degree to
from 1 980 to 1 990 (IPCC, 1 990). Improved understand­
which the radiative heating due to additions of a quasi­
ing of the impact of ozone depletion on global radiative
uniformly distributed tropospheric gas such as a CFC
forcing has, however, markedly altered this picture
may be equated with the spatially inhomogeneous cool­
(WMO, 1 992; IPCC, 1 992). It is now clear that the large
ing at the tropopause due to ozone depletion for the
ozone depletions observed in the lower stratosphere are
purposes of evaluating a net climate response (e. g. , Mol­
likely to influence temperatures near the tropopause
nar et al. , 1 994). Some studies suggest that ozone
(Lacis et al. , 1 990; Ramaswamy et al. , 1 992), implying
depletion may result in important dynamical changes
that in addition to their direct greenhouse warming, the
that modulate the realized climate response (Molnar et
indirect effect of ozone depletion is significant for
al. , 1 994). For the purposes of the present analysis, it
estimating the GWPs of ozone-destroying gases. Ra­
will be assumed that the indirect and direct radiative ef­
maswamy et al. ( 1 992) and WMO ( 1 992) concluded that
fects of halocarbons can be compared to one another in a
the globally averaged decrease in radiative forcing at the
globally averaged sense, an assumption that is currently
tropopause due to ozone depletion approximately bal­
being tested with detailed three-dimensional models (see
anced the globally averaged increase in direct radiative
Chapter 8 and IPCC, 1 994) .
warming in the troposphere related to the direct forcing
Model calculations show that radiative cooling is a
due to halocarbons during the decade of the 1 9 80s.
strong function of the vertical profile of the ozone loss
While changes in ozone have been reported in the upper
(Schwarzkopf and Ramaswamy, 1 993 ; Wang et al. ,
troposphere (see Chapter 1 ) , these are probably due to
1 993). This implies that it will be difficult to calculate
factors other than halocarbon increases (e. g. , changes of
these effects using a fully interactive two-dimensional
CO, NOy , etc . ) and do not affect the inference of halocar­
chemistry-dynamics model, since these tend to underes­
bon GWPs so long as the vertical profile of ozone
timate the ozone losses observed in the critical lowest
depletion can be characterized. If such changes were to
part of the stratosphere (see, e.g. , Hauglustaine et al. ,
mask the vertical extent of halocarbon-induced ozone
l 994a). Satellite and ozonesonde observations (see
loss, then the cooling tendency ascribed to halocarbons
Chapter 1) can, however, be used to characterize the
could be underestimated. Updated estimates of halocar­
shape of the ozone loss profile fairly well. It has been
bon radiative forcing are provided in Chapter 8 of this
shown by Schwarzkopf and Ramaswamy ( 1 993) that the
report, IPCC ( 1 994 ), and Schwarzkopf and Ramaswamy
uncertainty in the globally averaged ozone cooling is on

13. 29
OOPs, GWPs and C I- B r LOADING

Indirect Cooling Pa rti tioning Direct Heati ng Parti tion ing

1 99 0 1990

CFCs

HCFCs

Figure 13-9. Contributions of various gases to the total estimated radiative cooling (indirect) and h eating
(di rect) due to halocarbons i n 1990 (Adapted from Daniel et at. , 1994) . The adopted value of a for these
calculations is 40.

the order of ±30% for a broad range of assumptions re­ ic chlorine whenever the latter lies above this threshold
garding the magnitude of the ozone depletion observed value. Possible nonlinearities associated, for example,
during the 1 980s in the lowest part of the stratosphere with temperature feedbacks between ozone depletion
(i. e. , below the region where satellite data exist). This and polar stratospheric cloud frequencies have therefore
estimate does not, however, include the enhanced ozone been neglected in this study. The impact of changing
depletions that have been obtained in 1 992 and 1 993, nor UV radiation due to ozone depletion upon OH and hence
does it consider the large changes in ozone observed by tropospheric chemistry has also not been considered
the Stratospheric Aerosol and Gas Experiment (SAGE) here.
near the tropical tropopause (see Chapter 1 ) . Insofar as Insofar as significant ozone loss likely occurs only
these may be halocarbon-induced, these effects would for total equivalent effective stratospheric chlorine levels
tend to increase the global cooling and hence decrease above a certain threshold, the total indirect radiative
the GWPs of ozone-depleting gases shown below. cooling caused by any halocarbon depends upon the
Daniel et al. ( 1 994) combined estimates of radia­ abundances of others and cannot be specified indepen­
tive cooling for the 1 980s and their uncertainties (from dent of scenario. This implies that GWPs for halocarbons
the work of Schwarzkopf and Ramaswamy, 1 993) with based upon the indirect effects estimated for inj ection of
the detailed evaluation of past and future equivalent ef­ an infinitesimally small amount of added gas can no
fective stratospheric chlorine for each halocarbon longer be used to directly calculate the net radiative im­
described in Section 1 3 .3 to examine the net radiative pact of the true amount of that gas in the Earth' s
forcing that can be attributed to each halocarbon. They atmosphere; this limitation is similar t o that for methane
emphasized that both Antarctic and midlatitude total discussed above.
ozone depletions appear to be quite small prior to about Figure 1 3-9 shows an estimate of the contributions
1 980, but to increase rapidly after that time, suggesting of various gases to the total estimated radiative cooling
that a "threshold" for ozone destruction may have been (indirect) and heating (direct) due to halocarbons in
reached. They assumed that the indirect radiative cool­ 1 990 (Daniel et al. , 1 994). A key point noted by Daniel
ing for each halocarbon depends linearly upon its et al. ( 1 994) is that the CFCs are likely to be responsible
contribution to the total equivalent effective stratospher- for a much larger fraction of the estimated heating than

13.30
 OOPs, GWPs and CI- B r LOADING

C F C - 1 2 G lo ba l Warm i ng Po tent i a ls Hal o n 1301 Global Warmin g Potenti a l s

9000 1 0000

8000 "- d i rect

500 0
d i rect
70 00
"' 0
net
6000

Cl. 5000 - 5000

Cl.
3:
(.!) 3:
4 000 (.!) - 1 0000

3000
- 1 5 00 0
2000

- 20000
1 0 00

0 - 2 500 0
1990 2010 2030 2050 2070 2 0 90 1990 20 1 0 2 030 205 0 2070 2 090
Yea r Ye a r

Figu re 13- 10. Calculated time - dependent GWPs for CFC - 12 and halon - 1 30 1 , adapted from the study of
Daniel et a/. ( 1994) , for the basic Copen hagen scenario described in Section 1 3 . 3 (case A) and assuming a
valu e of a of 40. The denominator used i n these calculations i s based upon the carbon cycle model as
discussed in the text.

of the cooling, while for compounds such as the halons 1 30 l becomes large and negative when indirect effects
and anthropogenic CH3Br, the situation is reversed. are considered in this framework. Daniel et al. ( 1 994)
This is due to the enhanced effectiveness of brominated considered the following key uncertainties in deriving
compounds compared to chlorinated species for ozone the GWPs for halocarbons: (i) variations in the scenario
loss (see S ection 1 3 .4.2), by about a factor of 40. CCl4 for future concentrations of ozone-depleting gases, as in
and CH3CCl3, while not as effective as the bromocar­ the scenarios of Section 1 3 .3 , (ii) uncertainties in the
bons for ozone destruction, contain several chlorine globally-averaged relative efficiency of bromine for
atoms per molecule and release them readily in the ozone loss as compared to chlorine (a, assumed to lie
stratosphere, making them relatively effective ozone de­ between 40 and 200), and (iii) uncertainties in the mag­
stroyers (and hence cooling agents) as well. This nitude of the cooling in the lower stratosphere due to
introduces a new factor that would have to be dealt with uncertainties in the ozone loss profile (estimated to be
in the use of such indices in policy decisions, underscor­ about ±30% as noted above). They found that the GWPs
ing the difficulty of considering gases with multiple, and were not as sensitive to the adopted range of possible
very different, environmental impacts using a single scenarios for future concentrations of halocarbons nor to
simple index. Multiple impacts could require more so­ the exact values of the thresholds or scenarios assumed
phisticated policy tools. as to the uncertainties in the absolute value of the cool­
Figure 1 3 - 1 0 shows calculated GWPs for CFC- 1 2 ing and the value of a. This is consistent with the rather
and halon- 1 30 1 a s a function of time horizon adapted small differences in key aspects of the various scenarios
from the study of Daniel et al. ( 1 994), for the base shown in Table 1 3-3. The GWPs for bromocarbons were
Copenhagen scenario (case A) described in S ection 1 3 .3, found to be extremely sensitive to the chosen value of a,
assuming a value of a of 40, and using the Bern et al. while those for CFCs were quite sensitive to the adopted
carbon cycle model results for the denominator as in uncertainty in the total absolute radiative cooling in the
IPCC ( 1 994). As suggested by Figure 1 3- 1 0, the net 1 980s. Table 1 3-9 shows the range of 20- and 1 00-year
GWP of CFC- 1 2 remains positive while that of halon- net GWPs derived for the halocarbons including indirect

13.31
OOPs, GWPs and CI- B r LOADING

Table 13-9. Net GWPs per unit mass emission for halocarbons including indirect effects (adapted
from Daniel et al. , 1994). Relative to C02 using Bern model for decay fu nction (as in I PCC, 1994) .

Time Horizon = 20 1 0 Time Horizon = 2090

Uncertainty Uncertainty Direct Uncertainty Uncertainty Direct
in scenario, a in cooling in scenario, a in cooling
compound min max min max min max mm max
CFC- 1 1 1 900 2900 1 300 3000 5000 1 400 1 800 640 2200 4000
CFC- 1 2 6300 6900 6 1 00 6900 7900 6900 7 1 00 6500 7400 8500
CFC- 1 1 3 3200 3 800 2800 3 800 5000 3300 3500 2800 3800 5000
HCFC-22 3900 4000 3800 4000 4300 1 500 1 5 00 1 500 1 600 1 700
HCFC- 1 42b 3800 3900 3700 4000 4200 1 800 1 800 1 700 1 800 2000
CH 3Br - 1 8600 -4900 -6400 -3300 -5700 - 1 500 -2000 - 1 000
H- 1 30 1 -97200 -22400 -3 1 000 - 1 3800 6200 -87300 -2 1 600 -3 1 200 - 1 4200 5 600
H- 1 2 1 1 -92400 -2 1 500 -29600 - 1 3400 -50600 - 1 3600 - 1 8800 -8900
HCFC- 1 4 1 b 910 1 200 690 1 200 1 800 270 370 1 80 390 630
CH 3CC13 -780 -450 - 1 1 00 -420 360 -260 - 1 50 -360 - 1 40 1 10
CC4 - 1 800 -520 -2500 -430 2000 - 1 500 - 1 1 00 -2400 -630 1 400
HCFC- 1 23 1 20 1 70 67 1 80 300 37 52 20 54 93
HCFC- 1 24 1 300 1 400 1 300 1 370 1 500 4 10 430 390 430 480
HFC- 1 34a 3300 3300 3300 3300 3 3 00 1 300 1 300 1 300 1 300 1 300

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