JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 86, NO.

CI0, PAGES 9859-9868, OCTOBER 20, 1981

StratosphericEddy Diffusion Coefficients

From Tracer Data

S. T. MASSIE AND D. M. HUNTEN

Lunar and PlanetaryLaboratory, Universityof •4rizona,Tucson,•4rizona85721

Global distributions of nitrous oxide, methane, ozone, and carbon 14 are used to estimate four sets of
stratospheric
eddydiffusioncoefficients.
A photochemical
equilibriummodelcalculates
O(3p),O(•D), H,
HOe, OH, H202, NO, and NO2 densities,as a function of altitude, latitude, and time. The calculated
O(•D), OH, and observedCI densitiesare usedto obtainthe eddyprofilesassociated
with the methane
and nitrousoxide distributions,for altitudesbetween10 and 40 km. Application of a constantflux condi-
tion to the seasonallyaveragedozonedata yieldseddy valuesbelow 20 km. Time-dependentcarbon 14
calculationsproduceeddy coefficientsbetween 13 and 27 km. A compositeprofile is obtained by com-
paringthe four setsof coefficients.
Further, carbon 14 computationsare usedto testtheseprofilesas well
as those recommendedin reportsissuedby the National Academy of Sciencesin 1976 and 1979. The
compositeeddy profile producesthe bestagreement.

INTRODUCTION diffusioncoefficient,fs(x) -- ns(z)/M(z) = mixing ratio of spe-

One-dimensional models are still the workhorses of strato- cies s, and ns = number density of speciess.
sphericaeronomy,despitetheir obviousand well-knownlimi- In the steady state, the integral of the continuity equation
becomes
tations.Over the past decade,many profilesof the eddy diffu-
sion coefficientK have been proposedand used for research
or for assessmentof possibleeffectsof pollution. The usual
practice, followed in this paper, is to derive K from tracer K(z)
=M(z)
dL(z)
dz )-l
lf••(Ps(z)- Ls(z))dz
data. A paper by Johnstonet al. [1976] showedthat a sharp
testof sucha profileis to reproducethe data on excess•4CO•
(hereinafter•4C)from the largenuclearexplosions of the early
+
40
km
(Ps(z)- Ls(z))dz (2)

1960's.The great virtue of thesedata is that they have a time The boundary term at infinity is taken to be zero and Ps, Ls
dimension,sincethe tracer is far from a steadystate. H. S. are the chemical production and lossterms.
Johnstonhas informed us that the code used for the study of To obtain a global-averageprofile of K(z), both df/dz and
Johnstonet al. [1976] is no longer available. We have therefore (P - L) are weightedby the cosineof latitude and averaged
reconstitutedit and applied it to someof the more recentpro- accordingto the surfacesdescribedabove.
posalsfor K. A profile of K is then given by
In addition, we derive and test a new profile incorporating
information from the tracers N20, CHn, and 03. Global-mean
profilesfor eachtracerare obtainedin a coordinatesystemre- dz (Ps(z)
- Ls(z)
)dz
ferred to the mean tropopause.A standard inversion proce-
dure [Hunten, 1975b;Schmeltekopfetal., 1977]is then applied
to yield profilesof K. After minor reconciliation,the com-
+
40
km
positeprofileis testedagainstthe •4Cdata and found to be with the angle brackets indicating the average described
(Ps(z)- Ls(z)) dz (3)

consistent.
It differs
fromthe1975
profile
mainly
inlackingabove. Theintegral
issplit
uptoindicate
thatestimates
ofdf/
sharpdiscontinuities
andtherefore
beingsomewhat
greaterdz,(P- L) andKaredependent
uponextrapolation
foralti-
justabove
thetropopause. tudes above40km.Thevalue
ofCH4andN•_O astracers
is
INVERSION OF TRACER DATA well established[Wofsyand McElroy, 1973;Hunten, 1975b].
They have their sourceat the surface,are globally distributed,
Approach. We make the usual one-dimensionalapproxi- and are well observed.
mation to the equationsof eddy transport.In the lower strato- Ozone is a much less traditional tracer for one-dimensional
spherethe surfacesof stratificationare taken to be tilted andflow; most studiesemphasizethe deviationsfrom the mean
parallel to the mean tropopause[Johnstonet al., 1976; Wofsy, rather than the mean itself. Moreover, its chemical behavior is
1976].The height variesfrom 16 km over the equatorto 8 km complexand perhapsstill not fully understood.But its major
over the poles,exactly as prescribedby Johnstonet al. The virtue is that its flow is downward,and it thereforegivesa dif-
coordinate z isth• heightof thesesurfaces at 30ølatitude.The ferent kind of evidenceon the transportprocessesfrom the
transport of speciess is parameterized by the eddy flux ex- upward-flowingtracers.The carbon14 sharesthis property,as
pression well as possessing a time dimension.
verticalflux = -K(z)M(z)dfs(z)/dz MethaneandNitrousOxide. Inputsto (3) are the gradients
df?dz, obtainedfrom observationsas describedbelow, and the
where M(z) -- total atmosphericnumber density,K(z) -- eddy productionand lossterms that must be computedwith the
help of the observations.In our calculations, there are no
Copyright¸ 1981 by the American GeophysicalUnion. chemical sourcesof CH4 and N:O.

Papernumber IC0785. 9859

0148-0227/81/001
C-0785501.00
9860 MASSIE AND HUNTEN: STRATOSPHERIC EDDY COEFFICIENTS FROM TRACERS

TABLE 1. Globally Averaged Mixing Ratios and Chemical (P- L) Terms

Altitude,
km 109fN:O 106fCH4 106fo3 --{P-L)N:O --{P--L)cH4
I 316.0 1.54 0.030 1.8 3.5 +5
5 316.0 1.54 0.032 1.8 8.5 +4
10 316.0 1.54 0.050 1.7 8.4 +3
15 304.0 1.48 0.33 1.3 + 1 1.5 +3
20 251.0 1.28 2.2 1.2 +2 1.3 +3
25 177.0 1.09 5.7 5.1 +2 1.7 +3
30 112.0 0.93 6.5 9.6 +2 2.2 +3
35 51.0 0.76 6.2 6.1 +2 2.6 +3
40 16.0 0.60 4.7 1.9 +2 2.3 +3
45 5.4 0.47 2.9 5.2 + 1 1.3 +3
50 2.1 0.36 1.6 1.4 + 1 4.6 +2
55 1.1 0.27 0.86 4.3 1.2 +2
60 0.62 0.22 0.56 1.4 3.0 + 1
65 0.35 0.18 0.41 4.4 -1 8.3

(P-L) unitsare ½m-3 s--l;2.1 +4 means2.1 X 10n

The averagegradientsfor N20 were formed from the obser- CH4 + O(ID)• H2 + CH20
vationsof Goldanet al. [1980],Fabian et al. [1979],Ehhalt [see
1.3 x l0 -11exp(0 q- 50/T) (9)
Hard,1975],Tyson
etal. [1978],$chmeltkopf
etal. [1977],and
Heidt (seeHudsonand Reed [1979]). For CH4, the observa- CH4 + C1--• HC1 + CH 3
tions of Fabian et al. [1979], Bush[1978], Ehhalt [1974], Mar-
tell and Ehhalt (seeHard [1975]),and Heidt (seeHudsonand R7 •-•9.9 X 10-"- exp((-1359 q- 150)/7) (10)
Reed [1979]) were used.The CH4 observationsbelow 30 krn In the rates above, taken from Hudson and Reed [1979], the
altitude (seeHudsonand Reed [1979]),were obtainedat the uncertaintiesof the activationtemperaturesare specified.
northern latitudes of 4 ø, 32ø, 44ø, and 52ø. Goldanet al [1980] Calibration of the photochemicalmodel is accomplishedby
cite N20 mixing ratiosat latitudesof 9ø, 41ø, 71ø, and 90ø lat- comparingcalculatedOH numberdensitiesand column den-
itude. The observedmixing ratios were interpolated to 9ø, sities with the observations,reported in Hudson and Reed
22ø, 35ø, 47ø, 59ø, 71ø, and 85ø (the latitudesusedin the pho- [1979], of Andersonand of Burnett and Burnett. Calculated
tochemicalmodel, describedin the appendix).It shouldalso OH mixing ratios are presentedin Figure 1, for noon condi-
be noted that the mixing ratiosof CH4 and N20 are well de- tions at 35 ø latitude. These values are obtained from the den-
fined only up to 30 krn. The observationsby Ehhalt of N20 sitiesof equation(A 13),multipliedby 0.90. This factoris cho-
above 40 km altitude are upper limits, and the rocketsonde sen to yield agreementbetween theory and observation.(A
samplingof CH4 by Ehhalt [1974]and Martell and Ehhalt (see discussionof this scalingfactor is includedin the 'Uncertainty
Hard [1975])took placeovera continuous10 km rangeof ver- estimates'section.)Observedmixing ratiosfor the troposphere
tical height. On the basisof all of thesereferences,globally [Davis, 1976; Perner, 1976], and for altitudes above 30 km
averagedmixing ratio profilesof N20 and CH4 are presented
in Table 1.
As describedin the appendix,a photochemicalequilibrium 70 I I I
model calculatesthe valuesof (L) for both species.The pho- ß

tochemical equilibrium expressionsof London and Park 60

iI
[1974]are usedto calculateO(3p),O(ID), H, HO2, OH, H202,
NO, and NO2 densities.Values are computedat latitudesof 50
9ø, 22ø, 35ø, 47ø, 59ø, 71ø, and 85ø, in haft-hour time stepsbe-
tween noon and sunset,and during the fall and springequi-
o x /o
nox. For N20 the reactionsdetermining (L) are

N20 + O('D)--• NO + NO I-- 30

o,...•"x"
al ----6.1 x l0 -11exp (0 +_.50/7) (4) 20
-- CALCULATION
/!
N20 + O(ID)• N2 + O2 - - - OBSERVATION

R2 = 4.8 x l0 -11exp (0 -4-_

50/T) (5) /
ß
0 I I I I
N•_O+ hv--> N•_+ O(ID) (6) 16'ø 16•
OH VOLUME MIXING RATIO
and for CH4,

CH4 + OH --• CH 3 + H,•O Fig. 1. Photochemical equilibrium model calculations of OH,

multiplied by 0.90, at noontimeand 35ø latitude. Troposphericmea-
R4 = 2.4 x 10-"- exp((-1710 q- 200)/7) (7) surementsare by Davis et al [1976], open triangle;Philen et al [1978],
solidtriangle;and Perneret al [1976],opendiamond;arrow indicates
CH4 + O(ID)• OH + CH3 an upper limit. Observationsof Anderson (see Hudson and Reed
[1979]) are shown by cross,solid circle, open circle; the last were ob-
1.3 x l0 -lø exp(0 -4-_
50/T) (8) servedat solarzenith angle 81o and are multiplied by 2.
 MASSIE AND HUNTEN: STRATOSPHERIC EDDY COEFFICIENTS FROM TRACERS 9861

I ' I • I ' I ' I TABLE 2. O('D) Densitiesat 35ø Latitude

X>40øBURNET
T_ Altitude,km O(iD) Altitude,km O(iD)
X<40ø
LOGAN et ol - I 7.3-3 35 1.2 +2
(1978) MODEL 5 1.3-2 40 3.2 +2
CALCULATION - 10 2.0-2 • 5.2 +2
15 1.6-1 50 4.5 +2
20 1.8 55 2.6 +2
25 9.9 60 1.7 +2
30 3.4 + 1 65 1.3 +2
•5 •
Densities are equinoctial, noontime values. 7.3 -3 means 7.3 x
10-3 cm-3
ß
o

I
3,0
I I
2.0
I I
I.O
• I , I+-
2.0 3.0
Liu et aL [1980]. These papersexamine the CO and CHn oxi-
dation reactions.that can produce or consumeozone. For ex-
ample, ozone is formed by
SEC X

CO + OH -• CO2 + H (11)
Fig. 2. Calculated OH column densities,multiplied by 0.90, at
35 ø latitude. The Burnett and Burnett observations are for 40 ø lati-
H + O2 + M-• HO2 + M (12)
tude and are taken from Hudson and Reed [1979]. The Logan et al
[1978] model resultsare equinox values. HO2 + NO-• OH + NO2 (13)
NO2 + hv--> NO + O (14)
O + O2 + M-* 03 + M (15)
(Anderson;seeHudsonand Reed [1979]), are also displayed.
Net:
The measurementsof Andersonare for 32ø latitude. Although
there is a small deviationof the adjustedcurve from the obser- CO + 202 + hv--> CO2 + O3 (16)
vationsin the 3040 km region,the representationis generally
good. The use made of the 'observed'curve is describedbe- It is destroyedby
low.
HO2 + O3-• OH + 202 (17)
Column densities,adjustedby the same factor of 0.90, are
presentedfor 35ø latitude in Figure 2 at eachtime step.Again OH + 03 --> HO2 + 0 2 (18)
the observations(Burnett and Burnett,40ø latitude) are well
represented,exceptthat the morning-afternoonasymmetryis (seethe discussionin Liu et al. [1980]).At the suggestion
of a
not simulated by the model. referee,the relevant productionand lossratesfor ozone were
Unfortunately,there are no observations of O(ID) in the estimatedfor the 10-20 km region;additional reactionsfor the
earth's stratosphere.Table 2 presentscalculated noon condi- CHnoxidationchainwereincludedaccordingto equation(31)
tionsfor 35ø latitudeof O(ID) at the equinox.If futureobser- of Johnstonand Podolske[1978].From the net (P - L), the
vations were to differ markedly from the densitiespresented chemicaltime scale[O3]/(P - L) wasobtainedand compared
in Table 2, then the eddy coefficientsassociatedwith the ni- with the transporttime scale.H:/K, where H is the scale
trous oxide and methane data would require revision. height.Theycomeoutverynearlyequal,buttheuncertainty
Application of (3) and the photochemicalmodel yields the is probablya factor of 3. The agreementfound in Figure 3
eddy profile curves K(N20) and K(CHn) of Figure 3. Both suggeststhat in fact the transport may dominate. We have
curvesspecifya minimumvalueof K ,-, 4 x 103cm2 s-1 at 17 therefore omitted the possibleheight variation of ozone flux,
but somecaution is necessaryin acceptingthe result.
km. Above 17 km, the K(N20) and K(CHn) profiles increase
with altitude, with a 'scaleheight' of approximately8 km. Be-
low 17 km, they increasesharplyto a value between50 x 103 50
and 80 x 103 cm'- s-1 at 10 km.
Ozone. Dutsch[1971] and Hering and Borden[1965] cite 40- --

O3 partialpressures
and massdensities
as a functionof lati-
tude and seasonfor the stratosphere
below 30 km. Theseval-
ues,and the massmixingratiosof NAS [1979],for altitudes
above30 kin, are usedin the photochemicalmodel described
in the appendixand determinethe globallyaveragedmixing 20
ratio profile of ozonegivenin Table 1.
I0-
The ozoneflux into the troposphereis thoughtto have the
nearlyconstant
value-5 x 10løcm-2 s-l [Fishman
andCrut-
0 i i i i i i I , • , , , , i I ,
zen, 1977].Insertionof this flux into (1), with mixing ratios I03 I04 I;5
f(O3) given in Table 1, yieldsthe eddy coefficients K(O3) K (crna/sec)
shown in Figure 3.
This resultdependson the sourcesand sinksof ozonebeing Fig. 3. Four estimatesof the eddy diffusionprofile,basedupon
global distributionsand chemistryof N•_Oand CHn, time dependent
negligiblerelativeto transport.Troposphericchemistryhas inc calculations, andtheapplicationof a constant
downwarddirected
been discussedby Crutzen[1973], Chameidesand Walker flux(= -5.0 x 10løcm2 s-l) conditionto seasonally averagedozone
[1973],Fishmanand Crutzen[1977],Fishmanet al. [1979],and data.
9862 MASSIE AND HUNTEN: STRATOSPHERIC EDDY COEFFICIENTS FROM TRACERS

5O 50

CH4
4O 40- M

ß adjusted

20-
IO

o
i0 3 10
3 10
4 I;5
K (cma/sec) K (cma/sec)

Fig. 4. Methane distributioneddy values.The 'OH calculation' Fig. 5. Activationtemperatureuncertaintiesof reactions(4)-(10)

profileis identicalto the K(CH4) curveof Figure3. The 'OH adjusted' and (R1)-(R3) of Table A1 are usedto minimize and maximizethe
profileis derivedfrom calculatedOH densities, whichare correctedin
the 30-35 km altitude region. globally
averaged
chemical
(P- L)N2o
and(P- L)•ovt;.rms.
These chemicaltermsproducethe eddy profilesdisplayed

Carbon14. The paper of Johnstonet al. [1976]drew atten- shown in Figure 3 as 'K(C-14).' The value at 21 km is 2.3 x
tion to the existenceand utility of a data setfor 'nC left over 103cm• s-', closeto the averageof the estimatescitedabove.
from a large seriesof nuclear tests at the beginning of the Uncertaintyestimates. We next make estimatesof the un-
1960's.The chemical form is believed to be CO2; once the nat- certainties in the individual K(z) profiles just derived and
ural, steadystatecomponentis subtracted,the 'excess'forms a form a compositeprofile. The observationaldata have imper-
unique time-dependenttracer. Johnstonet al. presentedthe fect coveragein spaceand time, and errorscreep in from the
data in globally averagedform (their Table 5) for 13-27 km estimationof mean lossand production rates.
altitude and for 1963 January, April, July, October; 1964Jan- Of the chemical tracers,N20 is the simplestbecauseits loss
uary; and 1965 January. The actual data are from latitudes is primarily due to photolysis,reaction(6). There are no ob-
between 80øN and 30øS. The first profile was used as the ini- servationsof O('D) that is involvedin (4) and (5), but since
tial condition, and the subsequentevolution followed. The thesebranchesconstituteonly a few percent, the final uncer-
time-dependent version of equation (2) with no sourcesor tainty from this sourceis negligible.Photolysisrates depend
sinks is only on solar flux and ozone and N:O absorption.At the
lower altitudes the choice of ozone distribution makes little
difference. The data of Hering and Borden [1965], averaged
+ into four seasons,and thoseof Dutsch[1971] in two, were both
usedin derivationof K(N20). The resultsfor the Dutsch and
H(z) denotesthe atmosphericscaleheight, specifiedhere by
the Hering and Bordenozonedata differedby approximately
the 1976 U.S. Standard Atmosphere [NOAA, 1976].
Johnstonet al. computedthe time evolutionof 'nC pre- 5%. The effecton the methaneeddy coefficientsis also about
5%. Probablythe main limitation, however,is in the scopeof
dicted by (19) for sevenprofilesof K that had been proposed
the N20 observationsthemselves,particularly above balloon
up to that time. The predictionswere markedly different,and
altitudes.Estimatesof K are rather stronglydependenton the
only two of the profilespassedthe testof comparisonwith the
data. We have followed this procedure,with some modifica-
flux through the 40-kin level, as remarked above and dis-
cussedby Johnstonet al. [1979].
tions. Numerical solutionswere computedwith the GEAR or-
Methane shares this last limitation, but here the loss rates
dinary differential equation program [Hindmarsh,1974]. The
first and secondderivativeswere expressedby five-point finite
differencesand the altitude grid extendedfrom 1 to 51 km in 5O

half-kilometersteps.A smoothextrapolationextendedthe ob-

served 1963 mixing ratios to the 1-12 and 28-51 km altitude
.....ENVELOPE
! ,,,'•.)"J/'....
40 ß _

ranges.The lower boundary value was held constantat 3.0 x

10-'6 mixing ratio [seeJohnstonet al., 1976].The changeof f _ _

at the upper boundary was set equal to half its value at 51.5
km. Test caseswith analytic solutionswere usedto certify the _

GEAR program as applied to (19). A typical run time for the

GEAR program on an Interdata 8/32 is 700 s.
_

In addition, (19) can be applied directly at the level where

Of/Oz-- 0 to yield an empiricalvalue of K at that height,anal- i
o I I I I I I I I I I I I I I I I I I I I
ogousto the steady state expression(2). The necessarytime io 3 104 105
and height derivativeswere estimatedfrom the data [Johnston K (crna/sec)
et al., 1976, Table 5]. For the 5 epochsfrom January 1963 to
January 1964we find K(21 km) to be (1.5, 1.5, 1.8, 3.5, 4.1) x Fig. 6. The compositeeddy profile is basedupon the four curves
103 cm 2 K(N20), K(CHn),K('nC), and K(O3) of Figure3. An envelopeis
drawn around these four curvesand outlines the possiblerange of
A variety of K profileswas testedin a trial-and-error proc- eddyvalues,asobtainedin this study,for altitudesbetween10 and 40
ess. The best fit to the data was obtained with the profile km.
 MASSIE AND HUNTEN: STRATOSPHERIC EDDY COEFFICIENTS FROM TRACERS 9863

TABLE 3. Eddy-Diffusion Coefficients

Height,km NAS* [1976] NAS [1979] Johnston
[1979] Hunten[1975a] •nC Composite
1 100 270 300 100 100 100
2 100 210 300 100 100 100
3 100 160 300 100 100 100
4 100 120 300 100 100 100
5 100 94 300 100 100 100
6 100 70 300 100 100 100
7 100 54 300 100 100 100
8 100 43 300 100 100 100
9 100 34 150 65 100 100
10 100 27 20 30 8o 8o
11 20 21 7 30 30 30
12 17 17 6.5 30 17 17
13 14 14 6.6 16 10 8
14 12 11 6.2 2.3 7 5.8
15 10 9.2 4.7 2.3 5.2 4.6
16 9 7.8 4.4 2.7 4 4.0
17 7.8 6.6 4.3 3.0 3 3.9
18 7.0 6.0 4.3 3.3 2.6 3.9
19 6.2 5.5 4.5 3.7 2.3 4.1
20 5.8 5.4 5.0 4.2 2.3 4.6
21 5.8 5.6 5.6 4.5 2.4 5.1
22 7.0 6.0 6.0 5.2 2.6 5.8
23 8.8 6.5 6.5 5.6 3.2 6.6
24 11 7.3 7.4 6.4 4.2 7.5
25 13 8.6 8.2 7.2 5.0 8.5
26 16 11 8.9 8.0 6.4 9.5
27 20 14 9.7 9.0 8.1 10.6
28 25 18 10.5 10 9.8 12
29 31 22 11 11 12 13
30 37 26 12 12 14 14.3
31 41 32 12.3 13 16 16
32 47 38 13 15 17.4 17.4
33 52 44 13.3 16 19 19
34 60 52 13.5 18 21 21
35 66 59 14 20 23 23
36 73 68 15.4 22 26 26
37 80 78 17 24 29 29
38 88 88 18 28 32 32
39 98 98 19.7 30 36 36
40 108 105 22 34 40 40
41 120 112 24 38
42 130 120 26 41 49 49
43 140 128 29 47 55 55
44 150 135 31 52 62 62
45 160 142 34 59 67 67
46 170 150 37 63 76 76
47 180 157 40 72 84 84
48 195 163 43 80 92 92
49 205 170 47 90 102 102
50 217 177 52 100 112 112

Units are 103 cm2 s-•.

* NAS -- National Academy of Sciences.

involve much greater complexities.As seenfrom the reaction
list (7)-(10), the densitiesof both O(•D) and OH are impor- coefficients.
tam, with a small contribution from CI. Fortunately, we do
have observationsof OH, at leastfor heightsabove30 km. Al-
though the computed OH densitieswere multiplied by 0.9 to
improve the general agreementwith observations,the height
'profilesstill differ somewhat.As a partial sensitivitytest, an
'adjusted'OH density field (as a function of latitude, height,
and time) was generatedby applying at each height the ratio
of the 'calculated'and 'observed'curvesof Figure 1. It should
be remarked that this procedureworsensthe agreementob-
tained in Figure 2: The adjustedvalues are now 15% higher.
Comparisonof K(CHn) and K(adjusted)in Figure 4 givesan
idea of the sensitivityto the OH densities.
A further studywas made of the sensitivityto chemicalrate
The biggestproblemis with (7), betweenCHn and
OH, but all rates were varied to their error limits to estimate
boundson the lossrates.In additionto (4)-(10) of the text, the
ratesdetermining
the O(•D) density((R1)-(R3) of Table A1)
were varied simultaneouslyto their extremes.The resultsfor
K(N20) and K(CHn) are shown in Figure 5. CHn appears
much more sensitiveto uncertain chemistrythan
Use of the 0.90 scaling factor for OH decreasesthe CHn
eddy values by lessthan 10% above 15 km and by roughly
12% between 10 and 15 km. Further sensitivityof the CHn
eddy profile is revealedby usingan OH scalingfactor of 1.00,
includingthe reactionsCHn + O(•D) -->OH + CH3 and OH +
CHn --> CH3 + H20 in equation(A13), and replacingthe reac-
9864 MASSIE AND HUNTEN: STRATOSPHERIC EDDY COEFFICIENTS FROM TRACERS

5O
computations:the basicsetof Johnstonet al. describedabove
and a set correctedfor leakage into the southernhemisphere.
4O
HUNTEN
JOHNSTON /,,•/_/'•'
' ,•.•"'/ The factors are derived from their Table 7: The observed
..... COMPOSITE quantitiesare multiplied by 1.07, 1.09,and 1.32for July 1963,
January 1964, and January 1965, respectively.Most of the
computationsusedthe globally averaged'4C distributionof
January 1963as the initial condition.An additional set started
with the correspondingJanuary 1964 data.
The resultsare displayedin Figure 8 and Table 4. The 14C
data plotted for comparisonwere not correctedfor the leak-
o age. The numerical criterion of Table 4 is presented both
io 3 I0 4 I0 5 ways. This table showsvaluesof the quantity
K (cm2/sec)
27

Fig. 7. Eddy profilesadvocatedby the National•4cademyof Sci- 100 • im13 km

If,(obs)-f•(comp)l/f,(obs
) (20)
ences[1976, 1979]reportsand Hunten [1975a],Johnstonet al. [1979],
and this study.The Johnstonet al. profile is extrapolatedfor altitudes where the numerator is the absolute value of the difference of
between 40 and 50 km, and below 9 km.
observedand computedmixing ratios. Since there are 15 lev-
els, the resultsgiven should be divided by 15 to obtain the
mean percentdeviation.Resultsfor the January 1964starting
date are shown in parentheses.
tion ratesof reactions(R22) and (R28) by 1.14 x 10-13 exp
Two of the profileswere taken from reportsby the Com-
(1055/T) and 1.52x 10-14exp(649/T) [Lii et al., 1979;Wineet
mittee on Impacts of StratosphericChange of the National
al., 1981].The resultingCHn eddy profile differsfrom that of
Academy of Sciences[NAS, 1976, 1979]. The 1976 profile is
Figure 3 by +5, +4, +2, 0, -4, -9, -21% at 40, 35 ... 10 km
altitude. curve E of their Figure 7.1 and is based on methane and ni-
The InC data set is weakenedby somewhatlimited cov- trous oxide data. The 1979 result,which differsmainly below
10 km, is profile K• of their Figure B 9. It incorporatesevi-
erage,especiallyin height, and by the fact that the •4C was
dencefrom N•O, 03, and global-circulationmodeling.
largely absentfrom the southernhemisphereto startwith. The
Johnstonet al. [1979] presentan eddy profile basedupon a
small correctionsfor leakageacrossthe equatorare discussed
in the next section. study of nitrousoxide.This setof coefficients,and the K(N20)
profile of Figure 3, are in goodagreement.(Extrapolationsex-
Figure 6 presentsa compositeeddy profile basedupon the
tend the Johnston et al. values for altitudes between 40 and 50
four K(N20), K(CHn), K(O3), and K(•nC)curvesof Figure 3.
km, and below 9 km.) Both profilesare a factor of 2 smaller,
Two other curvesare also displayedwhich envelopthe four
profilesof Figure 3. CurvesK(N20) and K(CHn) of Figure 3
are in closeagreementbetween 10 and 25 km altitude. Weight
is givento theseprofilesin drawingthe compositeprofile. Be- JANUARY 1963
tween 25 and 40 km, the chemical reaction rate uncertainties
of CH4 are larger than thoseof N•O. Weight is given to the 25
K(N•O) profile in this altitude range. The compositeeddy
profile is extrapolatedto 50 km. The compositeprofile is tabu-
lated in Table 3 and displayedin Figure 6.
The tracer data analyzed here have little to say about the
valuesof K in the troposphere.For the compositeprofile we
have assumed values of 105 cm • s-• for altitudes below 10 km.
Time-dependentcalculationsfor •4C showthat thesevalues
yield better agreement between observationand prediction 415
than coefficients
that are lessor greaterthan 105cm• s-l. How-
ever,we consider the 105cm2s-l coefficients to be essentially
a
compromisebetweenother reported values.The NAS [1979] 0 .50 I00
eddy profileis below 105cm• s-• between5 and 10 km alti- 14C0•MIXINGRATIO
tude. Levine et al. [1980] simulate measuredprofiles of am-
moniaand proposeK to be greaterthan 2 x 105cm• s-• in the ' OBSERVATION
troposphere.Eddy values between0.4 and 2 x 105cm• s-• .... COMPOSITE (THIS PAPER)
have been derived in previousradioactivetracer studies(see ' . HUNTEN (1975 o)
the review by Hunten [1975b]).Thus, the global averageeddy
........ JOHNSTON (1979)
profile for the troposphereis uncertain.
ß-. NAS (1976)
CARBON 14 TESTING
---•--NAS (1979)
In this sectionwe extend the work of Johnstonet al. [1976] 14COE
to severalK profilesfrom the recent literature and to thosede-
rived above. These data are tabulated at 1-km intervals in Fig. ga. Theobserved
(globalaverage)14C
distribution
of January
1963.Thesemixingratiosare the initial valuesin the time dependent
Table 3 and illustratedin Figures3 and 7, Two versionsof the calculations.
Belowis shownthekeyto the resultspresented in Figure
InC data are usedfor comparisonwith the time-dependent 8b. Units for the mixingratio are 10-•6 by volume.
 MASSlE AND HUNTEN: STRATOSPHERIC EDDY COEFFICIENTS FROM TRACERS 9865

JANUARY 1964 14Ctestsof Johnstonet al. [1976]and offersa usefulvariant on

our similar compositeprofile.
25 Finally, Table 3 includesour compositeprofile and the 14C
E
profile derivedby trial and error.
• - - - As might be • the •*C eddy coeff•ents shcr•rthe
tlJ20 best agreementin Figure 8 and Table 4. The compositeand
Hunten profilesshowup next bestin the figure,but the former
r- ß does quite a bit better in Table 4. The Hunten profile pro-
duceslow mixing ratios below 15 km. The Johnstonprofile
•( 15
doesalmostaswell, but the two NAS profilesare distinctlyin-
ferior. They consistently
underestimate
the 14Cmixing ratios
o 50 ioo in the figure,and the observedprofilesare already on the low
sidebecausethey do not includethe correctionsfor leakageto
the southernhemisphere.The auxiliary tests,as far as they go,

-tu 20
';,5,, producethe sameranking.
CONCLUSIONS
-
The 14Ctestsconductedin thispapersuggest
that the NAS
ø [1976] and NAS [1979] eddy coefficientsare too large. The
Hunten [1975a] and Johnstonet al. [1979] profiles do consid-
•(15 erablybetterin the '4C testand are similarto the composite
eddy coefficientsderived in this study.We suggestuse of the
I I I ' I , , . , I
0 50 i00
compositeprofile until further evidence is available. More
over, any future proposalsshouldbe subjectedto the 14Ctest.
14co=MIXINGRATIO
We intend to maintain the ability to do this.
Fig. 8b. Comparisonof observedand predictedJanuary 1964dis- Many aspectsof the behavior of ozone require a com-
tributionsof '4C.The observed (globalaverage)distribution is tabu- plicated descriptioninvolving at least two dimensionsand
lated in Table 5 of Johnstonet al. [1976]. The predicteddistributions
use the eddy profilesof Figure 7. time. Nevertheless,the eddy coefficientsassociatedwith the
global averageof ozonebetween10 and 20 km altitude, a re-
gion where transportpossiblydominatesover ozone chemis-
at 40 km altitude,than the NAS [1976]and NAS [1979]eddy try, are not different from thoseobtained from other tracers.
values.The NAS [1979]eddy coefficients are derivedin part This result lends confidence to the usefulness of the one-di-
by application of a constantflux approximationto nitrous mensionaleddy formulation, as long as it is properly applied
oxidedata. This questionableassumptionmay be responsible to global or hemisphericmean behavior.
for the disagreement.
APPENDIX
We include the set proposed by Hunten [1975a], even
though the OH densitiesused to obtain the CH4 loss rates A photochemicalequilibrium model is usedto calculatethe
were considerablytoo small. This profile came out bestin the OH and O(ID) densities associated with reactions(4)-(10) of

TABLE 4. Sumsof the FractionalDifferencesBetweenObservedand PredictedCarbon 14 Distributions.Resultsin parentheses

refer to a
January 1964 startingdate.
Date NAS* [1979] NAS [1976] Johnston
[1979] Hunten[1975a] 14C Composite
Uncorrected
April 1963 153 210 162 259 144 189
July 1963 231 264 236 256 151 139
October 1963 375 379 387 305 143 246
January 1964 342 405 276 211 126 162
January1965 376 (307) 410 539 580 390 (362) 331 (369)
Total 1477 1668 1600 1611 954 1067
Corrected•
April 1963 175 229 158 253 174 192
July 1963 288 324 223 267 198 163
October 1963 402 430 389 333 177 261
January 1964 388 459 254 196 161 200
January1965 477 (371) 582 362 228 125(116) 252 (237)
Total 1730 2024 1386 1277 835 1068

Example:
i----27 lcra

153= 100i•13 • lorn If(0ob

.... tion-f(Oca•cu•ationl/[f(Oot,
.... tion]

wheref(0o•.... tion= observed

April 196314Cmixingratiosandwheref(0ca•,,i•t•on
= calculated
mixingratiosbasedupontheNational•tcad-
ernyof Sciences[1979] eddy coefficients.
* NAS = National Academy of Sciences.
•' The sumsare corrected
for lossof •4Cto the southernhemisphere.
9866 MASSIE AND HUNTEN: STRATOSPHERIC EDDY COEFFICIENTS FROM TRACERS

TABLE A1. Chemical Reactions and Rates

Reaction
Number Reaction Rate

R1 O(ID) q-N2--• O q-N2 2.0x 10-ll exp[(107_50)/T]

R2
R3
O(ID) q-02-•>
Oq-02
O(ID) + N2+ M -->N20 + M
2.9X10 --llexp[(67+50)+/7]
3.5X 10-37(T/300)-ø'45-q2•
R4 03 + hv-->O(ID) + 0 2 J4= 8.6X 10-3
R5 N20 + hv-->O(ID) + N2 J5-- 6.9 X 10-7
R6 02 + hv--> O + O J6-- 3.1 x 10-9
R7 03 + by-->O(3p)+ 02 J7- 9.1 x 10-3
R8 NO2 + hv-->O + NO J8-- 7.1 x 10-3
R9 O(3p)+ O3-->02 + 02 1.5x 10-ll exp(-2218/T)
R10 O(3p)+ 02 + M--> 03 + M 6.2X l0-34(T/300)-2'ø
Rll O(3p)+ OH--> H + 02 4.0 x 10-ll
R12 H20 q-hv-->H q-OH Jl2 -- 1.3x 10-7
R13 OH + CO--> H + CO2 1.35X 10-13(1 q-Patm)
R14 03 + H --> OH + 02 1.4x 10-lø exp(-470/T)
R15 H + 02 + M -->HO2q-M 5.5 X 10-32(T/300)-1'4
R16 H + HO2--> H2 + 02 1.5x 10-12
R17 03 + OH -->HO2+ 02 1.6x 10-12exp(-940/T)
R18 OH + H202-->HO2+ H20 2.96x 10-12exp(-164/T)
R19 O + H202-->OH + HO2 2.8 x 10-12exp(-2125/T)
R20 O + HO2--> OH + O2 3.5 x 10-ll
R21 03 + HO2-->OH + 202 1.1X 10-14exp(-580/T)
R22 OH + HO2--> H20 + 02 4.0 x 10-•l
R23 HO2 + HO2--> H202 + 02 2.5 x 10-•2
R24 NO + HO2-->NO2 + OH 4.3 x 10-12exp(200/T)
R25 H202 + hv-->OH + OH J25- 1.3x 10-4
R26 O(ID) + H20--> OH + OH 2.3 x 10-lø
R27 OH q-OH -->a20 q-O(3p) 1.0X 10-4 exp(-500/T)
R28 OH q- HNO3--• H20 q-NO3 8.5 x 10-14
R29 OH + OH + M -->g20 2 q-M 2.5 X 10-31 (T/300)-ø'8
R30 NO2 + O--> NO + 02 9.3 x 10-12
R31 OH + NO2 + M --} HNO3 q-M 2.6 X 10-30(T/300)-2'9
R32 NO + 03 -->NO2 + 20 2.3 x 10-12exp(-1450/T)
R33 O + H202--> H20 + 02 1.0x 10-15
The ratesfor reactions(R18) and (R33) are cited by F. Kaufman (privatecommunication,1980) and
Fonerand Hudson[1962].Reactionrate (R16) is taken from Huntenand McElroy [1970].All other rates
are from HudsonandReed[1979].Units for doubleand triple bodyreactionratesare cm3 s-l and cm6
s-l. Activationtemperatureuncertainties
are givenfor reactions(R1) and (R2). Dissociation
coefficient
values(s-1) are for noontimeconditions
at 65 km and 35ø latitude.

the text. Sevenlatitudes(9ø, 22ø, 35ø, 47ø, 59ø, 71ø, and 85ø)ures 3-9, 4-11, 3-8, 4-10, 3-10, 4-25, 4-12, 4-9, 4-27, and 4-17 of
are represented.The altitude grid extendsfrom ground level Hudson and Reed [1979]. The entries for alpha (equal to
to 65 km, in l-km increments. Methane and nitrous oxide (P [HO2]/[OH]) and H202 are photochemicalmodel values.
- L) terms are calculated between noontime and sunset, in Hudson and Reed [1979] is the primary sourceof solar flux
half-hour increments. Global (P - L) terms are obtained and absorption cross secti. on data. Ackermann [1971] solar
from individual valuesaveragedover 24 hours, latitude, and fluxesaugmentthe tabulationsgiven in Hudsonand Reed.At-
the seasonsof fall and spring. tenuationin the SchumannRunge oxygenbandsis calculated
With the reactionslistedin Table A l, photochemicalequi- with the two term expressionsgiven by Nicolet and Peeter-
librium valuesof O('D), O(3p), H, HO2/OH, OH, NO2, NO, mans [1980]. The temperaturedependentformulae of Moon-
and H202 are estimatedby expressions adaptedfrom London gat and Kidszus[1978] and $elwyn et al. [1977] compute the
and Park [1974]and shownin Table A2. [M] represents the to- O(ID) quantumyieldsand the N20 absorptioncrosssection
tal atmosphericnumberdensity.Equations(AI), (A2), (A3), values.
and (AI4) follow from photochemicalequilibriumstatements For wavelengthsgreaterthan 300 nm, multiple scattering
for O(ID), O(3p),H, and H202. Equations(A6), (A8), and effects are approximately incorporated. Wofsy [1978] com-
(AI3) follow from equilibrium expressions for HO2, NO, and parescomputeddensities of O('D) and O(3p),baseduponcal-
HOx (--H + OH + HO2 + HNO3). culationsleaving out, and incorporating,multiple scattering
The noontimedensitiesof O(ID), O(3p), ..- are calculatedat and planetaryalbedoeffects.Theseresultsare usedin equa-
eachlatitudein the orderpresentedabove.If a density,for ex- tions(A I)-(A 14). For example,the 0(ID) dissociation coeffi-
ample [NO2] in equation(A2), were not computedin a pre- cient J4 is multiplied by 1.3 at altitudesin the troposphere.At
vious equation, then the values given in Table A3 would be higher altitudes,J4 is multiplied by a smaller factor. J7,J8,J12,
used.The next time stepusesthe [NO2] valuesfrom the pre- and J25are all multiplied by factorsbasedupon the Wofsy
vious time step. The temperaturesin Table A3 are from the calculations for O(3p).
U.S. StandardAtmosphere[NOAA, 1976].Mixing ratiosfor Comparisonof calculatedO(3p), HO2, and O(3p)/o3 with
NOx, NO2, NO, HNO3, H20, C1,and C10 are takenfrom Fig- observedvalues [given in Hudsonand Reed, 1979]produced
 MASSIE AND HUNTEN.' STRATOSPHERICEDDY COEFFICIENTS FROM TRACERS 9867

TABLE A2. Reaction Scheme

Reactions Reaction Number

•[O•] + •[N•O]

[Op•')]
• (• +•)[O•] +•dO•]+•[•O•]
R910•] + R•o[O•][M]
(A2)

[H]= R•[O(•][OH] +Ju[H=O] +R•[OH][CO]

R•410•] + R•[O=][M] + R•6[OH]•pha
(A3)

A1• R•710•]
+R•s[H=O=]
+R•9[H=O•]
[O(•] [HI
[OH]+R•dO3[M]
[OH] (A4)

• • R•[NO] + R=o[O(•P)]
+ R=•[O•]+ R==[OH]+ 2R=•[OH]alpha
+ R•6[H] (A5)

= [HO=]
alpha[OH]=(A•/•) (A6)

•Ox] - [HNO•] + [NO] + [NO=] (A7)

•ta- [NO]• R•o[O(•P)]

+ Js+ R•[OH][M] (A8)
•O=] R•=[O•] + R=4alpha [OH]

[NO=] = ([NOx] - [HNO•])/(1 + beta) (A9)

beta
(A10)
•O] - ([NOx]
- [HNO•])1+ beta

A3 -- Ji2[H2O] q-J25[H202]q-R2610(ID)][H2
O] q-Ri910(3p)][H202] (All)

[HI
A4
=R27
+R22
alpha
+R•6
alpha
[-• +R23
alpha
2+R28
[HNO3]
[OH]+ R29[M] (A12)

[OH] -- (A3/A4)u2 (A13)

[H202]
--R23
alpha2[OH]2+R29[M][OH][OH]
J25+ R•s[OH]+ (R•9+ R3a)[O(3P)]
(A14)

good agreement. The primary goal of the photochemical To obtain satisfactoryagreementbetweenpredicted mid-
model,however,is to calculaterealisticOH and O(•D) den- latitude OH column densities,and the observationsof Burnett
sities.Therefore,as with the caseof the NOx compounds,ob- and Burnett [seeHudsonand Reed, 1979],the OH densitiesof
servedconcentrations are heavilyrelieduponin the photoche- equation (A13) are multiplied by 0.90. A 10% correction is
mical calculations. reasonable. The reaction rates and number densities com-

TABLE A3. Input Data (Mixing Ratios,Temperatures)for the Photochemical

Model

Altitude, km NOx NO2 NO HNOa H20 C1

10 5.5-10 2.0-11 2.5-11 5.0 -10 2.0-4 0
20 6.4 -9 1.1 -9 2.9 -10 5.0 -9 4.0 -6 0
30 1.1 -8 6.0 -9 2.0 -9 2.7 -9 5.2 -6 2.5 - 13
40 9.0 -9 3.0 -9 5.9 -9 7.0 - 11 5.7 -6 5.0 - 12
50 1.2 -8 1.0-9 1.1 -9 1.0-12 6.0 -6 1.0-11
60 1.7 -8 3.5 -10 1.7 -8 2.0-14 6.0 -6 1.4 -11

Altitude,km CO OH H202 Alpha T (øK) [M]

10 6.0-8 4.1 -13 5.8 -11 3.0 223 8.60 +18
20 1.3-8 1.1 -12 2.2-11 8.8 217 1.85 +18
30 1.0-8 2.7-11 4.2-10 5.2 227 3.83 +17
40 1.0-8 3.7-10 4.0-10 1.3 250 8.31 +16
50 1.0-8 7.6-10 2.7-10 1.0 271 2.14 +16
60 1.0 -8 1.3 -9 2.5 - 10 1.0 247 6.44 + 15

5.5 -10 means5.5 x 10-•ø. The CI mixingratiosarediurnalaverages,

obtainedby dividingobserved
daytimevaluesby 2. [M] is the total atmospheric
numberdensity(cm-3).Valuesof NOx, HNOa, H20,
CI, and CO are held constantthroughoutthe calculations.
9868 MASSIE AND HUNTEN: STRATOSPHERICEDDY COEFFICIENTS FROM TRACERS
prising equation (A13) do have uncertainties.For example,
the mixing ratio of water vapor in the stratosphereis uncer-
tain by far more than 10% [e.g., Hudsonand t•eed, 1979].
Acknowledgments.This work has been supportedby the NASA
Stratosphcric Program under grant NSG-7485. We thank Steven
Compton for programingassistance and the National ScienceFoun-
dation for its contribution to the purchaseof the computer.
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(ReceivedDecember 29, 1980;
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