GEOPHYSICAL

RESEARCH
LETTERS,
VOL. 17,NO. 9. PAGES1275-1278.
AUGUST1990

BALLOONOBSERVATIONS
OF NITRIC ACIDAEROSOLFORMATIONIN THE ARCTIC
STRATOSPHERE: I. GASEOUSNITRIC ACID
H. Schlagerand F. Arnold

Max-Planck-Institut
fiirKernphysik,
Heidelberg,
Federal
R.epublic
ofGermany
D. Hofmann and T. Deshler

Dept.ofPhysics
& Astronomy,
University
ofWyoming

Abstract. Measurementsof the altitude distributions of stratosphericwater and nitric acid vapourabundancesas
gaseousnitric acid and aerosolswere made in the winter measured by LiMS [GilleandRussell,1984,Russell et al.,
arcticstratosphereusingballoon-borne massspectrometer- 1984]. The resultingvaluesrangefrom about206 K at
and aerosolcountertechniques. The measurementstook !0 km altitudeto about 190 K at 25 km beingmarkedly
placeunderconditions of verylow stratospherictempera- larger(about1 to 12K, depending on altitudeandthewa-
tures, with minimum values of 186 K around 24 km alti- ter vapourabundance) than the thresholdtemperaturefor
tudebeingabout6 degrees belowthe existence tempera- watericeexistence (T(ICE)) [Arnoldet al., 1989].A tem-
ture(T(NAT)) for NAT (NitricAcidTrihydrat½) aerosols. peratureT _<T(NAT) is a necessary thoughnot sufficient
At theseheights,a localdepletionof gaseous nitricacidby requirement for efficient NAT-aerosol formation. From
upto about60%wasobserved suggestingtheoccurrenceof recent measurementsof gaseousnitric acid in the arctic
nitric acid incorporationinto aerosols,
whichwerein fact stratosphere [Arnoldet al., 1989]it seemsthat conden-
observed andwhoseinferrednitricacidcontent is roughly sattonaldepletionis slow.It hasbeenproposed [Arnold,
consistentwith the missinggaseousnitric acid. Our data 1990]that the delayedstart of efficientcondensation
in •
suggestthat rapid formation of NAT-aerosols associated coolingairparcelmay be due!o activationof a majorfrac-
with substantialcondensational
depletionof gaseous
ni- tion of the preexistingCN takingplaceonly at tempera-
tric acid occurredonly at temperaturesof about 3 to turesmarkedlybelowT(NAT) or at substantial supersat-
4 degrees
belowT(NAT) corresponding
to largeHNOa- urations. For an assessment of the role of NAT-aerosols
supersaturations, which are probablyrequiredfor activa- in settingthe scenefor polar ozonedestructionamunder-
tion of a major fractionof preexistingcondensation
nuclei. standingof the formationof theseparticlesis of vital im-
portance.
Introduction The presentpaper reportsa casestudy of NAT-aerosol
formationin the winterarcticstratosphere
involvingbal-
Nitric acid aerosolsformedin the winter/springpolar loon-bornemeasurements
of gaseous
nitric acid and aero-
stratosphere play •n important role in settingthe scene sols. The flightswerepart of the STRAFAM(german
for polar ozonedestructionby halogensvia surfacere- acronymfor: Stratospheric
dropsonde massspectrometer)
actionsand sedimentational denitrification(of. [Crutzen -campaign,whichwasa collaborativescientificeffortof the
and Arnold, 1986, Toon et al., 1986, Hamill et al., 1988, Max-Planck-Institut
f/it Kernphysik
(MPIK) Heidelberg
Pooleand McCormick,!988, Faheyet al. !989, Hofmann, andthe Universityof Wyomingat Laramie,andwhichtook
1989,Turcoet al. 1989, Arnold, 1990]). A criticalques- place at Kiruna in Northern Sweden. The two balloon-
tion of considerable current interest is how these aerosols flightsto bereportedhere,of whichonewasequippedwith
form,andto whichsizestheygrow.The particlesizecriti- aerosolcounters (Universityof Wyoming)andonewith a
cally controls surface reactions and sedimentationveloc- massspectrometer (MPIK, Heidelberg),tookplaceon the
ity. It is thought [Crutzenand Arnold, 1986, Toon et sameday under conditionsof very low stratospheric tem-
a!., !986, Arnold, 1990], that gaseousnitric acid under- peraturesresultingfrom large scalesynopticcooling,•nd
goesheterogeneous heteromolecularcondensation with wa- thereforewereparticularlywellsuitedfor investigations
of
ter vapour leading to solid aerosols,which have a compo- the evolution of nitric acid condensation and NAT-aerosol
sitioncloseto NAT (Nitric Acid Trihydrate)andthat pre- formation and growth.
existingH2SO4/tt20-aerosolsserveas condensation nuclei
(CN). The threshold temperature,
T(NAT), belowwhich Measurements
NAT-aerosolscanexist(in equilibrium),is determined
by
the concentrations
of gaseous
HNO3 and It20 and by the Theballoon-borne
dropsonde
massspectro.meter
(MS) of
thermodynamicdata for NAT. Laboratory measurements the MPIK is of a novel type similar to the one described
of the latter arenowavailable[HansonandMauersberger, by [Schlagerand Arnold, 1990]. A detaileddescription
1988],allowingto calculateT(NAT) for typicalaverage of the instrument used for the presentmeasurementswill
be givenin a separatepaper (H. Sch!ageret al., paperin
preparation,1990). A descriptionof the optical aerosol
counterof the University of Wyoming usedfor the present
Copyright 1990 by the American Geophysical Union.
measurements,and the details of the aerosolmeasurements
Paper number 90GL01620 are givenin a separatepaper[Holmannet al., 1990],ac-
0094-8276/90/90GL-01620503.00 companyingthe presentone.

1275
1276 Scklager
et al.: Nitric AcidAerosolFormationin the ArcticStratosphere

3O
The balloon flightsto be reportedincludedone flight I i I I"I"f"iiI \1 i I I I i III .... I I I I I I! iI -r'
__

with the mass spectrometer,which was launched by the KIRUNA '•' DROPS(a)
Universityof Wyomingteam on 31 January,1990 at Es- 31JAN1990
25 ................
range(150
km eastofKiruna;68øN,20øE).Thelaunchtime ß'..,.

was 00.15 LT, and the maximum altitude of 28 km was

reachedafter 2 hours. Besidesthe massspectrometer,the
balloonpackage
containedalsoan ozonesonde(University
of Wyoming) and temperaturesensors.The massspec-
20- -'-"-'.......... %\
........(HN0
. 3•EVZ...•iHS
PR&SION'-"--........
(70øNo
JAN)_ -
trometer measurementswere performedonly during the 15 , , ,, •,l,I , I , ,,,,,I i, , , ,,,,,1__
parachute-descent,startingshortlyafter the peak altitude
had been attained. In order to avoidpre- and in-flight >.+.MS DROPS (b) I
E
contamination,the vacuum-sealedmassspectrometerwas "25
openedonly after separationof the payload from the bal-
loon. An important methodicaspectis that, dueto the ab-
senceof sunlight,the flow tube of the MS was at ambient
gas temperature measuredby temperature sensorsinside
m
E 20 ,, • 'x i..•.
•_2.11
and outsidethe flow tube, and thereforeNAT-aerosoleva- 15 • ['• ..... I • • • •l h , • ,•,,,I I
poration inside the flow tube should not have occurred. In
30 ' ' ' ' .... ! x' ' ' •''•1 ' "''• "'"•1
this respect,the presentmeasurement differedfrom previ-
ousMS-measurements of the MPIK. Duringthe entirede- "--'"---••.•l•S STRAFAH
(c)
scentthe MS wasexclusively operatedin the ACIMS (Ac- KIRUNA
_
tive ChemicalIonisationMass Spectrometry)-mode with 25 30JAN
1989 %.."• -,5AT
negative ions. The altitude range coveredby the MS-
measurements was 28 to 17 km.

Results and Discussion 15 ....

Measuredconcentrations of gaseousnitric acid are shown'
in Figure la along with a monthly and zonally averaged
(January,70øN)profilemeasured by LIMS [GilleandRus-
sell, 1984]. Above25 kin, around22 - 23 km and below
18 km the present data are similar to L!MS, which of-
fered an altitude resolutionof only 3 - 5 km, and they are
markedly lower than L!MS witkin two particularly cold
layers(17 - 22 km and 23 - 25 kin). When compared made also with calculated equilibrium saturation HNOa-
with a previous rocket-borne dropsondemeasurementof concentrations,
theMPIK [Schlager andArnold,1990](seeFigurelc), the (b) Comparisonof presentdata with the condensed-phase
presentdata are in excellentagreement,exceptfor the de-
pletionlayers. The depletionlayersobservedin the present
measurernentmaybe dueto: (a) localcondensation with
resultingNAT-aerosols
still beingpresent;(b) denitrifica-
tion by previous sedimentationof nitric acid containing
aerosols;
(c) horizontaltransportof Mr poorin nitric acid
from lower latitudes.
Cause(c) seemsto be unlikely,considering
the ozone-
data [Hofmannet al., !990]. Cause(b) cannotbe en-
tirely excludedbut seemsto be unlikely, at least, for the
upper depletion layer, since no nitric acid excesswas ob-
servedbelowthat layer. Cause(a) seemsto be the rnost
likely explastationas will be discussedin the following:
Figure 2 showsthe altitude profile for the ambient gas
temperature measuredon the balloon of 31 January. I•
is characterized
by a thick layer with T < T(NAT) ex-
tendingfrom about16.5to 25 kin. The T(NAT) profile
alsogivenin Figure 2 was calculatedas mentionedabove.
Alsogivenin Figure2 is an altitudeprofilefor T(ICE).
The largestnegativevaluesfor AT = T(NAT)- T of up
to about -4 to -6 are reachedwithin two distinct lay-
ers around 23 - 25 km and 19 - 22.5 kin. Interestingly,
theselayers match the observednitric acid depletionlay-
ers(seeinsertin Figurelb) stronglysuggesting
cause(a)
to be responsiblefor the depletionlayers. Independent
108 109 10TM 1011
HNO
3 NUMBERDENSITY
(cm-3)
Fig. 1. (a) Measuredconcentrationsof gaseous nitric acid.
Also given for comparisonis a monthly and zonally av-
eraged (January, 70øN) nitric acid profile rneasuredby
LIMS (Limb ScanningInfrared Monitor of the Strato-
sphere)in 1979 [Gille and l{ussell,1984].Comparisonis
[1tNOa]Ev,with respectto NAT.
nitric acid concentration inferred from the aerosol mea-
surements, which took place 23 hours later in a very
similar stratosphericmeteorologicalsituation.Insert gives
AT = T(NAT)- T (curve1:00.15LT; curve2:23.25 LT).
(c) Comparison
of the presentdata with previouswinter
arctic measurementsof the MPIK Heidelberg.For details
seetext. Insert as (b).
strong support of this view comesfrom the balloon-borne
aerosol-countermeasurements,alsoperformedon January
31, 1990(23.25LT) (seeaccompanying paper[ttofmannet
al., 1990]). By that time the stratospheric
temperatures
above Northern Scandinavia were still similar to those of
the MS-flight(seecurve2 of Figure2), althoughthe local
temperature maximum around 22 km had disappeared,re-
suitingin a singlecold layer. Assumingthat the observed
aerosols[ttofmannet al., 1990] were NAT-aerosols,the
concentration of conaens•d-ph,se nitric cid ([ttNO3]AE)
can be estimated(seeFigure lb). It is roughlyconsis-
tent with the [I-INO3]AEinferredfrom the gaseous nitric
p,om ([ItNO]x =
both the MS- and aerosol measurements show that only
about 40 - 60% of the available nitric acid were incor-
porated into aerosols. By contrast, the equilibrium sat-
 Schlager
etal.'Nitric
Acid
Aerosol
Formation
intheArctic
Stratosphere 1277

30
f.....
25I I I I ':::
'• kx• T(NAT)
..'20
<C ...

15

185 190 195 200 205

TEMPERATURE (K)
Fig. 2. Atmospherictemperaturesmeasuredon the two
balloonflightsof 31 January,1990(curve1:00.15 LT;
curve2:23.25LT). Alsogivenarethresholdtemperatures
for the existenceof NAT- and water ice-aerosols.For details
see text.

urationHNO3-vapour
concentrationwithrespectto NAT,
(HNO3)Ev(alsoshownin Figurela) is muchsmaller
than
the measured
(HNO3). It seems that depletion
occurred
onlyin layers,whereT wasmarkedly
belowT(NAT),
or wherethe supersaturation, SA, of gaseousnitric acid
with respectto NAT was largerthan about 10. Proba-
bly a condensation/evaporation-equilibriumhadnot been
reached.Thecooling probablywastoorapidcompared to
condensational depletion.The latter process has a time
scalebeingmainlydetermined by the fractionf of pre-
existingactiveCN, temperature,and the condensational
stickingcoefficient,
a, beinglessthan 2 hoursfor f = 1
anda = i (cf. [Arnold,1990]). Sincethe aerosol data Fig. 3. Temperature mapsforthe30 hPa(a)- and50 hPa
implythat f wasin fact aboutone,a substantial decrease (b)-pressuresurfaces alongwithgeopotential heightcon-
of gaseousnitric acidwouldbe expectedto occurwithin tours(dottedcurves;trajectories of the air massesencoun-
lessthantwohours.Hence it seemsthatin theairparcel of tered by the balloon follow,very approximately,the dot-
interest
condensational growthofa majorfraction ofpreex- ted curves and the distancebetween the dotscorresponds
istingaerosols
startedonlywithinlessthantwohours
prior to an averageairparceltravel time of 6 hours;the arrow
to theencounter.
Otherwise,the depletion
wouldbe more marksthe directionof airparcel
motion),crossing
North-
pronouncedthan observed.By comparison, for f = 0.001 ern Scandinavia.
The northpoleis markedby a cross.The
and a = i the time scale would be about 24 hours. For thicksolidcontourmarksthethresholdtemperaturefor the
an a being smallerthan one these time scaleswould be existenceof NAT-aerosols.
The meteorologicaldata were
correspondingly larger.Hence,an alternativeexplanation provided
by theF•eeUniversity
of Berlin(K. Labitzke,B.
may be a larger f but smaller a. Naujokat,
and K. Petzold,
personalcommunication)'.
An inspection of themeteorological
situationon31
uary,1990at the30hPa-and50hPa-pressure levels(cor-
responding
toapproximately 19and23kmaltitude) (Fig- taken place within lessthan about 2 hoursbeforethe en-
ure3) revealsthat the airparcel
encounteredby the bal- counter,whichwould correspondto a temperaturearound
loonunderwent rapidlarge-scalesynoptic
adiabaticcool- 189 - 188 K. From the aerosolmeasurements of 31 January
ing. Around30 hPa, for example, the airparcelcooled in the coldlayer around22 km a total aerosolsurfacearea
withinabout20 hoursfromT(NAT) = 193K to 188K. densityof about5 x 10Scm 2 percms is estimated implying
Thusevenforf beingassmallas0.001,substantial
conden-a condensational lifetime of a gaseousnitric acid molecule
sationaldepletion
shouldbe expected,leading,however,of about 70 minutesfor a = 1. By comparison,a very sim-
to muchlargerandfeweraerosolsthanobserved [Arnold,ilar meteorological situationon 18 January,1989,but with
1990].Thereforeanalternative
viewmaybethattheob- AT beingonly -2 to -3 degrees,did not lead to condensa-
served
depletion
occurred
onlyshortlybeforetheencounter riohal depletionof gaseous nitric acid,aswasfoundfrom an
andwaspossibly inducedby activationof a majorfraction MS-measurement of the MPIK-Heidelberg[Arnoldet al.,
of the preexisting
CN. If so,this activationseems
to have 1989;Arnold,1990].On that day the periodof time, dur-
12 7 8 Schlageret al.: Nitric AcidAerosolFormationin the Arctic Stratosphere
ingwhichtheairparcel's
temperature
wasbelowT(N•T)
prior to the encounter,
wasalsoabout20 hours[Arnold,
1990]. Henceit seemsthat on 31 January,1990the lower
temperatures (AT = -4 to --6) weredecisive
in inducing
condensationaldepletionof gaseousnitric acid. If so, this
suggeststhat activationof most CN was inducedby the
lower temperaturesabout two hoursprior to the encounter
(at AT =--3 to-4).
Since numerous NAT-aerosols were formed, the above
cooling event should not induce significant sedimenta-
riohal denitrification. The sedimentationvelocity for NAT-
aerosolswith a radiusof 0.5 pm is only about 20 m per day,
around 20 km altitude.
Summary and Conclusions
The presentballoon.borne measurements of gaseousni-
tric acid and aerosols in the winter arctic stratosphereob-
servedlocal nitric acid condensationin an airmass,which
underwent rapid, large-scalesynopticcooling by about 5
degreesper day. At the time of encounterthe airmass
had cooledto 4- 6 degreesbelow the thresholdtempera-
ture for NAT-aerosolexistence.Interestingly,it seemsthat
substantialnitric acid condensationstarted only after the
airmasshad cooledto about 3 - 4 degreesbelowthe thresh-
old temperature, after a supersaturationof about 10 had
been built up. It is conceivablethat activation of a ma-
jor fraction of the preexistingCN took placeonly at large
supersaturation.Only after activation of most CN a rela-
tively rapid condensational depletionof gaseousnitric acid
may haveoccurred,and only if the condensational sticldng
coefficient,a, is closeto one. We concludefrom our mea-
surementsthat activationof most CN probably took place
at a supersaturationaround 10.
Acknowledgements. We thank G. Olson,J. Hereford, H.
Sauer,V. Wieder, H. V;Smel,and the personnelof Esrange
andDLR (Moraba)for helpin the project. We areobliged
to K. Labitzke,B. Naujokat,and K. Petzold(l•ee Uni-
versityof Berlin)for providingthe stratospheric
weather
maps.This projectwaspartly fundedby BMFT and NSF.
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(Received June 4, 1990;
revised July 16, 1990;
accepted July 20, 1990)