JOURNAL OF GEOPHYSICAL

RESEARCH, VOL. 103, NO. D9, PAGES 10,961-10,974, MAY 20, 1998

Sea-saltaerosolin coastalAntarctic regions

D. Wagenbach,F. Ducroz, R. Mulvaney, L. Keck, A. Minikin, TM 2 3

M. Legrand, J. S. Hall, 3 and E. W. Wolff 3 2

Abstract. Continuous year round recordsof atmospheric sea-saltconcentrations have been recovered three coastal at Antarctic stations(Halley, Dumont D'Urville, and Neumayer) at temporalresolutions typicallybetween1 day and 2 weeks.The recordswere evaluatedin terms of their spatialand seasonal variabilityas well as with respectto

chang in the relativeion composition airbornsea-salt es of particles. Annualmeansea-salt

concentrations between ngm-3 at Dumont vary 1400 D'Urville, ngm-3 at Neumayer, 850 and200ngm-3 at Halley, respectively. arethus They considerably thanthemean lower
levelspreviouslyobservedat the north tip of the Antarctic Peninsulabut are, at their lower end, comparable the level previously to reportedfrom Mawson.The representativeness the atmospheric of sea-saltdata appearsto be weak due to their high temporalvariability,strongimpactsof site specific aspects (suchas site topography)but also due to the nonuniformsamplingtechniques applied so far. In accordance with the ice core evidence,the seasonal changein the atmospheric sea-saltload is found to be clearly out of phasewith the seasonal cycleof the open water fraction offshorefrom the station as (with the exception Dumont D'Urville) the lowestconcentrations generally of are observed during the local summermonths.Major ion analyses bulk aerosoland of

concurrently sampled snow fresh show strong, a systematic depletion theSO]- to Na+ of
(C1-) ratioswith respectto bulk seawater, which appearedto be confinedto the local

winter year.During half thattime,sea-salt SO]- wasfound be depleted to typically by

60-80% along with a concurrent + deficit, Na whichis in accordance the precipitation with of mirabilite. significant No fractionation Mg2+, K+, andCa2+ between of seawater and sea-salt particles observed. is Laboratory experiments to simulate SOfailed the
fractionationin airborne seawaterdropletsor in the skin of seawaterbubblesat low air

temperatures. gave, They however, SO]- depletion factors, similar thefieldobservation to

in air and snow,in the remainingbrine of seawaterwhich was partly frozen below -8C to an artificial sea ice surface.It is suggested therefore that the mobilization of brine from the sea ice surfaceconstitutes important sea-saltsourcein winter which may dominate an the atmospheric sea-saltload at high latitudes of coastalAntarctica.
HBr [Mclnnes et al., 1994; Mozurkevich,1995], but also of reactive halogens[Vogt et al., 1996], to the remote marine Sea-salt particles produced by bubble bursting and wave troposphere. the contextof the Antarctictroposphere, In seacrest disruptionsprovide by far the largest flux of primary salt particlesare the only primary aerosols producedin releaerosolparticlesto the marine atmosphere. The supramicron vantquantities withinthe southpolarcell.They mayaddtherefraction of the marine aerosolbody is controlled therefore by fore a substantial fraction of seawatersulphateto the more this oceanic source leading to boundary layer loads around interestingdimethyl sulfid derived sulphateinventory of this 2-50 tzgseasaltper m3 which varystrongly a function as of region. This contributionhas to be estimated accuratelyvia wind speed[Fitzgerald, 1991]. Interest in atmospheric sea-salt other seawaterspecies. Further interest in Antarctic sea salt particles was recentlyreneweddue to their potential contribu- comes about since the Antarctic NHx, level is normally extion to the indirectradiativeforcingILarhamand Smith,1990], tremely low [Legrandet al., this issue].Sea salt thus provides as well as from their role in a series of heterogeneousair during modern times the only important alkaline counterpart chemicalprocesses responsible large fluxesof HC1 and to the otherwisedominatingacidic componentsmade up by as for
1. introduction

non-sea-salt (NSS)biogenic SO42-, methanesulfonate (MSA),

1Institut Umweltphysik, fiir University Heidelberg, of Heidelberg, and HNO 3. When sea-salt particlesbecomeexternallymixed Germany. with these species [Parungo al., 1986], additionalpathways et 2Laboratoire Glaciologie Gdophysiquel'Environnement mayexistto carrybiogenic de et de du sulphur andnitratedownto the ice
3British Antarctic Survey, NaturalEnvironment Research Council,

sheetsurface[Moseret al., 1990]. A relativelylarge data set on the sea-saltcontentof modern Cambridge,England. and pastAntarcticprecipitation been recovered has from var4Now AlfredWegener at Institute PolarandMarineResearch, iousice core studies[Legrand for and Delmas,1988;Clausen and Bremerhaven,Germany. Langway,1989;Delmasand Legrand,1989]. The clear ice core Copyright1998 by the American Geophysical Union. evidence for higher sea-salt levels during glacial times was generallyinterpretedas indicatingan intensifiedsea-saltproPaper number97JD01804. 0148-0227/98/97JD-01804509.00 ductionassociated with highercyclonic activity(higher stormFrance.

Centre National de la RechercheScientifique, Martin d'Hares, St.

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WAGENBACH

ET AL.: SEA-SALT AEROSOL

IN COASTAL ANTARCTIC

REGIONS

decreasethe influence of the very local sea-saltsource.For example,the ice shelf fetch for the most frequent easterly windsat NM maybe as low as 6.5 km, whereas goingeastward from Halley, no regionalice edge is reached. DDU differs considerably from the situationof the two ice sea-salt concentrations that would be needed to corroborate shelf stationsin being placedon a small island 1 km offshore these pictures are, however, sparse.Discontinuousrecords from the coastlineand in being subjectto strongmeridional from South Pole over the years 1979-1983 are the only such downslopewinds throughout the year (mean annual wind data from central Antarctica and were extensively used to speed -9.5 m s-). For a detailed description the site,see of study the episodicintrusion of maritime air massesto the Legrand al. [thisissue]. et Because its positionat 66S the of in and a smallermaxplateau [Bodhaine al., 1986]. At coastalAntarctica,where Pacificsector,a longer open water season et the sea-salt source of the polar ocean is seen much more imum seaice extent is seenat DDU in comparison HB and to strongly, records exists backto 1983at Neumayer[Wagenbach NM. Hence the general conditionsfor aerosol samplingat et al., 1988]andbackto 1987at Mawson[Prospero al., 1991]. DDU are quite similar to those at Mawson (Indian Ocean et They are supplemented shorter observations the tip of sector)where aerosol-chemical by at recordswere previously obyears. the Antarctic Peninsula[Savoieet al., 1993] which are, how- tained by Savoieet al. [1993] over several Aerosolcollection was achieved HB and DDU by continat ever, lessrepresentative the marginalice sheetregions. for As reviewedby Wagenbach [1996],no conclusive picturecouldbe uouslow volume sampling usingopen-facefilter holdersproderived so far from these records on their link to the annual tectedby a wind shield.In contrastto NM, no interruptionof seaice cycle,makingthe principalsourcearea responsible for the sampling procedure related to wind direction or wind highly elevated sea-saltconcentrations during winter essen- speedwas applied here. At NM, aerosolsamplingwas pertially unknown.Furthermore,there is still a serious uncertainty formed in a specialclean air satellitestationas described by aboutthe occurrence and the underlying process leadingto the Wagenbach al. [1988]with no major changes et exceptthat the enormousdepletionof sulphatein airborne sea-saltparticles station was moved in 1992 8 km to the southeast and that a seen in aerosol and precipitationat almost all coastalsites newly constructedclean air station was establishedthere in [Legrandand Delmas, 1985; Ivey et al., 1986; Gjessing, 1989; 1994 essentially applyingthe samesampling technique.On the Mulvaneyand Peel,1988;Wagenbach al., 1988;Minikin et al., basis the differentsampling et of methods outlinedin Table 1, the 1994]. In a collaborative effort the aerosolchemicalobserva- followingsystematic effectsmay be importantin assessing the of at tions at Neumayer(NM) have been extendedto the stations comparability the sea-saltloadsobserved the three sites: 1. Becauseof the relatively large geometric mean mass Halley (HB for Halley Bay) and Dumont D'Urville (DDU) in aerosolof the order of 10 order to increase spatialcoverage suchobservations the of and diameterof locallyproducedsea-salt to deducea detailed picture on the link betweenatmospheric m [O'Odowed al., 1997],the particlecutoffof the air intake et and glacio-chemical changes [Wolffetal., thisissue (a)]. In this systemscritically controls the observedsea-saltload. Since paper the atmospheric sea-saltrecordsrecoveredat thesesta- isokineticsamplingcould not be applied, sea-saltconcentrations will be discussed mainly in terms of their spatial and tions are expectedto be generallyunderestimated, especially At ventilated seasonal variabilityas well as with respectto the apparent duringhighwind speeds. NM (wherean actively sulphate fractionation observed betweenairbornesea-salt par- high volumestackoperates a kind of virtual impactor)the as ticles and seawater. particle cutoff diameter is empiricallyestimatedat around 6 m suggesting that the large sea-saltparticle mode is not completelysampled.

iness)overcompensating muchlargerseaice extentduring the that time [Petitet al., 1981]. Similarly,the sea-salt variability over the last 200 yearshas been attributedby Peel and Mulvaney [1992] to concurrentchangein the regionalsea ice and circulation pattern. Year-round observations atmospheric of

2.

Sampling Sites and Methods

2.

No such information

is available for the HB and DDU

A general overview of the climatologicalsituation at all three sitesunder investigation givenby K6nig-Langlo al. is et [this issue].Samplingtechniques and analyticalmethodsused by the differentgroups involvedare summarized Wolflet al. by [thisissue(a)]. In the followingsection, onlya brief outlineof theseaspects presented, is concentrating detailsrelevantfor on the sea-saltcomponent the Antarctic aerosolbody.In Figof ure i the geographical locationsof the stationsare shown togetherwith a zoomedview of their positionrelative to the (mean) coastline and the prevailing wind direction. Detailson the site specific sampling and analytical techniques sea-salt for aerosol are given in Table 1.
NM and HB which are both situated on ice shelves of the

open-face samplingsystems, but the much lower filter face velocityappliedhere (if compared the NM sampling to head) suggests evenlower cutoff diameter,especially an duringhigh wind speedevents. all three sites,aerosolscavenging the At in near-surface layerby driftingsnowmightfurther contributeto the underestimation the ambientsea-salt of level.Beingmainly dependent the site specific on snowdrift frequency(e.g., 40% at NM), this effect is expected be lessimportantat DDU to (island position), especiallyduring summer. On the other hand,for a givencomparable snowdrift situation,NM data are least affectedsincethe air intake is placedat 7-9 m abovethe
snow surface instead of 2 m at the other sites and since the

Atlantic sectorare subjectto a similar surfacewind pattern dominatedby zonalwindsmostfrequentlyfrom easterly directions. Apart from the lower mean annual wind speedat HB

pumpsare automatically switched during heavysnowdrift off periods.This fractionatingsampling NM providesthe most at
obvious difference from the otherwise continuous collection

modesat HB and DDU because situations with extremely high (6.2 m s- versus m s- at NM), the following 8.9 maindis- or lowwind speeds well aswith northerlywinds(puttingthe as tinguishing featuresmay be relevantfor the local atmospheric samplingsite downwindfrom the main station) are a priori sea-salt load as (1) the more southerly positionof HB (by 5) excluded. leadingto a shorterand delayedopenwater season well as as Laboratoriesin chargeof the designof the collectionprowere the BritishAntarcticSurvey to a relativelyhigh seaice fractionduringsummer and (2) the cedureand sampleanalyses generally larger distanceto the ice edge at HB which may for HB, the Laboratoire de Glaciologieet Gophysiquede

WAGENBACH ET AL.: SEA-SALT AEROSOL IN COASTAL ANTARCTIC REGIONS

10,963

HB5

Ice Shelf
Ice Sheet

Atka Bay

...

GVN

NM

Ekstrmm Ice Shelf

) . 1'0 km

DDU

Figure1. Position sampling in coastal of sites Antarctica year-round with chemical aerosol records. Lines
overoceanareasindicate 50% seaice coverage the duringwinter (dash-dotted lines)and duringsummer

(dotted lines), respectively (adopted Giovinetto Waters from and [1990]. referring this Sites to work shown are in detail respect their with to coastline topography main and wind direction (arrow). GVN denotes former the Georg Neumayer von station, isthe1991 HB5isthe1992 HB4 and sampling at Halley sites Bay, DDU and
is the Dumont D'Urville station.

procedure (typically than _+5% at all sites) less l'Environnementfor DDU, and the Institut ffir Umweltphysik matography for NM. The precision thesea-salt of determination calculated since the filter blank contributioncould be neglectedhere.

localK+ andCa contamination soilparticles 2+ by viaionicseawater species + or C1- aremainly Na controlled Although at droppings occur DDU, sea-salt at concentrations DDU and NM by the analytical uncertainty the ion chro- frompenguin of

Table1. Sampling Analyses and Methods Atmospheric of Sea-Salt Species theCoastal at Antarctic Stations Dumont
d'Urville, Halley, and Neumayer
Dumont d'Urville Halley Bay Neumayer

66S, 140E
Observational period
Collection interval

75S, 26W
Feb. 1991 to Feb. 1993
March

70S, 8W
1983 to Jan. 1996

Jan. 1991 to Dec. 1995

1-7 days
1.8 m above snow level

1-2 days
2 m above snow level

3-20 days(typical2 weeks)

7 m above snow level

Sampling system Air intake height

Aerosol filter

47 mm , 0.4/xm teflon open face

0.6 ms -

37 mm , 0.8/xm cellulosemembrane open face

0.4 ms -

240 mm , double cellulosefilters

in line

Filter face velocity Analyzedsea-salt species

and methods

1.1ms -a

Na+, K+, Mg2+,Ca 2+, SO42-, Br-' CI-,

ion chromatography

2+, 2+, CI-, Na+, Mg2+b:flameatomic absorption, Na+,K+, Mg Ca SO42-, Br-: ion chromatography so4-:
ion chromatography

aCorresponds 13% of air intakevelocity. to bCations available 1991only. for

10,964

WAGENBACH

ET AL.' SEA-SALT AEROSOL

IN COASTAL ANTARCTIC
lOOO

REGIONS

derivedvia Na + or C1- are shownto be unaffected such by events[Ducroz,1996].At HB, due to the relativelylow sea-salt level and the shortsampling intervals,the filter blank variability was found to be substantial, leading to 15% of samples

800
600

HB

falling below meanC1- detection of about ngm-3 the limit 8

C1- (defined as twice the standarddeviationof C1- blanks). For all sitesthe extractionefficiency the filters for seawater of ions is very closeto 100%; hence no corrections were applied. Again, a 100% collectionefficiencywas assumed HB and for
DDU membrane filters. At NM the double Whatman filters

400 200
0 6OOO

arrangedface to facewere individuallyanalyzedto correctfor particlepenetrations the first filter) whichwere foundto be (of around 10% exceptfor filters occasionally wetted by snowor
rime.

4500

I I

DDU

3000

I I

3.

Atmospheric Sea-Salt Records

1500
I I

In view of the very different sampling intervalsrangingfrom 1 day at HE, up to 7 daysat DDU, to typically2 weeksat NM, the continuousraw data of each site were formally collapsed into continuousseriesof 10 day meansmaking their temporal variabilitymore comparable. HE, C1- wasusedto infer the At sea-saltconcentrations sincecation analyses were availablefor 1991 only. At DDU and NM the commonlymore conservative

' I , I,

I,

I,
i NM

3OOO

2000

Na+ (seesection wasused 2) instead. Na+ andC1- data, The

respectively, are then expressed sea-saltconcentration as via the bulk seawater (ESW) content given by Witson [1975]. Where possible, references all made to other Antarcticsea-salt

1500
500

I I

data are basedon Na+, or alternatively C1-. To makethe on

atmospheric observations comparable possible ice core as as to results,mean concentration valuesare givenin the text generally as arithmetic means.
3.1. Intersite Variability

ooo ,
1991 1992

1993

1994

1995

1996

Atmosphericsea-saltrecordsover the years 1990-1995 are displayedat 10 day means for all three stationsin Figure 2. Common to all sites is the relatively high sample interval to sampleinterval variabilityoccurringthroughoutthe year (for details,see descriptive statistics 10 day meansgivenin secof tion 3.2). This behaviorof the atmospheric sea-saltsignalis seen also at other Antarctic stations[Savoieet at., 1993] includingSouthPole [Bodhaine al., 1986].It is expected et therefore that the episodicpropertiesof this signalmay be driven both by rapidly changingproductionrates and by varyingatmospheric transportsituations. The obviousdifferences the in
coastal records are the much lower mean level at HE in com-

Figure 2. Atmosphericsea-saltrecordsdisplayedas 10 day means for the overlapping sampling periods at Halley Bay (HE), Dumont D'Urville (DDU), and Neumayer(NM).

parison to the more similar ones of NM and DDU, and the outstanding summermaximumonly seen at DDU. The latter finding may be explainedby the unique islandpositionof this samplingsite, generallynot more than some100 m downwind from open water during December to March. The missing 1994/1995summerpeak supportsthis view sinceduring that seasonexceptionallysevere sea ice conditionsprevailed at
DDU until midsummer.

The relatively sea-salt low levelat HE of 200ngm-3, falling

below the respective meansat NM and DDU by a factor 4.4 and 7, respectively (see Table 2), is more difficult to explain, however. In contrastto the other sites, no vast open water areas exist offshorefrom HE during summersuggesting that ng The the differenceto NM and especially DDU during that sea- 200 ng m-3 at HB to 10,000 m-3 at MarshStation. to
son is due to a reduced local sea-salt source. However, similar

encesin the local openwater fraction are expected. Referring to the site climatologies givenby K6nig-Langto at. [this iset sue],NM is subjectto a 20% frequency blowingsnowdays of (i.e., heavysnowdrift aboveeye level), whereasonly 6% are reported for HB, respectively. This might explain part of the discrepancy compared the NM sea-salt to level asconnected to a differencein cyclonic activity.On the other hand, the sea-salt observations 1-2 day intervalsat HB are not significantly at correlated with the localwind speedand show,instead,that the very highestsea-saltconcentrations occureven duringmoderate winds.As addressed section2, the muchlongerice shelf in fetch during onshorewinds at HB (confinedhere to westerly oneswhich are relativelyweak and lessfrequent) may be one importantreasonfor the muchlower sea-salt concentrations if comparedto NM. However, sinceat both stations virtuallythe samesea-salt levelsin fresh (surface)snoware observed, also differences the aerosolsampling in systems (described secin tion 2) may be responsible the intersitediscrepancy. for Inspectionof the geographical distributionof the mean atmospheric sea-salt level in Antarcticasummarized Table 2 in (in comparison with relevantice core data) revealsa rather large spatialvariabilityamongcoastalsitescoveringa rangeof
latter value is difficult to assess, however, since no details on

intersite sea-saltgradientsbetweenHE and NM or DDU prevail duringthe whole winter season when no suchlarge differ-

the sampling site and collectionprocedureare givenby Savoie et at. [1993].It wouldbe hard to predicta typicalatmospheric

WAGENBACH

ET AL.' SEA-SALT AEROSOL

IN COASTAL ANTARCTIC

REGIONS

10,965

Table 2.

GeographicalDistribution of Mean Sea-Salt Concentrationsin CoastalAntarctic

Air and Snow

Snow, g- g
Site, Elevation, Distance to Coast, Air,

S
Weddell Sea sector

m asl

km

ngm

-3

Surface Snow

Firn Cores

Halley (75) 10 Ronne Ice Shelve(77-81 ) -80 BerknerIsland (79) 700-900

Atlantic sector

15 50-200 50-150

200 -.. .-.

1.4 a

1.7 a

..
.. 1.7 .. ..

1.6_0.7b
1.9_1.0 c 40 e 2.0 e 0.5_0.2 e

Neumayer ) (70
Ekstr0m Ice Shelve(-71 ) RitscherHochland(-79 )
Pacific sector

<42
<100 -1,000 5 270

10
30-100 200-300 <1 4

850 d
.-. ... 1,400 ...

Dumont d'Urville (66) D10 (66)

Other stations

90f
...

...
0.8 g

Mawson ) (68 Palmer ) (65 Marsh ) (62

SouthPole (90)

<1

coastal site coastal site

2,800 >1,500

330 h 3,900 h 10,000 h

62g
.. 0.03i

Surfacesnowdenotesfresh snowsampledconcurrentlyto atmosphericobservation. aWolffet al. [thisissue(b)].

bMinikin al. [1994]. et

CWagenbach al. [1994]. et
dRefers to 1983-1995.

eMoser[1991].

fDucroz [1996] (sampled during winterseasons only).

gLegrand al. [this issue]. et

hSavoie al. [1993]. et iTuncel al. [1989]. et

sea-salt concentration eachspecific for site from their position relativeto the relevantlarge scalephenomenaalone (suchas sea ice edge, main storm tracks,or regionalwind systems) if the verylocal situationhasthe major controlon the occurrence of high sea-saltevents.There are severalexamplesfor such local impacts:DDU and Mawson, althoughexperiencing similar downslopewinds, differ by a factor of 4 in their mean wintersea-salt level(seealsothe discrepancy betweenNM and HB addressed above). Similarly, concurrentsamplingsperformedon the DDU archipelago km apart by Ducroz [1996] 3 showsystematic sea-salt concentration differencesin the range of a factor 2 over a 6 week period in January.There are also doubtson the spatialand temporalrepresentativeness the of atmosphericobservations given the extremely high sea-salt concentrations the snowpack at NM (reflectingsaltydrift in

snow advectionfrom the upwind Atka Bay) and in surface snowat DDU aswell as the high temporalvariabilityindicated in Table 3 by the arithmetic mean to median ratio. The geometric standard deviation of the raw sea-salt data are 2.5 at

NM and DDU and 3.5 at HB which translatesto a rather high episodicity, showingthat roughly 10% of the highestconcentrationsexplainasmuchas30% of the total sampledsea-saltat NM and DDU and even 50% at HB. There is no surprise therefore that generalcirculationmodelsfailed to simulatethe present mean sea-salt concentrationand its seasonalcycle within the coastalAntarctic boundarylayer [Genthon,1992]. At least, where sea-saltrecords are available in daily resolution, local and large scale effects might be disentangled throughsynoptic analyses. The comparability betweensiteswill remain weak, however, until the sampling procedures are

Table 3. DescriptiveStatistics 10 Day Mean AtmosphericSea-Salt Concentrations of

Dumont d'Urville a Jan. 1991 to Dec. 1995 Annual Mean n Arithmetic s.d. 146 1360 1000 Annual Mean 71 200 180

HalleyBay b
Feb. 1991 to Feb. 1993

Neumayera
March Annual Mean 431 860 780 1983 to Jan. 1996

Summer

Winter

Summer

Winter

Summer

Winter

mean

36 2100 1570

33 1060 440

16 160 140

18 330 240

100 580 570

112 910 660

25%quartile
Median

790
1060

900
1750

810
990

70
140

40
70

150
240

340
630

230
350

470
690

75%quartile
Mean/Median

1600
1.28

2730
1.20

1300
1.07

260
1.43

290
2.29

490
1.38

1100
1.37

700
1.66

720
1.32

Sea-salt concentrations in ngm-3. Summer are refers November-April, to winterrefers May-October, denotes to n number datavalues, of
and s.d. is arithmetic standard deviation.

aCalculated from Na+.

bCalculated from C1-.

10,966

WAGENBACH ET AL.: SEA-SALT AEROSOL IN COASTAL ANTARCTIC

REGIONS

Firn Core

IO

HB

sea-salt maximumat HB and NM occurs duringthe winter half year which is also observedin the atmosphericrecords at Mawson[Prospero al., 1991]and SouthPole [Bodhaine al., et et 1986], as well as in almost all seasonally resolvedfirn cores [Mulvaney and Peel, 1988;Mosley-Thompson al., 1991;Miniet kin et al., 1994; Wagenbach al., 1994]. No seasonalcycles et were reported,however,for Palmer and Marsh [Savoie al., et 1993]lyingfar north closeto the tip of the AntarcticPeninsula. For the mid to high latitude southernhemisphere, Ericksonet al., [1986] predict from analyses wind speeddistributions of also a rather low winter to summer ratio in the sea-saltproductionrate (lessthan two betweenthe midwinter and midsummerperiods). The seasonal pattern at HB and NM is mainly driven by the low concentration levelsduring the summer monthswhich may be underestimated the HB data by in roughlya factorof 1.4 sinceseasaltwascalculated C1- (see via C1- losses discussed section4). Comparingthe mean arithin metic sea-salt concentration the midsummer J, F) with of (D, the midwinter months (J, J, A) given in Table 3, winter to summerratiosof 1.6 at NM and up to 2 at HB are obtained.A
further difference between the midsummer and midwinter sea-

salt situationis clearly seen at all three stationsin the higher variability of the 10 day means (expressed the mean to as medianratio in Table 3) duringsummer. This seasonal difference may reflect the proximityof open water during summer making it easier to produce extreme sea-saltpeaks during favorablehighwind speedepisodes. the basisof the station On climatologies described K6nig-Langlo al. [thisissue] by et there is no substantialchangein the surfacewind regime over the year at all three stationsand only a slight tendencyfor lower meanwind speeds occurat HB and NM betweenDecember to and February. Such a weak decreasein the storm activity NM during these months may not explain, however, the relative sea-salt minimum in the annualcycleregularlyappearingduring the open water seasonat NM, HB, and Mawson. Hence, except for the peculiar situation of DDU, the proximity of o 1.0open seawaterareasduring summeris not seenin the atmo0.5sphericsea-saltrecordsnor in firn cores of coastalregions. This posesquestionsabout the sea-saltsource,responsible 0.0 duringthe winter seasons shortterm (1-2 day) peaksregfor --3 ularly seen at HB and DDU in the range of some g m Jan Apr Jul Okt Jan Apr although seaice coverage well developed. the is Thesesources, finally leading to winter sea-salt maximum concentrations, Figure 3. Mean annual sea-saltcycle at Halley Bay (HB), Dumont D'Urville (DDU), and Neumayer(NM) displayed as wouldhaveto overcompensate reducedoffshoreopenwathe monthly means and normalized to grand averageconcentra- ter area,aswell asparticleremovalduringlongrangetransport tionsover the observational periodsshownin Figure 2 (except overthe seaice.The following potentialsources the winter for for Neumayerrepresenting period 1983-1995).In the top sea salt may be considered: the panelthe normalized meansea-salt cycle observed overthe last 1. Coastalpolynyas transiently openedby strong windsand 25 yearsin the firn core D 235 of the easternRonne Ice Shelf ocean currentsmay provide a local source,which, however, [Minikin, 1994] is shownfor comparison. cannotexplainthe hugepeaksseenin winter snowlayerseven 500 km southor at elevations around1000m asl (seeTable 2 therein). clearlycharacterized and homogenized. this context,a well- and references In 2. Leads responsiblefor an open water fraction in the defineddissection into a large and small sea-salt particle fraction by cyclon or (virtual) impactor stagesmay be recom- winter sea ice cover in the range of up to some 10% should mendedin future campaigns. Quantificationof the large sea- showa much weaker specificparticle productionrate due to salt fraction during snow drift episodes will remain the reduced wind fetch over water. On the other hand, an troublesome,however,due to its size distributionpartly over- increasedproductionof spume drops may be expectedfrom the surf zones prevailing at the rim of leads and ice floes lappingwith the size of blowingsnowcrystals. alreadyunder moderatewind speeds. 3.2. Seasonal Cycle 3. Puttingthe major sea-saltsourceduringwinter north of As shownin Figure 3, the mean annualsea-salt cycleseenat the sea ice edgewould require a much more efficientmeridiall three stationsis relativelyweak, if the distinctsummerpeak onal transport in the surface layer or an unrealisticallyinat DDU arisingfrom local seasprayis disregarded. The annual creasedproductionrate by bubble bursting.The scalelength
_
_

DDU

WAGENBACH

ET AL.: SEA-SALT AEROSOL IN COASTAL ANTARCTIC

100

REGIONS

10,967

for sea-salt particleremovaldetermined Minikin et al. [1994] by over 600 km on the Ronne ice shelfis around30% per 100km (samefor winter and summer)which can be regardedas a lower limit, due to much lower precipitationthere. Accordingly,the depletionin the atmospheric sea-saltload during a 1000 km transportover (sourcefree) sea ice would be larger
than a factor of 20.

i,

'
:

2O
-

::
:
,

In anycase,a dominating sea-salt sourcenorth of the actual sea ice edge would suggestthat the observedsea-saltlevel should vary broadlyin antiphase with the seaice extentwhich is clearlyin contradictionto what is observed aerosolsamin plesandice corerecords. conclusion, appears In it that noneof the openwater sea-salt sources addressed here mayexplainthe magnitudeand seasonal variabilityin the winter sea-saltload seenat the higher latitudesof coastalAntarctica.
4. Chemical Sea-Salt Fractionation

///,4d,'

DDU NM
HB

I
I

I I IIIIIJ
I I l iillj

I
I

I I IllIll
f I l itlij

I
I

I I IllIll
] I [Jill I

I
[

I I IIIII
I [ l iill

10

100

1000

10000

seasalt[ngrn-3]

Enrichments SO42- depletions halogens respect Figure 4. Expectedrelationship of or of with betweenthe relative uncerto seawaterin marine bulk aerosolare commonphenomena tainty (lo9 in theNSS-SO24 R - calculation Antarctic of winter arisingat remote marine sitesfrom additionalbiogenicnon- aerosolsamplesas a function of sea-saltconcentration. Pure of sea-salt (NSS)SO24contributions fromreaction other analyticaluncertainties 10% (solid line) and 5% (dashed and of which are taken independentof the concenacidicspecies (MSA, HNO3, N205) with the alkalinesea-salt line) are assumed levels identical SO42- Na+ (C1-) analyses. and for and pattioleg re. qnectivelv [Parunnat al__1986] During summer tration
winter level was at months huge a SO42surplus a clear deficit indeed TherealNSS-SO42-raw background data fixed 20ng and C1was m -3. The observed winter sea-salt at Dumont
observedat all three stationsdue to the relatively high atmospheric load of biogenicsulphur[Minikinet al., this issue]and NO- [Wagenbach al., this issue]during that season.Howet

reportedfrom NM [Wagenbach al., 1988] and a slightC1et

ever,during wintera significant SO42deficit(as previously most all data are well below the 100% uncertainty limit in quantifying NSS-SO42winteraerosol concentrations. surplus (relativeto Na+) wasevident all threestations. at No such systematic depletion SO42- bulkaerosol of in samples was
reported from remote marine sitesoutsidethe Antarctic region. In the following section,the emphasiswill be on the
4.1. Chloride Depletion

d'Urville (DDU), Neumayer(NM), and Halley (HB) are displayedin the lowerpanelby bars:25% quartile(left margin), median (centralmark), and 75% quartile (right margin).Al-

calculationof a meaningfuldifferencebetweentotal and sea-

salt SO42- a realistic if lowerlimit of the background NSSSO42depletion phenomenon itsunderlying and processes. SO42levelaround ng m-3 [Minikin al., thisissue] 20 et is
Acid-induced C1- mobilization may occur from airborne sea-saltparticlesor (as a samplingartifact) from sea-saltalreadyaccumulated the filter surface. on During the major C1depletionperiod December to February the typical depletion of the C1- to Na+ ratios withrespect BSW are a factorof 2.3 to at NM, 1.1-1.5 at DDU and ---1.4 at HB. The relatively high NM valuepossibly arises from the muchlongercollection time (1-2 weeks),whereasat DDU, C1- mobilizationis much less likely(although teflonfiltersare used)dueto the highsummer sea-saltlevel and the occurrenceof summer NH 3 concentra-

assumed.Such analyticallimitations are commonlyencountered, however,duringwinter at islandpositions the southin ern midlatitudes[Ayers and Ramsdale,1988],but possibly also --3 at Marsh Stationwhere seasalt maybe higherthan 20/g m [Savoieet al., 1993]. As illustratedin Figure 5, depending the individualseaon

saltcontribution, negative the NSS-SO42- reach may values up to 200ngm-3 in NM aerosol up to some ngg- in a and 100
firn core from the Ronne Ice Shelf. Similar figures are obtained from DDU and HB aerosol samplesas well as from fresh snowat HB and NM. This "apparent fractionation"of

sea-salt SO42between seawater airborne and particles leads to tions up to 5/zg m-3 observed Legrand al. [thisissue] a systematic of by et underestimation the mean annualatmospheric of via (double)mistchamber samplings. C1- depletionat HB NSS-SO42The generally muchlargerthan10%.It maylead, not ishighly uncertain to the lackof sufficient + data.Since however, due Na evento negative grand average NSS-SO24 - values in
generallyno major problem arisesin calculatingthe sea-salt ice coresdrilledrelativelynear the coast(e.g., BerknerIsland, contribution coastal in areasvia Na+, C1- depletions not North Dome [Wagenbach al., 1994]). Furthermore,serious are et
further discussed here.

misinterpretation MSAto NSS-SO42- [Wagenbach, of the ratio

1996;Legrandand Pasteur,this issue]aswell as of an eventual

4.2.

Sulphate Depletion

anticorrelation between NSS-SO42- seasaltin coastal and ice

et A significant SO42-depletion, recognized from negative core records[Wagenbach al., 1994] may be expectedby this NSS-SO42concentrations, first reportedby Gjessing phenomenon. example, was For SO42depletion not considwas

[1984]for firn samples from near the ice edge and by Wagen- ered by Savoieet al. [1993] in evaluatingtheir aerosol data, led high ratios during bachet al. [1988] at NM for winter bulk aerosol.As illustrated which to erroneously MSA to NSS-SO42in Figure4, the negative NSS-SO42values foundin winter winter.Peeland Mulvaney[1992]interpretedthe clearnegative they foundbetween NSS-SO42- C1- in the and aerosol at NM, HB, and DDU cannot be explainedby the correlation

ice of changes although SO42overall analytical uncertainty thecalculation NSS-SO42-:Dolleman corein terms climatic in of to the sea-salt SO42fraction not so highas to preclude is the depletionmighthavecontributedsubstantially the observed

10,968

WAGENBACH

ET AL.'

SEA-SALT

AEROSOL

IN COASTAL

ANTARCTIC

REGIONS

a)

.****

Summer

aerosol

3O0

o Winter aerosol

'..
o

-300

-600 0.00

0.50

1.00

1.50

2.00

Na+[IJg ] m'3

b)
600

Summer
300

snow
snow

o Winter

....

................................................................

-300

-600

O.O0

O.50

1. O0

1.50

2. O0

2.50

3. O0

3.50

4.00

4.50

cr [pgg-]
Figure5. (a) Scatterplot NSS-SO42of (calculated theBSWratio)versus + for thecomplete, via Na raw
aerosoldata set at Neumayer.(b) SameasFigure5a, but for shallow firn coredata usedin Figure3 and C1as BSW referencespecies. Linear regression linesrefer to winter data (associated with the May-September period for the aerosoldate and with approximately midwinterseason the firn core date). the for

coupling.An attempt is needed therefore to get at least a

lated via:

with x denotingthe ionic seawaterreference species(e.g.,

first-order correction NSS-SO42for whichis normally calcu- Na+) andk = [SO42-]/[x] denoting respective seathe bulk
[NSS - SO4 2-]: [SO42-]totalk[x]
water (BSW) ratio. As alreadyappliedfor firn coresof the WeddellSearegionbyMinikin et al. [1994]andfor NM aerosol

WAGENBACH ET AL.: SEA-SALT AEROSOL IN COASTAL ANTARCTIC

REGIONS

10,969

data by Wagenbach [1996], a formal downwardcorrectionof k

0.80

maybe achieved linearregression thewinterNSS-SO42by of dataversus + (alternatively Na C1-) or, less simple andgiving
the maximum correction, determining lowerenvelope by the of the wholedataset.Addingthe obtained(negative) slopeto the

conventionalvalue(i.e.,0.25in the case = Na+) gives k x the

corrected meank valuek' (k' -< k) associated with airborne sea-salt particles. For the NM aerosolexampleshown Figure in 5 the slope is -0.175, and the massratio k' becomes0.075

0.40

(instead 0.25)whichcorresponds a dramatic of to SO42depletionfactorf (definedasf - k/k') betweensea-salt particles and bulk seawaterof 3.3. In the caseof the firn core example (basedon C1-) of Figure 5, f is found to be 5.5. Alternatively, maybe obtainedby requiringthat the cork'
0.00 0.00

k'

O. k(S042'/N1) 10 0.20

BSW

025 I

relationbetween winterNSS-SO andNa+ (or C1-) becomes 4

a minimumwhichis a reasonable assumption coastalsitesat at leastfor high sea-saltconcentrations. This procedure(clearly b)
r 1.00

illustrating artificial the coupling between NSS-SO42- seaand

salt species) can be applied even to more scattereddata sets and may be usedto checkthe regression results.In the caseof the aerosoland firn core data alreadyprocessed above,f becomes4.1 and 5.3, respectively (see Figure 6). Regardingthe relativelylargescatterfor low concentration values,both meth-

0.50

odsare very sensitive the mostnegative to NSS-SO4 data points generallyassociated with high sea-saltconcentrations and tend to give an overestimated fractionationfactor. Also, further shortcomings (de-emphasizing need for a formally the highaccuracy k') are that the procedures rely on a more of still or lesssubjective data dissection into summer and winter valuesand that it is a priori unknownfor what seasons derived the k' are truly representative. Some hintson the seasonal occur-

0.00/
0.00

, ] , ,,

.....
0.05

k'
I

k(S042'/01 ') 0.10

BSW

0 14

rence artificially of reduced NSS-SO42values (conservatively defined being as lower than10ngm-3) at each station be Figure 6. Correlation may coefficient between r NSS-SO4 and drawn from Figure 7, however.At all stations,maximum fre-

quencies the occurrence underestimated in of NSS-SO42con- waterreference ratiok used calculate NSS-SO42to the values
sistentlyemergeduring midwinter.As illustratedin Figure 7, the levelingoff of depletionfrequencytoward the equinoxis

the seawaterreference speciesconcentrationversusthe sea-

with k' indicatingthe absoluteminimum of r: (a) for Neumayer winter aerosoldata shownin Figure 5 with Na+ as ambiguous to a steady due increase biogenic of NSS-SO42- seawaterreferencespeciesand (b) for firn core winter data shownin Figure 5 with C1- as referencespecies. during that period.

To provide common a basein calculating NSS-SO4 conthe Weddell Sea sectorrangebetween6.7 and 3.8 (mean 5 ___ 0.9) in the region up to 600 km inland on the easternRonne Ice Shelf [Minikin, 1994] with no obviousrelation to the ice edge distances and with similarf valuesalso at higher elevationsof Berkner Island.Interestingly, firn coresanalyzedsouth affected volcanic - from MountCerroHudson by SO4 (M. of NM showa decreasing trend with f closeto 3 and 2.5 at 70 Legrand,personal communication, 1997) and 2 yearswith cor- and 160 km distance from NM, respectively, downto 1.4 at the relationcoefficients below0.5, the grandaverage (referring RitscherHochland(1000 m asl,distance km) [Moser,1991; k' 300 to Na+) for aerosol freshsnow and becomes close 0.07.No Trefzer,1992].The reasonfor this pattern is not clear yet, but to attemptswere made at this stageto defineseasonally adjusted might be connectedto the differencein the seaice cycleat this k' values, hence = 0.07 correspondingthesea-salt k' to SO4 sectorif comparedto the Weddell Sea region (see following to Na+ massratio in bulk referencesea-salt particleswas section). normallyappliedin the respective papersfor aerosolaswell as 4.3. Sulphate Fractionation Process for snowsamples throughoutall seasons. TheSO4 depletion factor derived theabove f by procedure Gjessing [1989] suggested reemission (NH4)2SO4,fracof appearsto be almostindependentof the site specific sea-salt tionationduringfog formation., well asfractionation as during level. The value of f is virtually the same for NM and HB freezing of airborne seawaterdroplets as possiblereasonsfor aerosolsamples (4.1 and 3.6, respectively) is significantly the extremely but negative NSS-SO42concentrations foundin he coastal firn. The clear evidence that bulk aerosol is also delower at DDU (2.6): there is also no obviousdifferencein f betweenaerosoland fresh snow at each site which suggests pleted seawater - makes in SO4 onlyhislattersuggestion likely. that f is not very sensitive the particle size fraction consid- Indeed, - fractionation to SO4 during freezing seawater is of (ice) ered.Availablef valuesfrom 11 highresolutionfirn coresfrom a well known process[Richardson, 1976] which is basically
centrationwithin this specialJGR section,the most simple regressionmethod was individually applied for each year's aerosoldata sets,defining the winter subsamples June to as Augustor, instead,June to September. Surfacesnowsamples taken at HB and DDU in high temporal resolutionare processed identically. Excludingthe September1991 data already

10,970

WAGENBACH

ET AL.: SEA-SALT AEROSOL

IN COASTAL

ANTARCTIC

REGIONS

a)

--o-- Bay Neumayer ,/=\ /,,/q\ .-o- Halley , -, Dumont ?' -,,/ V ", D'Urville o" ,' ',\
60
(D O"

/ ,!

',

(D

.>
(D

40

, /

'\
20

0 Jan

Feb

Mar

Apr

Mai

Jun

Jul

Aug

Sep

Oct

Nov

Dec

b)
3.0

\
2.5

c:!X\ \, '

\ /

Neumayer

- '-' Halley Bay

2.0

,/_ \,\

- -- d'Urville Dumont

E
o

o
i

03
Z

1.0

0.5

0.0

Jan

Feb

Mar

Apr

Mai

Jun

Jul

Aug

Sep

Oct

Nov

Dec

Figure (a)Relative 7. frequency themonthly for occurrence ofseawater depletions SO42inaerosol samples
versus seasons. all threestations, For NSS-SO42values calculated the BSW ratio are assumed be via to

affected sea-salt by SO- depletionthey lower if are than10ngm-3. (b) Annual cycles NSS-SO42of
calculated the corrected via SO42- Na+ mass to ratioin bulkreference saltof 0.07andnormalized the sea to

respective average grand (shown indicate NSS-SO42to the increase toward equinox).

marinesites. Again,in the coastal drivenby the crystallization Na2SO 10H20 (mirabilite) pletioneffectat temperate of 4 is to by already occurring temperatures at below-8.2C. Since salt highArcticwhich subject hugecontamination anthrothe SO42during winter [Bartie, 1986], sea-salt defSO42crystals associated the ice lattice,the remaining are with brine pogenic

starts get increasingly to depleted SO42in (andto a much icitswould not be immediatelyrecognized.
lesser extent Na+) on progressive in cooling belowthiscritical
cold air temperatures to be expected is from the missing deIn a series laboratory of experiments, sea-salt particles were

therefore (fromclean, deep Atlantic)seawater samtemperature. connectiontheSO42Some of fractionation with produced,

ples,under air temperature conditions downto -28C at-

WAGENBACH

ET AL.: SEA-SALT AEROSOL IN COASTAL ANTARCTIC

REGIONS

10,971

tempting simulate observed to the SO42fractionation. The

main resultsof theseexperiments performed at the Institut ffir Umweltphysikby Keck [1994] are summarized below: In experiment1, spume dropletswere investigatedat low temperatures. Seawaterdropletssprayed into a sedimentation chamberat temperaturesdown to -24C showno significant fractionation the deposited in largeparticlesnor in the remaining airbornefraction.In contrastto fleshwaterdropletswhich may burstupon fleezing [Hobbs andAlkezweeny, 1968] due to volume expansion its still liquid core, no suchfragmentation of for seawaterdropletswas observedin experiment 1. In experiment2 the chemicalcompositionof jet and film dropletsgeneratedat variousambient temperatures was analysed. Sea-salt droplets produced by bubble bursting at air temperaturesin the range of +20 to -28C and analyzedin six size classes (0.4-11 /xm diameter sampled by an Anderson impactor)are alsofoundto be not significantly fractionate&In
as a function of particle size. Experiment 3 focused on the fleezing of the skin of air

sideredas well. Admittedly, none of the proposedprocesses are presently knownto be as effectiveas neededto explainthe

observed SO- depleted sea-salt load and to produce the

(small)particlemode typically encountered the long range in
transport of sea-saltaerosols.
4.4. Fractionation of Cation Species

Assuming that the partitioning of crystallized mirabilite (Na2SO410H20) betweenthe brine and the ice matrix is the

onlydominating SO- fractionation process, Na+ should then

be depletedas well in the brine. Taking C1- as the reference speciesfor BSW (halite precipitatesonly below -23C), a

simplemassbalancecalculation shows that the C1- to Na+ mass ratiowouldthenbe linearly related the SO- to Na+ to
ratio with a slope of -0.98 and an intercept of 2.045. Accord-

ingly,fromthe average SO- depletion factor - 3.57 with f respect Na+ found in aerosoland freshsnowduringthe to particular, systematic depletion no SO42effects wereobserved winterhalf year,a Na+ depletion factorwith respect C1- of to
1.1 is predicted.Indeed, inspectionof the winter aerosoldata

revealed meanNa+ depletion factors 1.14 + 0.09 at DDU, of

1.11 _+ 0.10 at NM, and 1.30 _+ 0.18 at HB among samples

bubbles the watersurface. slight at A SO42depletion the of

order of 10% was found in the skin of seawater bubbles which

showing negative NSS-SO4 values. shown Figure8, the As in

respectiveraw winter aerosol data roughly follow the theoret-

are forcedto freeze before burstingby increasing their lifetime artificially(addingof surfactants made up by detergent).

icalrelationship between Na+ andSO4 depletion the factors In experiment seawater 4, spray icing studied. was SO42was but indicatea systematically higherNa + depletionthanwould
be predicted from mirabilite precipitation alone. The significanceof this deviationis hard to assess view of the relatively in

found to be depletedby up to a factor of 4 if seawaterdroplets are sprayedat a low rate onto a cold surfaceand the water film was continuously removedfor analyses. Experiment 5 simulated the fleezing of seawatersuperimposed on sea ice. Depletion factors in the range of those observedin aerosoland snowwere easilyachievedif seawater was partly frozen at temperatureswell below -8C to the surface of artificial sea ice and the remaining liquid was removed for analyses. The resultsof experiments1, 2, and 3 gave no evidencefor a freezing inducedfractionationprocessoperating during the airborne state of the droplets or at the air water interface

highscatter the measured in ratiosand sinceanyNSS-SO4 contributionwas neglectedhere. This finding suggests that precipitation of mirabilite is the

controlling process the observed of SO42depletion sea-salt in particles. Indeed,regression analyses Ca2+, K +, andMg2+ of versusNa+ and C1 , respectively performedfor all winter
aerosol data sets,reveal no significantdeviation from the re-

spective seawater ratios(if the smallNa+ depletion with respectto C1- is takenin account). This is in accordance with the initial precipitation temperatures of the respective cryohydratesreported by Nelsonand Thompson[1954] and confirms

which mayexplain enormous the SO42depletion observed in

nature. Indeed, the complementary sea salt fraction enriched

that mirabiliteis the missing - compound. a conseSO4 As

quence,C1- excess concentrations the winter seasoncalcuof

in SO42- neverobserved surface was in snow evenclose the to

ice edge [Gjessing, 1989] and has to remain somewhereoffshore. From experiments4 and 5, one may infer that liquid brine containedin or superimposed ice floesconstitutes on the main sourceof the depletedsea-salt particles.Transportof the material onto the seaice surfacemay be achieved (1) depby ositionof spumedrops(produced over leads)on bare ice floes or on the overlying snowpack (followedby percolation)or (2) squeezing interstitialbrine out of young sea ice by thermal of ice volume contractionand expansion the interstitial brine of during progressive cooling [Doronin and Kheisin, 1977; Reeburghand Springer-Young, 1983]. A major complicationarises,however,in getting the brine airborne (i.e., fragmentedinto particlessmall enoughto become readily transportedby wind) and in overcomingthe dampingeffectof an overlyingsnowpack. Newly formed seaice (e.g., as occurringin leads)would be lessaffectedby a snow cover, whereas dry surface snow may be easily removed by strongwindsand may finallybe dumpedin leads.Again, strong windsmay mobilize the liquid brine from bare sea ice surfaces by spraying over the ice floe edgesor by drivingthe impacit tion of largespumedroplets(seeexperiment Alternatively, 4). wind-induced abrasion of salt crystalsformed at the ice/air interface from progressively concentratedbrine may be con-

lated via the BSW C1-/Na+ ratio are systematically overestimated by roughly 10% of the sea-salt C1- contained in the samples.C1 excess (and among otherspossiblyalso Br- excess)concentrations winter samples in with high sea-salt loads

are thustoo uncertain provideusefulresults Na+ is used to if as BSW reference species. Taking insteadof Na+ one of the
lessabundantcation species would not improve the situation sincetheseions are analyzedgenerallyat lower accuracy.Fur-

thermore, Legrand al. [thisissue] et showed Ca2+ andK+ that

are sensitive to contamination by Antarctic bird rockeries,

whereas + is suspected Wolff[1996]to migrate of Mg by out

sea-salthorizonsin deeper Antarctic firn core sections.

4.5. Implications SO24Fractionation of The clearevidence SO4 depletion sea-salt that in particles
is governedby precipitationof mirabilite constrains occurthe rence of this phenomena to a formation temperature well below -8C. Adding the hypotheses that the depletedsourceis brine formed at the sea ice surfaceimplies furthermore that particlesdirectlyproducedfrom ice free seawaterare not fractionated.Hence fractionationis confinedto periodswhen substantial amounts of sea ice prevail which may be subject to (radiative)surfacecoolingwell below -8.2C. The role of the

10,972

WAGENBACH

ET AL.: SEA-SALT AEROSOL

IN COASTAL ANTARCTIC

REGIONS

1.70 1.60 1.50 o

o o

1.40 o
1.30
o

oo o
o
o _,,., O0 o

'
o

0
_o-

00

1.20 BSW--1.00

O O(7 '"O O u 0' oO oo,,_ o 0 o O cn noOooo

_ o oo o oo
o
o
a

oo

0.90+

0.70 .... /
0.00

o I ....
0.50

o i /
1.00
BSW

....

ooo I ....
1.50 2.00

f-1 (S042-)

Figure8. Theoretical linearrelationship between Na+ depletion the factor (Na+) (withrespect C1-) f to andthereciprocal SO42depletion factor (SO42-) f(with respect Na+) in seawatermirabilite to if (Na2SO 4
10H20) is progressively precipitated and instantaneously removed(straightline). For definitionof depletion factors seetext. Data pointsrefer to raw winter aerosol f valuesfrom Halley Bay (HB), Dumont D'Urville

(DDU), andNeumayer (NM) with Na+ > 300 ng m-3 (in orderto minimize effectfromunknown the NSS-SO42contributions considered not here)andto C1- to Na+ mass ratios between and0.5 to take 3
accountof analyticaloutlyers.

annual sea ice and air temperaturecyclesis thus expectedto curringannual sea-saltmaximumin winter appear to be sigconfinethe most probableoccurrence surfacebrine forma- nificantly of depleted sea-salt in SO42-. tionsto the winter half year (see alsoFigure 7). It is expected

therefore that the SO42depletion factors derived above are

not commonly applicable the openwater season for (i.e., mid to late summerdepending the positionof the station).This on
sol and surfacesnowat DDU where the openwater season is longerand the mean seaice coverage smallerif comparedto is

5.

Conclusions

Atmosphericsea-saltloads at coastalAntarctic sites are

all seasons and significantly lower concentrations the Wedat dell Sea coast.The mean annual concentrations appearto be stronglyinfluencedby site specificaspects. This includesthe sampling position site with respect the coastline to and surface wind pattern, but also nonuniform samplingstrategiesand techniques. More effort is certainlyneededhere to achievea better definedlarge particlesampling order to improvethe in comparabilityof the results.Consequently, the site specific observations availableare generallyof questionable validity in givinga representative picturefor a generaluse (e.g., in general circulation model (GCM) validations). The main featurescommonto all recordsat higher coastal

by mayexplain relatively SO42the low depletion factor in aero- characterized an extremelylarge shorttime variabilityover f

the otherstations. Applying SO42- Na+ reference the to ratio

of 0.07 alsofor DDU midsummer samples (generally enhanced in seasalt) wasfoundby Minikin et al. [thisissue] lead to a to

20% overestimation NSS-SO42-. of They assumed therefore that no significant SO42fraction occurs DDU during at that
season.As addressedabove, alsof values in ice cores of the Weddell Sea sectorwhere ice coverageis more persistentappear to be enhancedover their counterpartsfrom the more

easterly position theAtlantic in sector. SO42No aerosol data

are presented Savoie al. [1993]from Marsh (62S), by et which amongthe sitesin questionis least influencedby sea ice and Antarctic latitudes include, first, no echo of the seasonalsea ice where extremely high sea-salt concentrations prevail year- cycle(e.g.,of the respective offshore openwaterfraction).This round. Inspection theNSS-SO42- points presented is shownby the fact that (with one peculiarexception)at all of data they for Palmer (65S)revealed,however,only relativelyfew neg- sitesthe lowest sea-saltlevel occursduring summer.Conseassociated strong with winter sea-salt ative values despite rather a highsea-salt (3900 m-3). quently,the major source level ng Accordingly, a givensite at the coast,seasonally for adjusted f peaksappearsto be not simplyrelated to the commonbubble valuesneed to be established, example,by considering for the bursting process operatingat openwater areas.A second comsitespecific temperatureand seaice climatology the summer monfeature a systematic, of is strong, depletion sea-salt of SO42of compared to half year.The assumption, confirmed that seaicebrine in aerosoland snowsamples the winter seasons not yet, provides SO42the fractionated particles suggests seaice bulk seawater. that Here major unknowns still existwith respectto constitutes major sea-saltsourcefor high latitude coastal the seasonal well as to the spatialoccurrence this phethe as of Antarctica. This is becausein that region almost all aerosol nomenon. The latter finding,persistently ignoredin mostof the previsamples ice core horizonsresponsible the regularlyocor for

WAGENBACH

ET AL.: SEA-SALT AEROSOL IN COASTAL ANTARCTIC

REGIONS

10,973

ousglacio-chemical studies coastal in regions,deserves further

Hobbs, P. V., and A. J. Alkezweeny,The fragmentationof freezing

attention orderto obtain in reliable winterNSS-SO42values. water dropletsin free fall, J. Atmos. Sci., 25, 881-888, 1968. J.P., D. Morgan, Thusevaluations biogenic of SO42- corerecords ice maybe Ivey,AntarcticM. Davis,V. Ser. B, 38,and G. P. Ayers,Methansulfonate in ice, Tellus, 376-379, 1986.
significantly improved: particularconcerning in their quantitative relationshipto MSA as well as their (possible)intimate connection sea-salt to records throughthe spatio-temporal sea ice variability. Althoughfirst laboratoryexperiments suggest that brine suconstitute the hidden source for winter sea-salt aerosol, field Keck, L., Experimentalsimulationof possible sulphatedepletionin polar sea salt aerosol(in German), M.S. thesis,Univ. Heidelberg, Heidelberg, Germany, 1994. K6nig-Langlo, G., J. King, and P. Pettre, Climatologyof the three coastal Antarcticstations DumontD'Urville, Neumayer, andHalley, J. Geophys. Res., this issue. Latham, J., and M. H. Smith, Effect on global warming of winddependent aerosol generation at the ocean surface,Nature, 347,
snowchemistry Terre Adelie (Antarctica),Ann. Glaciol., 7, 20in
25, 1985.

perimposed seaice is depleted SO42on in and thusmay

372-373, 1990. experiments still urgentlyneededto identifythe controlling are Legrand, M., and R. J. Delmas, Spatial and temporal variations of mobilization process get the brine airborne.Confirmationof to

theproposed of seaicebrinein the observed role SO42frac-

tionationwould make the seaice coverthe dominatingsea-salt Legrand,M., and R. J. Delmas,Solubleimpuritiesin four Antarcticice cores over the last 30,000 years,Ann. Glaciol., 10, 116-120, 1988. source(at least) with respectto coastalAntarctic snowfields sulfate ratio in with far reaching implicationsfor the interpretation of the Legrand, M., and E. C. Pasteur,MSA to non-sea-salt coastalAntarctic aerosol and surface snow,J. Geophys. Res., this respective long term ice core records. issue.
Legrand, M., F. Ducroz, D. Wagenbach, R. Mulvaney, and J. Hall,
Ammonium in coastal Antarctic aerosols and snow: Role of the

Acknowledgments.We thank the overwintering crewsat Dumont D'Urville, Halley, and Neumayerfor carefulsamplecollections well as as U. Trefzer and E. Lehrer for analyzingpart of the Neumayer samples and for their encouragement data editing, and E. Pasteur in and N. Holman for analyzing someof the Halley snowsamples. The work was partly fundedby the German ScienceFoundation(DFG) and by specialgrantsof the Alfred-Wegener Institute for Polar and Marine Research(Bremerhaven) the Institut ffir Umweltphysik to as well asby the EuropeanCommunitySTEP programwithin the project, Polar AtmosphericChemistry.

polar oceanand penguinemissions, Geophys. J. Res.,this issue.

Mclnnes, L. M., D. S. Covert, P. K. Quinn, and M. S. Germani, Measurementsof chloride depletion and sulfur enrichmentin indi-

vidual sea-saltparticles collectedfrom remote marine boundary layer,J. Geophys. Res.,99(D4), 8257-8268, 1994. Minikin, A., Spurenstoff-glaziologische Untersuchungvon Eisbohrkernen des Filchner-Ronne-Schelfeis, Antarktis: Bestimmungder Tiefenverteilung und der Kontinentalleffekte ionischer Aerosolkomponenten, Ph.D. thesis,Univ. Heidelberg, Heidelberg, Germany, 1994. Miniken, A., D. Wagenbach,W. Graf, and J. Kipfstuhl, Spatial and temporal variations of the snow chemistryat the central FilchnerRonne Ice Sheet, Antarctica, Ann. Glaciol., 20, 283-290, 1994.

References

Ayers, G. P., and S. L. Ramsdale,Wet depositionof excess sulfateat Macqarie Island, 54S, Atmos. Chem., 7, 317-323, 1988. J. Barrie, L. A., Arctic air chemistry:An overview,in Arctic Pollution, edited by B. Stonehouse, 5-23, CambridgeUniv. Press,New pp.
York, 1986. Bodhaine, B. A., J. J. DeLuisi, J. M. Harris, P. Houmere, and S. Bauman, Aerosol measurementsat South Pole, Tellus Ser. B, 38, 223-235, 1986.

Minikin, A., M. Legrand,J. S. Hall, D. Wagenbach,C. Kleefeld, E. W. Wolff, E. C. Pasteur,and F. Ducroz, Sulfur-containing species (sulfate and MSA) in coastalAntarctic aerosol and precipitation,J. Geophys. Res., this issue. Moser, K., Raum-Zeit-Variation der chemischenZusammensetzung desFirns antarktischer Randgebiete, Ph.D. thesis, Univ. Heidelberg, Heidelberg, Germany, 1991. Moser, K., D. Wagenbach, and K. O. Mtinnich, Nitrate in coastal Antarctic shallowfirn cores:Comparisonof seasonal pattern and
total fluxes,Ann. Glaciol., 14, 349, 1990.

Clausen,H. B., and C. C. Langway,The ionic depositsin polar ice

cores, in The Environmental Record in Glaciers and Ice Sheets,

DahlemKonferenzen, editedby H. Oeschger and C. C. Langway, pp. 225-248, John Wiley, New York, 1989. Delmas, R. J., and M. Legrand,Long-termchanges the concentrain tions of major chemicalcompounds (solubleand insoluble)along deep ice cores, in The Environmental Record in Glaciersand Ice Sheets, DahlemKonferenzen, editedby H. Oeschger and C. C. Langway, pp. 319-342, John Wiley, New York, 1989.
Doronin, Y. P., and D. E. Kheisin, Sea Ice, Amerind Publ., New Delhi,
1977.

Mosley-Thompson, J. Dai, L. G. Thompson,P.M. Grootes, J. K. E., Arbogast,andJ. F. Paskievitch, Glaciological studies Siple Station at (Antarctica):Potentialice-corepaleoclimatic record,J. Glaciol.,37,
11-22, 1991.

Mozurkevich, M., Mechanismsfor the release of halogensfrom seasalt particlesby free radical reactions, Geophys. J. Res., 100(D7),
14,199-14,207, 1995.

Mulvaney, R., and A. Peel, Anions and cations in ice cores from Dolleman Island and Palmer Land Plateau, Antarctic Peninsula,
Ann. Glaciol., 10, 121-125, 1988.

Ducroz,F., Etude de la composition chimiquede la basseatmosphere Nelson,K.H., and T. G. Thompson,Depositionof saltsfrom seawater by frigid concentration, Mar. Res., 13, 166-182, 1954. J. des rgions c6tires antarctiques(station francaisede Dumont D'Urville), Ph.D. thesis, pp., Univ. Joseph 299 Fourier de Grenoble, O'Odowed, C. D., M. H. Smith, I. E. Consterdine, and J. A. Lowe, Marine aerosol, sea salt, and the marine sulphur cycle: A short Grenoble, France, 1996.
Erickson, D. J., J. T. Merrill, and R. A. Duce, Seasonal estimates of
review, Atmos. Environ., 31, 73-80, 1997.

globalatmospheric salt distributions, Geophys. sea J. Res.,91(D1),

1067-1072, 1986.

Parungo,F. P., C. T. Nagamoto,J. Rosinski,and P. L. Haagenson,A studyof marine aerosols over the PacificOcean,J. Atmos. Chem., 4,
199-226, 1986.

Fitzgerald,J. W., Marine aerosols: review,Atmos. Environ.,Part A, A

25, 533-546, 1991. Genthon, C., Simulations of desert dust and sea-salt aerosols in Ant-

Peel, D., and R. Mulvaney, Time-trends in the pattern of oceanatmosphere exchange an ice core from the Weddell Sea sectorof in
Antarctica, Tellus, 44, 430-442, 1992.

arcticawith a general circulationmodel of the atmosphere,Tellus

Ser. B, 44, 371-389, 1992.

Giovinetto,M. B., and M. M. Waters, Dependenceof Antarctic surface massbalanceon temperature,elevation,and distanceto open ocean,J. Geophys. Res., 95, 3517-3531, 1990. Gjessing,Y., Marine and non-marine contribution to the chemical compositionof snow at the Riiser-Larsen ice shelf in Antarctica,
Atmos. Environ., 23, 155-160, 1984.

Petit, J. R., M. Briat, and A. Roger, Ice age aerosolcontentfrom east Antarctic ice core samplesand past wind strength,Nature, 293,
391-394, 1981.

Prospero, M., D. L. Savoie,E. S. Saltzman,and R. Larsen,Impact of J. oceanicsources biogenicsulphuron sulphateaerosolconcentraof

tions at Mawson, Antarctica, Nature, 350, 221-223, 1991.

Gjessing, Excess Y., and deficit of sulfatein polar snow, Atmos.Environ., 23, 155-160, 1989.

Reeburgh,W. S., and M. Springer-Young, New measurements sulof fate and chlorinityin natural seaice,J. Geophys. Res.,88, 2959-2966,
1983.

10,974

WAGENBACH ET AL.: SEA-SALT AEROSOL IN COASTAL ANTARCTIC

REGIONS

Wilson, T. R. S., Salinity and the major elementsof seawater,in Chemical Oceanography, 1, editedby J.P. Riley and G. Skirrow, vol. Savoie,D., et al., Nitrogen and sulfurspecies Antarcticaerosols in at pp. 365-413, Academic,San Diego, Calif., 1975. Mawson, Palmer,andMarsh(King GeorgeIsland),J.Atmos.Chem., Wolff, E. W., Location,movementand reactionof impuritiesin solid 17, 95-122, 1993. ice, in ChemicalExchange Between Atmosphere Polar Snow, the and Trefzer, U., Comparison the ion composition aerosoland fresh of of NATO ASI $er.,vol. 1(43), editedby E. W. Wolff and R. C. Bales, pp. 541-560, Springer-Verlag, New York, 1996. snowsamples from the Neumayerregion,Antarctica(in German), M.S. thesis,Univ. Heidelberg,Heidelberg, Germany, 1992. Wolff, E., J. S. Hall, R. Mulvaney, E. Pasteur,D. Wagenbach, and Tuncel, G., N. K. Aras, and W. A. Zoller, Temporal variationsand M. Legrand,Relationship betweenchemistry air, freshsnow,and of sources elementsin the southpole atmosphere, Nonenriched of 1, firn coresfor aerosol species coastal in Antarctica, Geophys. J. Res., and moderatelyenriched elements,J. Geophys. Res., 94, 13,025this issue(a). 13,038, 1989. Wolff, E. W., M. Legrand, and D. Wagenbach,Coastal Antarctic Vogt, R., P. J. Crutzen, and R. Sander, A mechanism halogen for aerosol and snowfall chemistry, Geophys. J. Res.,this issue (b). release from sea-salt aerosol in remote marine boundary layer, Nature, 383, 327-329, 1996. F. Ducroz and M. Legrand,Laboratoirede Glaciologie G6ophyet Wagenbach,D., CoastalAntarctica:Atmosphericchemicalcomposi- siquede l'Environnement Centre National de la Recherche du Sciention and atmospheric transport,in ChemicalExchange Between the tifique, BP 96, 38402 St. Martin d'Hres, France. (e-mail: mimi@ Atmosphere Polar Snow,NATO ASI Ser.,vol. 1(43), editedby alaska.grenet.fr) and J. S. Hall, R. Mulvaney,and E. W. Wolff, BritishAntarctic Survey, E. W. Wolff and R. C. Bales,pp. 173-199, Springer-Verlag, New York, 1996. Natural Environment Research Council,High Cross, MadingleyRoad, Wagenbach, U. G6rlach, and K. Moser, Coastalantarcticaerosol: Cambridge 30ET, England,U.K. (e-mail:rmu@pcmail.nerc-bas. D., CB The seasonal pattern of its chemicalcomposition and radionuclide ac.uk;ewwo@pcmail.nerc-bas.ac.uk) content, Tellus, 40, 426-436, 1988. L. Keck,A. Minikin, andD. Wagenbach, Institutfiir Umweltphysik, Wagenbach, D., W. Graf, A. Minikin, U. Trefzer, J. Kipfstuhl, Universityof Heidelberg,Im NeuenheimerFeld 366, D-69120 HeidelH. Oerter, and N. Blindow,Reconnaissance chemical of and isotopic berg,Germany.(e-mail:aminikin@awi-bremerhaven.de; wa@uphysl. firn properties top of Berkner Island,Antarctica, on Ann. Glaciol., uphys.uni-heidelberg.de)
Richardson,C., Phaserelationshipin sea ice as functionof temperatures, J. Glaciol., 17, 507-519, 1976.
20, 307-312, 1994.

Wagenbach,D., M. Legrand, H. Fischer,F. Pichlmayer,and E. W. Wolff, Atmosphericnear-surface nitrate at coastalAntarcticasites, J. Geophys. Res., this issue.

(ReceivedMarch 24, 1997;revised June 12, 1997; accepted June 18, 1997.)