QuaternaryScienceReviews28(2009)1354–1366 ContentslistsavailableatScienceDirect Quaternary Science Reviews journal homepage: www.elsevier.com/locate/quascirev Sea ice variations in the central Canadian Arctic Archipelago during the Holocene Lindsay L. Varea,b, Guillaume Masse´ a,b,1, Thomas R. Gregoryb, Christopher W. Smartb, SimonT. Belta,b,* aPetroleumandEnvironmentalGeochemistryGroup,UniversityofPlymouth,DrakeCircus,PlymouthPL48AA,UK bSchoolofEarth,OceanandEnvironmentalSciences,UniversityofPlymouth,DrakeCircus,PlymouthPL48AA,UK a r t i c l e i n f o a b s t r a c t Articlehistory: AseaicerecordforBarrowStraitintheCanadianArcticArchipelago(CAA)ispresentedfortheinterval Received22October2008 10.0–0.4cal.kyrBP.ThisHolocenerecordisbasedprimarilyontheoccurrenceofaseaicebiomarker Receivedinrevisedform chemical, IP25, isolated from a marine sediment core obtained from Barrow Strait in 2005. A core 27January2009 chronologyisbasedon14CAMSdatingofmolluscshellsobtainedfromtenhorizonswithinthecore.The Accepted28January2009 primaryIP25dataarecomparedwithcomplementaryproxydataobtainedfromanalysisofotherorganic biomarkers, stable isotope composition of bulk organic matter, benthic foraminifera, particle size distributionsandratiosofinorganicelements.Thecombinedproxydatashowthatthepalaeo-seaice recordcanbegroupedaccordingtofourintervals,andthesecanbecontextualisedfurtherwithrespect totheHoloceneThermalMaximum(HTM).Springseaiceoccurrencewaslowestduringtheearly–mid Holocene (10.0–6.0cal. kyr BP) and this was followed bya second phase (6.0–4.0cal. kyr BP) where spring sea ice occurrence showed a small increase. Between 4.0 and 3.0cal. kyr BP, spring sea ice occurrenceincreasedabruptlytoabovethemedianandweassociatethisintervalwiththeterminationof theHTM.Elevatedspringseaiceoccurrencescontinuedfrom3.0to0.4cal.kyrBP,althoughtheywere morevariableonshortertimescales.Withinthisfourthinterval,wealsoprovideevidenceforslightly lowerandsubsequentlyhigherspringseaiceoccurrenceduringtheMediaevalWarmPeriodandthe Little Ice Age respectively. Comparisons are made between our proxy datawith those obtained from otherpalaeo-climateandseaicestudiesfortheCAA. (cid:2)2009ElsevierLtd.Allrightsreserved. 1. Introduction theseandclimatevariabilitycontinuestogaininmomentum,with the relative contributions that natural forcing and anthropogenic The sensitivity of the Arctic to climatic changes is most effectshaveontheseassociations,attractinganadditionalfocus. convincingly demonstrated by the recent acute and dramatic In order to gain a greater appreciation of the significance of changes to its permafrost and sea ice cover (Stroeve et al., 2007, anthropogenicinputsonclimaticchanges,itisvitaltounderstand 2008;Perovichetal.,2008).Thisobservationofrapiddecreaseinsea natural climate variability both in modern times and throughout icecoveroverthelast30yearshasreceivedconsiderableattention history, including during the Holocene. Gaining a greater knowl- fromarangeofclimatescientists(Johannessenetal.,1999;Vinnikov edgeofrecentandlonger-termseaicevariabilityshouldcontribute etal.,1999;ComisoandParkinson,2004;Serrezeetal.,2007;Stroeve fundamentally to this understanding since sea ice is such a key et al., 2008) and it has been speculated that continued sea ice componentof the Earth’s climate system(Comisoand Parkinson, reduction may open the North West Passage within the Canadian 2004). Satellite-based passive microwave methodology has ArcticArchipelago(CAA)tointernationalshipping,withthepassage providedadetailedrecordofseaicecoverageforthelast30years, able to sustain a prolonged shipping season (Howell and Yackel, but extended historical datasets are either scarce or lacking in 2004;Schelletal.,2008).Givenanarrayofsuchmotivatingfactors, detailduetothelimitednumberofdirectobservationalrecordsor researchintoseaice,seaiceextent,andtherelationshipsbetween indirectaccountsfromproxystudies. Recently,weproposedtheuseofanovelbiomarker(IP25;Fig.1; compound1)producedbyseaicediatomsasanewproxyforArctic * Corresponding author. Petroleum and Environmental Geochemistry Group, sea ice (Belt et al., 2007). IP25 is a mono-unsaturated highly University of Plymouth, Drake Circus, Plymouth PL4 8AA, UK. Tel.: þ44 1752 branchedisoprenoid(HBI)thatisbiosynthesisedspecificallybysea 584799;fax:þ441752584709. icediatomsandwehaveshownittobestableinsedimentsbelow E-mailaddress:[email protected](S.T.Belt). 1 Present address: UMR 7159 LOCEAN, Institut Pierre-Simon Laplace, 4 Place Arcticseaice.Asaresultofthisstability,webelievedthatquanti- Jussieu,ParisCedex05,France. fication of IP25 in sediments had the potential to provide 0277-3791/$–seefrontmatter(cid:2)2009ElsevierLtd.Allrightsreserved. doi:10.1016/j.quascirev.2009.01.013 L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 1355 inBarrowStrait,whichconnectsBaffinBaywiththeArcticOcean viaLancasterSoundandViscountMelvilleSound(Fig.2).Barrow Strait is bounded to the west bya sill and gradually increases in 1 2 depthintheeasttowardsLancasterSound(PrisenbergandBennett, 1987).Thesillinfluenceswatercirculationthroughthestrait,and watersareamixofsouthwardflowfromtheArcticOcean,eastward Fig.1. StructuresofIP25(1)andC25:2(2). flowfromtheCanadaBasinandwestwardflowfromtheBaffinBay area. Jones et al. (2003) report a predominantly Pacific origin, a continuous, high-resolution sea ice record for the Holocene (at althoughthishasnotalwaysbeenthecase,withamajorchangein least).Giventhispotential,wequantifiedtheabundancesofIP25in the marine circulation involving a switch in the dominance of a marine sediment core obtained from the North Icelandic Shelf AtlanticandArcticwaterswithintheNorthernCanadianArcticat (Masse´ et al., 2008); a location where comprehensive historical approximately6.0cal.kyrBPfortheeasternBaffinIslandcoast,but records for sea ice variability existed and could be used for aslateas2–4kyrBPforthecentralregionincludingBarrowStrait comparative purposes. Significantly, IP25 abundances in the core (Williamsetal.,1995). demonstrated numerous correlations with historical sea ice records, and these were supported further by diatom-based sea surfacetemperaturereconstructions(Masse´ etal.,2008). 2.2. SeaiceintheCAA Forthecurrentstudy,wedecidedtofocusonalocationinthe CAA(BarrowStrait;Fig.2)forwhichprevioushistoricalseaicedata During the Last Glacial Maximum (LGM), the CAAwas totally were relatively scarce (Gajewski and Atkinson, 2003; Ledu et al., covered by the Laurentide and Innuitian ice sheets (Dyke et al., 2008). This paper provides a long-term (ca 10.0–0.4cal. kyr BP) 2002).TherecessionoftheicemarginincloseproximitytoDevon record of sea ice conditions for Barrow Strait within the central Island,SomersetIslandandnorthernBaffinIsland(north,westand CAA,basedmainlyonvariationsintheabundanceandfluxofIP25in south of Barrow Strait, respectively; Fig. 2) began approximately morethan 600 individual horizonsobtained froma marine sedi- 10kyr BP (Dyke et al.,1996a,b; Dyke,1999, 2008), with the final mentcore.SincetheIP25biomarkerisbiosynthesisedselectivelyby remnants of ice disappearing approximately 8kyr BP, following seaicediatomswhichbloomtypicallyinApril–May,theunderlying arapidincreaseintemperature(Dykeetal.,1996a,b;Dyke,1999). sedimentaryrecordcanbemorespecificallyinterpretedintermsof Inmoderntimes,theCAAhasbeencharacterisedbythepres- reflectingspringseaiceconditions,andweusethisinterpretation ence of sea ice throughout the year (Melling, 2002). During the hereafter. The data are interpreted further with relation to the winter months, between November and May, the entire CAA is climatic event commonly referred to as the Holocene Thermal completelycoveredbyice,withmaximumiceextentoccurringat Maximum(HTM).TheprimaryIP25proxydataarecomplemented thebeginningofMay.Inlatespring,thebreak-upoftheseaiceis by other chemical, biological and physical analyses including initiated, with the emergence of a number of polynyas. The distributionsofotherorganicbiomarkers,stableisotopecomposi- minimum ice extentoccurs in September, following which, rapid tion(d13C)ofbulkorganicmatter(OM),abundancesofarangeof growth in sea ice generally occurs. More locally, Barrow Strait is geochemical elements, occurrence and accumulation rates of characterised by dense land-fast ice from November until early benthicforaminifera,andsedimentparticlesizedistributions. June, with a relatively short ice-free season in August and September(PrisenbergandBennett,1987). 2. Regionalsetting AlthoughitisrecognisedthatmodernArcticseaicecoverhas been declining over the last few decades (Serreze et al., 2007; 2.1. TheCanadianArcticArchipelago(CAA)andBarrowStrait Perovichetal.,2008),withadecreaseinSeptemberseaiceextentof 7.8% per decade over the last 30 years (Stroeve et al., 2007), The CAA is a complex array of islands, with narrow channels decliningseaiceextentwithintheCAAbetween1978and1996has interconnectinglargerbasins.Thisstudyconcentratesonalocation been reported to be statistically insignificant (Parkinson et al., Fig.2. Mapofthesamplinglocation(ARC-3)andtheCanadianArcticArchipelago. 1356 L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 1999). Parkinson et al. (1999) noted that there are a number of times and mass spectra (full scan mode recorded every 8–16 regionalfactorsinfluencingthechangestoseaicecover,withthe samples).RelativeabundancesofIP25andanHBIdiene(C25:2)were unique characteristics of the CAA responsible for a slower than calculatedonthebasisofthemagnitudesoftheirGC–MSresponses average response in this region. Only relatively few studies, compared with those of the internal standard, with these ratios however,haveattemptedtoconstructaseaicehistoryforBarrow corrected according tothe mass of sediment analysed. Individual Strait between the timing of the ice margin retreat in the early n-alkaneswerealsoquantifiedusingthismethodandbycompar- Holocene and these contemporary observations (e.g. Ledu et al., isons of GC–MS responses with those of standards of known 2008). concentrations. Analytical reproducibility was checked using a standard sediment with known abundances of biomarkers and 3. Methods alkanes for every 8–16 sediment sample extractions (analytical error<5%,n¼8). 3.1. Fieldmethods AnITRAXcorescannerusingnon-destructiveX-rayfluorescence (XRF) detection was used to determine the geochemical charac- Thecurrentstudyisbasedontheanalysisofapistoncore(ARC- teristics of the archived core sections. For the current study, 3,99.2mminternaldiameter),collectedduringtheCCGSAmund- a 0.5cmstepsize resolutionwas selected, with a 40s XRFcount sen ArcticNet cruise (August/September 2005). The 641-cm core time.Theanalysisprovidedgeochemicaldataforawiderangeof wastakenfromawaterdepthof347m(Lat:74(cid:2)16.050;Long:91(cid:2) elements, including calcium (Ca), iron (Fe), titanium (Ti) and 06.380). The core was divided into six 100-cm sections plus rubidium (Rb). Down-core profiles were created using either ashortersectionatthetopofthecore.Eachsectionwaslongitu- absolute peak area integrals for individual elements or ratios of dinallysplit,withonehalfarchivedattheBritishOceanSediment these integrals for different elements (e.g. Ca/Fe). The peak area CoreResearchFacility(BOSCORF,UniversityofSouthampton,UK). integralswereconsideredtobeproportionaltotheabundanceof Theremaininghalfwassub-sectionedata1cmresolutionandeach each element (Rothwell et al., 2006). Since the abundances of horizonwasfurtherdivided,withonehalffreeze–dried,theother aluminium(Al)werebelowthelimitofdetectionoftheITRAXcore storedinacoldroom(þ4(cid:2)C). scanner, an alternative method of analysis was employed. Evenly spaced (100cm) horizons were selected and subjected to 3.2. Datingofthesedimentsequence acombinednitric(HNO3),hydrochloric(HCl)andhydrofluoric(HF) acidtotaldigest,followedbyquantitativeanalysisofAlbyinduc- Dating Arctic sedimentary archives can pose difficulties that tivelycoupledplasma–opticalemissionspectroscopy(ICP–OES). arisemainlyfromthepaucityofmicro-andmacrofossilswithinthe Particle size analyses were undertaken using a Malvern Mas- cores. For the core used in the current study, we previously tersizer2000laserparticlesizer.Samplesoffreeze–driedsediment reportedaconventionalradiocarbonageof9.15(cid:3)0.2kyrBPforthe (ca 0.5g) were taken at 10cm intervals throughout the core and bottomofthecore(641cm),whichwasobtainedby14CAMSdating material was dispersed ultrasonically in 0.1% sodium meta- of foraminifera (Neogloboquadrina pachyderma (s)) (Belt et al., phosphate solution (5mL; 1min). Particle size measurements 2007). Due to the extremely low abundance of these and other (5replicates)weremadeusingaredandbluelaserfor30s,with foraminiferapresentthroughoutthecore,wechosetodetermine a particle refractive indexof 1.53 and a light absorption value of the chronology of the core using 14C AMS analyses of bivalve, 0.005. Individual distributions of particle sizes were calculated gastropodandscaphopodshells.IntactbivalveshellsofPortlandica usingpreviouslyreportedmethods(FriedmanandSanders,1978) arctica,previouslyreportedbyDykeetal.(1996a),wereidentified according to the following classifications – clay: <4mm; silt: insomehorizonsandusedfor14CAMSdating.Insomecases,intact 4–60mm; sand (coarse): 60mm–2mm. Dry sediment densities shells were supplemented by shell fragments of gastropods, sca- weredeterminedforthesamehorizonsbyconsiderationof%water phopods and unidentified bivalve species, though some were contentandfixedsedimentspecificgravity(2.65gcm(cid:5)3). thoughttobeofHiatellaarctica(Dykeetal.,1996a).Shellmaterial Stableisotopecomposition(d13C)measurementsweremadeon from ten horizons were 14C AMS-dated (Beta Analytic, USA), and sub-samplesoffreeze–driedsediment(100mg)at10cmintervals conventional radiocarbon ages converted to calibrated ages (cal. throughout the core using an elemental analyser coupled with kyrBP)with theCALIB 5.0.1 program(Stuiverand Reimer,1993), a dual inlet mass spectrometer (Finnigan, DeltaplusXP). Sediment usingthecalibrationdatasetMarine04,whichincorporatesaglobal samples were decarbonated with 10% HCl (1mL) prior to d13C oceanreservoircorrectionof400yr.Anadditionalregionalmarine analysis.Standarderrorswere(cid:3)0.1&. reservoir correction (DR) of 290(cid:3)40yr was also applied, taken Benthic foraminifera (>63mm) were picked from sediment fromArcticBay,NWBaffinIsland(McNeelyetal.,2006).TypicalDR samples at 10cm intervals down-core. Oven-dried sediment values for the eastern CAA, taken from the marine reservoir samples were disaggregated in 10% sodium hexametaphosphate correction database (http://intcal.qub.ac.uk/marine/), range from solution (50mL), thenwet-sievedthrough a 63mm mesh. Where 180(cid:3)80yrto435(cid:3)56yr. possible,>250specimensofbenthicforaminiferawerepickedfrom each sample. However, this was not possible in samples from 3.3. Laboratorymethods 450cm to 0cm since there were very few specimens. Benthic foraminiferal accumulation rates (BFARs, number of specimens For biomarker analyses, an internal standard (7-hex- cm(cid:5)2kyr(cid:5)1)werecalculatedas:numberofspecimenspergramof ylnonadecane;0.1mg)wasaddedtoaliquotsoffreeze–driedsedi- dry bulk sediment(cid:4)linear sedimentation rate (cmkyr(cid:5)1)(cid:4)dry ment material (ca 1g), which weresubsequentlyextracted using bulkdensity(gcm(cid:5)3). dichloromethane/methanol(3(cid:4)3mL;2:1v/v)andultrasonication. Solventwasremovedfromthecombinedextractsusingnitrogen. 4. Results The resultant total organicextract (TOE)waspurified usingopen column chromatography (silica), with hydrocarbons (hexane; 4.1. Corechronology 6mL) collected as a single fraction before being analysed by gas chromatography–mass spectrometry (GC–MS). All biomarkers The14CAMSdataobtainedfromanalysisofmolluscshellsiso- wereidentifiedonthebasisoftheircharacteristicGC–MSretention lated from ten horizons from the ARC-3 core are summarised in L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 1357 Table1andinFig.3.Notably,therearenoreversalsintheprofile calibrated radiocarbon date (kyr BP) and a date corresponding to the lowest horizon measured 0 2 4 6 8 10 (623.5cm;9684cal.yrBP)isconsistentwithacalibrateddateof 0 9680cal.yrBPobtainedpreviouslyforN.pachyderma(s)obtained from the bottom of the core (641cm). For the purposes of the currentstudy,wehaveconstructedtwocontinuouscorechronol- 100 DBD (g cm-3) 0.5 1.0 1.5 2.0 ogies that are bound mainly by the upper (56.5cm) and lower (623.5cm)14CAMS-datedhorizons.Forconsistency,onlytheAMS 100 dates obtained from mollusc shells have been used to construct 200 200 theseprofiles.Thetwochronologies(Fig.3)havebeenobtainedby linear interpolation and third-order polynomial fitting of the ten cm) 300 AlinMeSardaitnetse.rFpoorlathtieonlowweasstseexctteionndeodfthuesicnogret(h6e235.57–76.54–16c2m3.)5,tchme cm) 300 epth ( 400 section.Differencesbetweenthetwoprofilesareca(cid:3)50yrforthe h ( D 500 pt upper (<350cm) section of the core and ca (cid:3)100–150yr for the e D 600 lowersection.Sinceourdataareinterpretedintermsoffourbroad 400 intervalswhichrangebetween1.0and4.0kyr(seefurtherSections 4and5forspecificintervals),weconsiderthesesmalldifferences to be insignificant, and we have opted to use the polynomial 500 interpolation model for definition of intervals throughout. Samplingat1cmintervalsresultsinaneffectiveageresolutionof 6–40yr. The higher sedimentation rates observed for the upper sectionofthecoremostlikelyreflectthelowerconsolidationatthe 600 core-topasindicatedbylowersedimentdensitiesforthissection (Fig.3).However,sinceconsolidationcannotsatisfactorilyexplain theenhancedsedimentationrateatthebaseofthecore,wesuggest Fig.3.14CAMSdatesoftenhorizonsfromtheARC-3coretogetherwithdepth/age that the latter may possibly be attributed to some glaciomarine modelscorrespondingtolinearinterpolation(dashedline)andthird-orderpolynomial (solid line). The sampling interval is defined by the ‘core-top/bottom’ boundaries. sedimentinputfollowingicesheetretreatatthebeginningofthe Inset:sedimentdrybulkdensities(DBD). Holocene.Indeed,anincreasein%coarseatthebaseofthecoreis consistent with this hypothesis, although other parameters (e.g.BFARs,Ca/Fe,Ti/Rb)suggestthatthisisnottheonlycontrib- indicativeofvariationsinspringseaiceoccurrence,andthesecan utor to increased average particle size (see later). Finally, in the be grouped into relatively broad intervals as follows. The IP25 presentstudy,biomarkerandotherproxydataarepresentedand abundances are lowest in the first or bottom section of the core interpreted for the interval defined by the age–depth model (10.0–8.0cal. kyr BP), before increasing slightly in the second (10.0–0.4cal.kyrBP)anddoesnotincludetheupperca50cmof section(ca8.0–3.2cal.kyrBP).Thereisanabruptenhancementin thecore. theIP25abundanceprofileatca3.2cal.kyrBP,afterwhich,abun- dancesremainhigherthanthosefoundforthelowersectionsofthe 4.2. IP25andotherbiomarkers core, and a greater variability exists between adjacent horizons. Given the variability in the sediment accumulation rates, we InspectionoftheabundanceprofileoftheseaicebiomarkerIP25 calculated IP25 fluxes from the abundance, sediment density and alongtheARC-3core(Fig.4(a))revealsanumberoffeatures.Firstly, sedimentationrateprofilesinordertogetabetterappreciationof itisclearthatIP25ispresentineachoftheca600horizonsana- changes in IP25 delivery to the sediments on a more consistent lysed, resulting in a continuous, high-resolution record. Since temporalscale.TheIP25fluxprofile(Fig.4(b))isslightlydifferent inverse accumulation rates range from ca 6 to 40yrcm(cid:5)1, the fromthatdescribedforIP25abundancesandtemporalchangesto uninterrupted presence of IP25 in each of the horizons provides fluxesarebestgroupedintofourintervals.Firstly,theIP25fluxesare evidenceforthecontinuousoccurrenceofseaicebetweenca10.0 lowestfortheinterval10.0–6.0cal.kyrBPconsistentwithrelatively and0.4cal.kyrBPonsub-tomulti-decadaltimescales.Secondly, lowspring sea ice occurrence throughout this time. Between 6.0 thereareanumberoftrendsintheIP25abundanceprofilethatare and4.0cal.kyrBP,theIP25fluxesincreaseslowlybeforeanabrupt Table1 SummaryofradiocarbonagedeterminationsfortheARC-3core.Themediancalibratedagesareusedfortheconstructionofthedepth/ageprofiles(Fig.3). RadiocarbonagedeterminationsforARC-3 Depth Materialdated Laboratorysample Measuredradiocarbon Conventional 2-sigmacalibrated Mid-pointcalibrated (cm) number(Beta) age(yrBP) radiocarbonage(yrBP) agerange(cal.kyrBP) age(cal.kyrBP) 56.5 Bivalvefragments–possiblyP.arctica 247356 660(cid:3)40 1060(cid:3)40 0.29–0.50 0.4 82.5 Bivalvefragments 247357 960(cid:3)40 1380(cid:3)40 0.54–0.75 0.65 180.5 Largebivalvefragments 247358 1640(cid:3)40 2080(cid:3)40 1.24–1.48 1.36 368.5 P.arcticafragments 247359 3590(cid:3)40 4010(cid:3)40 3.48–3.81 3.65 403.5 Bivalvefragments 247360 3860(cid:3)40 4270(cid:3)40 3.82–4.14 3.98 477.5 Gastropodandbivalvefragments 247361 5680(cid:3)40 6060(cid:3)40 6.02–6.30 6.16 515.5 P.arcticavalveandscaphopodfragments 247363 7930(cid:3)40 8330(cid:3)40 8.38–8.63 8.5 555.5 P.arcticaandbivalvefragments 247364 8370(cid:3)60 8780(cid:3)60 8.95–9.33 9.14 577.5 P.arcticaandbivalvefragments 247365 8450(cid:3)40 8880(cid:3)40 9.07–9.41 9.24 623.5 P.arcticaandbivalvefragments 247366 8840(cid:3)40 9270(cid:3)40 9.52–9.85 9.68 640.5 N.pachyderma 210008 9150(cid:3)200 10.31–9.05 9.68 1358 L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 Fig.4. TemporalprofilesofbiomarkersintheARC-3core(ca600samplingpoints):(a)IP25abundances;(b)IP25fluxes;(c)differencesbetweenIP25fluxesandthemedian. increaseisseenduringathirdintervalfrom4.0to3.0cal.kyrBP.In 2providesstrongevidencethat,inthiscase,thesetwocompounds thefourthphasefrom3.0to0.4cal.kyrBP,thefluxesremainhigh, originatefromacommonsource(seaicediatoms).Thisisfurther but with great inter-horizon variability, consistent with the IP25 supported by the similar and distinctive stable isotope composi- abundance profile. These changes to the IP25 fluxes are further tion (d13C¼ca (cid:5)19& to (cid:5)21&) of these two biomarkers in the illustratedbyconsiderationofthedifferencesbetweenindividual ARC-3 core (Belt et al., 2008). In order to investigate any differ- fluxesandthemedian.Inparticular,thisrepresentation(Fig.4(c)) encesbetweenthesetwoprofiles,were-expressedtheabundance showsthattheIP25fluxesarehigherthanthemedianafter3.0cal. of the diene as a percentage of the combined abundances of the kyrBPwithnonegativedeparturesandsomefurtherincreasein twoHBIs(Fig.5(c)).Thisprofiledemonstratestheclosecorrelation thelastsection(ca0.8–0.4cal.kyrBP). betweentheabundancesofIP25andthedieneintheuppersection Analysis of the GC–MS chromatograms of the purified hydro- of the core (3.0–0.4cal. kyr BP), but also reveals that, prior to carbonextractsrevealed,inadditiontoIP25,thepresenceofanHBI 3.0cal. kyr BP, there is a small, but steady enhancement of the diene(C25:2),identifiedascompound2(Fig.1)onthebasisofits dienerelativetoIP25tothebaseofthecore. characteristic mass spectrum and GC retention index. Since this GC–MSanalysisofthehydrocarbonextractsfromeachsediment isomer has been reported in marine sediments from both the horizon from ARC-3 also revealed the presence of a suite of Arcticandmoretemperateregions(Johns,1999;Beltetal.,2007), n-alkanes,inadditiontothetwoHBIbiomarkers.Giventheubiq- itisnotconsideredtobeasdefinitiveasaniceproxybiomarkeras uityof n-alkanes and the difficulties associated with interpreting IP25,butitisworthnotingtheextremelyclosesimilaritybetween their abundances, we chose not to focus on these biomarkers in the flux profile of this isomer compared to that of IP25 for the detail. However, we quantified the accumulated abundances and ARC-3core(Fig.5).ThesimilarityintheprofilesofIP25anddiene fluxesofthehighmolecularweightn-alkanes(C27þC29þC31)to L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 1359 Fig.5. ComparisonbetweentemporalprofilesofIP25andC25:2:(a)differencesbetweenIP25fluxesandthemedian(b)differencesbetweenC25:2fluxesandthemedian;(c)%C25:2 determinedfromthecombinedabundancesofC25:2andIP25. trytomakeanassessmentofhigherplantorterrigenousinputsto 4.3. Benthicforaminifera thesediments(Yunkeretal.,1995;FernandesandSicre,2000;Stein and Macdonald, 2004). Analysis of the n-alkane flux profile Benthic foraminiferal accumulation rates (BFARs; number of (Fig.6(b))doesnotrevealanysignificantenhancements,andfluxes specimenscm(cid:5)2kyr(cid:5)1)arecommonlyusedasarecordofpalaeo- are below the median for the majority of the bottom–middle productivity(e.g.HergueraandBerger,1991;Smart,2002).Inthe sectionsofthecore(ca8.6–3.4cal.kyrBP).Themuchmorenotable present study, our analysis focused on the identification of indi- variations seen in the fluxes of the IP25 and C25:2 HBIs are not vidual species together with combined abundances and fluxes, observed for these n-alkanes, especially the substantial enhance- rather than on down-core variations between species (a more mentsintheHBIfluxesafter3.0cal.kyrBP. detailed species-level analysis will appear elsewhere; Gregory Inadditiontothesebiomarkeranalyses,wedeterminedthestable et al., submitted for publication). Islandiella norcrossi, Islandiella isotope(13C)compositionofthebulkorganicmatter(OM)inorderto islandica,Elphidiumclavatum,CibicideslobatulusandBuccellafrig- assessforsignificantchanges(ifany)toitssource.d13Cvaluesrange ida,whicharefoundinshelfareasoverlainbyseasonallyice-free fromca(cid:5)22&intheuppersectionofthecoretoca(cid:5)25&atthecore waters (Murray, 1991), were identified as the major species, bottom,withthemostabruptchangeoccurringatca4.0cal.kyrBP accountingfor>85%ofthetotalabundances.BFARs(Fig.6(d))were (Fig.6(c)).Thesevaluesliewithinthetypicalrangefoundformarine- highest between ca 10.0 and 8.4cal. kyr BP before diminishing derivedOM(e.g.Go˜nietal.,2000;SteinandMacdonald,2004;Go˜ni rapidlyfromca8.4to4.0cal.kyrBP.After4.0cal.kyr,foraminifera etal.,2005;Beltetal.,2008). were virtually absent. These reductions in the BFARs were 1360 L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 Fig.6. Temporalprofilesof(a)differencesbetweenIP25fluxesandthemedian;(b)differencesbetweenlongchainn-alkanefluxesandthemedian;(c)d13CforbulkOM;(d)BFARs (totalbenthicforaminiferalaccumulationrates;numberofspecimenscm(cid:5)2kyr(cid:5)1);(e)%coarsefraction(>63mm). accompanied bya concomitant increase in the % benthic forami- (Fig.7(b))showsauniformdistributionthroughouttheARC-3core, niferalfragments,indicativeofcarbonatedissolution. consistent with a continuous deposition of geochemically similar material.Timineralshaveahighresistancetochemicalweathering 4.4. Bulksedimentgeochemistry within sediments (Rothwellet al., 2006) and, assuming that Tiis derived predominantly by the aluminosilicate phases, it can As a complement to the organic biomarker analysis, we also provide information on any changes in the detrital or lithogenic analysedvariousinorganicelementsandparticlesizedistributions component. Aluminium content can provide an independent intheARC-3coreinordertoprovideadditionalinformationonthe measureofthedetritalconstituentofthesediment.AlthoughanAl lithogenicandbiogenicproperties. profile was not achievable using the XRF methodology, the Al Firstly, we measured Ti/Rb ratios to investigate any possible content of the core was measured (albeit on a relatively small lithogenic changes to the source of the sedimentary material number of samples) via dissolution of selected horizon sub- deposited(Croudaceetal.,2006).AprofileoftheTi/Rbratiodata samplesandanalysisbyICP–OES.ConsistentwiththeTi/Rbprofile L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 1361 Fig.7. Temporalprofilesof(a)differencesbetweenIP25fluxesandthemedian;(b)Ti/Rb;(c)%Al;(d)Ca/Fe. andinterpretation,theAlcontentofthecoreshowslittlevariation 5. Discussion (Fig.7(c))withanaverageabundanceof3.9%wt,withintherange typicalofmarinesediments(Chester,1990;O’Brienetal.,2006). The majority of palaeo-reconstruction studies for the CAA are Secondly,weassessedthecontributionofbiogenicmaterialto basedonarchivalrecordscorrespondingtochangesinambientand thesedimentbydeterminationofCa/Feratiosasapotentialpalaeo- seasurfacetemperatures.Theseclimatereconstructionscomefrom productivity indicator (Croudace et al., 2006). The Ca/Fe ratios a variety of lacustrine, marine and ice core records, and include (Fig.7(d))arelargelyinvariantintheuppersectionoftheARC-3core evidence from the Agassiz ice cores (Koerner and Fisher, 1990), (4.0–0.4cal.kyrBP),whereasbefore4.0cal.kyrBP,theCa/Feratio various microfossil assemblage distributions including diatoms increasesandreachesaplateauatca7.0cal.kyrBP.Anexceptionto (Smith, 2002; Podritske and Gajewski, 2007), calcareous micro- thisplateauregionoccursbetweenca9.2and8.8cal.kyrBPwhere fossils, dinoflagellate cysts(Levac et al., 2001; Mudie et al., 2001, thereisanabrupt,thoughtransientincreaseintheratio. 2005,2006),andpollenrecords(Gajewski,1995).Evidenceforsea Finally, particle size analysis of the ARC-3 core shows silt iceconditionswithintheCAAcomesfromrelativelyfewandnon- materialtobethemajorsizefraction,rangingbetween72and95%. continuousarchivalrecordssuchasbowheadwhaleremains(Dyke Themostsignificantchanges,however,areobservedinthecoarse et al., 1996b; Savelle et al., 2000), marine mollusc assemblages fraction (dry sediment >63mm). The coarse fraction shows an (Dyke et al.,1996a), the presence of driftwood located on raised overalldecreaseup-corefromca5%atthebaseto<1%betweenca beaches (Dyke et al., 1997) and dinoflagellate cyst assemblages 2.8and0.4cal.kyrBP(Fig.6(e)).Ithasbeensuggestedthatthe% (Leduetal.,2008).Suchstudieshavefocussedonnumberofice- coarsefractionisareliableproxyofcarbonatedissolutionindeep- free months during the year and whether permanent sea ice seacarbonates(e.g.,VolbersandHenrich,2002),withareduction conditions prevail. For example, Dyke et al. (1996b) and Savelle indicative of the breaking up of foraminiferal tests into smaller et al. (2000) used the postglacial remains of bowhead whales to fragments(e.g.,WuandBerger,1991). propose a period of maximum postglacial warmth between 10.5 1362 L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 and8.5cal.kyrBP,andtheprevalenceofsevereiceconditionsat termsofagreaterterrigenousinput.However,theabsenceofany 8.5–5.0cal. kyr BP, with most of the channels within the CAA major enhancement in the higher molecular weight n-alkanes containingicethroughouttheyear.Bowheadwhaleremainswere (Fig.6(b)),oftenassociatedwithterrigenousinputs(Drenzeketal., again found in some areas within the CAA after 5.0cal. kyr BP, 2007),arguesagainstthisand,forthemiddlesectionofthecore(ca indicating a slightly warmer period, with a further period of 8.6–3.4cal.kyrBP),theoppositeistrue(viz.arelativedepletionin increased sea ice after 3.0cal. kyr BP. Analysis of dinoflagellate then-alkaneflux).Instead,thehigherd13Cvaluesassociatedwith cysts,foraminiferaanddiatomsinArcticsedimentshavebeenused thetopsectionofthecore,inparticular,mostlikelyrepresentsan to infer sea surface temperature and sea ice conditions, but this enhancementinseaice-derivedOMrelativetothelowersections. approach has been limited to Baffin Bay, Lancaster Sound and Recently,wedemonstratedthatd13CvaluesforIP25andothersea furthereastintheCanadianArctic(e.g.Levacetal.,2001;Mudie ice-derivedbiomarkers,lietowardsthehigheror‘heavier’endof etal.,2005;Leduetal.,2008). the marine OM range, typically between (cid:5)19& and (cid:5)21& (Belt The data presented in this study are therefore interpreted etal.,2008).Assuch,thed13Cdataareconsistentwithapredomi- mainlyintermsofimprovingourunderstandingofseaicevaria- nantly marine-derivedorigin for the bulk OM with an increasing tions within a region of the CAA (Barrow Strait) throughout the contributionfromseaiceOM,especiallysinceca4.0cal.kyrBP. Holocene.Theinterpretationsarebasedprimarilyonthevariations Thus far, we have interpreted changes in IP25 abundances in inabundanceandfluxofaseaicebiomarker(IP25)withinamarine sedimenthorizonsasbeingreflectiveofvariationsinspringseaice sedimentcore.Arangeofotherproxydataisalsopresentedandthe occurrenceatthedifferenttimesofdeposition.Potentially,theIP25 extenttowhichtheycomplementtheIP25dataisdiscussed. abundance profile may be influenced during certain intervals by TheIP25abundanceandfluxprofiles(Fig.4(a–c))suggestvari- sedimentologicalfactors,suchasachangeinprovenance.Logically, ablespringseaicecoverforBarrowStraitduringtheHolocenewith such influences would be most apparent for intervals where the no periods of ice-free conditions during the spring–summer, at IP25abundanceiseither‘low’orundergoesanabruptchange,since least for the temporal resolution (ca 6–40yr) afforded by the the‘true’abundancecouldhavebeenalteredbyanexcesssupplyof sediment accumulation rates.The lowIP25 fluxes fromca 10.0 to e.g.terrestrialsediment,icerafteddebrisoraturbidite(Scheffler 6.0cal. kyr BP provide evidence for relatively low spring sea ice etal.,2006;Marshetal.,2007).FortheARC-3core,bothTi/Rband% occurrence during this interval. This was followed by a cooling Al profiles show uniform distributions down-core, with no inter- phasewithprogressivelymoreseaicebetween6.0and4.0cal.kyr ruptions,providingstrongevidencethattherehasbeencontinuous BP,although IP25 fluxes remained below the median level during deposition of geochemically similar material, with no significant thisinterval(Fig.4(c)).ArelativelyrapidincreaseinIP25fluxesin changesinthesourceofsedimentdeposited(Croudaceetal.,2006). athirdphase(4.0–3.0cal.kyrBP),indicatesamajorchangetothe Thus,weattributechangesinIP25abundanceswithinthesediment spring sea ice occurrence at this time, and this was followed by horizonstotemporalvariationsinspringseaicecover. a final interval, where IP25 fluxes are highest. The fluxes in this We investigated foraminiferal fluxes, % coarse (sediment fourthintervalaresignificantlymorevariablethanthoseobserved particle size) and Ca/Fe to give additional proxy data to the IP25 for the early to mid Holocene, indicative of greater variations in recordand,inparticular,provideevidenceforchangestoprimary spring sea ice occurrence on shorter timescales, although fluxes production as a result of temporal sea ice variations. Previously, remainedabovethemedianthroughoutthistime,symptomaticof Levac et al. (2001) analysed abundances and distributions of aprolongedperiodofcoldconditions. dinoflagellatecystsinnorthernBaffinBaytogetherwithchangesin TheoccurrenceandprofileofasecondHBIbiomarker(diene2), diatomfluxesclosetonorthwesternBaffinIsland(Shortetal.,1994) alsoprobablyderivedfromseaicediatomssinceithasanextremely and the coasts of Baffin and Devon Islands (Williams,1990) and similar stable isotope (d13C) signature to that of IP25 (Belt et al., concluded that these could be influenced by sea ice cover with 2008),providestrongsupporttotheseprimaryconclusions.Theflux higherproductionunderlowiceorwarmerconditions.Leduetal. profileofthisdiene(Fig.5(b))closelymatchesthatofIP25(Fig.5(a)) (2008) also analysed dinoflagellate cysts to infer, consecutively, and can be described by the same four time intervals. However, warmer and colder intervals in the mid- and late Holocene in whentherelationshipbetweenthetwoisomersisconsideredmore LancasterSound,ca300kmeastofthecurrentcoresite(Leduetal., closelybylookingatthe%contributionfromthediene(Fig.5(c)), 2008).Assuch,weanticipatedthattheforaminiferalfluxprofilein arelativeenhancementinthismoreunsaturatedisomerisnoted thecurrentstudywouldbeinverselycorrelatedwiththatofIP25, priortoca3.0cal.kyrBPtowardsthebaseofthecore.Thischangeis butthiswasnotstrictlythecase.BFARsweresignificantlyhigherin subtle, but is consistent with the preferential formation of more theca10.0–8.0cal.kyrBPinterval,beforediminishingrapidlytoca unsaturated HBI isomers at higher diatom growth temperatures 4.0cal.kyrBP,afterwhich,veryfewspecimensweredetectedatall. (Rowlandet al., 2001) and this, in turn, endorses the proposal of ThelowBFARsbetween8.0and4.0cal.kyrBParenotatfirstsight awarmerperiodintheearlytomidHolocene. consistentwithlowspringseaiceoccurrencesindicatedbytheIP25 ThestableisotopiccompositionofthebulkOMinthesediments fluxes, although the higher BFARs in the 10.0–8.0cal. kyr BP further supports the biomarker data, particularly for the warmer intervalare.Weattributethisdifferencetotheonsetofadissolu- early–mid Holocene. Interpreting d13C data for bulk OM in Arctic tion event starting at ca 8.0cal. kyr BP and this is even more sedimentsisnotstraightforwarddue,inpart,tothemixednatureof significantafter4.0cal.kyrBP.Theproposalofadissolutioneventis the OM, together with difficulties in assigning well-defined end furthercorroboratedbyreductionsinthe%coarseandbiogenicCa members for OM from various sources. However, it is generally (Ca/Fe)composition of thesedimentsat8.0cal.kyrBPandespe- agreedthatd13Cvaluesformarine-derivedArcticOMliewithinthe cially after 4.0cal. kyr BP. Carbonate dissolution is further evi- range(cid:5)19&to(cid:5)24&(e.g.Go˜nietal.,2000,2005;Beltetal.,2008) dencedbytheverylowplanktonicforaminiferal abundancesand althoughawiderrange(ca(cid:5)17&to(cid:5)30&)hasalsobeenreported enhancedcorrosionandfragmentationofmicro-andmacrofossils, (SteinandMacdonald,2004).TerrigenousOMisgenerally‘lighter’ particularlyintheuppersectionsofthecore(<4.0kyrBP).Amore thanmarineOMwithad13Crangeof(cid:5)26&to(cid:5)28&(Stein and detailed account of the up-core dissolution based largely on Macdonald,2004).Assuch,thed13CvaluesforbulkOMfromthe changes in distributions and preservation of individual forami- ARC-3core((cid:5)22&to(cid:5)25&)liefirmlywithintherangeofmarine- nifera and macrofauna can be found elsewhere (Gregory et al., derivedOM.Thegeneraltrendtowards‘lighter’ormorenegative submitted for publication). Dissolution is likely controlled by d13Cvaluestowardsthebottomofthecoremightbeinterpretedin anumberoffactorsincludingCO2levelswhichareinfluencedby, L.L.Vareetal./QuaternaryScienceReviews28(2009)1354–1366 1363 amongstotherthings,originofwatermassesandseaicecover.For Our conclusions can be compared with others drawn from example,thedissolutionofforaminiferaobservedatca8.0kyrBP previous palaeo-climate studies, including those that address sea in Baffin Bay (Aksu, 1983) has been attributed to CO2-enriched icecover.Firstly,thecontinuousoccurrenceoftheIP25biomarker, Arctic water entering through the Arctic channels (Dyke et al., andthereforeofseasonalseaiceconditionsbackto10cal.kyrBP, 1997), while changes in distributions of foraminifera in Barrow confirmstheretreatofthemainicemarginswithinBarrowStraitby Strait suggest a transition from Atlantic to Arctic water masses, this time (Dyke, 1999; Dyke et al., 2002; Kaufman et al., 2004). notablyat4.0–2.0kyrBP(Williamsetal.,1995).Withrespecttosea Secondly,thefourmaindiscreteintervalsofspringseaiceoccur- ice, Wollenburg and Kuhnt (2000) demonstrated that dissolution rence presented in this study compare very favourably with the was higher under seasonal ice cover which aligns well with our summericemeltrecordoftheAgassizIceCap(KoernerandFisher, ownfindingsofhigherdissolutionup-corewithincreasingspring 1990;Fisheretal.,1995),withrelativelylowspringseaicecondi- sea ice occurrence. As such, it is the occurrence of carbonate tions aligning well with high summer ice melt during the early– dissolution within the core, particularly after ca 4.0cal. kyr BP, midHolocene(Fig.8).Theabruptandpersistentincreasestoseaice ratherthantheoccurrencesofforaminiferaasaproductivityindi- duringthemid–lateHolocene(<ca4.0cal.kyrBP)arereflectedin catorthatprovidesevidencefortheproposedtemporalchangesto the low ice melt phase for the Agassiz Ice Cap. Thirdly, our seaice.However,sincethereareanumberofalternativeexplana- conclusions are consistent with those of Levac et al. (2001) who tions for dissolution including the influence of different water constructedaseaicedurationprofilefornorthernBaffinBayusing masses,weconsiderthisobservationtobesupportiveratherthan transfer functions of dinocyst assemblages. These authors definitive. concludedthatseaicecoverwaslow(oratleastlowerthanpresent In summary, these proxy data can be interpreted in terms of daylevels)priortoca4.5kyrBP,followedbysignificantly higher providingevidenceforthevariableoccurrenceofspringseaicein sea ice duration between this point and modern times. For Lan- four intervals: (1) A period in the early–mid Holocene (ca 10.0– caster Sound, east of Barrow Strait, the prolonged early to mid 6.0cal. kyr BP) where the spring sea ice occurrence was at its Holocene warm period, as predicted from dinocyst assemblages lowest;(2)Ashorterinterval(ca6.0–4.0cal.kyrBP)wherespring (Ledu et al., 2008), terminated around 2.9kyr BP, with a shift sea ice occurrence steadily increased, but remained below the towardscoolersummertemperatures.Thislatterobservationisin medianfortheHolocene;(3)Abriefinterval(ca4.0–3.0cal.kyrBP) closeagreementwiththeseasonalseaicerecordforBarrowStrait, wherespringseaiceoccurrencesincreasedrapidly;(4)Aperiodin derivedfromthebiomarker(andotherproxy)datapresentedhere. the late Holocene (ca 3.0–0.4cal. kyr BP) where spring sea ice Probably the most extensive previous proxy record of palaeo- occurrencewasat its highest. There is some evidencefora short seaicereconstructionintheCAAhasbeenmadebyconsideration termdecreaseinspringseaicetowardstheendofthislateHolo- of the occurrences of bowhead whale remains in raised beach ceneinterval(ca1.2–0.8cal.kyrBP),followedbyafinalincreasein deposits throughout the archipelago (Dyke et al., 1996b; Savelle thelast0.4kyr(0.8–0.4cal.kyrBP). et al., 2000). The basis of this proxy is the argument that the Fig.8. Temporalprofilesof(a)IP25fluxes;(b)summericemeltrecordfortheAgassizIceCap(datafromhttp://www.ncdc.noaa.gov/paleo/icecore/polar/agassiz/melt.html).
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