This file was created by scanning the printed publication. Errors identified by the software have been corrected; however, some errors may remain. GLOBAL BIOGEOCHEMICAL CYCLES, VOL. 10, NO. 3, PAGES 473-482, SEPTEMBER 1996 Diffusional flux of CO: through snow: Spatial and temporal variability amongalpine-subalpinesites RichardA. Sommerfeld,William J. Massman,andRobertC. Musselman U.S. Department of AgricultureForestService,RockyMountainForestandRangeExperiment Station,Fort Collins,Colorado Arvin R. Mosier U.S. Departmentof AgricultureAgriculturalResearchService,FortCollins,Colorado Abstract. Threealpineandthreesubalpine sitesweremonitored for upto 4 yearsto acquire dataonthetemporalandspatialvariabilityof CO2flux throughsnowpacks. We conclude that the snowformeda passivecapwhichcontrolledthe concentration of CO2at the snow-soil interface,whiletheflux of CO2intotheatmosphere wascontrolled by CO2production in the soil. Seasonal variabilityin theflux at all siteswascharacterized by earlywinterminima followedby a risein flux thataveraged 70% abovetheminimaoverabouta 1-monthperiod. The seasonal variabilitywasnotrelatedto soiltemperatures whichremainedrelatively constant.Interannual variabilitywassmall,andspatialvariabilitywassmallerthanpreviously reported.Spatialvariabilityon a scaleof 1 to 10 m waslessthan30% of theaveragefluxes andnotsignificantly greaterthanestimated errorin mosteases.Spatialvariabilityon a scaleof 10- to 100-m was about a factor of 2 and on a scale of 100 to 1000 m was about a factor of 4. The 100-to 1000-mvariabilitywascomplicated by thefactthatthesiteswerein different ecosystems, alpineandsubalpine, andat differentelevations.We attributethesmallvariability at the 1- to 10-mscaleto thedeepsnowcover,from 1.4 to 5 m. We hypothesize that horizontaldiffusionunderthesnowcoverreducedsmall-scale horizontalgradients, whilethe insulatingeffectof thedeepsnowcoverkeptthesoiltemperature andmoisturerelatively constant. Equivalent annual wintertime fluxaveraged about 95g C m'2yr'l inthealpine and about 232g Cm'2yr'l inthesubalpine sites.Measurements ofCO2concentrations at0.2and 0.5 m in thesoilof oneof thesubalpine sitesindicatedthatproduction earlyin thesnowseason occurredat or below0.5 m whileproduction between0.5 m, andthe surfacebecameimportant afar the start of the melt season. Introduction The flux of CO2 throughsnow coversmay constitutean importantpart of the carbonbalancein alpine and subalpine ecosystems [SommerfeM et al., 1993]. Snowmaycoverbetween 44 and 53% of the land areaof the northernhemisphere during the winter [Barry, 1992]. In high elevationand high latitude areasthe soil may be snowcoveredfor the greaterpart of the year. The insulating effectof deepersnowcoverscanallowthe underlyingsoilto maintaintemperatures above -6.5'C, whichis thoughtto be the lowesttemperatureat which CO2 production occurs[Coxsonand Parkinson,1987]. CO2productionin soils varies in time and space,and this variationis reflectedin variationsin the fluxes throughsnow. It is importantto characterize this spatialandtemporalvariabilitybothto evaluate theimportance of subnivian CO• production onthe globalcarbon Thispaperis notsubject to U.S. copyright.Published in 1996by the .american Geophysical Union. Papernumber96GB01610. 473 budgetandto help understand the controlson CO2production under snow. We have measuredthe fluxes of CO2 through snowpacksat alpine and subalpinesites in the Glacier Lakes Ecosystem Experiments Site(GLEES)in southcentralWyoming for four seasons.The resultsshouldprovidea basisagainst which other measurements can be compared. Musselman [1994] gives a comprehensivedescriptionof the GLEES. Sitesfor SampleLocations To investigatethe spatialvariabilityof CO2flux, six sitesat separationsbetweenabout 50 and 2000 m were established. Three of the sites were representative of the local alpine ecosystem, andthreewere representative of the local subalpine ecosystem.In selectingthe sites,we attemptedto maximizethe differencesin CO2 productionby choosingsiteswith different vegetation, soil development,and wetness. To evaluate temporalvariability,one alpine and one subalpinesite were maintainedfor more than 3 years. Four additionalsiteswere sampledfor onesnowseasoneach;two in 1992-1993andtwo in 1993-1994.At five of the siteswe established pairsof sampling 474 SOMMERFELD ET AL.: DIFFUSIONAL FLUX OF CO• THROUGH SNOW locationsseparated by 2 to 4 m. At the sixth(subalpine)sitewe usedfour of the samplinglocationsdescribedby Mosier et al. [1994],whichwere separated by 5 m eachandincludedsample tubesat 0.2 and 0.5 m in the soil. This site was sampledin 1992-1993 Alpine Sites The alpine sites are locatedat the alpine and subalpine ecotoneat the GLEES. The main alpine site at about3290 m abovesealevel (HILL) was maintainedfor 3 years,April 1991 throughJune 1993. The site is a dry, wind-exposedridge between East and West Glacier Iatkes and the environment here isharsh.Thewindaverages 11m s4 inthewinterand5 m s4 in the summer.The vegetationis primarily grassesand cushion plants; although there are a few small, scattered,Picea engelmannii,Abies lasiocarpa,Juniperuscommunisvariety depressa,and Salix brachycarpanear the site. Groundcover speciesfound here include Vacciniumscoparium,Festuca brachyphylla, andSelaginella densa.Vegetative coveris sparse. Soilsare thin and rockywith very little soil development. The maximummowpackhere averages1.8 m, about 90% of the averagefor GLEES [Musselman,1994], and the well-drained soil dries soonaRer mowmelt. This site is the highestin elevationandthereforehasa loweraverageair temperature with the snowmeltbeginninglater in the seasonthan averagefor GLEES. This sitewaschosenbecauseit wasexpectedto havea relativelylow CO2 flux. The two samplelocationsat this site wereseparated by about4 m. The secondalpine site, West Glacier Lake (WGL), at the elevation of the HILL site and about 400 m to the southwest was sampledfrom late December1993 throughApril 1994. It is a largealpinemeadow,fed by snowmeltearly in the season,but typicallybecomingdry in Julyor August.It is protectedfromthe prevailingwind directionby topography andnearbytrees.There is a considerable amountof exposed rock. Primarycoverspecies are Geum rossii and Sibbaldia procurebens. Artenna•qa umb•qnella,Potentilia diversifolia, Danthonia intermedi, Juncusdrummondii, Vacciniumscopariumand Carex rossii alsooccuron the site. The two samplelocationsat this sitewere separated by about3 m and were sampledfor one snowseason in 1993-1994. The third alpine site, a wet alpinemeadow(WAM) located about200 m northeastof the HILL site in a smallgully,was sampled from November 1992 through June 1993. An ephemeral streamrunsthroughthe gullyin the springandearly sununer,fed by a large, uphill snowpack. The gully also accumulates the deepestsnowpack of all the sites;5 m during the samplingyear. The area is vegetatedprimarily with Deschampsiacespitosa, Carex nigricans, and Caltha leptosepala, with smalleramounts of CarexaquatilisandJuncats drummondii present. The site is somewhat shelteredfromthe prevailingwinds and is surroundedby sparseforest near timberline. Soil is thicker than the nearby HILL site. Vegetationis alsodenser,becau• of the protection andwetter conditionsthan the HILL site. This site was sampledfor one snowseasonin 1992-1993at two samplelocationsseparated by about 4 m. SubalpineSites The main subalpinesite (BRK) was maintainedfor 4 years, April 1991 throughMay 1994. It was chosento contrastwith the main alpine (HILL) site. The BRK site is a smallmeadow, about25 m in diameter,surrounded by forestexceptfor a small openingleading to a larger open area about 20 m to the southwest.The surrounding forestprotectsthe locationfrom prevailingwinds. Wind belowthe canopytop averages about3 m s4 in winter and about2 m s'• in the summer. The common species areDeschampsia cepitosaandCalthaleptosepala.Soils are shallow,rocky,and dry after snowmelt.The environment is muchlessharshthanthealpinesite. The soilappears to holdits moisturelonger,and beingat lower elevation(3180 m), it is warmer. This sitewaschosen with the expectation thatthe CO: flux wouldbe higherthan at the alpinesites. The two sample locations at this sitewereabout10 m eastof the forestedgeand wereseparated by about3 m. The secondsubalpinesite(FOR) is about100m westof BRK in a densePicea engelmanniiforest stand,with almost no understoryvegetationpresent at the site, but Vaccinium scopa•umoccursin the immediatearea. Thereis a thick layer of freewoodydebrisandduff fromtwigsandneedlesfromthe overstory trees. The snowpack hereis thethinnestandspatially the most variablein depth. This site was sampledfor one season,September 1993 through April 1994 at locations separated by about2 m. Locations M3, M4, M5, andM6 (3 to 6 in the workof Mosier et al. [1993])were 130 (M6) to 145m (M3) westof BRK. They are in a wet meadowabout20 m wide by 70 m long,alonga relativelyflat drainagebasin,with a ephemeralstreamchannel which flows during snowmeltbut, the stream dries after snowmeltis complete,generallyin early Julyto early August. M3 and M4 grade from the drier Picea engelmanniiforest towardthe wettercenterof the meadow.Commonspecies here are Deschampsiacepitosa and Caltha leptosepala. Salix planifolia occursfrequentlyon the east edge (M3) of the meadow.The centerof the meadow(M5 andM6) is wet, with characteristicspeciesbeing E•geron ursinusand Plantago tweedyi. Also presentare Trisetumspicatumand Achillea millefolium.The four samplelocationswere eachseparated by about5 m each, startingabout3 m east of the forestedge. Samplingwas conductedfrom Decem• 1992 throughMay 1993. This sitewas chosenwith the expectation that it would havethehighestCO• fluxes. Methods At each site, gas collectors[Soreinertialet al., 1991] were installed at the soil surface before accumulation of the •nal snowpack.Accesstubingwastapedto a 3-m-longpieceof 1/2 inch(13 nun)metaltubingsetverticallymorethan1 m fromthe samplelocationto allow sampling withoutdisturbing the snow directlyoverthe samplelocation.After thewinter'ssnowcover beganto accumulate,sampleswere drawnfrom the collectors andfrom the ambientatmosphere on a variableschedule.The snowdepthat thetimeof sampling wasmeasured by theheight of themetaltubingabovethe snowsurfaceat eachlocation.The samples wereanalyzed by gaschromatography. Thediffusional SOMMERFELD ET AL.: DIFFUSIONAL FLUX OF CO• THROUGH SNOW fluxesthroughthe snowcoverswere estimatedby two different methods. When snowstratigraphy datawere availablefrom snowpitsdugwithin 1 dayof the sample,themodelof Massman et al. [1995] was used. This was the moreaccuratetechnique becausethe model accountsfor layer porosity,tortuosity,and thickness.At othertimesa voltune-weighted meanporosityand total snowthicknesswere used. The volume-weighted mean porosities wereestimated frominterpolations of snowpit data. 475 calibrationaccuracy.Whenthe 4000 ppmvtankwasexhausted, we concentrated our calibrationeffortsin the range0 to 2000 ppmv where the gas chromatograph exhibited nonlinearities largerthan2%. This wasjustifiedby the manycomparisons betweenthe 2000 and 4000 ppmv tanks which were linear within 2%. We assumed from the calibration data between 2000 and4000 ppmvthat extrapolation from 4000 to 10,000ppmv couldbe donewith sufficientaccuracy for our purposes.This assumption is requiredto recoverdatagreaterthan4000 ppmv. Gas Analysis Data in this range (about 14% of the total) were initially of the Gascollectorinstallations at the baseof the snowpacks were unexpected.Becauseof the extrapolation,the accuracy concentrations above about 2500 ppmv is conservatively as described by Sommerfeld et al. [1991]. Soil gascollectorsat to be 5%, andfor simplicityin the followingwe have M3 throughM6 were sectionsof 1/8 inch (3 mm) stainless estimated robingembedded in epoxyin 1 inch(25 ram)polyvinylchloride taken a conservativeestimate of the accuracyof all measurements as 5%. Thereare threemeasurements (about1% (PVC) robing. Eachsectionof stainless robingpiercedthe wall of the total) above 6000 ppmv, but since the nonlinearfly of the of the PVC tubingat a samplinglevel from 0.1 to 0.5 m. The ends of the stainless sections were finished flush with the outsidesurfaceof the PVC tubingat eachlevel. The otherends protruded abovethe soil surfacewhen theseprobeswere forced intoclosefittingholescoredin the soil.The levels0.2 and0.5 m in the soilweresampledfor oneseason in 1992-1993. Twenty-mLnylonsyringes wereusedto drawthe gassamples and transport them to a Hewlett Packard 9730 gas chromatograph with a 3 M I-IaysepD columnand a thermal conductivity detector.Sampleswereanalyzedwithin4 hoursof collection.Testsshowedthat samplesof 2000 partsper million by volume (ppmv) stored in the syringes decreasedin concentration by about5% in 24 hours. In 1991,standardgasesof approximately 350 and2000 ppmv fromAir Products,Inc. were usedas workingstandards for the analyses.Startingin 1992,the 350 ppmvworkingstandard was calibratedagainsta primarystandardtank of 343.2 ñ 0.4 ppmv obtained from the National Institute of Standards and Technology. In addition, higher-concentration working standards of approximately 1000, 2000, and 4000 ppmvwere calibratedagainsta mixtureof 99.99% CO• (Air ProductsInc.) anddry artificialair. Mixing was doneusingmassflow meters calibratedagainsta Hastingsmodel HBM-1A bubble flow meter,whichhasan accuracyof betterthan 1%. The precision measurementsdecreasedwith concentration,we believe their accuracyis also within our estimate. As discussed below, the errorsinvolvedin estimating the porosities of the snowcovers for the flux calculations are greaterthan 5%, so the errorsof theseanalyses are smallcompared to othererrors. SnowpackProperties The mostimportantsnowpropertiesfor the estimationof diffusionalflux are the porosityprofilesand the layer thicknesses [Massman et al., 1995]. Snowpitsweredugat timesthroughout eachwinterto determiae theporosity profiles frommeasurements of densities andstratigraphy usingstandard snowpit techniques. Pitsweredugascloseaspractical to the sampling sitesbut not socloseas to affectthe gasflux at the sampling sites.All sitesexceptFORhadsnowpacks whichwere relativelyfiat anduniform. Therefore the stratigraphy of the samplingsiteswas assumedto be the sameas that determined fromthe snowpits,with individual layerslinearlyscaledfor differences in snowdepth.Thisassumption maynothavebeen accuratefor the FOR site. Snow pits were backfilledafter stratigraphy determinations. For samplingtimesthat did not correspond closelyto the snowpit times, we used a time- weighted average of thevolume-weighted meanporosities of the snowpitsbeforeandal•erthesampling dates. was better than 1%. On occasion,the precisionof the gas E•ence has shownthat if the layeringis properly chomatograph was no betterthan2% as estimatedfrom scatter identified,scatterin density(porosity)measurements within in the calibrationsusingthe workingstandards.Thereforewe each layer is about 10%. Since this scatteris random, of thesecalibrations,as estimatedfrom the scatterin the results, conservativelyestimate the accuracy of the calibration inaccuracies in theaverages areexpected to decrease by na, measurements as ñ 2% in the range300 to 4000 ppmv. wheren is thenumberof layers,usuallyabout10. However,the The calibrations allowed determination of the calibration constant (ppmv/signal curvearea)for the range0 to 4000 ppmv. This calibrationand subsequent operationshowedthat the gas chromatograph hada small,nonlinearresponse in the range0 to 2000 ppmv, which varied from run to run. A linear extrapolation from0 through350 ppmvcouldresultin an error at and above 4000 ppmv of up to 5%. This result was unexpected sincethis typeof instrument is usuallyassumed to be linearwithin about2% overits entirerange. To compensate for this behaviorbetween0 and 2500 ppmv, we fitted a polynomial to theworkinggascalibrations for eachdayandused thatcalibration curveto correctthegasanalyses.Fortherange0 to 2500 ppmv, accuracyis about 2%, the estimateof the snowpitswereduga fewmetersfromthegasmeasurement sites andoftenporosities wereestimatedfromthe porosities of the two snowpits closestin time. We thereforeconcludedthat unless thelayersweremorethan20 cmthick,takingmorethan onesampleperlayerwouldnotmateriallyincrease theaccuracy of the porosityestimates.We makea conservative estimateof the accuracy of the volume-weighted meanporosityestimates as 10%. The error estimatemustremainsomewhatsubjective basedon ext•rience. An objectiveestimateof the errorwould haveinvolveddestroying the samplesite. Icelenses wererare. Onlysinglelayerswereobserved in pits dugafterthe middleof April, andtheydisappeared in about2 weeks.Theirporosity is difficultto characterize. However,they 476 SOMMERFELD ET AL.' DIFFUSIONAL FLUX OF CO• THROUGH SNOW Table 1. Comparisonof Fluxes Estimatedby a Layer Model and a Volume-Weighted-Mean PorosityModel for Days on Which Snow Pit Information Was Available Site Layer Model VWM Model Mean Average, mgm'2s'• Average DifferencesofDifferences StandardDeviation 0.0149 0.0123 0.0188 0.0176 0.0266 0.0261 0.0005 0.0008 0.0009 0.0008 0.0011 0.0011 cch HILL-A HILL-B WAM-A WAM-B BRK-A BRK-B 0.0143 0.0114 0.0178 0.0168 0.0255 0.0250 areverythincompared to thetotalsnowthickness, sothatlarge errorsin estimating theirporosities addonlya smallerrorto the volume-weighted porosities.The influenceof an ice layerwould onlybe dramaticif its porositywere 0, but suchice layersare neverobservedin this region. That suchlayersdo not exist is shownby the concentration profilesreportedby SommerfeM et al. [1993], Mast et al. (1994), Massman,et al. (1995), and unpublished profilesobtainedduringthe courseof this study. These profiles were basically linear and thus showed no evidencefor anysignificantimpermeable layer. Flux Calculations Assumingone dimensionalflux, the diffusionalflux follows Fick's law 0.0004 0.0012 0.0001 0.0002 0.0002 0.0004 Results StratigraphyModel Comparisons Beforeflux datafromindividualsiteswereevaluated, it was necessary to det•e and correctany inaccuracy involvedin usingvolume-weighted meanporosities whensnowpit data werenot available.A comparison betweenthe fluxescalculated usingthe layer modeland fluxescalculated usingvolumeweightedmeanporositiesfrom 28 setsof concentration datais shown in Table1. Errorscreated byusingthevolume-weighted meanporosities areup to about+5% andaveraged +4.4% of the flux for all the measurements. On the basisof our results, diffusional fluxescalculated for timeperiods withoutsnowpit datawerereduced by4.4%. Thiscorrection wasalsoappliedin determining averagefluxespresented in Table2. Alpine Sites J=-•xD dz I-HLL Data for the I-IILL site include measurementsfrom April1991through June1993.Theaverage fluxesfortheperiod studied areshown in Table2. Thetwolocations differbyabout where• is the porosityof the layer,x is the tormosity of the 6% of the averageflux, not a significant difference givenan layer,D is the diffusioncoefficientfor CO2 in air and dc/dz is errorestimateof 11%. The standard deviationof the daily the concentration gradientacrossa uniformlayer. We assumed differences is about30% of the flux indicatingshort-time that x = 1. Tortuosityis a difficultquantityto measureand variations in the fluxes. The seasonal temporal variabilityis proved impossible for the number of samples taken. Nevertheless,limited measurementsof the tormositiesof snow consistent from year to year. Eachyear exhibitsa minimtun earlyin thecalendar year,a riseto a maximum whichbeginsat aboutthetimeof onsetsnowmelt,anda dropbeforethe snow (W. Massman et al., manuscript in preparation, 1996)suggesting disappears (Figurela). The riseaveraged about95%overthe minima with a duration of about 1 month. thatwe mayhaveoverestimated ourfluxby 10to 25%. Windpumping mayalsoaffectthe flux [AlbertandHardy, WAM. Forthisstudy,the lowestdatapoint(WAM A, May 1995;Massmanet al., 1995;W. Massmanet al. manuscript in 25, 1993) was removedfrom the data set. At the time that preparation, 1996] However,the magnitude of the effectis still measurement was made,water was observed to be running unclear. beneath thesnowcover.In a few daysa largeholeopened in The snowdepthandthe diffusioncoefficientof CO2in air are thissnowcoverandtheconcentrations at thissampling location knownto betterthan 1%. Thus,apart from tortuosityand droppedto about2000 ppmv. Becauseof the waterflow, we possiblewind effects,mostof the errorresidesin estimatesof think this point is more representative of the concentration concentration (5%)and porosity(10%). A conservative estimate upstream of this samplinglocation. Temporalvariabilityis of the accuracy of the productof porosityandconcentration is similarat the two samplelocationsbothof whichexhibitthe then11%[Goodman, 1960]whichwetakeastheaccuracy of the earlywinterminimaanda riseto a maximumaveraging 70% fluxestimates. Again,theestimates at theFORsitemaynotbe higherovera 1 monthperiod,corresponding approximately to thisaccurate because of variablesnowdepth.If ourestimate of theonsetof melting.Thissitehasanaverage fluxintermediate the accuracyof the of the concentration measurements is between theotheralpinesitesandthe subalpine sites(below). degraded to 10%, the overallerrorwouldbe 14% [Goodman, The averages differby about10%, andthe standard deviationof •960]. thedailydifferences is about15%of theaverage flux. Bothare layersnear sitesM3-M6 indicatea value between0.75 and 0.9 SOMMERFELD ET AL.' DIFFUSIONAL FLUX OF CO2 THROUGH SNOW 477 Table 2. Summaryof CO2Fluxes Location Numberof Hill A Hill B WGL 2 WGL 4 WAMA WAMB BRK A BRK B FOR A FOR B M3 M4 M5 M6 25 25 7 5 12 10 30 30 9 7 11 g 11 11 Coefficientof Standard Deviation Average,mg Samples m':s4 CO• Variation 0.44 0.0043 0.0097 0.0103 0.0088 0.0071 0.0136 0.0167 0.01 g9 0.01 g4 0.0140 0.0229 O.O372 0.0369 0.0320 0.0359 0.35 0.30 0.37 0.37 0.37 0.27 0.19 0.65 0.37 0.17 0.21 0.25 0.15 0.0046 0.0024 0.0026 0.0051 0.0062 0.0050 0.0035 0.0090 0.0084 0.0062 0.0076 0.0080 0.0055 Maximum 0.0224 0.023g 0.0112 0.0096 0.0265 0.0304 0.0330 0.0253 0.0363 0.0394 0.0494 0.04g0 0.0476 0.0456 M'mimum 0.0040 0.0042 0.0054 0.0044 0.003g 0.0115 0.0093 0.0071 0.0064 0.0156 0.0293 0.0233 0.0215 0.0300 Range 0.0184 0.0196 0.0057 0.0052 0.022g 0.01 g9 0.0247 0.01 g2 0.0300 0.022g 0.0200 0.0247 0.0261 0.0156 $. D. of Daily Differences 0.0032 0.0012 0.005g 0.0040 0.0151 0.0043 0.0034 closeto the estimatederror of 11%, indicatingno seasonalor short-time 0.04 -- HillA ¸ Hill B + 0.00 i i i i [ i i i 1991 1992 i i 11993 difference between locations. This site had the thickestsnowpack, whichshouldhavebeenthe mosteffectivein decreasing horizontalgradients. WGL This sitehad averagefluxesabout20% smallerthan the HILL siteandwith a smallerrange. Temporalvariabilityis similarbetweenthe two samplelocationsand to the HILL site, with the earlywinter•m risingto an average80% higher overa 1-monthperiod. In this casethe rise startedwell before the melt period(Figurel c). The averages differ by about15%, andthe standarddeviationof the daily differencesis about16%, onlyslightlyhigherthanthe estimatederror. Thusthe seasonal andshort-termdifferences maynothavebeensignificant. SubalpineSites q- WAM A 0.04 -- ¸ WAM B BRK. The most extensive data are available from the BRK site (Figure ld). The 1991 data collectionbegan in the beginningof April and continuedto the end of March 1994. In 1992-1994, minima in the fluxes were observed in the first b 0.00 ;19'92' 963' + WGL 2 0.04-- ¸ WGL 4 - c 0.00 I1993 i i I • 994 i i Figure 1. Timeseriesof CO• at thedifferentsites:(a) HILL, (b) WAM, (c) WGL, (d) BRK, (e)FOR, and(f) M3 - M6. quarterof eachyear, and maximawere observedin April at approximatelythe time that melt starts. In 1991-1993 the maximaare followedby a distinctdropin flux just beforethe snowdisappears.The maximaaveragedabout25% higherthan the minimaandroseoverabouta 1-monthperiod. Rangesand averagesof the fluxesare in closeagreementfor the 4 years. The averages differby about10%, nothigherthanthe estimated error. The standarddeviationof the daily differencesbetween the locationsat this site is about 20% of the averageflux, indicatingsomeshort-time variabilitybetweenthefluxes. FOR. This site showedthe greatestrangeof fluxesbut also had the early winter minima rising to maxima averaging60% higherin about2 weeks. The rise startedbeforethe onsetof meltingandpersistedabout1 month. Driftingandto a smaller extentinterception causedunevensnowdepositionwhichmade it difficultto estimatethe effectivesnowdepthat eachlocation. The averageflux was aboutthe sameas BRK. The averages differedby about20%, and the standarddeviationof the daily differences wasabout80% of the averageflux, bothsignificantly largerthanthe estimatederror. However,because the estimated errorin the porosityand depthmay not be reliableat this site, the20% differencebetweenaverages maynotbe significant. 478 SOMMERFELD ET AL.: DIFFUSIONAL FLUX OF CCh THROUGH SNOW 0.04 + BRK A -- 0.00 i i ¸ i i BRK B i i i i i i 11992 11993 1991 i i 1994 d FOR A 0.04 -- ¸ ¸ FOR B + + 0.00 -I- M3 -I- M5 ¸ ¸ M4 M6 0.04 0.00 I 1992 1993 I 1992 I I 1993 Figure 1. (continued) M3 through M6. There is a greatertemporalvariation amongthe measurements at thesefour samplelocationsthanat any but the FOR site. However,they all exhibitminimaand maximasimilarto thoseof theothersites.An average70% rise overthe minima startedbeforethe onsetof meltingand lasted about6 weeks. The averagesdifferedby almost50% across locationsprobably,reflecting different soil regimes at the locations.The standarddeviationof the daily differenceswas about10% of the averageflux, whichis not significantly larger than the estimated error. the slope of the linear regressionto the 0.5-m data is substantially lowerthantheslopes of0.2and0 m. Also,R2for 0.5 m is lower for all thesedata, and the concentrations at 0.5 m arehigherfor mostof theperiod.However,at thebeginning of snowmelt theconcentrations amongthedepthstendto converge. A constant concentration throughout the depthof soil, combined withthemeasured flux throughtheoverlying snow,impliesthat there is a distributed source in the soil between 0.2 and 0.5 m. Discussion Soil concentrations. Figures 2a-2d show the temporal TemporalVariability variationof the concentrations at the soil surface,0.2 and 0.5 m belowthe soil surface.All locationsat this site showa general Longer-termtemporalvariability amongall the locations increasingtrend in concentration duringeach sampleseason. show distinct similarities. Concentrations at the snow-soil Table3 givesthe parameters of linearfits to data. For all cases interface increase from the start of the snow season until the SOMMERFELD ET AL.: DIFFUSIONAL FLUX OF CO• THROUGH SNOW DEPTH 10000 -- I • 479 IN SOIL ocm 20 cm 5000 •ANUARY I I JANUS.' APRIL 1993 1993 b. M4 a. M3 10000 5000 JANUARY APRIl. 1993 c. M5 1993 d. M6 Figure 2. Temporalvariationof CChconcentrations at the soilsurface,andat depthsof 0.2 and0.5 m in the soil,at samplelocations (a) M3, (b) M4, (c) M5, and(d) M6. startof themelt season.Figure3 showsa representative plot of concentration andsnowwaterequivalentwith the axesscaledfor correspondence betweenthe two curves.Fick's law showsthat if the flux is constant, the concentration is linearlyrelatedto the snowdepthand inverselyrelatedto the porosity. If the snow depthis constant, the concentration will increasewith increasing snowwaterequivalent.Figure3 showsthatthe concentration at thebaseof the snowpack tracksthe snowwaterequivalent. Figure2 showsthatthe concentration at the baseof the snowpack at M3-M6 increasessteadily. In contrast,the diffusio• fluxes(Figure l f) showdistinctminima. The most extreme case of this behavior was at WAM A, where the concentration increasedmonotonically up to a maxim.urnof 10,464ppmvwhilethe flux (Figurelb) wentthrougha distinct minimumand then a maximum. The changebetweenthe minimumandmaximumwasaboutaverageforthisstudy.Thus, to a first order, control of the concentrationat the snow-soil Table 3. Linear TemporalTrendsof C02 Concentrations in Soil interface isthesnow depth, whilethefluxismainly controlled by production in the soil. In somecases,concentration increased by more than an order of magnitudefrom the start of snow accumulationto the time of maximum accumulation,while the Level, m _ CO• Concentration, ppmv/day M3 0.93 flux went througha minimumand then a maximum. Secondordercontrolof the concentration is by meansof the flux from the soil. This is indicatedby the factthatthe concentration and snow water equivalent(SWE) plots do not track perfectly (Figure3). If the SWEwereconstant, Fick'slaw showsthatthe concentration would changeproportionalto the flux. Data 0.0 38 -0.2 38 0.95 -0.5 26 0.80 0.0 38 0.94 -0.2 38 0.79 -0.5 16 0.70 of 3 overthe minimumbecauseof flux changes but that the concentration was observedto changeby morethan a factorof 10. It is alsointeresting thatthe veryhighconcentration nearthe M4 M5 0.0 27 0.86 -0.2 -0.5 29 14 0.90 0.65 0.0 31 0.83 -0.2 38 0.93 -0.5 22 0.88 M6 presented hereshowthatthechange couldbeashighasa factor time of maximum flux before snowmelt at WAM A indicates that the productionof CCh is not limited by high CCh concentrations up to at least1%. It is possiblethatproduction or consumption of CChoccursin the snowpack.Suchprocesses within the snowthat affectthe flux wouldcauseflux divergence whichwouldbe evidencedby 480 SOMMERFELD ET AL.: DWFUSIONAL FLUX OF CO• THROUGH SNOW -- 1oo 4000 -- 1992 I • BRK-A • BRK-B - 5o 1993 Figure3. Concentrations of CO•at themow-soilinterface andthesnowwaterequivalent at BRK,the main subalpinesite. nonlinearities in concentration profilesnot relatedto porosityor tortuositydifferences. Sommerfeldet al. [1993] show such evidencefor the BRK (their "Subalpine")site in 1991. The production of CO: in the snowat that siteaddedat most10% to the total flux. Subsequentprofiles, includingprofilestaken duringthis study,indicatethat the 1991production in the snow wasan extremeevent. Mast et al. [1994] fittedtheir CO:-snow profiledatawithlinearregressions R2 between 0.82and0.99, similarlyindicatinglittle if anyflux divergence in the snow. Likewise,storageprocesses withinthe snoware not likely to be importantontimescales of morethana few hours. In the dry snowpack, surfaceadsorption ontheiceis insignificant [Ocampo and Kilnget, 1983]. In a wet snowpack at 10% liquid water content, a cubic meter of snow with a CO2 concentration increasing from0 to 1000PPMV, the storagein solutioncould absorb 2 to3 hours ofCO:ata fluxrateofabout 0.02mgm'2s4. Approximate calculationsshoxv that flushing of CO: by downward movingmeltwateris about2-ordersof magnitude less than the upwardfluxes we measured. Winstonet al. [1992] measuredlower fluxesfrom the top of the snowthan from the soil. However,they hypothesized that the CO: was channeled alongtree trunk and stem macrochannels at their site which couldaccountfor the discrepancy.This processwas possible onlyat ourFOR site,butbecause of driring, thetreewellswere not as well developedas thosedescribedby Winstonet al. [1995]. Theseresultsleadto the conclusion thatthe maincause of temporalvariabilityin the concentrations at the soil surfaceis the snow layer which forms a passive,porouscap over the samplinglocationbut that snowprocesses do not affectthe flux significantly ontimescales greaterthana fewhours.In all cases the flux reachesa maximumat approximately the time the snow water equivalentreachesa maximum:oppositethe behavior expectedif the snowpackwere controllingthe flux. The diffusionmodelwe usedandthe concentration profilesshowthat ice lensesarenota significant factorin ourflux estimates. Thus it is clear that there is a secondarycause of concentration variabilitywhichis relatedto temporalvariability in the fluxesinto the baseof the snowpack.Withoutsignificant sources or sinksof CO• in the snow,processes in the soilcontrol theflux. Theseprocesses weresignificantly differentamongour differentsites, as would be expected. Differencesbetween locationsat eachsiteweremorevariable. Sometimes theywere greaterthanthe estimatederrorandsometimes not. All sitesexhibita minimumin flux earlyin the winter. This is in agreement with the measurements of Winston et al. [1995], who attributed the minimum in their measurements to low soil temperature. A flux minimum early in the winter is also apparentin the measurements of Brookset al. [1995]on Niwot Ridge, Colorado. Three candidatesfor causingtemporal variationsin CO2fluxesfrom the soil are temperature changes, soilmoisturechanges,andpopulationchanges in the soilbiota. Figure4 showsthe 5- and 20-cmsoil temperatures at two sites, onenearthe alpineandonenearthe subalpinesites. ARer the establishment of a significantsnowcoverin late November, thereis no significantchangein the soil temperatures.These remainaround-1ø to IøC, well abovethe approximately -6.5øC thatCoxsonandParlanson[1987]giveas a cutofftemperature. for biologicalactivity. The constant temperature lastsuntil the snowmeltsawaywhenthereis a steeprise in soiltemperature. Notethattherisein CO• production beginsbeforetherisein soil temperature.The temperaturechangesat 0.5 m, whichappears to be nearthe sourceof CO• production, wouldbe evensmaller. Thussoiltemperature changes cannotbe a factorin thetemporal variabilityof the fluxesat thesesites. It is possiblethat air temperaturechangesaffected root respirationat those sites wherevegetation protrudedabovethe snowpack, mainlyin the subalpine.However,this couldnot be the caseat WAM, where the snowpack was 3 m deepon January28 and 4 m deepon February27. The othertwo alpine siteswere alsofar enough from prong vegetationthat air temperaturerelatedeffects areunlikely. No soil moisture measurements are available for these time periods.However,watervaporis transported fromthe soil into the snow cover during the courseof the winter, driven by temperate gradients[SmithandBoyne,1982]. Thesesitesare characterizedby a clefmiteonset of melting each year, as contrasted with otherclimateswheremeltingmayoccurseveral timesduringthe winter. Moistureflowsbackintothe soilfrom thesnowpack whensignificant meltingoccurs.Finally,highsoil moisture leads to anaerobic conditions, which limits CO• production, causinga decreasein flux. Brookset al. [1996] observedsuchdecreases in soil moistureat their alpine site. However,theminimumsoilmoisturewhichtheyobserved seems too high to limit microbialactivity. Furthermore,someof the risesto maximaappearedto start beforethere was significant melting. While the variationin CCh may correlatewith the SOMMERFELD ET AL.: DIFFUSIONAL FLUX OF CO: THROUGH SNOW 481 15-- 10-- 5-- -5 a Alpine b Subalpine Figure4. Temperatures at 0.05 and0.2 m in thesoilat (a) GlacierLakesEcosystem Experiments Site towerand(b) BrooklynLake Tower. expected changes in soil moisture,this remainsa Slx•ulation chosenin an attemptto maximizethe differences.Thesediffer bylessthana factorof 4 between thealpineandsubalpine. The Thepopulation dynamics of thesoilbiotaresponsible forthe spatial variability betweenthese two types of sites is production of CO•arenotknown.Brookset al. [1995]speculate complicated bythefactthattheyrepresent different ecosystems. thatthevariations in CO• flux .whichtheyobserved weredueto TheWGL siteis, in fact,about420 m fromtheI-BLLsite,but a combination of factorsaffecting microbialactivity.We think the difference in flux is less than a factor of 2. thismaybethemostpromising explanation. which should be tested. Errors SpatialVariability It is apparent fromFiguresl a-lf thatthe horizontal spatial variability ona scaleof about1 to 10m is notverygreat.Table 2 liststhestandard deviations of thepaireddifferences for each sampling siteforeachsampling day. M3 is pairedwithM4, and M5 is pairedwithM6 for thisanalysis.The largestdifferences are for the FOR site.Herethe averagefluxesdifferby about The measurement of gasflux acrossthe Earth'ssurfacehas problems whichhavenotbeenentirelyresolved.Most studies use sometype of chamberembeddedin the surface. Here we haveuseda method whosephysics is basically simple,Fick's law diffusionthrougha porousmedium.Because thismethodis notdirectlycomparable to othermethods, we havegivena more 50%, and the standarddeviationof the differencesis about 80% detailed discussionof errors than is usual. We have concluded that most of the error resides in the estimates of the snow oftheaverage fluxforthelocation.Thishighvariability maybe theresultof treewellsasdescribed by Winston et al. [1995]or porosity andthattheseerrorscannotbe evaluated objectively withoutgreat,andprobablyunwarranted, effort. Thereforewe the variablesnowdepthobserved.For the othersitesthe within have made what we considera' fair and conservativeestimate of sitevariations on a scaleof a few metersrangebetween32% our errors. Our error analysisindicatesthat estimatesof CO• (HILL) and 8% (M5-M6). Thus they are of marg'mal fluxesthat differ by lessthan 15% may not be significant. significance comparedto the overall accuracyof these However,flux differences greaterthan25% aresignificant. measurements. TheHILL sitehasa largepercentage difference becauseits averageflux is low, but the standarddeviationis consistent with those at the other sites. Zimovet al. [1993]and Winstonet al. [1995]reportmuch higher small-scalespatial variability. We attribute the differencein our resultsto the fact that our snowpacks were muchdeeperand of lowerporosity.By impedingthe vertical flux, the deepersnowpackwould allow horizontalfluxes to decrease the spatialdifferences betweenthe sampling locations. Our snowpacks werealsoflat with no macrochannels causedby treethinksor stems,exceptat the FOR site. It is alsopossible that someof the measurements of Zimov et al. [1993] and Winstonet al. [1995] were influencedby wind pumpingwhich wouldhavea stronger influencewith thinner,moreporoussnow covers[AlbertandHardy, 1995;Massmanet al. 1995]. Analysisof differences betweensiteswithineitherthealpine or subalpine indicates thatspatialvariabilityof averageflux ona scaleof 10 to 100m is withina factorof 2 (Table2). Largescalespatialvariabilityover100-to 1000-mspacing is alsolow, eSlXXiallyconsideringthe fact that the different sites were Conclusions CO• flux valuesestimated in this study. yieldedequivalent annual wintertime fluxesthataveraged about 95 g C m'2yr4 in thealpine andabout 232gCma yr4 inthesubalpine sites.This compares withanannual fluxrange of29 to 95g C m'2yr4 for tundraand 120 to 550 g C m'2 yr4 for borealforestand woodland(Raich and Schlesinger, 1992). Sincethe snowcovered periodcanbe morethan70% of the year,the winter CO• flux shouldbe significantin the carbonbalancein the ecosystems we studied[Sommerfeld etal., 1993]. Temporalvariabilityin CO• concentrations at the soil-snow interface wascaused primarilyby the variabilityin snowwater equivalent of the overlying snow. Secondary variations in CO• concentrations were causedby variabilityin the flux from the soil. Spatialvariationin flux on a scaleof about1-10 m was small in thisstudy.Averagefluxdifferences betweenlocations at each of the samplesitesweregenerally not significantly largerthan 482 SOMMERFELD ET AL.: DWFUSIONAL FLUX OF CO2 THROUGH SNOW the estimatederror. This was probablythe resultof the deep Massman,W., R. Sommerfeld,K Zeller,, T. Hehn, L. Hudnell, and S. Rochelle,, CO2 flux througha Wyoming seasonalsnowpack: snowpack,whichwouldhave facilitatedhorizontaldiffusionto Diffusional effects, pressurepumping effects, and eddy decrease horizontalgradients.Differencesbetweenlocationsat covariance measurements, in Biogeochemistry of Seasonally eachsitewere sometimes differentfor samplingdaysindicating Snow-CoveredCatchements, editedby K. A. Tonnessen, M. W. someshorter-term flux variations.Spatialvariabilityon a scale Williams, and M. Tranter,IAHS Publ.-228, 71-80, 1995. of 10 to 100m wasabouta factorof 2. Spatialvariabilityonthe Mash M. A., D. W. Clow, and R. G. Striegl,Flux of carbondioxide scaleof 100 to 1000 m was about a factorof 4, but this seemed correlated with elevation. Almostall of the cch originates in the soilbelowthe snowso that temporaland spatialvariationsin the fluxesthroughthe snowmustbe causedby variationsin soilproduction.An early winterminirotanin CO2production was observed at all sites. The minima are similar to those observedat Niwot Ridge Colorado[Brookset al., 1996] about150 km fromthe GLEES andin Manitoba[Winstonet aL, 1995]approximately 1500km from the GLEES. However, the cause of the early winter minirotanin production is obscure.Oar datadidnotsupport air or soiltemperature variations asa cause.Whilethevariationin flux probablycorrelates with soilmoisturedepletioncausedby thermalgradients, themount of depletion doesnotappearto be great enoughto limit CO2 production[Brookset al., 1995; Mosieret aL, 1993]. Theroleof population dynamics of thesoil microbiota remainsan openquestion. 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S., and D. Parkinson,Winter respiratoryactivityin aspen woodlandforest floor litter and soils,Soil Biol. Biochem, 19, 4959, 1987. Goodman,L. A., On the exact varianceof products,J. Am Stat. Assoc., 55, 708-713, 1960. R. A. Sommerfeld,W. J. Massman,and Robert C. Musselman, U.S. Departmentof AgricultureForest Service,Rocky Mountain Forest and Range ExperimentStation,240 W. ProspectRd., Fort Collins, CO 80526. A. R. Mosier, U.S. Departmentof Agriculture, Agricultural ResearchService,P.O. Box E, Fort Collins,CO 80522. (Received•mber 5, 1995; revisedMay 22, 1995; acceptedMay 23, 1996.)