European Society for Isotope Research

VI Isotope Workshop

Abstracts

29. June - 4. July 2002 Tallinn, Estonia

Preliminary isotope results on carbonatesegregations in red clay on the pediment

of the Mátra Hills (NE-Hungary)

Bernadett Bajnóczi1, Zoltán Horváth2, Attila Demény1,Andrea Mindszenty2

1 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budapest,Hungary, bajnoczi@geochem.hu, demeny@geochem.hu; 2 Eötvös L. University,Budapest, Hungary, hzoli@iris.geobio.elte.hu, andrea@iris.geobio.elte.hu.

A 10 m thick redclayeysoil-sedimentcomplexsituatedon thepedimentof theMátra Hills (NE-Hungary) includes unusually large amounts of secondarycarbonatesegregations.The age of carbonateprecipitation is presently notknown, however, huge amountsof carbonateare uncommonin soils of thePannonianBasin under Holoceneclimate. The goal of our investigationis toprovidesomenewdatafor determinationof theorigin andpossibleprecipitationmechanism of carbonate.

Thestudiedred clay complexof proposedLate Plioceneto Quaternaryageisexposedon themarginsof the Mátra Hills (NE-Hungary),in theopenpit of theVisonta lignite mine. Shallow lacustrine to terrestrial (alluvial) sediments(including lignite) of Late Pannonianage form the bedrock of the red claycomplex, which is covered by Quaternary loess and alluvial sediments.Sedimentaryfeaturesof the red clay point to a resedimentedorigin probablyfrom the weatheredsoil mantle of the nearbyMátra Hills. However, in situpedogenesiswith vertisol characteristicsalsocontributedto the formationof thecomplex(Horváthet al., 2001).The red clay representsa warm Mediterranean-type climate before the Pleistocene loess deposition under cool and dry climate.

Theredclay complexcontainscarbonateasnodulesandconcretionsof 1 to 20cm sizein sporadicdistribution.PreliminaryCL investigationof drusycalciteinthe concretions shows that it is free of Mn, possibly reflecting precipitation underoxidizing conditionssuggestingpedogenicorigin. However,a few thin bandsofbright luminescencemight be interpretedassignsof transientphreaticepisodesresultingperhapsfrom temporarygroundwatersaturation.In caseof pedogenicorigin we supposethat transferandreprecipitationof carbonateoccurredundersemi-arid climate after leaching probably from the overlying loess.

Stable carbon and oxygen isotope composition of carbonateconcretionscomposedof drusyandfine-grainedcalciteandinternalpartof micritic noduleswere determined. Micritic carbonate nodules from a 10 m thick section including underlying LatePannoniansilty clay, clay and overlying loess have δ13CVPDB values between–11.9and–8.9‰with a meanof -9.9‰.δ18OVPDB valuesaremainly from –8.9to

–7.0‰, however,somenodulesfrom the loess(-6.0‰) and the immediatelyunderlyingredclaysample(-10.4‰)havedifferentdata.Thedifferencebetweenoxygenisotopevaluesfrom redclay andloessindicatesthat theformationof theconcretions is not simply the result of the redistribution loess-carbonatedissolution and reprecipitation.

Carbonisotopecompositionof pedogeniccarbonateis thoughtto becontrolledby theδ13C valuesof soil CO2 resultingfrom soil respiration.Consequently,δ13Cvalues of soil carbonatereflect the types (C3 and C4) of vegetationcover(Cerling,1984).The carbonisotopecompositionof the carbonatenodulesfromthe red clay complexsuggeststhat the vegetationwasC3-dominatedwith up to20%C4 flora. This typeof vegetationrefersto a wet climateandcontradictsourinitial assumption that carbonate precipitation occurred under semi-aridconditions.

The carbonateconcretionsshow internal zonationwith micritic and fine-grainedcarbonateat themarginsanddrusycalcitegrowninto thevug.Thestableisotopecompositionsdisplay a systematicchangewith increasingdepletioninboth13C and 18O from the marginstowardsthe interior. Outermicritic andfine-grainedcarbonatehasδ13CVPDB valuesbetween–10.0 and –9.1‰ and δ18OVPDB

values from –6.3 to -5.9‰, while inner drusy calcite crystals have δ13CVPDB

valuesbetween–12.3 and –11.5‰ and δ18OVPDB values from –7.6 to –7.0‰,respectively.This trend indicatesthat the precipitationof the recognizedzonesoccurred from the margin towards the interior, and was accompaniedbyenrichmentin the heavyisotopesin the first carbonateprecipitate.Isotopedataindicate that carbonatemass probably did not exchangeisotopes with theenvironmentandthe developmentof carbonateconcretionsoccurredin a closedsystem.This also suggeststhat the observedCL zonation could have beenresultedby diffusion controlled crystal growth rather than by changingredoxconditions (Paquette et al., 1993).

References

Cerling, T. E. 1984. The stable isotope composition of modern soil carbonate andits relationship to climate. Earth Planet. Sci. Lett., 71, 229-240.Horváth, Z., Mindszenty,A., Michéli, E. & Berényi-Üveges,J. 2001. Large-scale early Quaternarysoil erosion and resedimentationalong the upliftingnorthernmarginsof the PannonianBasin. Abst. Vol. of the 21st ‘InternationalAssociationof Sedimentologists’Meeting of Sedimentology,3-5 September2001, Davos, Switzerland, p. 153.Paquette,J., Ward, B. W. & Reeder,R. J. 1993. Compositionalzoning andcrystalgrowthmechanismsin carbonates:A newlook at microfabricsimagedbycathodoluminescencemicroscopy. In Carbonatemicrofabrics (Rezak, P. &Lavoie D. L., eds.), 243-252. Springer Verlag, Berlin.

Advances in irm-GC/MS Technology andApplications

Sylveer M. Bergs, Andreas W. Hilkert, Dieter Juchelka

ThermoFinnigan MAT GmbH, Barkhausenstr. 2, D-28197 Bremen, Germany

For 13C/12C ratio determinationthe GC combustionsystemwas introducedin1988,openingthewide field of compoundspecificisotopeanalysis(CSIA). Thistechniquecombinesthehigh purificationeffectof GC with the utmostprecisionof isotoperatio massspectrometry.Nowadaysthe combustiontakesplacein acapillary ceramicreactorwithout a loss in separationefficiency. Togetherwiththedevelopmentof moresensitiveisotoperatio massspectrometers(IRMS) andmore matureGC/C interfacesthe ability of δ15N (1992) and δ18O (1996) wereadded.After the developmentof an IRMS systemwith energy filter for thesuppressionof low energyHe+ ions interferingwith m/z 3, thehigh temperatureconversiontechnologywas madecommerciallyavailablefor δ2H analysesviaGC/TC/IRMS (1998).

With the ability of compoundspecific isotopeanalysisof the major bio-elementsandtheir isotopes13C, 15N, 18O and2H newquestionscanbeanswered.Thus, today's requestsare more related with modern sample introductiontechniques,choice of GC columns, advanced GC technology, optimizedconversiontechnologyand interfacingto the IRMS aswell as the IRMS itself.Thesenewchallengesconcerntheimprovementof sensitivityandGC resolutioncombinedwith full automationfor higher samplethroughput.Discussingtheneuralgicpointsin the GC-IRMS systemapplicationexampleslinked to sampleintroduction techniques, GC- and reactor technology will be shown.

OSL dating of Holocene sediments from lake Baikal:investigating properties of extracted quartz grains

A.Bluszcs1, P.Moska1

Radiocarbon Laboratory, Institute of Physics, Silesian University of Technology, Gliwice,Poland, piotr.moska@radiocarbon.gliwice.pl

Lake Baikal contains a unique sediment record that spans over approximately30 million years and may be used for continental paleoclimate reconstructions.So far, material obtained from the Baikal Drilling Project have been used as abase for such reconstructions over a period of several million years. Data onlithology, sedimentology and dating results of the 600 m long core has beenalready published (Kuzmin et al., 2000), yet the most dramatic gla-cial/interglacial transitions had not been fully investigated. The work undertakenin the Gliwice Luminescence Laboratory is part of an international researchproject CONTINENT aimed specifically at high resolution reconstruction ofclimatic conditions in Holocene and Eemian periods. A number of gravitationalcores has been cored from different location on the lake to provide undisturbedsediment record covering the last ca 150 ky. Different climate parameters may bededuced from organic and inorganic components of the deposited matter. Toplace them on time scale an independent source of chronological information isnecessary.

OSL is one of the methods selected for dating Lake Baikal sediments and onlycapable to provide absolute dating for the Eemian period.

We started our investigation at the topmost section of cores that should coverthe Holocene period to study the OSL properties of quartz grains and to selectthe most suitable grain size for further measurements. The main problem in thatquartz abundance in the bulk sediment is extremely low (usually 1 per mille orless) and amount of sediment is limited by the core diameter and desiredtemporal resolution. Quartz grains of eolian origin seem to form only a part oftotal quartz extracted from the sediment. Presence of feldspars in some layers,despite the concentrated HF treatment, is another factor causing problems duringOSL measurements and result analysis.

We will present the first assays of equivalent dose determinations andcharacteristics of OSL signal recorded from extracted grains. The first resultsgenerally agree with the supposed Holocene origin of the investigated sedimentlayers.

References

Kuzmin, M.I., Karabanov, E.B., Prokopenko, A.A., Gelety, V.F.,Antipin, V.S.,Williams, D.F., Gvozdkov, A.N. (2000) Sedimentation processes and new ageconstraints on rifting stages in Lake Baikal: results of deep-water drilling.International Journal of Earth Sciences 89/2, 183-192.

Stable isotope analyses of Early Badenian Pectinidesfrom Retznei Quarry, Styrian Basin: implications

for seasonality and growth rates.

Ana-Voica Bojar, Hartmut Hidden, Alois Fenninger

Department of Geology and Paleontology, Karl-Franzens University, Heinrichstrasse26, A-8010 Graz, ana-voica.bojar@kfunigraz.ac.at

The shellsof Pectinidesare known as well suitedto provide environmentalinformationthroughisotopicanalysis.We analysedthreelargecalcitic shellsofGigantopectennodosiformisandonebrachiopodshellof a Terebratulidaeindet.,which were collectedfrom the Early Badeniandepositsof the Retzneiquarry.Thequarryis situatedwithin the Styrianbasinandcropsout patchreefdepositscoveredby clastics.The whole sequencehas an Early Badenianage (Friebe,1990, 1991).

Studyof thin sectionunderpolarisedlight showpreservationof shalesinternalstructure. Microbeam analysesindicate that shells entirely consist of low-magnesiumcalcite. According to these data we consider that the effect ofdiagenesis was minimal.

The shellswere sequentiallysampledalong the dorsoventral axis (averagesampleseparation1.5-2 mm). Isotopic analysiswere performedusing an auto-matic Kiele II line. Analytical precision is 0.1‰ for both δ18O and δ13C. The Pectinides shells of Gigantopecten nodosiformis show δ18O values in rangeof –3 to 0‰ (PDB).At thattime salinity variationsdueto continentalfreshwaterinput are consideredminimal and the large intrashell variability of 3‰ isinterpretedto indicatesignificant seasonalinducedtemperaturevariations.Thedatasuggestthat theclimatein southernAustriaduringtheearlyBaddeniantimewas subtropicalwith pronouncedseasonality.The δ18O profiles indicatedthatthe shellsgrowth in c. 2-3 years.In contrast,the δ18O datafrom a Brachiopod(Terebratulidaeindet. ) from the clasticsdepositsof the Upper LagenideZoneindicate cooler middle annual temperatures with weak seasonal variations.

References

Friebe, J. 1990. LithostratigraphischeNeugliederungund SedimentologiederAblagerungendes Badenium (Miozaen) um die Mittelsteirische Schwelle.Jahrbuch der Geologischen Bundesanstalt 133/2, 223-257.Friebe,J. 1991. Neotektonikan der MittelsteierischenSchwelle(Oesterreich):Die “Steierische Phase”. Zentralblatt fuer Geologie und Palaeontologie I, 45-54.

Carbon and oxygen isotope anomalies across theDevonian Carboniferous extinction boundary,

Eastern Alps, Austria

Ana-Voica Bojar 1, Franz Neubauer 2

1Department of Geology and Palaeontology, Karl-Franzens University, Heinrichstrasse26, A-8010 Graz, Austria, e-mail: ana-voica.bojar@kfunigraz.ac.at2Department of Geology and Palaeontology, Paris-Lodron University,Hellbrunnerstrasse 34, Salzburg, Austria, e-mail: franz.neubauer@sbg.ac.at

The mass extinction recognized at the Devonian/Carboniferous(D/C)boundary representsthe sixth largest extinction of the Phanerozoic,withpractically the sameextent as the Frasnian-Famennianmassextinction. Thisaffected many organisms, such as conodonts, ammonoids, echinoderms,trilobites, ancient agnatian and placodermian fishes, continental plantcommunitiesand, secondaryostracodes,foraminifera and corals (Flajs et al.,1988;Simakovet al., 1993).Theextinctionwasfollowed aftera shorttime by aphaseof radiationand biotic innovations.This phasewas characterizedby thediversity andblossomof certaingroupsof organismsas for exampletetrapods(Walliser,1996).The D/C extinctionhasbeenassociatedwith the world anoxiceventrepresentedby organicrich depositsknown asthe HangenbergShale.Thedevelopmentof the HangenbergShaleis interpretedto havebeenrelatedto aninversionwithin the oceancirculation (Holser et al., 1996; Caplanand Bustin,1999).Geochemicaldatahaveput in evidenceiridium anomaliesnearthebottomand the top of the shales.The origin of theseanomaliesis still underdebate.They may be relatedto an asteroidimpact or to limestone-shalelithologicaltransition.

Thereareonly a few D/C transitionswithin a homogenouslithological section.One of theseis the Steinbergsectionof the EasternAlps (Nössing,L., 1974;Ebner,1980).Throughthe useof detailedgeochemicalinvestigationswe showthattheD/C boundaryis theeffectof severalevents.Our data,togetherwith thatdescribedin the literature,demonstratethat indeed,an asteroidimpactoccurredat the D/C boundary.However this event is clearly younger than the anoxicHangenberg event, which had started already in the late Devonian.

References

Caplan, M.L. and Bustin, R.M., 1999. Devonian-CarboniferousHangenbergmassextinctionevent,widespreadorganic-richmudrockandanoxia:causesandconsequences.Palaeogeography,Paleoclimatology,Palaeoecology148, 187-207. Ebner, F. 1980. Conodont localities in the surroundings of Graz/Styria.

Abhandlungen der Geologischer Bundesanstalt Wien 35, 101-127.Flajs, G., Feist, R. and Ziegler, W. (eds.). 1988. Devonian Carboniferousboundary:resultsof recentstudies.CourierForschung-InstitutSenckenberg100,240p.Holser,W.T., Magaritz,M. andRipperdan,R.L. 1996.Global IsotopicEvents,in Walliser,O.H., ed.,GlobalEventsandEventStratigraphyin thePhanerozoic,Springer Verlag, 63-88.Nössing, L. 1974. Die Sanzenkogel-Schichten (Unterkarbon), einebiostratigraphischeEinheit des Grazer Paläozoikums:Mitt. Naturwiss. Ver.Steiermark 105, 79-92.Simakov, K.V. 1993. The dynamics and biochronological structure of theHangenbergianbioevent. Palaeogeography,PalaeoclimatologyPalaeoecology104, 127-137.Walliser, O.H. 1996. Global events in the Devonian and Carboniferous,inWalliser, O.H. , ed., Global Eventsand Event stratigraphyin the Phanerozoic,Springer, Berlin, 225-250.

Holocene rapid climatic oscillations in the sub-Mediterranean continental environment, recorded

in a stalagmite from Poleva Cave (SouthernCarpathians, Romania)

Silviu Constantin1, Ana-Voica Bojar2, Joyce Lundberg3, Stein-ErikLauritzen4

1 “Emil Racovita” Institute of Speleology, str. Frumoasa 11, R-78114 Bucuresti 12,Romania.2 Department of Geology and Paleontology, Karl-Franzens University, Heinrichstr. 26,A-8010 Graz, Austria.3 Department of Geography and Environmental Studies, Carleton University, Ottawa,Ontario K1S 5B6, Canada.4 Department of Geology, University of Bergen, Allégaten 41, 5007 Bergen, Norway.

In the pastyears,a largenumberof papershavebeendedicatedto the useofspeleothems as paleoclimatic indicators by measuring the stable isotopes (usually18O andδ13C) variationsalongtheir axis,which reflectvariationsin meanannualsurfacetemperature.The developmentof the U-seriesTIMS dating techniquesallowed a very accuratetime-calibrationof suchprofiles, thus enablingdirectcorrelationswith both marineoxygenisotopiccyclesandwith other recordsofglobal climatic change.

Since the supply of percolationwater (and thus, speleothemdeposition)isgenerallypreventedboth during very cold or very warm climatic episodes,itappearsvery likely that thespeleothemsformedeitherat northernlatitudes(e.g.in the sub-Arctic) or southern latitudes (e.g. the Mediterranean)may onlypreservean incompleterecordof climatic variations.For this reason,our studieshave focused on speleothemscollected from caves located in the sub-mediterraneanregionof SW Romania,reasonablyfar from the influenceof theNW Europe(Atlantic) circulation and also from the arid conditionsof the SEMediterranean.

StalagmitePP10hasbeencollectedfrom PolevaCave,locatedin the closevicinity of the DanubeGorge(SW Romania).It is a “candlestick”stalagmite,c.70 cm-long;its diameterdecreasesfrom some5–6cm at thebase,to some2–2.5cm after only 18 cm and remains constantsuggestinga rapid growth andpossibly evaporative(low relative humidity) conditions(Dreybrodt, 1988). ApreliminaryU-seriesalpha-spectrometricdateof thebase2.5 cm yieldedanageof 61.7±11ka; the relatively high error of the dating is dueto the low uraniumcontent(~0.05ppm)of thesample.Sevenhigh-resolutionTIMS-dateshavebeensubsequentlyperformed on sub-samplestaken along the speleothem;theyyieldedagesin correctstratigraphicalorder,rangingfrom ~48 ka at ~7 cm fromthebaseto ~3 ka at c. 5 cm belowthetop,with typical analyticalerrorsof 1–2%(2� ) for ages younger than 15 ka.

The morphologicandstructuralanalysisof the growth laminaetogetherwiththe interpretationof TIMS and alpha datessuggestthat the speleothemhasexperienceda brief episodeof growthcessationjust before~48 ka, anda longerdepositionalhiatuslocatedin time somewherebetween~25ka and~12ka whichcorrespond to the last glacial maximum.

Along thespeleothemaxis,154stableisotopessampleswerecollected,at 0.5cm intervals,andanalyzedfor δ18O andδ13C, with typical standarddeviationof±0.1 ‰. The time-resolutionof the samplingcorrespondsto ~ 2 ka/sampleforthelower partof thestalagmite(slow-growing)andto ~150–40years/sampleforthe upper (candlestick-like)part whosegrowth was considerablyfaster. Thishigh resolution has enabledthe identification of severalclear-marked,rapid,climatic oscillations during the last 12,000 years or so.The isotopicprofile of the lower part of the stalagmiterevealsseveralclimatic

oscillations during Marine Isotope Stages(MIS) 4 and 3, which are well-documentedfrom other continentaland marine records,such as the deglacialeventat ~54 ka, an importantglacial eventbetweenc. 47 and 41 ka, and themarked warming between ~ 32 and 28 ka (Denekamp).This profile alsoconfirms the conclusionsof Constantin& Lauritzen (1999) that the climateduringMIS 4 wasnot cold enoughsuchasto preventspeleothemgrowth,whileon thecontrary,no calcitedepositionhasbeensofar documentedduringthe lastglacial maximum, even at those lower latitudes.

The upper part of the stalagmitehas delivereda detailedoxygen isotopicprofile over the last 12 ka, recordingseveralimportant rapid oscillationsthatmay be correlatedglobally. The Younger Dryas (YD) event has beenclearlyrecordedat ~10.5ka, as well as a very well markedcooling at ~8.2 ka, whichwas abouthalf the amplitudeof the YD event (Alley et al., 1997). A generaltrend of climate warming follows (including rapid variation episodeswithamplitudesaslargeas±1.5‰),culminatingwith two spikesat ~5.2and~3.2ka.Overall, the isotopicprofile recordedby stalagmitePP10during the last 10,000yearsis consistentwith the onerecordedby stalagmitePP9form the samecaveandreportedby Constantinet al. (2001).Thewarm3.3ka-eventseemsto havearegionalextentsinceit is clearly recorded,with roughly the sameamplitude,inboth stalagmitesfrom Poleva cave and in PU2 stalagmite from westernCarpathians(Onacet al., in press)— a region that lies underthe Atlantic cli-matic influence.

References

Alley, R., B, Mayewski,P.,A, Sowers,T., Stuiver,M., Taylor, K., C, Clark, P.,1997.Holoceneclimatic instability: A prominent,widespreadevent8200yr ago.Geology 25/6, 483–486.Constantin,S. & Lauritzen,S.-E., 1999. Speleothemdatingsin SW Romania.Part1: Evidencefor a continuousspeleothemgrowth in PesteraClosaniduringOxygen Isotope stages5-3 and its paleoclimatic significance.Theor. Appl.

Karstology 11-12, 35–46.Constantin,S., Onac,B. P., Fleitman,D., & Tamas,T. 2001. Pastvegetationchangesin karst areasas revealedby a comparativeisotopic study of twoHolocene speleothemsfrom Romania. IGCP 448 Newsletter 2001, KarstDynamics Lab., Guilin, China, 67–73.Dreybrodt, W. 1988. Processesin karst systems.Physics, chemistry andgeology. Springer Verlag, Berlin, Heidelberg, 288.Onac, B. P.,Constantin, S., Lundberg, J., & Lauritzen, S.-E.(in press). Isotope-climate record in a Holocene stalagmite from Ursilor Cave (Romania). J.Quaternary Science.

Genetic characterization of natural gases by stablecarbon and hydrogen composition in the southern

part of Pannonian Basin-Croatia

Veronika Culjak, Irenka Stankovic

INA-Division Of Strategic Development, Research and Investment, Research andLaboratory Testing Department, Geochemical Laboratory, 10002 Zagreb, Lovin-ciceva 1, Croatia; e-mail: veronika.culjak@ina.hr; irenka.stankovic@ina.hr

Naturalgasesoccurin varietyof environments.In deeperstratagasesareoftenassociatedwith petroleumandcondensate.Originatedfrom varioussourcerocksand specific environments,gaseoushydrocarbonswith their specific stablecarbon and hydrogen composition enable us to trace their origin.Geochemicalcharacterizationof natural gasesfrom five gas-condensatefieldsand some exploring wells, in the southernpart of PannonianBasin-Croatia,mainly accordingto stablecarbonandhydrogenisotopevariationsin methane,but concerninggas composition and other geochemicaldata, are presented.These gas and gas-condensatefields are nowadays the most productivehydrocarbon areas in Croatia.

Stablecarbonisotopevaluesin methanerangebetween–34.9to –39.2‰,anddeuteriumbetween–155to –163‰. Compositionof thegasesshowsvariationsin contentof higherhydrocarbons(C2+ 2.5 to 14.0mol %). Accordingto Schoell(1983) these gases can be classified as thermogenic condensate associated gases.

High maturity micrinite structureof the unidentified sourcemorphologykerogen (Bari

�. G. et al., 1998)mostlyterrigenousorigin (δ13C –27.5to –30.1‰)

were recognizedby pyrolitic and optical methods in the sedimentsfromnorthwestpartof theDravaDepression,whatimply thatsucha kerogencouldbeprecursor for hydrocarbons in the studied area.

Key words: Natural gases, stable isotope composition, Pannonian Basin, origin

Table 1: Chemical and isotopic data on hydrocarbons of the natural gases

Sampl e CH4

mol%

*C2+

mol%CO2

mol %δ13CCH4

‰δDCH4

‰Gola-8 40.3 10.8 53.5 -34.9 -161Gola-6 42.3 7.5 52.3 -35.1 -163Kal-14 73.7 13.0 13.6 -38.1 -161Kal-3r 79.9 13.2 11.3 -38.9 -163Kal-2 74.4 12.8 13.2 -39.2 -Mol-26 � 69.0 7.6 22.7 -37.2 -Mol-31 68.6 7.9 23.6 -35.7 -155Mol-38 71.3 8.2 20.2 -36.5 -158Gak-10 80.8 2.5 14.8 -37.2 -St.Gra-1 77.0 12.3 11.2 -39.0 -159St.Gra-6 75.6 14.0 10.9 -39.1 -160

*normalized C2+

Oxygen isotope and trace elements constraints forupper mantle metasomatism in Northern Victoria

Land (Antarctica)

Dallai L.1, Perinelli C.2, Armienti P.3

1Centro per lo Studio del Quaternario e l'Evoluzione Ambientale – CNR, Università diRoma "La Sapienza", P.le Aldo Moro 5, 00185 Roma.2Dipartimento Scienze della Terra, Università di Camerino - Via Gentile III da Varano,62032 Camerino.3Dipartimento Scienze della Terra, Università di Pisa - Via Via S. Maria 56, 56126 Pisa.

Mantlexenolithsfoundin Cenozoicalkali-basaltsfrom NorthernVictoria Land(Antarctica) are coarse to porphyroclastic spinel-lherzolites and spinel-harzburgites. Equilibrium pressure-temperatureestimates indicate that thexenolithsequilibratedin a rangeof temperaturesbetween950 and 1070 °C, atpressures between 1 and 1.7 GPa.

Whole rocks chemical data show that these xenoliths are enriched inincompatibleelements,and indicate they were affectedby variable degreeofcryptic metasomatism.Mineral phasesforming the xenolithsweremeasuredforoxygenisotopecompositionby laserfluorination,andfor traceelementsconcen-tration by LAM–ICP–MS. The oxygen isotopecompositionof clinopyroxene(5.3 ± 0.1 ‰) and orthopyroxene(5.4 ± 0.2 ‰) are similar, and indicatemagmaticequilibrium at high temperature.The δ18O valuesof olivine are highandconstant(5.7 ± 0.1 ‰), abovethe δ18O valuesreportedfor olivine in spinellherzolites and unaltered mantle nodules (e.g. Gregory and Taylor, 1986;Harmonet al., 1987;Matteyet al., 1994).Negativeδ18O pyroxene-olivinevaluesdefinenon-equilibriumoxygenisotopefractionation(Matteyet al., 1994),that isinterpretedin termsof metasomaticalterationof the lithosphericmantlebeneaththe area.

OrthopyroxeneREE patternsarequite uniform, whereasclinopyroxenesREEpatterns,showa progressiveLREE enrichment,very similar to thosereferredtoporousflow melt percolationprocesses(Navon and Stolper,1987,Bodinier etal., 1990; Bedini et al., 1997). LREE enrichedsamplesshow higher oxygenisotope disequilibrium betweenolivine ad orthopyroxene,whereasnegativeolivine-clinopyroxene fractionation seems unrelated to the degree ofmetasomatism.Olivine δ18O valuesin metasomaticandunalteredsamplesmayindicate a δ18O-enriched mantle source before metasomatismoccurred.Alternatively, thesevaluesmay be the product of the metasomaticstage,thepyroxeneδ18O values reflecting mineral re-equilibrationwith the host lava(5.8‰; Harmon and Hoefs, 1995) during partial melting.

References

Bedini, R.M., Bodinier, J.-L., Dautria, J.-M., Morten, L. 1997. Evolution ofLILE-enriched small melt fractions in the lithospheric mantle: a case study fromthe East African Rift. Earth Planetary Science Letters, 153, 67-83.Bodinier, J. L., Vasseur, G., Vernieres, J., Dupuy, C., and Fabries, J. 1990.Mechanisms of mantle metasomatism; geochemical evidence from the Lherzorogenic peridotite. Journal of Petrology, 31, 3, 597-628.Gregory, R.T. and Taylor, H.P. Non equilibrium, metasomatic 18O/16O effects inupper mantle mineral assemblages: Contributions to Mineralogy and Petrology,93, 124-135.Harmon, R.S. and Hoefs, J. 1995. Oxygen isotope heterogeneity of the mantlededuced from global 18O systematics of basalts from different geotectonicsettings: Contributions to Mineralogy and Petrology, 120, 95-114.Harmon, R.S., Kempton, P.D., Stosch, H.G., Hoefs, J. Kovalenko, V.I. andEonov, D. 1987. (18)O/(16)O ratios in anydrous spinel lherzolite xenoliths fromthe Shavaryan-Tsaram Volcano, Mongolia: Earth and Planetary Science Letters,81, 193-202.Mattey, D., Lowry, D. and Macpherson, C. 1994. Oxygen isotope composition ofmantle peridotite: Earth and Planetary Science Letters, 128, 231-241.Navon, O. and Stolper, E. 1987. Geochemical consequences of melt percolation:the upper mantle as a chromatographic column. Journal of Geology, 95, 3, 285-307.

Stable isotope compositions of CO2 in backgroundair and at polluted sites in Hungary

Attila Demény1 and László Haszpra2

1Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budapest,Budaörsi út 45, H-1112, Hungary2Hungarian Meteorological Service, Institute for Atmospheric Physis, Budapest, P.O.Box39, H-1675, Hungary

Air samples were taken at three sites in Hungary for stable isotopemeasurementson CO2. In order to producecomparabledatafor unpollutedandpolluted sites,a gaschromatograph-basedCO2-separationmethodwas appliedinsteadof the widely usedN2O-correctionmethod.Air samplingwasconductedat two siteswith drying in orderto obtainreliableoxygenisotopecompositions.Thestableisotopemeasurementsrevealeda complexdiurnalvariationduringthewarm monthsat the site with strongvegetationactivity. The preferreddiffusionof 12C into leafscauses13C- enrichmentin theair CO2, andthis processcanalsobe observedin separateδ13C-δ18Ο correlations.Apart from this separateδ13C-

δ18O correlation,polluted and unpollutedsitescan not be distinguishedby the

δ13C-δ18O distribution, indicating that anthropogenicand biogenic CO2 havesimilar isotopic characteristics.

Plottingcarbonisotopedataasa functionof the inverseof CO2 concentrationhelped determine end-membercompositions of mixing components.ThebackgroundCO2 (i.e. CO2 free from local influences)has the sameisotopiccomposition throughout the region, whereasthe biogenic componentshowssignificantseasonalvariationsat K-pusztathat may be relatedto changingsoilprocesses.The Hegyhátsálstationshowssimilaritieswith the samplescollectedduring the cold seasons at K-puszta.

The comparisonof dataobtainedat different sitesrevealedthat variationsinwind speedhas a strong influence on the isotopic compositionsthrough CO2

accumulation potential. Thus, standardizedsampling methods have to bedeveloped for future intercomparison of data from different sampling networks.

This work wasfinancially supportedby the HungarianAcademyof Sciences(to A.D., AKP 97-55 2,5/19) and the HungarianScientific ResearchFund (toL.H., OTKA N 31783).The stableisotopedataof Hegyhátsálwere measuredand kindly provided by the NOAA Climate Monitoring and DiagnosticsLaboratoryto L. H. in the frameworkof the cooperativeair samplingnetworkproject.

Trace element and isotopic evidence for subduction-related carbonate-silicate melts in mantle xenoliths

from the Pannonian Basin, Hungary

Demény, A. 1, Vennemann, T.W.2, Hegner, E.3, Embey-Isztin, A.4,Homonnay, Z.5, Milton, J.A.6

1 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budapest,Budaörsi út 45., H-1112, e-mail: demeny@sparc.core.hu2 Institute for Geochemistry, University of Tuebingen, Wilhelmstr. 56, Tübingen, D-72074, Germany3 Institute for Mineralogy, Petrology and Geochemistry, University of München,Theresienstrasse 41/III, D-80333 München, Germany4 Department of Mineralogy and Petrology, Hungarian Natural History Museum,Budapest, Ludovika tér 2., H-1431 Pf. 137.5 Department of Nuclear Chemistry, Eötvös Loránd University, Budapest, Pázmány P. s.2, H-1117, Hungary6 School of Ocean and Earth Science, Southampton Oceanography Centre, EuropeanWay, Empress Dock, Southampton, SO14 3ZH, UK

Carbonateglobules, interpreted as carbonatitic melt, occur in peridotitexenoliths of Plio-Pleistocenealkali basalts from the Carpathian-Pannonianregion. The carbonateglobules are hosted in amphibole-bearingglass veinswithin shearedperidotitexenolithsof Szentbékálla,BalatonHighlands,Hungary,a well-studied locality of basalt-hostedxenoliths. Primary magmatic texturalfeaturesandchemicalcompositionsof the glassare compatiblewith a primarynatureof theveins,indicatingthattheir chemicalandisotopiccompositionswerenot altered.Laser-ablationICP-MS analyseshavebeencarriedout on carbonateand glass.The carbonateglobulesare zonedwith the centralpart depletedintrace elements (e.g. Ba, La, Ce, Y, etc.), whereas the trace elementconcentrationsof theglobules’marginsapproacha compositionsimilar to thoseof theglass.This distributionindicatesdisequilibriumbetweenthecarbonateandsilicate phasesand suggestsdifferent origins. Traceelementratios sensitivetocrustalcontamination(e.g.,Ce/Pb)arevery low in the centresof the carbonateglobules,suggestingthat crustalcontaminationplayedan importantrole in theformation of carbonate.

Theoxygenisotopecompositionsof associatedamphiboleandglass(δ18O=6.1and5.9 ‰, respectively)areslightly higher thantypical averagemantlevaluesfor such phases.The difference in δ18O valuesbetweenglassand amphibolewould be in agreementwith glassformationby partial melting. StableC andOisotopecompositionsof unalteredcalcitedroplets(δ13C about–14‰, δ18O about22 ‰) are very different from those of primary mantle-derivedcarbonatitesthough. Theseisotopic compositionsmay indicate a secondaryorigin of thecalcite (e.g.,infillings of vugs).However,primary magmatictextures,the trace

element zonations observed and the isotopic composition of associated glasssupport a primary origin for the globules representing carbonate melt.

The trace element ratios (e.g. Ce/Pb, Nd/Pb, etc.) and stable isotopecompositions strongly suggest an origin for a carbonate-silicate melt fromsubducted lithosphere. Sr isotope compositions of calcites are in agreement witha subducted crustal component. We suggest that fluid-rich melts may haveinfiltrated the upper mantle rocks in two stages: 1) a fluid or fluid-rich meltinfiltrated and interacted with the mantle peridotite producing amphibole withδ18O values similar to that typical for mantle; 2) subsequently, a carbonate-bearing melt or fluid derived from subducted crust infiltrated the metasomatisedperidotite reacting with the amphibole and causing carbonate crystallization.

The study was financially supported by the Hungarian Scientific ResearchFund (to A.D., OTKA T 029078). The ICP-MS work was carried out in an ECfunded Large Scale Analytical Facility (SOCFAC, contract no. HPRI-CT-1999-00108).

Stable isotope compositions in carbonatitecomplexes of the Kola Peninsula

Demény, A.1, Zaitsev, A.2,3, Sindern, S.4,5, Wall, F.6, Sitnikova, M.A.2,6,Karchevsky, P.I.2,6

1 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út.45, 1112 Budapest, Hungary2 Department of Mineralogy, St. Petersburg State University, 7/9 University Emb.,199034 St. Petersburg, Russia3 Institut für Mineralogie, Petrologie und Geochemie, Universität Freiburg, Albertstr.14a, 79104 Freiburg, Deutschland 4 Institut für Mineralogie und Lagerstättenlehre, RWTH-Aachen, Wüllnerstr. 2, 52056Aachen, Deutschland5 Institut für Mineralogie, Correnstr. 24, 48149 Münster, Deutschland6 Department of Mineralogy, The Natural History Museum, Cromwell Road, London SW75BD, UK

Stablecarbonandoxygenisotopecompositionsof the carbonatitecomplexesof theKola-KareliaRegioncollectedfrom publisheddatasets(Khibina,Kovdor,Sallanlatvi,Sokli, Telyachi,Tiksheozero,Turiy andVuorijarvi) aswell as newdata obtained from the Sallanlatvi, Siilinjarvi, Sokli, Turiy and Vuorijarvicarbonatiteshavebeencompiledin this paper.Theinvestigatedsamplescoveredseveral carbonate minerals (calcite, dolomite, burbankite) and carbonatitecrystallizationstagesin orderto havea completeview on carbonatitegenesisandevolution. After the recognition of processesthat can modify the originalcompositions (Rayleigh fractionation during crystallization, degassing,hydrothermal alteration, crustal contamination), primary compositions unaffectedby secondaryprocesseswere determined.Beside uniform primary oxygenisotopecompositionsa largeδ13C variationfrom normalmantlecompositions(~-6 ‰) to rather high δ13C values(~ -2 ‰) appear in the studiedcomplexesindependentof emplacementage. The data are best explained by mantleheterogeneity caused by CO2 metasomatism.

The phoscorite-carbonatiterelationshiphasalsobeeninvestigatedon thebaseof stableisotopedata.The two rock typesfollow thesameevolutionaryschemein the Sokli complex supporting the carbonatite-silicateliquid immiscibilityhypothesis.The phoscoritesof the Vuorijarvi complexshow a significant δ18Odifferencefrom thecarbonatitesthatmayberelatedto carbonate-silicateisotopeexchangeat decreasingtemperatures,however, the δ13C data would be inaccordancewith a commonorigin. A different relationshipappearsin the Turiymassif,wherethephoscoritesandcarbonatitesnot only havedifferentradiogenicisotopecompositions,but their δ13C valuesalso differ significantly, indicatingthat they are derived from separate sources.

This study was financially supportedby the HungarianScientific ResearchFund (OTKA T 029078).

Determination of 34S/32S sulfur isotope ratio in theproducts of coal combustion process.

M. Derda1, R. Wierzchnicki, A.G. Chmielewski

1Institut of Nuclear Chemistry and Technology, Warsaw, Poland,mder@orange.ichtj.waw.pl

Power generation is based on the fossil fuel combustion all over the world.These fuels contain sulfur and are the main source of antropogenic sulfur, mostlyemitted to the atmosphere in the form of sulfur dioxide. Sulfuric acid which isthe product of oxidation and reaction with atmospheric water is one of thecomponents of acidic rain. Since SO2 emission has a great impact onenvironment and human health conditions different technologies have beenapplied for air pollution control. Very important is evaluation of economicresponsibility for emitted pollution. Therefore scientist look for suitable markerwhich could be used as environmental tracer.

There are no other methods beside sulfur isotope ratio measurements toinvestigate fate of antropogenic sulfur (emission and desulphurization products)in the atmosphere and environment.

This method may be applied to investigate of different air pollution controltechnologies as well, for example method can be used to establish further fate ofby-products e.g. elution of gypsum from landfilled waste.

The solid samples (coal, ash, slag) were taken from power station Bechatow todetermine sulfur isotope ratio (34S/32S) in coal combustion process. Samples ofthe flue gas and product from desulphurization process were investigated as well.Product from desulphurization process is a gypsum. The mixture origin in aconsequence of outlet gases irradiation.

Each form of sulfur has been prepared by extraction of its compounds fromsolid samples taken from power plant and transformation into a stablecompounds, which can be subsequently converted into a gas phase (SO2) formass spectrometric analysis. The obtained results are presented in the paper.

Study of water-soluble sulfates in a tailings profilefrom El Teniente porphyry copper deposit (Chile)

by sulfur and oxygen isotopes

Bernhard Dold and Jorge E. Spangenberg

1 Earth Sciences Department, University Lausanne, 1015 Lausanne, Switzerland,Bernhard.Dold@cam.unil.ch, Jorge.Spangenberg@imp.unil.ch

The sourcesof sulfatein the stratigraphyof oxidizing sulfidic mine tailingsimpoundmentCauquenesfrom theEl Tenienteporphyrycopperdepositin Chilewere investigatedby sulfur andoxygenisotopes.The water-solublesulfatecanhaveits origin by thedissolutionof primaryanhydriteandgypsumpresentin theore mineralogy or by the oxidation of sulfide minerals due to exposuretooxidizing conditions during mining activity. The geochemistry of these tailings isdescribedin detail by (Dold, 1999; Dold and Fontboté,2001). The upperfourmetersconsistsof an unsaturatedzonewith a 1 - 1.5 m deeplow-pH oxidationzone (pH 1.7-4.5) at the top. The pore water in the unsaturatedzone ischaracterizedby high sulfate values reaching 21 600 mg/l, whereasin theprimarysaturatedzoneconstantsulfatevaluesof about1800mg/l areobserved.The δ34Spy of pyrite of El Tenientedepositaverages-1.0‰ CDT, andthe δ34Sanh

and δ18Oanh for anhydritein the primary ore assemblageaverage+10.2‰ CDT

and+7.5‰ VSMOW, respectively(Kusakabeet al., 1984).The calculatedδ34Svalues for total sulfur in the ore forming fluid is +4.5‰ (Kusakabe et al., 1984).

Thewater-solublefractionof thetailingssampleswasprecipitatedby saturatedBaCl2 solution. The sulfur isotope analyseswere performedby combustion-isotoperatio massspectrometryusing a Carlo Erba 1108 elementalanalyserconnected to a Finnigan MAT Delta S isotope ratio mass spectrometer(EA/IRMS). The oxygen isotope compositions were determined by hightemperature conversion – elemental analyser connected to a Finnigan MAT DeltaXL IRMS (TC/EA/IRMS). The reproducibility of the δ34S and δ18O are betterthan 0.2‰ and 0.3‰, respectively.

Resultsshowa cleardifferentiationof sulfur andoxygenisotopicvaluesin theupper three metersof the tailings stratigraphyin relation to the underlyingsaturatedprimary zone(Fig. 1). The δ34SSO4 valuesrangefrom -0.4 to +1.4‰ inthe unsaturatedzone and indicate strong influence of pyrite oxidation in theisotopicsignature,whereasthe valuesin the saturatedzonerangefrom +2.2 to+3.9‰.This increaseof theδ34SSO4 valuescanbeinterpretedin two ways:1) theresultof a mixing betweensulfatefrom oxidationof pyrite (-1.0‰) andsulfatefrom anhydrite(+10.2‰), or 2) the low pH (~ 4.5) of the tailings due to theappliedacid circuit leadsto (partial) dissolutionof ore andsupergenesulfides,resulting in δ34SSO4 value close to the total sulfur of the ore forming fluid

(+4.5‰). The δ18OSO4 valuesrangefrom -4.7 to -1.3‰ in the unsaturatedzone

and from -1.1 to 4.5‰ in the saturatedzone. The low δ18OSO4 values in theunsaturatedzone suggestsferric iron as main electronacceptorin the pyriteoxidation (Taylor and Wheeler, 1994; Taylor et al., 1984).

Figure 1. δ34SSO4 and δ18OSO4 values from the water-soluble fraction in the Cauquenes tailingsimpoundment from El Teniente porphyry copper deposit, Chile.

References

Dold, B. 1999. Mineralogical and geochemicalchangesof copper flotationtailings in relation to their original composition and climatic settings -Implications for acid mine drainage and element mobility. Ph.D. Thesis,University of Geneva, Geneva, 230 pp.Dold, B. andFontboté,L. 2001.Elementcycling andsecondarymineralogyinporphyry copper tailings as a function of climate, primary mineralogy, andmineral processing.Special Issue: Geochemicalstudies of Mining and theEnvironment, J. Geochem. Explor., 74, 3-55.Kusakabe,M. et al. 1984. Oxygen and sulfur isotopic compositionof quartz,anhydriteandsulfideminralsfrom El TenienteandRio Blancoporphyrycopperdeposits, Chile. Bulletin of the Geological Survey of Japan, 35, 583-614.Taylor, B. E. and Wheeler, M. C. 1994. Sulfur- and Oxygen-IsotopeGeochemistryof Acid Mine Drainagein the WesternUnited States:Field andExperimentalStudiesRevisited.In: C. N. Alpers and D. W. Blowes (Editors),EnvironmentalGeochemistryof Sulfide Oxidation. ACS SymposiumSeries,Washington, pp. 481-515.Taylor, B. E., Wheeler, M. C. and Nordstrom, K. D. 1984. Stable isotopegeochemistryof acidminedrainage:experimentaloxidationof pyrite. Geochim.Cosmochim. Acta, 48, 2669-2678.

Notes on relative measurements, dinosaurs andpaleohumidity

Tomasz Durakiewicz1,2, Zachary Sharp3

1Los Alamos National Laboratory, Condensed Matter and Thermal Physics Group,NM87545, Los Alamos, USA, tomasz@lanl.gov; 2Maria Curie-Sklodowska University,Institute of Physics, 20-031 Lublin, Poland, 3University of New Mexico, Dept. of Earthand Planetary Sciences, Albuquerque, NM 87131, USA, zsharp@unm.edu

We use oxygen isotopic composition of dinosaur tooth enamel as apaleohumidityindicator.In the caseof dinosaurfossils the fractionationfactorsfor biogenicphosphateas well as (in most cases)the isotopic compositionofwater remain unknown. The direct determinationof body temperatureof ananimal by useof isotopetechniquesis thereforeimpossible.We measureandcompare results from several dinosaur species from Nemegt, Dhadokhta,Barungoyot and Kirtland formations.

Measurementsareperformedfor thesameherbivorespeciesliving in differentclimatesandfor herbivoresandcarnivoresin the sameclimate.It is known thathumidity drives the body water isotopic compositionof herbivoresdue to theprocessof the Rayleigh distillation of leaf water. By the use of relativemeasurementsand advancednumerical modeling we are able to excludeunknownsand estimatepaleohumidityconditions.The error propagationstudyby Monte-Carlomethodperformedwithin theKohn'smodelallowsusto suggesthumidity and water compositionas the most important factors influencing theherbivorebody water isotopecomposition.Foodwatercontent,metabolicratesand water economy index are, respectively,the most important factors forcarnivores.

We concludethat temperatureestimationsderivedfrom oxygenisotoperationsof enamelmaynot be reliablein the caseof extinct speciesdueto the unknownbody water - phosphatefractionation.Relativemeasurementsperformedeitheron a differentiatedset of samplesof both herbivoresand carnivoresfrom thesamesite, or on the samespeciesin different climatic conditions allow toovercome the unknown fractionation problem for paleohumidity estimations.

Stable carbon isotopes as dietary indicator ofprehistoric populations from the Baltic Sea areas

Gunilla Eriksson1, Kerstin Lidén1, Lembi Lõugas2

1Archaeological Research Laboratory, Stockholm University, SE-106 91, Stockholm,Sweden, gerik@arklab.su.se Kerstin.Liden@arklab.su.se2Institute of History, Rüütli 6, EE-10130 Tallinn, Estonia, lembi14@mail.ee

Stablecarbonand nitrogenisotopemeasurementson collagenfrom ancienthuman,as well as animal, bone have beenused to determinethe sourcesofproteinin ancientdiet in manypartsof the world including the Baltic area.Thecomplicatednatural history of the Baltic Seacan, however,causea problemsincethevaryingmarineinfluenceeffectsthe isotopicsignature,i.e., themarineend-value.Themethodis albeitapplicablein this areaaslong asanend-valueisdetermined at the specific time period of interest.

The transition from one subsistenceto anotherduring prehistory can bedetectedastransitionsin thediet. A transitionin diet canbedefinedasa changein the total amountsof food consumedor a changein frequencyof the differentresourcesincludedin the diet. The importanceof dietary transitionsis not onlybecauseof the transition per se but also becauseof its significanceto otherfactors determiningour lives, such as economy,health, demography,socialcomplexity,etc.Transitionsin diet canbestudiedonseveraldifferent levels,i.e.,betweenpopulations,within populations,betweenindividualsbut alsowithin anindividual. By the use of different tissue we can study changesover anindividual’s life.

Stablecarbonandnitrogenisotopeanalysescanbeappliedin bothhumandietinvestigationsand in the study of (pre-)historicfaunas.We havestudiedpigs,dogs,seals,etc.at coastalsitestogetherwith peoplefrom thesamesiteswho gottheir subsistencefrom the sea. Here we find interesting differencesin dietbetweenhumansanddogs.In thestudyof migratinganimals,theseanalysesarealso useful.

Elucidation of the origin and dynamic groundwaterin the ecosystem of Movile Cave, Romania,

using environmental isotopes

Lucia Feurdean, Victor Feurdean

National Institute for Research and Development of Isotopic and MolecularTechnologies, P.O. Box 700, 3400 Cluj-Napoca 5, Romania, luci@l40.itim-cj.ro

The stable isotopes content of waters collected from study area providedimportant information about the unusual subterranean ecosystem of MovileCave, which is based on chemoautotrophic conditions and was discovered in1986 in S-Dobrogea, Romania. As a conservative tracer in carbonate rocksdeuterium was used to determine the unelucidated problems of the water originin cave and flow path in cave area.

The hydrogen and oxygen isotopes from waters indicates that groundwater inMovile Cave area has meteoric origin. The deuterium content of the waters from the cave area is lower than δ2H of thewaters from the semiarid lowland of the Dobrogea district, indicating that theirrecharge area is located at high altitude.

Time series of the deuterium concentration from groundwater samples bothfrom the aquifer in Mesozoic limestone and from the unconfined aquifer inSarmatian limestone exhibit a distinct seasonal effect and a lower deuteriumconcentration in summer than in winter. This six-month phase shift of theisotopic composition variations with respect to normal succession of seasonalmaximum and minimum values of precipitation and lower δ2H average valuesare due to the contribution of the watershed of the more elevated inland (from thePrebalkan Plateau) during summer. The study indicates that the intrusion ofwater in the karst occurs by conduit flow controlled by the hydrostatic pressureand the geometry of conduit.

The interconnection between aquifers is point out by correlation between theδ2H values and total salinity content. The water of Movile Cave is the result ofthe mixing of two end members that have different hydrogen isotope ratios.The spatial variation of the deuterium content delineated the areas with verticalinflow and the flow path of groundwater from deep aquifer. The discharge of thedeep aquifers occurs through faults and karstic channels into overlying aquifer.The cave and the Karaoban Lake is the discharge area of two main componentsof groundwater: the first is coming from southwest and has isotopiccharacteristic similar to lower altitude water (~500 m) and the second is movingfrom southeast and has the isotopic composition similar to high altitude water(>1000 m). The Movile Cave and Karaoban Lake are connected and the cavewater discharge by overflow mechanism that offers to cave the isolation ofatmosphere.

References

Craig H. 1961. Isotope variations in meteoric waters. Science, 133: 1702-1703.Flora O. and Longinelli A., 1989. Stable isotope hydrology of a classical karstarea, Trieste, Italy. In Isotope Techniques in the Studies of Hydrology ofFractured and Fissured Rocks: 203-213, IAEA, Vienna.Feurdean L. and Feurdean V. 1999. Deuterium as natural tracer in groundwaterfrom neighbouring area of Danube Delta Biosphere Reserve. Isotopes Environ.Health Stud. 35: 183-211.Feurdean L., Feurdean V. and Oraseanu I. 2001. The use of deuterium as naturaltracer to point out groundwater flow from karst area. Case study. In NewApproaches Characterizing Groundwater Flow (eds. Seiler & Wohnlich): 59-63.Balkema, Rotterdam.Sarbu S. M., Kane T. C. and Kinkle B. K. 1996. A chemoautotrophically basedgroundwater ecosystem. Science, 272: 1953-1955.

Evidence and constraints revealed byenvironmental stable isotope in the

chemoautotrophic system of theMovile Cave, Romania.

Lucia Feurdean, Victor Feurdean, Serban Sarbu

National Institute for Research and Development of Isotopic and MolecularTechnologies, P.O. Box 700, 3400 Cluj-Napoca 5, Romania, luci@l40.itim-cj.ro

The stableisotopes(2H, 13C, 34S) contentfor samplesfrom the areaof thechemoautotrophicecosystemof the Movile Cavehavebeenutilised to providean independentmeansof informationaboutthe life in this closedsystem,whichhavegroundwaterrich in H2S (8-12mg/l) andanatmospherepoor in oxygen(7-10%), rich in CO2 (2-3.5%) and containing significant amount of CH4 (1-2%).

The 13C contentof caveorganicmatterexhibit low valuesof δ13C (between–47.5and –37.5‰)and reflect not at all the isotopic compositionof the localorganicmaterialsfrom surfaceand subsurface.The concentrationof 13C fromareavicinal to caveis typically to aquaticand terrestrialcommunitiesthat usephotoautotrophiccarbon fixation (between–30 and –23‰). This discrepancysuggestsotherway of carbonfixation in the trophicweb andis possiblethat theorganic matter is derived from organismsmore lipid-rich biosynthesizedbychemosyntheticmicroorganismswhich use H2S as energy sourcefor carbonfixation.

Gasescollectedfrom thegroundwater(H2S) andthecaveatmosphere(CH4 andCO2) have isotope ratios that point out the following:

1.The groundwater from cave is not originated from Black Sea. The δ34S valuesrange between+3.5 to +4.2‰ for cave, being rich in 34S versus isotopiccomposition of deep water from Black Sea (-40‰).

2.Thesulphurisotopecontentfrom H2S (+5.9 to +8.3‰) andSO42- (+1.1‰)

presenta contrasttrendversusthe generaltrendof the isotopic fractionationofthemicrobially mediatedsulphurtransformations.In cavewasnot recordedH2S

with δ34S values lower than that of the SO42- reactant.

3.Thecarbonisotopedatafor CO2-CH4 pairs(-23‰ for CO2 and–56.5‰forCH4) of the cavegasescannotclearly delineatedthe biogenicmethaneorigin asmarine or non-marine provenance.

4.The equilibrium carbon isotope fractionation betweenCH4 and CO2 is

αc=1.35 indicating that the CO2 reductionpathwayfor methanogenesisis veryimprobableand the naturalconditionsof the caveapproachof the laboratoriesconditions of the closed system kinetics.

5.The hydrogenisotopecontent from CH4-H2O pairs (-197‰ for CH4 and–90‰ for H2O) cannot clearly differentiate the CO2 reduction or acetatefermentationaspathwayof biogenicmethaneaccumulationin cave.Therangeinδ2H valuesof CH4 correlatedwith δ13C valuescannotelucidatemethanogenesisand the formation environment (marine or non-marine).Carbonand oxygenstableisotoperatios for samplesof carbonatedecreaseinsuite limestone bedrock-detachedoolites-botryoidal calcite crusts-aragonitecrustscoveringthepassagefloor (from –1‰ to –20‰ for δ13C andfrom +1‰ to–10‰for δ18O). Isotopicdatasupportthehypothesisthatcondensationcorrosionis major mechanism currently affecting the morphology of cave.

References

SarbuS. M., KaneT. C. andKinkle B. K. 1996.A chemoautotrophicallybasedgroundwater ecosystem. Science, 272: 1953-1955.Sarbu S. M. and Lascu C. 1997. Condensationcorrosion in Movile Cave,Romania. Journal of Cave and Karst Studies, 59 (3): 99-102.Schoell M., Hwang R. J., CarlsonR. M. K. and Welton J. E. 1994. Carbonisotopic composition of individual biomarkers in gilsonites (Utah). Org.Geochem. 21, 6/7: 673-683.Whiticar M. J., FaberE. andSchoellM. 1986.Biogenic methaneformation inmarine and freshwaterenvironments:CO2 reductionvs. acetatefermentation-Isotope evidence. Geochim. Cosmochim. Acta, 50: 693-709.

Differences in the climates of catchment areas asreflected by isotopic characteristics of the Danube

and Tisza Rivers, Hungary

István Fórizs1, Péter Juhász2

1 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budapest,Hungary, forizs@geochem.hu; 2 Water Resources Research Centre Plc., Budapest,Hungary, mitvisz@attglobal.net

Thereis an indirect link betweenthe surfaceair temperatureand the stableisotopecompositionof precipitationin local andregionalscale(e.g.Ró

�anskiet

al. 1993,Clark & Fritz 1997).The lower is the annualmeantemperatureof anarea the more negative is its annual mean δ18O value (linear relationship).

Figure 1. Stable oxygen isotope composition of water of the Danube andTisza rivers in the period of March 2001 – Fabruary 2002.

The Danubeand the Tisza rivers, the two biggestrivers going throughtheCarpathianBasin,havecatchmentareaswith differentannualmeantemperature.The Danube’scatchmentareais of higherelevationthenthat of the Tisza’s,sothe annualmeantemperatureof the former oneis lower. This differenceis wellreflectedin thestableoxygenisotopecompositionof theriver waters(Figure1),although the relationshipbetweenthe δ18O value of river water and the airtemperature is not so simple.

Theoretically,organismsliving in theriver waterarein certainkind of oxygen

isotopeequilibrium with the waterandin this way the climateof the catchmentarea is recorded in the isotopic composition of e.g. shell carbonates.

Figure 2. Stable carbon isotope composition vs. stable oxygen isotope compositionof Unioids living in the Danube and Tisza rivers. Open circles indicate average values

for the Danube and the Tisza.

Shellsof Unio Crassus, U. Pictorum and U. Tumidus from the DanubeandTiszarivers havebeenstudiedfor their stableisotopecomposition.Both carbonandoxygenisotopecompositionsdiffer significantly in the two rivers (Fig. 2).Regardingthe oxygen isotopecomposition,the Tisza water is enrichedin 18OversusDanubewater (Fig. 1) and this differenceis well reflectedby the shellcarbonates(Fig. 2). The carbon isotope composition shows even greaterdifferencebetweenthe two rivers (Fig. 2). This observationcanbea goodbasisfor identifying thepalaeo-riverbedsof theDanubeon theGreatHungarianPlain,whereDanube’sriverbedhasbeenmoveda lot duringgeologicaltime, andnowit is difficult to makedifferencebetweenthepalaeo-sedimentsof theDanubeandof other rivers by means of traditional methods. This work was financed by OTKA (Hungarian Sci. Res. Fund) T035032.

References

Clark, I., Fritz, P. 1997. Environmental Isotopes in Hydrogeology. LewisPublishers, Boca Raton – New YorkRó

�anski, K., Araguás-Araguás,L., Gonfiantini, R. 1993. Isotopic patternsin

modernglobalprecipitation.In ClimateChangein ContinentalIsotopicRecords.American Geophysical Union, Geophysical Monograph 78, 1-36.

High precision soil and atmospheric trace gasstable isotopic measurements for monitoring

sources and fluxes of CO2

Francois Fourel1,Simon Davis1, Andy Phillips1, John Morrison1, StephanieN. Dudd1, Guy Bilodeau2, Claude Hillaire-Marcel3, Jean-Francois Helie3

and Louis Varfalvy4

1Micromass UK Ltd, Floats Road, Wythenshawe, Manchester M23 9LZ; 2Micromass Canada, Pointe-Claire, Qc, Canada;3GEOTOP, UQAM, CP8888, Mtl, Qc, Canada;4Hydro-Quebec, Montreal, Canada & Chaire de Recherche en Environnement Hydro-Quebec-CRSNG-UQAM

Reliableinformation relating to sourcesand sinks of CO2 is essentialwhenmonitoring changesin atmosphericemissions,effects of emission reductionstrategiesandgeneralcarboncycling within a given ecosystem.Studiesof CO2

sampledfrom atmosphericand soil gasesoften involve the analysisof largenumbersof samplesrequiring high throughput,automatedsamplepreparationandtheability to dealwith traceamountsof analyte.TheMicromassTraceGasTM

inlet allows theanalysisof CO2, N2O andCH4 in traceconcentrations(ppb levelandbelow). Volumesof lessthan100 ml of ambientair canautomaticallybepre-concentrated, purified and analyzed.

We present the use of the TraceGasTM to investigate CO2 cycling inecosystems,through the measurementof the isotopic signatureof soil gases.Emissionsof naturalCO2 from an areaof seasonalgrasslandin California arecomparedto a secondplot where the majority of CO2 is derived from theaddition of elevatedquantitiesof bottled gas (manufacturedfrom fossil fuel).Significantshifts in the isotopicsignatureswereobservedbetweenthetwo plots,thusdemonstratingthe ability of the techniqueto identify areasof pollution andanthropogenic influences.

In addition, we presentthe outcomeof a recentstudy monitoring 13CO2 inatmosphericlow pCO2-samplesover a hydro-electric reservoir in Quebec,Canada.In this case, the IsoPrime IRMS configured with the MultiFlowTM

samplepreparationsystemhasbeenusedto obtain13C measurementsin samplesstoredin 12ccExetainervials. The studyassesseshow variousfactors,suchasclimatic events,the proximity of riverine vegetationand inputs of dissolvedorganic carbon, influence the 13C – CO2 signature of the overlying air. Benefits ofthe systemfor the analysisof 13C in CO2 include full automation,and highsample throughput and capacity (~3 mins per sample; > 250 samples per day).

Biogeochemical and isotopic study of the Jurassicshales in a sub-Alpine basin, southeastern France

Karine Gauchat, Jorge E. Spangenberg, Valérie Schwab and Johannes Hunziker

Institut de Minéralogie et Géochimie, Université de Lausanne, Switzerland,Jorge.Spangenberg@img.unil.ch

The Callovian-Oxfordianblack shaleformation(so-called"TerresNoires") ofthe southeasternbasin,France,sub-Alpinerange,providesa natural laboratoryfor a biogeochemicalstudyof regionalmetamorphism.In the Oxfordianshales,two maindomainsarerecognizedon bothsidesof theDignethrustfault gradingfrom diagenesiswith T < 150°C to low grademetamorphismwith T � 250°C(Guilhaumouet al. 1996). The shalescontaincalcareouslayerswith septarianconcretions,which sometimesdisplayspectacularmineralization(quartz,calcite,celestite,dolomite,barite,whewelitte,etc.;Martin 1985).This mineralizationisgenerallyassociatedwith petroleum-likehydrocarbons(HCs) (Spangenberg&Meisser1998).Thesehydrocarbonsmay be formed by different processes:(1)formationin situ of HCs by thermalmaturationof theorganicmattertrappedinthe concretions,(2) infiltration of HCs throughlate fracturesat a burial depthnearthe “oil-window” of the surroundingshales,or (3) infiltration of migratingpetroleumoriginatedin deepersourcerocks. We apply molecularand carbonisotopicanalysesof individual compoundsto studytheorigin of theHCspresentin these septarian concretions.

The stableisotopecompositionsof carbonatesfrom the shales(δ13C = 0.6 ±0.2‰, δ18O = -2.3 ± 0.2‰) indicate a marine origin. The δ13C valuesof theseptariancarbonatesvary in the following order:~ -27‰ in thecortexcalcite,~-22‰ in the inner matrix, ~ -1‰ in the earlyseptarianfracturescements,and~0‰ in theauthigeniccalcite.Theisotopicδ13C vs.δ18O covariationsindicatethatthe concretions grow through the iron-reduction to the sulphatereduction/fermentation zones until a depth of ≈ 10 m (e.g., Irwin et al. 1977). Theisotopiccompositionsof thekerogens,bitumensandindividual n-alkanes(Table1) excludethe hypothesisof infiltration of migratedpetroleum.The Rock Evalparametersand the δ13C values(≈ -24‰) of the shaleskerogens suggestaterrestrialcontributionto the marineorganicsource(Table1). The isotopicallylighter kerogens(up to 2‰) and n-alkanes (up to 3‰) of the septarianconcretionspoint to a more bacterialorganic source.The isotopically lighterbitumenof theshalesandseptariancomparedto the associatedkerogenindicateindigeneityof the HCs (Table1). The similar distributionof the n-alkanesandbiomarkersextractedfrom the matrix and interior of the septarianconcretionssupportthe in situ formationof the HCs. Having establishedthe indigeneityofthe hydrocarbonsin the septarianconcretions,the comparisonof the molecularandisotopicchangesfrom theseptarianandshaleshydrocarbonsrecordthermal

generation/degradation in a closed vs. open system. The first Rock Eval data,isotopiccompositionsof the organicfractions,and

the moleculardistributionsof the biomarkersindicatea higherthermalmaturitytowards the Digne fault (Table 1).

A systematic isotopic and petroleum-geochemicalstudy methodologicallysimilar to the presentstudy and comparingthe hydrocarbonsfrom the shales(opensystem)with thosefrom theconcretions(unquestionableclosedsystem)ina profile acrosstheDignefault will furtherour understandingof the thermalandchemical evolution of the hydrocarbons during regional metamorphism.

Table 1. Median δ13C and n-alkanes distribution in the shales, and in the septarianmatrix and interior, “Terres Noires”, S-E basin, France. a: shales; b: septarian matrix

c: septarian interior n.a. : not analysed.

Distance toDigne fault

δ13Ckerogen

(‰, PDB)δ13Cbitumen

(‰, PDB)δ13Cn-alkanes

(‰, PDB)

n-alkanes(mode)

� 90 km a -24.0 ± 0.1 -24.8 ± 0.1 -24.7 ± 1.2 C15 – C27 (C18)

b -25.1 ± 0.2 -28.4 ± 1 -28.8 ± 0.7 C12 – C34(C17)

c n.a. -28.8 ± 0.1 n.a. C12 – C34 (C19)

� 40 km a -23.8 ± 0.1 -25.3 ± 0.5 -26.6 ± 0.6 C14 – C28 (C16)

b -25.6 ± 0.4 -26.1 ± 1 -28.0 ± 0.7 C11 – C32 (C15)

c n.a. -26.1 ± 1 n.a. C12 – C31 (C17)

� 35 km a -23.6 ± 0.1 -24.8 ± 0.2 -25.5 ± 0.8 C15 – C28 (C17)

b -25.8 ± 0.6 -26.2 ± 0.6 -28.6 ± 0.6 C12 – C31 (C14)

c n.a -27.4 ± 0.4 n.a. C12 – C28 (C15)

References

Guilhaumou, N., Touray, J. C., Perthuisot, V. & Roure, F. 1996.Palaeocirculationin the basin of southeasternFrance sub-alpine range: asynthesisfrom fluid inclusionsstudies.MarineandPetroleumGeology,13, 695-706.Irwin, H., Curtis, C. D. & Coleman,M. 1977. Isotopic evidencefor sourceofdiageneticcarbonatesformed during burial of organic rich sediments.Nature,269, 209-213.Martin, R. 1985. Les septariasde marnesoxfordiennesde la Drôme et desHautes-Alpes (France). Schweizer Strahler, 7, 13-41.Spangenberg,J. E. & Meisser,N. 1998.Geochemistryof the OrganicMineralEvenkitein SeptarianConcretionsin the Oxfordian Marls of the FrenchAlps.The Eighth Annual V.M. GoldschmidtConference,30 August - 3 September,1998,Toulouse,France,Abstractvolume,MineralogicalMagazine,62A, 1436-1437.

Use of stable oxygen isotopic composition ofsea ice, snow and water to study the mass-balance

of sea ice in the northern Baltic Sea

Mats A. Granskog 1,2, Tõnu Martma3, Rein Vaikmäe3

1Division of Geophysics, Department of Physical Sciences, University of Helsinki,Finland, mats@iki.fi; 2Arctic Centre, University of Lapland, Finland; 3Institute ofGeology, Tallinn Technical University, Estonia

Stableoxygenisotopicpropertiesof seaice havebeenwidely usedto studytheincorporationof snow into the seaice cover in Antarctic waters(Langeet al.,1990;Jeffrieset al., 1994,1997;Kawamuraet al., 1997).Recentstudiesindicatethat thecontributionof snowis very importantfor the thickeningof the landfastice sheetin the Gulf of Finland(Kawamuraet al., 2001).However,the methodsemployedin theAntarcticarenot directly applicableto the Baltic Sea,sincetheconditionsin the Baltic Seawaters(e.g. Fröhlich et al., 1988; Punninget al.,1991), are much more variable than in the Antarctic.

The structuraland stableoxygen isotopic propertiesof sea ice, snow andsurfacewatersamplescollectedfrom landfastseaice in the northernBaltic Sea,betweenlatitudes60.2°and65.7°N,andlongitudes21.3°and26.9°E,wereusedto estimatethe contributionof snow-iceto the total seaice thickness,and thefraction of snow in the snow-ice and in the total ice thickness.

The textural analysisof the seaice coresrevealeda generalstructureof agranular surface layer and a columnar basal layer. Using different isotopiccriteria to distinguish snow-ice layers from other ice types we estimatethatsnow-icecontributedan averageof 24 to 32% to the total ice thicknessin thestudyregion.Granularfrazil-ice andtransition(intermediategranularcolumnar)ice alsocontributedsignificantly to the total ice thickness.The snowfraction ofthe total ice thicknesswas18 to 21%, a significant amountwhencomparedtootherseaicezones.Maximumvaluesfrom Antarcticseaiceare14-16%(Jeffrieset al., 1997).Hence,snowseemsto play a very importantrole in the thickeningof the sea ice cover in the Baltic Sea.

The methodsapplied could be improved to give even better estimates,especiallyby improvingtheknowledgeof thetemporalvariability of theisotopicpropertiesof the snow and seawaterincludedinto the ice cover.However,ourresultscan be regardedas plausibleestimatesfor the contributionof snow-iceand snow to seaice growth in the northernBaltic Sea.This study showsthatthereis a needfor moresystematicmonitoringof the isotopicpropertiesof riverinflow, precipitation and seawaterin the northern Baltic Sea,where data isvirtually non-existent (see also Fröhlich et al., 1988; Punning et al., 1991).

References

Fröhlich,K., J. Grabczak,andK. Rozanski.1988.Deuteriumandoxygen-18inthe Baltic Sea, Chem. Geol., 72, 77-82Jeffries,M. O., R. A. Shaw,K. Morris, A. L. Veazey,andH. R. Krouse.1994.Crystal structure, stable isotopes,and developmentof sea ice in the Ross,Amundsen and Bellingshausen seas, Antarctica, J. Geophys . Res., 99, 985-995Jeffries,M. O., A. P.Worby,K. Morris, W. F. Weeks.1997.Seasonalvariationsin the properties and structural composition of sea ice and snow in theBellingshausen and Amundsen seas, Antarctica, J. Glaciol., 43, 138-151Kawamura,T., K. I. Ushima, T. Takizawa, and S. Ushio. 1997. Physical,structuralandisotopiccharacteristicsandgrowth processesof fast seaice in theLützow-Holm Bay, Antarctica, J. Geophys. Res., 102, 3345-3355Kawamura,T., K. Shirasawa,N. Ishikawa, A. Lindfors, K. Rasmus,M. A.Granskog,J. Ehn, andMatti Leppäranta.2001.Time seriesobservationsof thestructure and properties of brackish ice in the Gulf of Finland, the Baltic Sea, 33, 1-4Lange,M. A., P. Schlosser,S. F. Ackley, P. Wadham,and G. S. Dieckmann.1990. 18O concentrationsin seaice of the Weddell Sea,Antarctica,J. Glaciol.,36, 315-323Punning,J.-M., R. Vaikmäe,andS. Mäekivi, 1991,Oxygen-18variationsin theBaltic Sea, Nucl. Geophys., 5, 529-539

Siderite-water oxygen isotope fractionationin low temperatures - new data on unusual

specimen from Baltic Sea

S. Halas1 and R. Chlebowski2

1 Mass Spectrometry Laboratory, Institute of Physics, Maria Curie-SklodowskaUniversity, 20-031 Lublin, Poland, e-mail: halas@tytan.umcs.lublin.pl;2Institute of Geochemistry, Mineralogy and Petrology, Warsaw University, Zwirki iWigury 93, 02-089 Warsaw, Poland

Themotivationof this studywasa greatimportanceof naturalsiderite,whichis most frequentlyformedin low temperatures(T) at seabottom.On the otherhandthereareno experimentalfractionationfactorsbetweensideriteandwaterdeterminedfor T<30oC. Also theoreticalpredictionsmade so far are highlydivergent at low T.

The first calculationwas madeby Becker (1971) on the basisof statisticalthermodynamicmethod.We reproducetheresultsof this calculationin Fig.1,butwith the following modification:The resultsof 103lnfsiderite

1/3 weretakenfrom hisPh.D. Thesis, while 103lnfwater were taken from Hattori and Halas (1982).

In the sameway we haverecalculateddatafrom Golyshevet al. (1981).Thisline is very close to that obtainedfrom Becker’s calculation.Note that therecalculatedBecker’s line differs somewhatfrom that given by Becker andClayton (1976). The new line is shifted towardshigher valuesof 103lnα byabout1.0, i.e. it is in favor of lately calculatedcurve by Zheng (1999). Thatcurve was calculatedby his modified incrementalmethod (Zheng 1999 andreferencestherein), using 103lnfwater from Hattori and Halas (1982). A largedivergencebetweenthat curveandthe two remainingis seen.Having accesstosideritesformedin well determinedconditionsat Baltic Seabottom,we analyzedtheir δ18O in order to establish low temperature fractionation factor.

Samplesof sideriteselectedfor analyseswere takenfrom the placeof theirformationfrom thewreckageof a sunkenship,in theshallowlittoral zoneon thebottomof the Baltic Sea.This site is locatedat depthof 5-7 m, ca.500 m fromtheshore(ChlebowskiandKowalski 1999).The transportedcargoincludesironplatesandbars.Theequipmentincludesbarrelsfilled with woodtar, thematerialusedthosedays for protectionof woodenelementsof ships.The catastropheleading to the sinking of the ship with equipmentand membersof the crewaccordingto written sourcestook placeon the Baltic Seaduring a stormon the27th of September1785.Thepresent-dayrock wasformedunderthe isolationofthe spilled wood tar.

Fig.1. Low temperature isotope fractionation between siderite and water. Lines aretheoretical plots, whereas points are experimental data.

Sideriteswere analyzedon CO2 preparedby 100% H3PO4 undervacuumat50oC, the reactiontime was 1 week.Acid fractionationfactor was takenfromRosenbaumandSheppard(1986).From δ18O calculatedvs. VSMOW and δ18Owater assumedto be +7.0‰ accordingto Frölich et al. (1988), 103lnα werecalculated.Thesevaluesfall into a narrowrange,from 33.0to 34.4‰, which isshownin Fig.1.Consideringa possiblevariability of δ18Owater of order1 permil,we obtain most appropriate crystallization temperaturewhen we use therecalculated Becker’s curve.

References

Becker R.H. 1971. Carbon and oxygen isotope ratios in iron-formation andassociatedrocks from the HamersleyRangeof WesternAustralia and theirimplications. Ph.D. Thesis, University of Chicago.BeckerR.H. and Clayton R.N. 1976. Oxygen isotopestudy of a Precambrianbanded iron-formation. Hamersley Range. Western Australia. Geochim.Cosmochim. Acta 40, 1153-1165.CarothersW.W., Adami L.H. andRosenbauerR.J.1998.Experimentaloxygenisotopefractionationbetweensiderite-waterandphosphoricacid liberatedCO2siderite. Geochim. Cosmochim. Acta 52, 2445-2450.Chlebowski R. and Kowalski W. 1999. Petrographic and mineralogical studies of

contemporarysedimentsdevelopedon the wreck of a ship on the Baltic Seabottom. Archiwum Mineralogiczne LII, 141-162.FröhlichK., GrabczakJ.andRozanskiK. 1988.Deuteriumandoxygen-18in theBaltic Sea. Chem. Geol. 72, 77-83.GolyshevS.I., PadalkoN.L. and PechenkinS.A. 1981. Fractionationof stableisotopes of carbon and oxygen in carbonate systems. Geokhimia 10, 1427-1441.Hattori K. and Halas S. (1982) Calculation of oxygen isotope fractionationbetweenuranium dioxide, uraniumtrioxide and water. Geochim.Cosmochim.Acta 46, 1863-1868.Mortimer R.J.G. and Coleman L. 1997. Microbial influence on the oxygenisotopic composition of diageneticsiderite. Geochim. Cosmochim.Acta 61,1705-1711.RosenbaumJ. and SheppardS.M.F. 1986. An isotopic study of siderites,dolomitesand ankeritesat high temperatures.Geochim.Cosmochim.Acta 50,1147-1150.Zheng Y.F. 1999. Oxygen isotope fractionation in carbonateand sulfateminerals. Geochem. J. 33, 109-126.

Use of Cu2O and NaPO3 for SO2 extractionfrom sulfates for isotopic analysis

S. Halas and J. Szaran

Mass Spectrometry Laboratory, Institute of Physics, Maria Curie-Sklodowska University,20-031 Lublin, Poland, e-mail: halas@tytan.umcs.lublin.pl;

Recentlywe haveimprovedthe SO2 extractionmethodfrom sulfateswhich isbasedon the useof sodiummetaphosphate(NaPO3). In the original approach(HalasandWolacewicz1981) sulfatesamplereactedwith NaPO3 in a ceramicboatplacedinto a quartzglasstubeheatedto 800oC by small resistancefurnace.That methodhad two drawbacks:(1) NaPO3 also extractedtracesof sulfateseither from ceramicboat or quartz glass, (2) high quality ceramic boatsareexpensive.Thefirst drawbackwasnoticedwhenwe tried to analyzesmallerandsmallersamples(Halasand Szaran1999). Thus we replacedceramicboatsbyboatsmadeof analyticalgradeCu foil and loweredthe reactiontemperaturetoavoid evaporationof visible fraction of NaPO3 which may react with quartzglass.Neverthelesslittle dropletsfrom time to time escapedfrom the boat toquartz glass wall. To suppressthis phenomenonwe applied admixture ofvanadium pentaoxide(Halas and Szaran 2001). The reaction predominatlyproceededat temperaturesbetweenmeltingpointsof NaPO3 (610oC) andof V2O5

(690oC). In this rangethe liquid phasesaturatedthepulverizedV2O5 resultingnoescapeof NaPO3 dropletsonto quartzglasswall. The optimumtemperaturewasfound (800oC) at which SO2 extraction is completed within 7 min.

The only drawbackof this improved approachis toxicity of the V2O5.Thereforein this studywe replacedit successfullyby cuprousoxide.Moreover,analytical grade Cu2O is much cheaper than V2O5.

Table 1. Results of δ34S measurements of SO2 extracted from NBS-127at various amounts of Cu2O.

Run BaSO4 [mg]

NaPO3 [mg]

Cu2O [mg]

δ50 δ34S VCDT

[‰]Mean δ34S

1 10 33 53 20.65 20.98 2 12 36 48 20.90 21.25 3 11 33 44 20.96 21.32 21.15±0.07 4 11 33 33 20.63 20.96 5 9 27 18 20.89 21.24

In test extractionswe usedvariousproportionsBaSO4 : NaPO3 : Cu2O asindicatedin Table1, which wereloadedinto Cu boat.The reactiontemperaturewas 750oC, while degas proceededat 300oC over 10 min. Reaction wascompletedwithin 15 min. The amountof SO2 andδ34S wastestedby meansof

dual inlet and triple collector massspectrometer.The spectrometerwas set onSO+ peaks and δ50 was measured:

� 50 � I 50 � I 48sample

I 50 � I 48working standard

� 1 x "103 ,

where I48 and I50 are heights of major and minor peaks, respectively.Theresultsareshownin Table1, whereδ50 wereconvertedto δ34S versusVCDTstandard according to the rules described by Halas and Szaran (1999 and 2001).

It is seenfrom Tablethatthereactionyieldsreproducibleresultsin wide rangeof Cu2O admixture. The observationof solid remainingin the Cu boat (Fig.1)

indicatesthatoptimumquantitiesof Cu2O appearto beaboutthesameasthatofNaPO3.Thebestreproducibilityof SO2 extractionis achievedwhenthequartzglasstubeis “activated” insideby severalmilligrams of V2O5 at ca 800oC. This thin V2O5

layer probably protects against extraction of spurious sulfates from quartz glass.

References

Halas S. and WolacewiczW. 1981. Direct extractionof sulfur dioxide fromsulfates for isotopic analysis. Anal. Chem. 53, 686-689.HalasS.andSzaranJ.1999.Low-temperaturethermaldecompositionof sulfatesto SO2 on-line 34S/32S analysis. Anal Chem. 71, 3254-3257.HalasS.andSzaranJ.2001.Improvedthermaldecompositionof sulfatesto SO2and massspectrometricdeterminationof δ34S of IAEA SO-5, IAEA SO-6 andNBS-127 sulfate standards. Rapid Commun. Mass Spectrom. 15, 1618-1620.

The use of stable isotopes in aquaticsystems influenced by environmental impact in

metropolitan areas (Berlin, Germany)

Hans-W. Hubberten1, Andrea Knappe1, Asaf Pekdeger2, Peter Möller3

1Alfred Wegener Institute, Potsdam, Germany, hubbert@awi-potsdam.de; 2FreieUniversität Berlin, Germany; 3GeoForschungsZentrum Potsdam, Germany

Public water supply of Berlin municipal area largely dependson bankfiltration. Theproductionwells aregenerallysituatedcloseto thesurfacewatersandextractabout70 % bankfiltrates.Thecontinuouslydecreasingrunoff of thesurface waters at nearly constantsewageinput leads to increasingsewagetreatmentplant outlets (STPO). During low water periods the proportion ofSTPOin thesurfacewatermaybelocally up to 90 %. Thereforetheinfluenceofthe surfacewater quality on bank filtrates is of great interestfor securingthedrinking water supply.

In this study the stable isotope compositionsof different surfacewater,groundwaterandbank filtrates werecomparedwith otherSTPOindicatorslikethe rareearthelementGadolinium,EDTA andBoron to verify the applicabilityof stable isotopes to environmental impact on various aquatic systems.

In our caseit could be shownthat surfacewater haveheavierstableisotopecomposition than the groundwater which is extracted for drinking waterpurposes.As indicatedabovefor the drinking waterextractionbankfiltration isused which is a mixture of surface water and ground water in differentproportions.

The treatedsewagereflectsmainly this mixture asno major influenceduringthe treatmentcanbe observed.The STPOarelighter thanthe surfacewaterandheavier than the ground waters. This gives an effective tool to study theproportionsof sewagein surfacewaterandvia surfacewaterin bankfiltratesandextractionwells. The mixing proportionsof surfacewater, ground water andSTPO can be calculated.

At transectswhich wereconstructedbetweenlake waterandextractingwell,transporttimescouldbestudiedasthesurfacewatershoweda distinct variationin time. In thesurfacewatertherewasa temperaturechangebetweenwinter andsummer from 5°C to 20 °C. However the temperaturetransport in theundergroundwasabouttwo timesslowerthanthe water,indicatedby the stableisotopes.Due to their ideal tracerbehaviorthe stableisotopesprovedto be themost effective tracersfor bank filtration and environmentalimpact to aquaticsystems in Berlin.

Are Isotopic Mixtures Ideal?

Gábor Jancsó

KFKI Atomic Energy Research Institute, H-1525 Budapest 114, P.O. Box 49, Hungary,jancso@sunserv.kfki.hu

Isotopicmixtures, i.e. mixturesof isotopomers(isotopomersare speciesthatdiffer solely in isotopiccontente.g. CH4 andCD4) havelong beenconsideredastextbook examplesof ideal solutions.Thereforethe study of the deviation ofsuchsolutionsfrom theidealbehavioris of specialinterest.Thedeterminationofthevaporpressuresof isotopicmixtureswith known isotopiccompositionis oneof the most convenient ways for investigations of this kind.

High-precisionvaporpressuremeasurementson mixturesof isotopomers(36Ar- 40Ar, H2 - D2, CH4 - CD4, C6H6 - C6D6, HCl - DCl, H2O - D2O, H2S - D2S,NH3 -ND3) haveshownthat eventhesevery simple mixturesexhibit small, but stillsignificant,deviationsfrom the ideal behavior.The magnitudeof the deviationsin terms of the excess Gibbs energy in isotopomer solutions is two to three ordersof magnitudesmaller than excessfree energiestypically observedin binarymixtures of non-isotopic simple molecules.

The deviationof isotopicmixturesfrom the ideal behaviorcanbe accountedfor in termsof thedifferencein themolarvolumesof isotopicmolecules(“molarvolume isotope effect”). Theoretical analysis demonstratesthat the internalvibrationsin the moleculesmakesignificant contributionsto the excessGibbsenergy,thereforeproperconsiderationof the volume dependenceof molecularvibrationsof the componentmoleculesis essentialto the understandingof theproperties of isotopic mixtures.

References

Jancsó,G., Rebelo,L.P.N., Van Hook, W.A. 1993. Isotopeeffects in solutionthermodynamics:excesspropertiesin solutionsof isotopomers.Chem.Rev.,93,2645-2666.Jancsó,G., Rebelo, L.P.N., Van Hook, W.A. 1994. Nonideality in isotopicmixtures. Chem. Soc. Rev., 23, 257-264.Calado, J.C.G., Jancsó,G., Lopes, J.N.C., Markó, L., Nunes da Ponte, M.,Rebelo,L.P.N.,Staveley,L.A.K. 1994.Theexcessthermodynamicpropertiesofliquid (CH4 + CD4). J. Chem. Phys., 100, 4582-4590.Rebelo,L.P.N., Dias, F.A., Lopes,J.N.C.,Calado,J.C.G.,Nunesda Ponte,M.,Jancsó,G. 2000. Evidencefor nonideality in the fundamentalliquid mixture(36Ar +40Ar). J. Chem. Phys., 113, 8706-8716.

Tracing atmosphere - biosphere sulphur exchange:S and O isotope ratios in spruce needles

Mariusz Orion J� drysek a, Adam Kału� nya, Jochen Hoefsb

a) Laboratory of Isotope Geology and Geoecology, University of Wrocław, Cybulskiego30, 50-205 Wrocław, POLAND, MOJ morion@ing.uni.wroc.pl AKplum@ing.uni.wroc.plb) Institute of Geochemistry, University of Göttingen, Goldschmidtstr.1, D-37077Göttingen, GERMANY, jhoefs@gwdg.de

IntroductionFor more than 100 years,sulphur depositionhasbeenin generalthe most

importantacidifying factor for thehydrosphere,pedosphereandbiosphere.Evenwith thedeclineof acidrain sincethemid-70’s,Europeis still oneof theworld'slargestacid rain regions,and the so called Black Triangle (the region of SEGermany,NW CzechRepublicandSW Polandis themostheavilycontaminatedregion in Europe(Sobik et al. 1997). It is clear from numerousobservations[Gebaueret al. 1994,Bruckneret al. 1993] that treescannotpreventa passiveuptakeof considerableamountsof gaseousand aerosolcompoundsincludingSO2, becausethesesubstancesdiffuse throughthe stomata.In polluted regions,nearlyall sulphatein spruceneedlesoriginatesfrom atmosphericSO2 [e.g.Hornet al. 1989, Gebauerat al. 1994]. The primary aim of this study was toinvestigateisotoperatiosof organicand inorganicsulphurin spruceneedlestoassessthe anthropogenicimpactvia atmosphericSO2. Therefore,the biosphericpart of the anthropogenicsulphurcycle was investigatedin a heavily pollutedareaat theNorthernslopeof KarkonoszeMts., SW Poland(J� dryseket al 2002).Spruceneedles,from a 900 m vertical transect(400 to 1300 m asl), werecollectedon two consecutivedaysof spring1998andoneday of winter 1999.Concentrations(sulphatesulphur ((SO4

2-)n) and organic sulphur ((Sorg)n)) andisotoperatios of organicsulphurand sulphatefrom spruceneedleshavebeenanalysed.

Results and DiscussionDuring spring (SO4

2-)n contentswere lower (mean0.066 wt %) and (Sorg)ncontentswere higher (mean 0.0836 wt %) comparedto the winter sampling(mean0.0147and 0.0663wt ‰ respectively).Both concentrationvalueswereratherconstantwith respectto altitude(J� dryseket al 2002).However, valuesδ34S(SO4

2-)n increasedfrom 4.80to 9.77‰ andδ34S(Sorg)n from 0.03to 7.19‰,with increasingaltitude(Fig. 1). This is attributedto an increasein atmosphericSO2 concentrationandlight intensity,which leadsto anincreasedextractionfrom

needlesof 34S-depletedH2S. The ∆34S(SO42- - Sorg)n valuevariedfrom –0.80to

7.57‰ andshowsa very goodcorrelationto the abundanceof duston needles

(Fig. 2). Higherabundancesof dustmay limit foliar ventilationand,thus,higher∆34S(SO4

2- - Sorg)n valuesreflect conditionswhich arecloserto sulphurisotopeequilibrium in the sulphate-organicsulphur system, whereaslower values∆34S(SO4

2- - Sorg)n characterisea higher ventilation rate and more dynamicconditions for the sulphur system in needles.

The spring δ34S(SO42-)n value was on averageabout1.9 ‰ higher than the

winter δ34S(SO42-)n value,but theδ34S(Sorg)n valuesweresimilar in bothseasons.

This relationshiparguesfor an intensivereductionof sulphatestoredin needles,which is the source of organic sulphur and H2S.

Fig. 1. Variations of sulphur isotopecomposition of sulphate and organic

sulphur in spruce needles, with respect toaltitude

Fig. 2. Differences in sulphur isotopecomposition of sulphate and organic sulphur inspruce needles versus the dust abundance on

needles. Higher abundances of dust correspondto higher ∆34S(SO4

2- - Sorg)n values (forinterpretations see text).

The δ18O(SO42-)n decreaseswith altitudedueto the altitudinal 18O-depletionof

atmosphericprecipitation and increasedformation of needle sulphate fromatmosphericSO2. The isotopeeffect relatedto a reductionprocessduringspring

can be also seenat higher altitudesby a negativecorrelationin δ18O(SO42-)n –

(SO42-)n versus δ34S(SO4

2-)n - (SO42-)n of spring needles (J� drysek et al. 2002).

Fig. 3. Variations of sulphur isotope composition of sulphate and organic sulphurin 4 age class spruce needles, with respect to altitude

Likewise, older needles show significantly higher isotope ratios as compared toyounger generation needles. We believe that winter and older needles showtrends of an advanced oxidation of the sulphur dioxide assimilated which resultsin increasing concentration of O- and S-isotope enriched sulphate. Thus, the dataconcerning separate age-class needles support this model.

Fig. 4. Variations of sulphur isotope composition of organic sulphur in 4age class spruce needles, with respect to altitude

Conclusions1) H2S extraction is the most likely mechanismto control variations in theobserved d-values both in organic and inorganic sulphur systems. 2) Dustabundanceon needlesmaycontrolvariationsin theD-valuesin organic-inorganic sulphur system.

AcknowledgmentsSincerestthanksare due to Mr. R. Przybilla, Ms. Reuberand Ms. A. Weber-Weller for isotoperatio analysesandMs. B.DoroszkoandMs. E. Białek for theirhelpin laboratorypreparation.This studywassupportedfrom theCommitteeforScientific Researchgrants, University of Wroclaw S-grant and HumboldtFoundation.

References

BrucknerG., GebauerL. andSchulzeE-D. 1993.Uptakeof 15NH3 by Piceaabiesin closed chamber experiments. Isotopenpraxis Environ. Health Stud., 29, 71-76.GebauerG., GiesemannA., SchulzeE-D. andJägerH-J.1994.Isotoperatiosandconcentrationsof sulphurandnitrogenin needlesandsoils of Piceaabiesstandsas influencedby atmosphericdepositionof sulphur and nitrogen compounds.Plant and Soil, 164, 267-281.Horn R., SchulzeE-D. and HantschelR. 1989. Nutrient balanceand elementcycling in healthyanddecliningNorway sprucestands.Ecol. Studies,77, 444-455J� drysek M.O., Kału� ny A., Hoefs J. 2002. S and O isotoperatios in spruceneedles as a tracer of atmosphericpollution. Jour.GephysicalResearch-Atmospheres (in press).SobikM., Bła� M. andQuiel F. 1997.Contributionof fog precipitationin waterflux and pollutant depositionthe ecosystemsof westernSudetes.(in Polish,English abstract). In: Conf. Proc. "GeoekologiczneProblemy Karkonoszy",Przesieka,15-18.10.1997.(printed by ACARUS, Pozna� , Poland),vol. 1, pp.151-163.

Air-pollution effect and Paleotemperature Scaleversus δ13

C Records in Tree Rings and in a PeatCore (Southern Poland).

Mariusz O. J� drysek1, Marek Kr� piec2, Grzegorz Skrzypek1,Adam Kału� ny1 and Stanisław Hałas3

1 - Laboratory of Isotope Geology and Geoecology, University of Wroclaw, Cybulskiego30, 50-205 Wroclaw, POLAND;2 - Department of Stratigraphy and Regional Geology, University of Mining andMetallurgy, Mickiewicza 30, 30-059 POLAND;3 - Mass Spectrometry Laboratory, M. Curie-Skłodowska University, 20-031 Lublin,POLAND.

IntroductionNumerousobservationsand calibrationsof the δ13C responseof plants to

environmentalvariationsshowthedominanceof climatic or atmosphericfactorson ∆13C discrimination in plants, including temperature,water availability,atmospheric CO2, H2O and SO2 concentrations (e.g. Hemming et al. 1998, LeavittandLong 1989,Martin andSutherland1990,Saureret al. 1995,J� dryseket al.1996, 2002, Schleseret al. 1999, Loader and Hemming 2000). On the otherhand,no appreciableanthropogenicchangein δ13C was observedin tree-ringsfrom Finland(Robertsonet al. 1997)andpeatin PolandandThailand(J� dryseket al. 1995,1996)during the XX century.Thus,this paperaims to addressthefollowing three objectives:(i) what doesthe isotopevalue in organic matterrepresent,(ii) how does the isotope signal quantitatively representclimaticparameters? (iii) assess the role of pollutants and natural environmental factors invariationsof isotopesignaturein treerings cellulose.To do this carbonisotopeanalysesof peatprofiles from the KarkonoszeMts. (SW Poland)and tree-ringcellulosefrom Wisła river valley in the Kraków region (S Poland)havebeencarried out. The samples analysed represent approximately the last 1,100 years.

ResultsThe δ13C profile in peat from the Szrenicapeatbog rangesfrom -26.74 to

-21.81 andthe δ13C valueof treerings rangefrom −27.82to –21.94‰ (Fig. 1,2, 3). The observedvariationsin the δ13C valuesof the peatsamplesand treerings from Polandin generalcorrelatedwith eachother (Fig. 1). This suggeststhat the δ13C value of organic matter in terrestrial conditions is generallycontrolled by the same environmental factors. On average,over the lastmillennium (X - XIX century), the δ13C of peat cellulose has been 1.8 ‰isotopically heavier compared to the corresponding tree ring cellulose value.

DiscussionIt is not possibleto providea precisecalibrationof isotopesignaturesin tree

rings, as the assimilationisotopeeffect dependsmostly on local microclimaticconditionsandspecificspeciesdemands.In the regionunderstudy,temperaturewas the dominant factor controlling the δ13C value of tree ring cellulose and peat-bog Sphagnum before the XIX century. It is estimatedthat, in the temperateclimate of Poland,the carbonisotopefractionationbetweenliving plants andatmosphericcarbondioxide (∆13Cp-a) for C3 plantsis about−0.26‰ / 1°C. Thiscorrespondsto 2.1 ‰ / 1000 m of elevation.Sincethe mid-XIX, in the Wisłavalley whenthe river wasregulatedandwaterdeficit in the neighbouringareasbecamecommon,wateravailability playsa primary role in isotopefractionationof the vegetation.However,in contrastto precipitation(Fig. 2), the temperature(Fig. 3) of the periodof the late wood growth doesnot correlateto d13C value.This may suggestthat, in contrastto manyauthors,waterdeficit/abundancebutnot temperature controls isotope fractionation during photosynthesis.

Fig. 1 δ13C in tree-ring cellulose (oaks trees near Kraków, S Poland) and in total organic matter ofpeat core profiles (Szrenica, SW Poland) compared to the temperature variations for lowlands in

England (after Lamb 1977). Data for tree rings are plotted as the running average in 15 yearsperiods. The upper row symbols shows positively (p), negatively (n) or no correlated (0) drifts inisotope signatures and temperature parameters. The symbols -, 4 and > represents: (-) increase, (4)

decrease and (>) not synonymous drift in the respective parameter.

Sincethe 1955,just after the „Lenin” steelworksstartedoperation,pollutionbecamethe dominantfactor controlling the carbonisotopesignatureof plants.Contaminationof the atmosphereby fossil fuel burning from the “Lenin”steelworksincreasedthe δ13C valueof treering celluloseby about1.3 ‰. Thiswas probably causedby an increasedconcentrationof atmosphericpollution(SOx and dust) limiting the ventilation rate of the stomata.

Fig. 2 δ13C from late wood of oak tree ringsversus rainfall (May-July).

Fig. 3 δ13C from late wood of oak tree ringscellulose versus weighted average temperature

between 25.07. – 08.09. (latewood grow period)(oak trees near Kraków, S Poland).

Conclusions1. Although, it is not possibleto providea universallyprecisecalibrationas

assimilationisotopeeffectsdependmostlyon local microclimaticconditionsandspecificspeciesdemands.In theareastudied,precipitationhasbeenfoundto bethe limiting factor controlling carbonisotopevariationsin tree ring cellulose.This calibrationis valid for the time from the middle of XIX till the middle ofXX centuries.

2. A remarkableanthropogenicimpact causedby the neighbouring"Lenin"steelworksin NowaHuta(constructedin 1954nearKraków),asshownin Fig. 2,suggests that such a calibration should be limited to the pre-industrial time. 3. It has been observed that contamination of the atmosphere by the products offossil fuel burning from the “Lenin” steelworks(mostly SOx and dust etc)

increased the δ13C value of tree ring cellulose by about 1.3 ‰.

AcknowledgementsThis studyhasbeensupportedby and"S” and“W" grantsat the University ofWrocław and IAI.

References

Hemming, D.L. Switsur, V.R. Waterhouse,J.S. Heaton, T.H.E. and Carter,A.H.C. 1998.Climatevariation and the stableisotopecompositionof tree ringcellulose: an intercomparisonof Quercus robur, Fagus silvatica and Pinussylvestris. Tellus, 50B(1): 25-33.J� drysek, M.O. Skrzypek,G. Wada, E. Pazdur,A. Hałas, St. Vijarnsorn, P.

Takai, Y. and Ueda, S. 1996. δ13C and δ34S in peat: possible tool forpaleoenvironmentalreconstruction.Proceedings(editor in chief: Bottrell, S.H.Assoc.editors:Alpin, A.C. McArtur, J.M. Newton,R.J.Krom, M. Raiswell,R.),Fourth InternationalSymposiumon the Geochemistryof the Earth Surface,Ilkley, Yorkshire,England,U.K., 22-28July 1996.,held underthe auspicesof:The InternationalAssociationof Geochemistryand Cosmochemistry,pp. 221-224.J� drysek,M.O. Kału� ny, A. Hoefs, J. 2002. S and O isotoperatios in spruceneedlesas a tracer of atmosphericpollution. Jour.GephysicalResearch–Atmospheres (in press).Leavitt, S.W. Long, A. 1989.The atmosphericδ13C recordas derivedfrom 56Pinyontreesat 14 sitesin thesouthwesternUnitedStates,Radiocarbon,31 469-474.Lipp, J.Trimborn,P.Fritz, H. Moser,H. Becker,B. andFrenzel,B. 1991.Stableisotopes in tree ring cellulose and climatic change. Tellus, 43B, 322-330.Loader,N.J.andHemming,D.L. 2000.Spatialvariationsin pollenδ13C correlatewith temperature and development timing. Holocene (submitted).Martin, B. Bytnerowicz, A. and Thorstenson,Y.R. 1988. Effects of AirPollutantson the Compositionof StableCarbonIsotopesδ13C of Leavesandwood, and on Leaf Injury. Plant Physiol., 88, 218-223. Robertson,I. Rolfe, J.Switsur,V. R. Carter,A. H. Hall, M.A., Barker,A. C. andWaterhouse,J.S.1997.Signalstrengthandclimaterelationshipsin 13C/12C ratiosof tree ring cellulose from oak in southwestFinland. GeophysicalResearchLetters, 24, 1487-1490.Saurer,M. Siegenthaler,U. and Schweingruber,F. 1995. The climate-carbonisotoperelationshipin tree rings and the significanceof site conditions.Tellus47B, 320-330Schleser,G. H. Helle, G. Lücke,A. andVos,H. 1999.Isotopesignalsasclimateproxies:theroleof transferfunctionsin thestudyof terrestrialarchives.Quatern.Sci. Rev., 18, 927-943.

The late Ordovician carbon isotope trendin Estonia, its significance in stratigraphy

and environmental analysis

Dimitri Kaljo, Linda Hints, Tõnu Martma and Jaak Nõlvak

Institute of Geology at Tallinn Technical University, 7 Estonia Blvd., 10143 TallinnEstonia, kaljo@gi.ee, hints@gi.ee, martma@gi.ee, nolvak@gi.ee

Stablecarbonisotopeshavebecomewidely usedin different fields of geology,includingcorrelationof sequencesandelucidationof environmentalparameters.Until last years main attention was paid to the latest Ordovician, where theHirnantian positive carbon isotope excursionis well known (Marshall et al.1997;Kump et al. 1999;Kaljo et al. 2001),but recentlyseveralpapershavebeenpublished also about Caradocand early Ashgill sequences(see Referencesbelow). Thanksto thesepublicationsand the new datawe haveobtainedfromseveral sectionsof Estonia (Kõrgessaare,Orjaku, Viljandi), we consider itpossibleto suggesta generalpatternof the late Ordovicianδ13C changes,whichseems to reflect the actual trend more or less adequately.

The following main δ13C positive pre-Hirnantianexcursionshave beendetermined in the late Ordovician: one in the mid-Caradoc (value reaching 2.2‰,Ainsaaret al. 1999),two in the lateCaradocandonein theearlyAshgill (Kaljoet al. 1999)in Estoniaandseveralin theMohawkiansectionsin North America(Patzkowskyet al. 1997;Ludwigsonet al. 2001;Fanton& Holmden2001;etc.).The Mohawkian excursionsare partly only preliminarily published (values2–3‰), and their exact positions in terms of graptolite biozonationare notknown. Nevertheless,the occurrenceof theseexcursionsshowsthat the smallδ13C positiveshifts(valuescloseto 2‰), identifiedin Estoniain theCaradocandearlyAshgill, mayhavetheir counterpartsin North America.If thecorrelationofthese isotopic events is proved biostratigraphically,the global or at leastsubglobal significance of the earlier excursions mentioned will become evident.

Our dataset coversthe latest12 Ma of the Ordovician,beginningwith theKinnekulleK-bentoniteBedat 455Ma. At leastfour minor pre-Hirnantianshiftsof δ13C valuesanda short(0.5 Ma) but strongHirnantianshift (6-7‰) occurredduring this time span.The valuesof the earlierexcursionsaretwo - threetimessmallerthanthoseat the very endof the period.The Hirnantianshift is usuallyinterpretedas an eventcausedby a glaciation,but different other mechanismshavebeensuggestedaswell (Marshallet al. 1997;Kumpet al. 1999).Theearlierminor shifts too arebelievedto be relatedto glaciations,but alsodifferentotherglobalor morelocal reasons(e.g.sealevel changes,increasein burial of organiccarbon, tectonic movementsand changes in weathering, etc.) have beenconsidered(op. cit.). Often nearly all thesereasonsare tied to some glacial

processes.If this provescorrect,thenthey appearto advocateabouta long butfluctuating glacial epoch in the late Ordovician.

In many casesinterpretationsof the isotopic eventsarearguableor differentexplanationsareequallypossible.Herethebiostratigraphystepsin andmaygivedecisive hints. Vice versa, simultaneousapplication of carbon isotope andgeologicaldata may greatly contribute to the solving of severalcomplicatedproblemsof correlation, sedimentaryhistory and palaeogeographyinvolvingBaltica, Gondwana and Laurentia.

References

Ainsaar,L., Meidla, T. & Martma,T. 1999.Evidencefor a widespreadcarbonisotopic event associatedwith late Middle Ordovician sedimentologicalandfaunal changes in Estonia. - Geol. Mag., 136, 49-62.FantonK. C. & HolmdenC. 2001.Sealevel forcing of Late Ordoviciancarbonisotope excursions. - In: GSA Annual Meeting, Nov. 5.-8. 2001.Kaljo D., Hints L., Hints O., Martma T. & Nõlvak J. 1999. Carbon isotopeexcursionsand coeval biotic–environmentalchangesin the late CaradocandAshgill of Estonia.- In: Kraft P. & FatkaO., Eds.,Quo vadisOrdovician?ActaUniv. Carolinae, Geol., 43, 507–510. Kaljo D., Hints L., MartmaT. & Nõlvak J. 2001.Carbonisotopestratigraphyinthe latest Ordovician of Estonia. - Chem. Geol., 175, 49–59.Kump, L.R., Arthur, M.A., Patzkowsky,M.E., Gibbs, M.T., Pinkus, D.S.,Sheehan,P.M. 1999.A weatheringhypothesisfor glaciationat high atmosphericpCO2 during the Late Ordovician.-Palaeogeogr.,Palaeoclim., Palaeoecol., 152,173-187.LudvigsonG. A., Witzke B. J. GonzalezL.A., CarpenterS. J. & Hasiuk F. J.2001. New complexitiesin the expressionof Late Ordovician carbonisotopeexcursionsstraddling the Turinian-Chatfieldianboundaryinterval. - In: GSAAnnual Meeting, Nov. 5.-8. 2001Marshall J.D., BrenchleyP.J.,MasonP., Wolff G.A., Astini R.A., Hints L. &Meidla T. 1997.Global carbonisotopiceventsassociatedwith massextinctionandglaciationin the lateOrdovician.- Palaeogeogr.,Palaeoclim.,Palaeoecol.,132, 195-210.PatzkowskyM.E., Slupik L.M., Arthur M.A., PancostR.D. & FreemanK.H.1997.Late Middle Ordovicianenvironmentalchangeandextinction:Harbingerof the Late Ordovician or continuationof Cambrianpatterns?- Geology, 25,911-914.

Radon in deep water wells on Cracow area

E. Kochowska, J. Mazur, K. Kozak

The Henryk Niewodnicza � ski of Institute of Nuclear Physics , Cracow, Poland. e-mail:kochowsk@alf.ifj.edu.pl

The method and the results of radon concentration measurements in deep watersamples are presented. Since May 2000 the measurements of radon concentrationin water wells on Cracow area have been carried out - both in deep wells (depthof about 50-70 meters) and in other private wells (depth of about 10 meters).

TheionisationchamberAlphaGUARDPQ2000PROalongwith theadditionalspecial equipment AquaKIT were used for the determination of radonconcentration in water samples. The scheme of the set-up is shown in Fig. 1.

Figure 1. Scheme of the measurement set-up (AlphaGUARD with AquaKIT).

Themeasurementconsistsof treecycles:the watersampleis degassedfor tenminutesusing a pump, then thereis twenty minutesof “not-pumping” and theprocedurerecurs.Radonconcentrationin watersampleis calculatedaccordingtothe formula [1]:

C water � C air� V system � V sample

V sample

�k � C o

[Bq/m3]

Cwater – radon concentration in water sample [Bq/m3]Cair –radonconcentrationin the set-upafter expelling radonfrom watersample[Bq/m3]Co – radon concentration in the “empty” set-up (without water sample) [Bq/m3]Vsystem – interior volume of the measurement set-up [ml]Vsample – volume of the water sample [ml]k - radon distribution coefficient [-]

A total of 36wellswereexaminedasregardsradonconcentrationin water– 25

AlphaGuard

AlphaGUARD

AlphaPUMP

AlphaPUMP

inoutdegassing vessel

security vessel

3

2

1

4

deepwells and 11 private ones(mainly from Wola Justowskaarea– part ofCracow).Wola Justowskais a regionwheretectonicsfaultsoccurandradoncaneasily migrate from deep basementstructure [2]. The obtained results arecollectedin Table1 andthe distributionof radonconcentrationin all measuredsamples is shown in Figure 2.

Table 1. Statistical analysis of the results

all wells private wells deep wellsBq/l

Average ± standard error 3.73 ±0.51 4.85±1.13 3.23±0.52Mediana 2.91 4.09 2.7

Standard deviation 3.05 3.75 2.62Range 0.05 - 11.51 0.45 - 11.51 0.05 - 11.18

Confidence level (95%) 1.03 2.52 1.08

Figure 2. Distribution of radon concentration in all water samples from Cracow region.

These preliminary results do not show the direct correlation betweengeologicalstructureandradonconcentrationin watersamples.However,furtherinvestigation is needed and planned to be undertaken.

References

1. AquaKIT Manual. 1997. Genitron GmbH, Germany2. Swako� J, Kozak K, PaszkowskiM, et al. 2002.The measurementsof radonin soil gason Cracowarea.(in Polish),INP ReportNo 1895/B,Online.Internet:http://www.ifj.edu.pl/reports/1895.pdf

Stable isotope (C, N, O, S) patterns of the Idrijamercury mineralization, western Slovenia

Jošt V. Lavri� , Jorge E. Spangenberg

Institut de Minéralogie et Géochimie, Université de Lausanne Switzerland,Jost.Lavric@img.unil.ch

An ongoing detailed geochemical study of the Middle Triassic cinnabar depositof Idrija (Slovenia)aimsto unravelthe formationof the associationof mercuryand aromaticpetroleumin hydrothermalsystems.Idrija deposit(12.7 Mt ore,145.000t Hg) is hostedin UpperCarboniferousto Ladinianbeds.Thehost-rocksweresampledat differentscales,includingregionaloutcrops(BC) andhost-andfracture-filling carbonatesin the mine (HC and FFC). The geochemicalstudyincludesmajor and traceelementlithogeochemistry,carbonateδ13C and δ18O,δ34S of the sulfur minerals, and molecular and isotopic (δ13C, δ15N, δD)biogeochemistryof the ore-associatedorganicmatter.Here we summarizetheresultsof the stableisotopeinvestigationsof the host and ganguecarbonates,bitumens (extractable organic matter) and kerogens, and sulfur minerals(cinnabar, pyrite, gypsum, barite). The host carbonates have a marine isotopic signature, and a positive correlationin δ13C vs.δ18O space.A trendtowardlighter isotopiccompositionis observedinthe sequence: BC (δ13C = –2.2 to +5.2 ‰, δ18O = –7.0 to –0.8 ‰ PDB), HC (δ13C= –1.8to +5.6‰, δ18O = –9.7to –1.1‰), FFC(δ13C = –0.3to +5.0‰ andδ18O= –11.2to –4.4‰ δ18O). Thehighly mineralizedHC samplesaredepletedin 18O(up to 3.5‰) comparedto thebarrenHC samples.Theisotopicallylight oxygenmay be explainedby higher temperatureat the ore site or re-equilibrationwithcirculating isotopically light water. A contribution of isotopically light waterreleasedduring diagenetic/hydrothermalalterationof clays from silty beds,orformedby sulfatereductioncannotbeexcluded.Thespatialvariationof the � 18Ovalueson regional,mine and outcropscaleconfirms the channelizednatureofthefluid-rock interactionin a fracture-controlledhydrothermalsystem.Thelargeoverlapof thecarbonateδ13C valuesfavorstheHC asthemaincarbonsourceforthe fracture-filling carbonates.

Theisotopiccompositionof thekerogens(δ13CKER = –29.0to –23.1‰, median

= –26.3; δ15NKER = –1.2 to +4.6 ‰, median = 0.6) indicates a terrestrial

contributionto the marineorganicmatter.The scatterof the δ13CKER valuescanbeattributedto theoriginal compositionalvariability of thesedimentaryorganicmatter.No significantdifferencesbetweenbarrenandmineralizedsampleswereobservedwithin the distinct lithostratigraphicunits. The bitumensfrom barrenand mineralizedhost rocks are enrichedin 13C (up to 2.7 ‰) comparedto theassociatedkerogens(δ13CBIT = –27.7to –22.8‰). This may indicatethat Idrija

host rocks are stainedby: (a) local hydrocarbons,which were enrichedin 13Cduringhydrothermalalteration,or (b) mixed indigenousandisotopicallyheaviermigrated hydrocarbons.

The gypsumsamplesare within the rangeof Permianto Middle Triassicmarinesulfates(+12.3and+16.4‰ CDT). Sulfur isotopevaluesof (sedimentaryand hydrothermal)pyrite cover a wide range(δ34S = –22.4 to +59.6 ‰). Thepyrite from Middle Triassicfault zonesandthe bituminous"Karoli" (Ladinian)ore hasvery uniform valuescloseto –1 ‰, which points to a commonsulfursource.Baritehasvaluesof +46.6to +52.3‰. Thesehighly positivevaluesmayreflect crystallizationfrom a 34S-enrichedpool in a highly remobilizedore.Thecinnabarδ34S valuesare(1) very variableat mine scaledown to hand-specimenscale (δ34S = –19.9 to +22.0 ‰), (2) have a clear bimodal distribution, and (3) are34S-enrichedstratigraphicallyupwardsfrom Permianto Upper Ladinian beds(Fig. 1).

Figure 1. Ranges and medians of δ34S values of sulfides andsulfates from Idrija deposit.

Sulfur from 34S-depleted sedimentary pyrite and possibly organo-sulfurcompounds,could accountfor the isotopically lightest valuesand the bimodaldistribution. The δ34S-patternssuggestmultiple sulfur sourceswith Permo-TriassicevaporitesandTriassicseawaterastheheavyend-members,anda deep-seatedsource of isotopically lighter sulfur. Varying proportions of mixingbetweenthesesources,and changesof physicochemicalconditions(pSS, pO2,pH, andT) explainthe variationof thesulfur isotopicsignaturesat the differentscales.We concludethat the stableisotopegeochemistryof the gangueandoreminerals record distinct pulses of mineralizing fluids and rapid (isotopicdisequilibrium) ore precipitation at Idrija.

Anthropogenic changes in the Wielopolka Rivercatchment, Southern Poland, inferred from

overbank sediments using 210Pb.

Edyta Łokas1, Przemysław Wachniew2, Leszek Starkel3, El � bietaCzy� owska3, Piotr G� bica3

1Instituteof NuclearPhysics,Kraków, Poland,vlokas@novell.ftj.agh.edu.pl;2Universityof Mining and Metallurgy, Kraków, Poland, 3Department of GeomorphologyandHydrology, Institute of Geography and Spatial Organisation, Polish Academy ofSciences, Kraków, Poland.

Overbankdepositsof rivers have been used to study past anthropogenicchangesof riverine environments,e. g. hydrological regimesand heavymetalcontamination.Floodplain sediments depositedduring flood eventsare: animportantfactor of river systemgeomorphology(Macklin andLewin, 1993),asignificant componentof catchmentsedimentbudgets(Lambert and Walling,1987)andcanrepresentimportantlong-termsinksfor manycontaminants,e. g.heavy metalsand pesticidesassociatedwith fine material mobilized from theupplandcatchments(Macklin et al., 1994;Hudson-Edwardset al., 1999,Owenset al., 1999).Due to importanceof overbanksedimentsin the assessmentof theanthropogenicenvironmentalchangethereis an increasingneedfor informationregardingratesandspatialpatternsof overbankdeposition.The210Pbmethodhasbeenrecognizedasa suitablemeansto estimateratesof overbankdepositionforthe last 100 years (He and Walling, 1996).

Themainaimof thestudywasanattemptto usethis noveltechniquein caseofoverbanksedimentsof the WielopolkaRiver, the tributary to the Wisłoka Riverin SouthernPoland.TheWielopolkaRiver waschosenastheobjectof thestudybecauseits overbanksedimentsareeasilysampledwithout time-consumingandexpensive corings. Moreover, hydrological and sedimentologicaldata areavailable for the Wielopolka catchment since 1885.

Useof 210Pb to estimateratesof overbanksedimentationdiffers significantlyfrom its use for dating of lacustrinesediments.210Pb containedin floodplaindeposits has two components: atmospheric and catchment-derived210Pb.Estimation of sedimentationrate averagedfor the sedimentprofile requiresdetermination of catchment-derivedunsupported210Pb inventory and 210Pbcontentin fluvial sediment(He and Walling, 1996). This is accomplishedby210Pb and 226Ra activity measurementsfor overbanksedimentsand soil corescollected above the inundation level.

Five 1.0 – 1.5 m long overbanksedimentcoresand three soil coreswerecollectedin theWielopolkacatchment.210Pband226RaactivitiesandCu, Cd, Zn,Pb and Cr concentrations(Flame Atomic Absorption Spectrometry)weremeasured.Mineral fractions and other parameterscharacterizinggrain size

Figure 1. 210Pb activities and heavy metal concentrations in core W1a.

distribution (skewness, curtosis, etc.) were determined for the collected overbanksediment profiles. The most important component of the sediments are silty clayswith sandy layers. Supplementary hydrological data concerning the Wielopolkacatchment including daily average water levels since 1885 to 2000 and detailedoccurrence of extreme flood water levels were compiled. Data on Wielopolkawater levels for 1900-2000 show significant lowering (by 1 m) of average annualwater levels in the period 1900-1950. Water level lowering was related to riverregulations and lowering of the erosion base.

The substantial body of information and data creates a framework forreconstruction of historical anthropogenic impacts on the environment of thecatchment. Land-use changes and river regulations influence hydrology andsediment load in rivers and streams of the catchment. These anthropogenicchanges are reflected in varying sedimentation rates and grain size compositionsof overbank sediments. Heavy metals released into the hydrological cyclebecome associated with fine sediments and can be retained in floodplaindeposits.

Acknowledgments

This study was sponsored by the Ko � ciuszko Fundation.

References

He Q. and Walling D. E. 1996. Use of fallout Pb-210 measurements toinvestigate loger-term rates and patterns of overbank sediment deposition on thefloodplains of lowland rivers. Earth Surface Processes and Landforms, 21, 141-154.Hudson-Edwards K.A., Macklin M.G. and Taylor MP, 1999. 2000 years of

sediment-borne heavy metal storage in the Yorkshire Ouse basin, NE England,UK, Hydrological Processes, 13, 1087-1102.Lambert C. P. and Walling D. E. 1987. Floodplain sedimentation: A preliminaryinvestigation of contemporary deposition within the lower reaches of the RiverCulm. Geografiska Annaler, 69A, 47-59.Macklin M. G. and Lewin J. 1993. Holocene river alluviation in Britain.Zeitschrift fuer Geomorphologie, 88, 109-122.Macklin M. G., Ridgway J., Passmore D. G. and Rumsby B. T. 1994. The use ofoverbank sediment for geochemical mapping and contamination assessment:results from selected English and Welsh floodplains. Applied Geochemistry, 9,689-700.Owens P. N., Walling D. E. and Leeks G. J. L. 1999. Use of floodplaindsediment cores to investigate recent historical changes in overbank sedimentationrates and sediment sources in the catchment of the River Ouse, Yorkshire, UK.Catena, 36, 21-47.

Atmospheric CO2 concentrations and �

13Cmeasurements along a hemispheric course

(2001/2002 , Italy to Antarctica)

Longinelli A.*, Lenaz R.**, Ori C.**, Selmo E.*

University of Parma, Department of Earth Sciences, Parco Area delleScienze, 157A,43100 Parma, Italy. ** C.N.R., Institute of Marine Geology,Area della Ricerca, ViaGobetti 101, 40129 Bologna, Italy.

Continuous measurements of atmospheric CO2 concentrations were carried outduring the last few years between Italy andAntarctica showing that the largestgrowth rate took place between 1996 and 1998 between 20° and 45° North whilesouthern belts show an almost constant growth rate.Anthropogenic activitiesclearly affect both CO2 concentrations and growth rates. Apart from theisotopically negative values observed in highly polluted areas, a negative trend ofthe carbon isotopic composition of atmospheric CO2 was observed acrosstheAntarctic Convergence Area during the 1998/1999 expedition with nochanges in the atmospheric concentration of CO2. A variation of the δ13C ofatmospheric CO2 with no detectable change of the CO2 concentration involvesthe rate of the net air-sea CO2 fluxes with no deviation of ƒ CO2 fromatmospheric equilibrium values. Previous authors suggested a seasonalvariability of the regional CO2 fluxes, the summer values and the distribution ofthe ƒ CO2 values being essentially under biological control. The hypothesis of abiochemical origin of the light carbon isotope valuesmeasured in the atmosphericCO2 across the Antarctic Convergence Area was suggested. In fact, surfacewaters around Antarctica are characterized by the highest annual nutrientconcentration found globally, a condition maintained by the elevated supplyfrom upwelling circumpolar deepwaters. During the 2001/2002 expedition toAntarctica, 24 four liter air samples were collected mainly across the AntarcticConvergence Area to check the reliability of the previous measurements andinterpretation. The treatment of the samples and the measurement of the carbonisotopic composition of atmospheric CO2 in the 2001/2002 samples will start atthe beginning of April so that the new results obtained will be presented at theTallinn meeting.

Isotopic composition of precipitationin Italy: a first overall map

Longinelli A., Selmo E.

University of Parma, Italy - Departmentof Earth Sciences -Parco Area delle Scienze157A 43100 Parma,Italy

During thelastyearsmeanmonthlysamplesof atmosphericprecipitationwerecollectedover different periodsof time rangingfrom one to eight yearsat 78different stations throughout Italy. These sampleswere measuredfor theiroxygen and hydrogen isotopic composition to obtain basic information forhydrologicalandmeteorologicalstudiesin this area.On the basisof the resultsobtaineda first map of the isotopic compositionof precipitationsin Italy hasbeen drawn up. The main features of this map are the following: 1) no latitudinalgradienthasbeenfound along the Tyrrheniancoastfrom Sicily to the Italian-Frenchborder,probablybecausethe weightedyearly meanvaluesare affectedby a partial contributionfrom seawaterspray;2) a minor latitudinal gradientisfoundin thesoutheasternmostsectionof thecountry(Apulia), partially favouredby the local morphology;3) a marked “shadow effect” of the Apenninesisapparentalongthesouthernsectionof thePovalley andalongthecentralsectionof the Adriatic coast;4) the contributionof watervapourfrom thenorthernmostsectionof theAdriatic seaaffectstheeasternandcentralsectionsof thePoplain;5) the “shadoweffect” of the Alps is considerablysmallerthanexpected;6) theisotopicverticalgradientscalculatedin ninedifferentareasandbasedon groupsof two to five different stations vary but are essentially close to about -0.2 ‰/100meters; 7) when mean monthly temperaturevalues were available, theirrelationshipwith the isotopiccompositionof precipitationwas found to be, onaverage,very poor; 8) the relationship betweenmean � 18O and mean � Dcalculatedfor thecollectionlocationsshowslargeshiftsof boththeslopeandthedeuteriumexcesswhencomparedto theglobalmeteoricwaterline. Theseshiftsaredifferent for northern,central,andsouthernItaly; 9) in a few casesa markednegativization of the isotopic values related to the “amount” effect is apparent.

Holocene and Late-Glacial Isotopic Recordsfrom NW England: calibration of temperature

and precipitation records

J. Marshall & members of the Hawes Water Research Group

Dept. of Earth Sciences, University of Liverpool, Liverpool, UK,isotopes@liverpool.ac.uk

An understanding of the impact of past climate change on the terrestrialenvironment requires the development of quantitative indicators ofpalaeotemperature and palaeoprecipitation. We have obtained a very high-resolution, Late Glacial and Holocene oxygen isotopic record from HawesWater, Lancashire, UK that has been calibrated by a detailed field monitoringstudy of carbonate precipitation in the modern lake.

The calibration study has identified the mode and season of carbonateprecipitation and we have determined a local relationship between isotopicfractionation and temperature that is significantly different from conventionalequilibrium relationships.

The post glacial sediment oxygen isotopic record reveals a degree of climaticinstability that is greater than recognised in previous isotopic studies of sitesfrom the Atlantic margin of NW Europe. Four oscillations in the Late-Glacialinterstadial before the onset of the Younger Dryas Stadial are marked by sharpnegative excursions in the δ18O record of the carbonate sediments andaccompanied by marked changes in chironomid populations and the pollenrecord. The early Holocene is marked by a further 2 marked oscillations and amarked submillenial cyclicity.

The oscillations are interpreted as cold events: they correlate with eventsrecognised in marine and lacustrine temperature proxy records as well as theisotopic record from the Greenland ice cores. The interpretation is constrained bythe results of a study of carbonate precipitation in the modern lake. Resultssuggest that there has been a significant change in lake water composition orchange in relationship between temperature and water composition since theLate-Glacial.

Comparison of the isotopic record with the faunal temperature recordsdemonstrates that the Hawes Water isotopic record, is very strongly dominatedby temperature change. Simple calculations based on conventional relationshipssuggest a 7˚C maximum temperature difference from interstadial optimum toYounger Dryas Stadial. This value and the magnitude of individual Late Glacialoscillations, compare well with estimates from terrestrial (coleopterid) andmarine (diatom sea surface temperature) records. All are significantly greaterthan the, independently calibrated, 4.2˚C change documented from a chironomidrecord from Southern Scotland. Such differences in palaeothermometers need tobe resolved if the impacts of climatic events are to be fully understood.

An ice core record from Lomonsovfonna,Svalbard: viewing the isotopic data in relation

to climate and environmental conditions

T. Martma1, R. Vaikmäe1 , V. Pohjola2 , J. Ivask1, E. Isaksson3 ,J. Moore4 and H. A.J. Meijer5

1Institute of Geology at Tallinn Technical University, Tallinn, Estonia, martma@gi.ee,vaikmae@gi.ee, ivask@gi.ee; 2Departement of Earth Sciences, Uppsala University,Uppsala, Sweden, veijo.pohjola@geo.uu.se; 3Norwegian Polar Institute, Tromsø,Norway, elli@npolar.no; 4Arctic Center, University of Lappland, Rovaniemi, Finland,jmoore@levi.urova.fi; 5Centre for Isotope Research, Groningen, Netherlands,meijer@phys.rug.nl

In April of 1997a 121m deepice corewasretrievedfrom thesummitof the600km2 Lomonosovfonnaice field, thehighestice field at Spitsbergen(1230masl). The ice core site, drilling procedure,analytical techniques,climate at thedrill site andthe backgroundto the projectaredescribedin Isakssonandothers(Isakssonet al., 2001) and Pohjola and others (Pohjola et al., 2002). Radarmeasurementsat the core site suggestedthat the bottom was nearly reached.Dating with a glaciological flow model (Nye, 1963)using the 1963 137Cs peak(Pinglot et al., 1999) and the Laki 1783 eruption (Kekonen et al., 2002) asreferencehorizons,suggestthat the core containsat least800 yearsof climateand environmental information.

Theicecorewassub-sampledin 5 cm piecesin orderto detectseasonalsignalsandbeableto providethebestpossibledating.Suchhigh-resolutionanalysishasnot previouslybeenperformedon Svalbardice cores.Our analysishasinvolvedthe most commonspecies,suchas Na+, K+, Mg2+, Ca2+, Cl-, NO3-, SO4

2-, NH4+,

acidity (H+), δD and δ18O. The analysissuggestthat annualor pseudo-annualsignalsarepreservedandthis hasmadeit possibleto obtainanannualtime scaleat least back to the early 18th century using δ18O (Pohjola et al., 2002).

Our studyof the Lomonosovfonnaice coreshowsthatSvalbardice corescanprovide importantinformation on both local and regionalclimate variability inthe Arctic despite their relatively low altitude and periodic melt.

References

Isaksson,E. and14 others.2001. A newicecorerecordfrom Lomonosovfonna,Svalbard:viewing thedatabetween1920-1997in relationto presentclimateandenvironmental conditions. J.of Glaciol., 47, 335-345.Kekonen,T., J.C.Moore,R. Mulvaney,E. Isaksson,V. PohjolaandR.S.W.vandeWal. 2002,(in press).A 800yearrecordof nitratefrom theLomonosovfonna

ice core, Svalbard. Annal.Glaciol., 35Nye,J.F.1963.Correctionfactorfor accumulationmeasuredby theice thicknessof the annual alyers in an ice sheet. J. of Glaciol., 4, 141-150Pinglot, J.-F., M. Pourchet,B. Lefauconnier,J.O. Hagen, E. Isaksson,R.Vaikmäe and K. Kamiyama.1999. Investigationsof temporalchangeof theaccumulationin Svalbardglaciers deuctedfrom nuclear testsand Chernobylreference layers. Polar Res., 18(2), 315-321.Pohjola,V.A., J.C.Moore, E. Isaksson, T. Jauhiainen,R.S.W.van de Wal, T.Martma, H.A.J. Meijer and R. Vaikmäe.2002 (in press). Effect of periodicmelting on geochemical and isotopic signals in an ice core fromLomonosovfonna, Svalbard. J.Geophys.Res., 107.

Hydrogen and oxygen isotopes in ice wedges -paleoclimate variability and pathways of

atmospheric moisture in Northern Siberia

Hanno Meyer1, Alexander Dereviagin2, Hans-W. Hubberten1

1 Alfred Wegener Institute for Polar and Marine Research, Research Unit Potsdam,Potsdam, Germany, hmeyer@awi-potsdam.de; 2 Moscow State University, Faculty ofGeology, 119899 Moscow, Russia, dereviag@online.ru.

Continuouspermafrostis wide-spreadin thenon-glaciatedcoastallowlandsoftheLaptevSearegionin NorthernSiberia,andmay reacha thicknessof severalhundredmeters.In the frameof the multi-disciplinaryresearchproject"SystemLaptev Sea 2000", four working areashave been selectedfor stable isotopeanalysesof ice wedges:the south coastof Big Lyakhovsky Island (73°10'N,143°50'E), the Bykovsky Peninsula,50 km SE of the Lena delta (71°40'N,129°30'E)andtwo locationsin thecentral(72°20'N,126°20'E)andwesternLenadelta(72°50'N,123°10'E).In the easternLaptevSeaarea,atmosphericmoisturetransportedfrom the Atlantic meetsPacific precipitation (Kuznetsova1998).Additionally, this regionis characteristicfor a specialandvery ice-rich type (upto 80 Vol %) of permafrostcalled"Ice Complex".Theice wedgeswithin theIceComplexmay reachheightsof up to 40 m and widths of 5 m. The presentedresultsof isotopic analyseson ice wedgesof the Ice Complex,as well as ofunderlying and covering deposits allow: (1) the reconstruction of thepaleoclimatehistory from 60 ka BP until present,(2) the identificationof site-specificpropertiesinfluencingthestableisotopiccompositionin ice wedges,and(3) combinedwith literature data from the Taymyr Peninsula(Siegertet al.,1999; Boike, 1997) the identification of moisture sourceregions for winterprecipitation.

The applicationof hydrogenandoxygenisotopesfor paleoclimatestudiesinice bodies is consideredto be one of the best methodsfor paleotemperaturereconstruction.Thecombinationof H andO isotopeshasseldomlybeenappliedto ice wedgesbeing a considerableextensionof the method.Ice wedgesareprincipally formedby repeatedfrost cracking,trickling of snowmeltwaterintofrost cracks,which freezesimmediatelybecauseof the negativetemperaturesofpermafrost,leadingto the formation of an ice vein. Consequently,ice wedgesmay reflect meanannual winter temperatures.The temporal variation of thestableisotopic compositionof ice wedgescorrespondsto relative variationsofwinter temperatures.Additionally, the d excess as an indicator for non-equilibrium fractionation processesmay provide information on the moisturesourceregionsfor winter precipitation,but alsoon the processesleadingto icewedge growth.

The resultsof our studiesin the Laptev SeaRegion indicate pronounced

changes in the regional climatic history. The stable isotope data show very coldtemperatures around 200 ka and 55 ka BP, still cold and constant winterconditions between 50 and 22 ka BP and a sharp temperature rise for thePleistocene-Holocene boundary. The three western regions are presently fed by aNorth Atlantic moisture source region. For Big Lyakhovsky Island, anothersource region (presumably the Pacific) could be distinguished. In the westernregions, a displacement of this marine source of the winter precipitation to theNorth occurred between 18.5 ka and 11.2 ka BP, being possibly linked with thedecay of the LGM ice sheet. Nevertheless, for the paleoclimate interpretation ofice wedges, it has to be ascertained that no secondary effects i. e. exchangeprocesses at the boundary ice wedge - ice-rich sediment changed the stableisotope signal.

References

Boike, J. 1997. Thermal, hydrological and geochemical dynamics of the activelayer at a continuous permafrost site Taymyr Peninsula, Siberia. Rep. Polar Res.242, 104 pp.Kuznetsova, L. P. 1998. Atmospheric moisture content and transfer over theterritory of the former USSR. In Second International Workshop on Energy andWater Cycle in GAME-Siberia, 1997 (Ohata, T. et al., eds.), pp. 145-151.Siegert, C., Derevyagin, A. Y., Shilova, G. N., Hermichen, W. D. & Hiller, A.1999. Paleoclimatic indicators from permafrost sequences in the Eastern TaymyrLowland. In Land-Ocean Systems in the Siberian Arctic: Dynamics and History(Kassens, H., ed.), pp. 477-499. Springer, Berlin.

14C dates of peat for reconstruction ofenvironmental changes in the past

Danuta J. Michczy� ska1, Anna Pazdur1, Sławomir � urek2

1Department of Radioisotopes, Institute of Physics, Silesian University of Technology,Bolesława Krzywoustego 2, 44-100 Gliwice, Poland, e-mail:asia@radiocarbon.gliwice.pl, Pazdur@zeus.polsl.gliwice.pl2Institute of Geography, � wi � tokrzyski University, � wi � tokrzyska 15, 25-406 Kielce,Poland e-mail: slavomir.zurek@pu.kielce.pl

Since the seventiesan analysisof the frequencydistribution of 14C-datedsamplesin a time scalehas beencarried out for severalselectedgeographicregions (ex. Geyh, Streif, 1970; Go� dzik, Pazdur,1987, Michczy� ska et. al,1996). The radiocarbondating method, which was primary used simply todetermineage of sedimentcontaining dated samples,becomesan importantsource of information on the course of some geologic processes in the past. The resultof radiocarbondatingis given asmeasuredradiocarbonageT anditslaboratoryuncertaintyDT. In the casewhenwe havea largesetof radiocarbondatesfor specifiedtype of depositsandthesedatescoverconsiderablerangeintime and areawe can createthe frequencydistribution of datesby summingnormal distributions connectedwith particular dates.The probability densityfunction is given by equation:

where: Ti and DTi are respectivelyage and uncertaintyof i-sampleand N isnumberof all dates.Thegraphreceivedin this way hascharacteristicpeaksandgaps.An interpretation of the frequency distributions is based on two basicassumptions:

1.The numberof 14C datedsamplesis proportional to the total amountoforganic matter deposited in sediments

2.Totalamountof organicmatterin sedimentsdependson palaeogeographicalconditions.Near 540 radiocarbondatesof peat from Polandwere selectedfor statisticalanalysis.All datescamefrom Gliwice RadiocarbonLaboratory.Peatis a typicalorganicmaterial,often datedusing 14C method.Receivedradiocarbonagesarereliableanddo not requirecorrectionbecauseof “hard watereffect” or isotopicfractionation(Pazdur,1982).Thesefactsdecidedthis typeof depositwaschosenfor analysis.Analyseddatescomefrom mireswherepeatoccursto theroof or iscoveredby different formationsless than 50cm thickness.None of mires waspreservedfrom beforethe last glaciation,so analysisis limited to the Holocene

andLatePleistocene.An exampleof globalprobabilitydistributionof 14C datesis presented on Figure 1.

Figure1. Probability distribution of 14C dates of peat samples from theterritory of Poland (except Baltic Coast). Peaks and gaps can beregarded as time periods when environmental conditions were

favourable and unfavourable for peat deposition.

Preliminary results suggest usefulness of statistical analysis of radiocarbon datafor reconstructionof environmentalchangesin the past. There were noticedinterestingdependenciesbetweenfrequencydistributionof 14C for Baltic Coastandothergeographicregions.Furtherresearchwill bebasedon bigger14C datessets to meet statistical requirements.

References

GeyhM.A., Streif H. 1970.Studieson coastalmovementsandsea-levelchangesby means of the statistical evaluation of 14C-data. Procedings of the“Symposiumon coastalgeodesy”held in Munich on July 20 to July 24, 1970:599-611.Go� dzik J.,PazdurM.F. 1987.Frequencydistributionof 14Cdatesfrom Polandin the time interval 12-45 kyr BP and its palaeogeographicalimplications.Zeszyty Naukowe Politechniki � l � skiej, s. Matematyka-Fizyka, 56,Geochronometria Nr 4: 27-42.Michczy� ska D.J., Michczy� ski A., Goslar T., PazdurA., PazdurM.F. 1996.Statystycznaanalizadanych radiow� glowych w badaniachzmian � rodowiskanaturalnegow przeszło� ci. Wst� pne wyniki. Zeszyty Naukowe Politechniki

� l � skiej, s. Matematyka-Fizyka, 79, Geochronometria Nr 13: 193-201.

0 4000 8000 12000 16000Calendar age BP

0

4

8

12

Inte

nsity

Peat - 404 dates(without Baltic Coast)

The influence of the changes of radiocarbonconcentration in the past on statistical inference

concerning time intervals.

Adam Michczy� ski

Department of Radioisotopes, Institute of Physics, Silesian University of Technology,Bolesława Krzywoustego 2, 44-100 Gliwice, Poland,e-mail: amichcz@radiocarbon.gliwice.pl

The problemthat geologistsor archaeologistsoften must to solve is how toappoint time intervals of phenomenon(geological phase or archaeologicalculture) basing on a group of radiocarbon dates associated with thisphenomenon.Typical methodof treatmentof suchgroupof relatedradiocarbondatesis to createcumulativeprobabilitydistributionby summingdistributionsofparticular calibrated dates.The highest probability 50% or 68% confidenceintervals of this distribution are usually interpreted as time limits of thephenomenon.However, the changesof radiocarbonconcentrationin the past,which are presentedin form of calibrationcurve, causethat relation betweenradiocarbonand calendar(calibrated) date is ambiguousand time intervalsestimatedby the method presentedabove may be very different from realintervals in calendar scale.

The problem of influence of calibration curve on statistical inferenceconcerningtime intervalswasmentionedfirst time in lateeightiesby StuiverandReimer(StuiverandReimer,1989).They showedthat in badcircumstancesthelargedistortionof probability distributionmayoccur– in their examplethe partof calculatedcumulativeprobability distribution retainedin the original (real)time interval is about 50%.

This papertries to presentmorecomplexdiagnosisof theproblem.In ordertoattainthis the following computersimulation(similar to thatStuiverandReimerdid) is used:a) The calendar time interval of simulated phenomenon is assumed.b) A certainnumberof calendardatesare drawn from assumedinterval. Thisprocess simulates collecting of samples.c) For eachcalendardatethe correspondingradiocarbonageis determinedfromthe calibration curve.d) Eachof theseradiocarbonagesis thenassigneda standarddeviationandthenradiocarbon date is drawn. This procedure simulates measurement process.e)Eachof radiocarbondatesis calibratedandappropriateprobabilitydistributionof calibrated date is calculated.f) All distributions are summed.g) Cumulativeprobability distribution for all datesis comparedwith assumedinitial calendar time interval.

References

Stuiver M., Reimer P., 1989. Histograms obtained from computerizedradiocarbon age calibration. Radiocarbon, Vol 31, No.3: 817-823.

Investigation Of 34S/32S Isotope For The SystemGaseous SO2 - Nitrobenzene SO2 Solution

A. Mikolajczuk1, R. Wierzchnicki, A.G. Chmielewski

Institute of Nuclear Chemistry and Technology, Warsaw, Poland1 amik@orange.ichtj.waw.pl

Sulfur isotope fractionation factor between SO2 dissolved in nitrobenzene andSO2 in gas phase has been investigated experimentally in this study.

The experiments were performed for normal pressure at temperature range 20 -71 oC. Mass spectrometer was applied for analyses of the samples after theirchemical transformation to SO2. Special chemical methods for SO2 dissolved innitrobenzene transformation have been developed.

Fractionation factor depends on temperature and results are reported in thepaper.

On sources of errors by dating lake sediments,especially indicated by the varying radiocarbon

activity of some recent water plants from Estonia

Ingrid U. Olsson1, Enn Kaup2

1 Department of Physics, Uppsala University, Sweden, Ingrid_U.Olsson@Fysik.UU.SE;2 Laboratory of Isotope-Palaeoclimatology,Institute of Geology at Tallinn TechnicalUniversity, Estonia, kaup@gi.ee

Since the early days of radiocarbondating it has been known that lakesedimentsoften or mostly yield too old 14C agesbecauseof contaminationbyallochthonousmaterialunlessthe terrestrialcomponentis chosen,now possiblewith the AMS technique.The pretreatmentprocedureis also important for thequality of theresult.Anotherreason,alsomentionedearly,for too old agesis thedepressedactivity of submergedmacrophytesandalgaedueto a slow exchangebetween the atmopheric and in water dissolved CO2. In this study a few, eleven, Estonian water plants from three lakes were chosen.The completepaperis publishedby the authorsin Radiocarbon43, 2001,809-920. The investigation is part of an extensive study and performed as acollaborationbetweenthe laboratoriesin Tallinn andUppsala.As a background,results from earlier studies by different scientists were summarized.

Although the actual14C activity doesnot give a figure on the reservoirageothermethodsasextrapolatingthe apparent agesof the sedimentlayersto thesurface also fail.

Problemswith the actual measurementsarosesince some samplesweremeasuredin Tallinn without any13C determination.Otherstudiesindicaterangesof a few per mil for well determinedspecies.The statistical uncertainty issometimesas large as 1‰. A survey of publishedand unpublishedvalues,mainly from theUppsalaLaboratoryrevealedconsiderablerangesfor eachof theused Potamogéton and Myriophýllum species.

In this study (Lake Äntu Sinijärv, Lake Päidreand Lake Punso)the HCO3-

contentwas 300, 200 and ≤ 30 mg/L, respectively.The reservoireffect wasexpectedto bemostlya hard-watereffect(a specalcaseof reservoireffect)in thefirst mentionedlakes.A low 14C/12C ratio in e.g. agedwater will also yield areservoireffectexceptfor thecontributionbecauseof slow exchangeasexpectedfor the third lake.

Thecrustdepositedon a Ceratophýllumdemérsumsamplein L. Äntu Sinijärv(floats freely underwater) was also examinedand found to be about7% lessactivein 14C thanthe organicfraction.This indicatesthat the 14C/12C ratio of asubmergedplantmaybequitedifferentfrom thatof thebicarbonateof thewater.Resultson sampleswith a root stock,asNuphar lútea , shouldbe treatedwithcaresincenutrientsstoredin the root stock will be usedand causea memory

effect reflectedin different activities in the stem(grown in early seasonbelowthewatersurface)andthe floating leavesfrom the summergrowth. In L. Punsothe decreasingatomic-bombactivity thuscausedthe leavesto appearabout6%lessactive than the stems.In the samelake emergentCarexandPotamogétonnatans had activity values between the two for Nuphar but Carex lower than P.

In L.Päidre the Potamogéton and Myriophýllum as as well as theCeratophýllumsampleall had∆14C activities in a rangeabout9 to 1% whereasthe floating leavesof Nupharlúteahada deltavalueabout15%,ratherclosetothat of the atmosphere.It is recalledthat most valuesgiven in this study havestatistical uncertaintiesclose to 1%. Finally two results, in literature, onMyriophýllumsamplesfrom a 4th lake(L. Kahala)indicateda slightly depressedactivity. Indeed,there are too few values on the atmospheric14C activity inEstoniafor the actualyearsto allow absoluteconclusionsaboutthe excess.Thewater plant sampleswere collected 1990 and 1992 except for the L.Kahalasamples collected 1994 and 1995.

The origin of the sediment,the composition,is not only dependenton whatlakeis actualbut alsowherein thelakethesampleis takenandmaychangewithtime during the lake´shistory. This studywaslimited to macrophytesbut algaecontributeto the sediment.The sedimentcloseto the surfacemostly yield toohigh ∆14C values since the plants are affected by atomic-bombtests - quiteimportant after 1955.

It is stressedthata reservoireffect is seennot only in hard-waterlakesbut alsoin soft-waterlakes.A reservoireffect dependson the dissolvedcarbondioxideusedby theautochthonousplants.Thesituationis complicatedsincesomeplantsusethe carbondioxide in the sediment.A supply of e.g. erodedmaterial is acontamination.

Carbon isotopic composition in tree-rings:a temperature record and a tool

for biomonitoring CO2 level

Sławomira Pawełczyk, Anna Pazdur

Silesian University of Technology, Institute of Physics, Department of Radioisotopes,Gliwice, Poland, e-mail:pazdur@polsl.gliwice.pl

Treesare not passive,but rather interactivemonitorsof environment.Treespreservean annuallydatablerecordextendingfor many thousandof year.Thecompositionof wood consistsmainly of carbon,oxygen and hydrogen.Treesparticipatein the carboncycle and form organic matter, amongothers fromcarbon acquired through photosynthesis.Carbon comes from natural andanthropogenicsources.Every vegetationperiodtreeforms a ring, andthereforethegrowth rings representan integrationof thosevariablesduringeachgrowingseason.By assessingthe natureof variationsin the treewidths, it is possiblebyusing conventionaldendroclimatologicaltechniquesto reconstructsomeaspectof thepastenvironmentalchange.Sometimesit is very difficult, becausegrowthof individual treedependson manyfactorssuchas:temperature,humidity, lightintensity, changes in soil moisture, rainfall, insect attack.

The developmentof tree is dependedupon the climatic and environmentalconditionsunderwhich it grows.Stableisotopevariationswithin the tree-ringmay provide valuable information about past climatic changes.Becausetreecellulose is formed from carbon acquired through photosynthesisits stableisotoperatio reflect that of atmosphere.Although the carbonatomsof cellulosecome from atmospheric CO2, the δ13C value of cellulose is not the same as that ofatmosphericCO2. Diffusion via stomataandcarboxylationdiscriminateagainstheavier isotope. Environmentalvariables,such as temperature,precipitation,humidity, light intensity,changesin soil moisturecontroldegreeof fractionationand thus δ13C values.

14C/12C and 13C/12C ratios can reflect correspondingatmosphericCO2

concentrationduring formation of the ring. Fossil fuel combustionresults inemissionof CO2 to the atmospherelacking 14C isotope.This reflectsin decrease

of radiocarbonconcentration(“Suesseffect”). Depressionof δ13C canbecausedby anthropogenicactivity (fossil fuel combustion),too. In particular ∆14C andδ13C could be used insteadof (non-existent)historic CO2 concentrationdata.Nevertheless,many factors may disturb atmosphericCO2 level reconstructionfrom tree-rings,including the choiceof wood constituentfor analysis,effect ofrespired CO2 and influence of climatic factors.

Investigationsof isotopic carbon composition in annual tree-rings from

ecologically clean Augustów Wilderness region (22°58’E, 53°51’N) wereundertakenin C-14 Laboratoryin Gliwice. In that time a seriesof radiocarbonconcentrationmeasurementsin single tree-ringsand δ13C in the entire organicmatter and in α-cellulose were carried out.

Values of δ13C were determinedfor the entire wood and for latewooda-cellulose. Latewood � -cellulose is an adequatematerial for palaeoclimaticreconstruction.The techniquefor the extractionof � -cellulosebasedupon thesodium chlorite oxidation methodof Greenutilizes ultrasonicbath and smallSoxhletthimblesto prepareα-cellulosefrom latewood.This techniqueyields amaterial with sufficient homogeneityas required for isotopic compositionmeasurements.Thepureα-cellulosewasthenplacedinto individual pyrex tubeswith cupper oxide and sealedunder vacuum. The tubes were heatedto atemperatureof 450°C for 18 hours. The resulting gases were separatedcryogenically,and the CO2 was collected.Isotoperatios were measureusingmass spectrometer and are reported using the standard

� notation.

∆14C values in 102 rings (from AD 1861 to 1962) of a pine growth inAugustówWildernesswere measured.Measurementsof ∆14C were madewiththe liquid scintillation method using Quantulus 1220. After mechanicalprocessingand resin extractionin Soxhlet apparatus,the wood sampleswereconvertedto Li 2C2 by combustionwith lithium, thento C2H2 by addingwatertoit, and finally to C6H6 in a catalyst process.

Stablecarbonisotoperatios in tree rings may provide valuableinformationabout past climatic conditions. δ13C values were compared to averagetemperaturein July – August for Warsaw (from AD 1899 to 1968). Thecorrelationcoefficient was 0.49 and indicatesa significancelevel better than0.001‰.Consideringimpact of anthropogenicandphysiologicaleffectson theδ13C values,period 1949 – 1968 was excluded.In such casethe correlationcoefficient was 0.71 and indicates a significance level better than 0.001‰.

Stable isotope variations within tree ring may also provide valuableinformation aboutpastCO2 level. However,valuesof δ13C in wholewoodare

connectedwith longer time of vegetationperiod than δ13C for α-cellulose.Values of δ13C were comparedto estimatedCO2 emission for Poland. The

correlation coefficient betweenδ13C in the entire wood and estimatedCO2

emission(from AD 1890to 1968)was–0.54(n=79,p<0.001)but betweenδ13Cin α-celluloseandestimatedCO2 emission(from AD 1910to 1962)was,in turn,–0.40 (n=53, p<0.001).

∆14C were comparedto estimatedCO2 emission for Poland. Correlation

coefficientbetween∆14C andestimatedCO2 emission(from AD 1910to 1955)was –0.33 (n=50, p<0.02).

Preparation of bone samples in the GliwiceRadiocarbon Laboratory for AMS radiocarbon

dating

Natalia Piotrowska1, Tomasz Goslar2

1 Silesian University of Technology, Institute of Physics, Radiocarbon Laboratory,Krzywoustego 2, 44-100 Gliwice, Poland, natalia@radiocarbon.gliwice.pl; 2 Pozna �Radiocarbon Laboratory, Rubie � 46, 61-612 Pozna � , Poland, goslar@radiocarbon.pl

Radiocarbonmethodis widely usedfor datingmanytypesof materials,whichcontain carbon in organic (e.g. wood, charcoal,peat, fossil soils) as well asinorganic (e.g. carbonates,shells) form. Animal bonescontain both fractions,howeverthe mostcommonlydatedcomponentis collagen– a basicprotein ofconnective tissue.

Developmentof acceleratormassspectrometry(AMS) techniquein the 80’senabled14C datingof samplescontainingaslittle asmilligrams of carbon.Thisresultedin elaborationof manymethodsof bonepreparationin which carbonisseparatedfrom specific compoundsor fragmentsof molecules(Hedges& vanKlinken 1992).

In the Gliwice RadiocarbonLaboratory,a systemfor preparationof samplesfor AMS datinghasbeenbuilt (Goslar& Czernik2000).At first it wasusedtoproducegraphitetargetsfrom plant macrofossilsand sediments.Measurementsof 14C content was performedin Leibniz-Labor for RadiometricDating andIsotope Research, Kiel, Germany.

In this studywe extendedour capabilitieswith the preparationof bones.Wedealt with 3 methods;the first was the classicalLongin methodof collagenextraction,which had beenroutinely usedfor large bonesin radiometric 14Claboratoryin Gliwice, andhasbeenadaptedfor smallsamples(LA). Thesecondmethod(LB) includesadditionaltreatmentof powderedbonein alkali solution(Gurfinkel 1987).In the third one(N) carboxylcarbonis separatedfrom aminoacidsobtainedafter hydrolysisof proteins(Nelson1991).This methodis moreselectiveand thus lesssusceptibleto contamination,howeverit is much moretime-consumingthan the Longin method. Suitability of above methodswastestedon 2 bonesamplesfrom MagurskaCavein TatraMts., SouthernPoland.Theseand the other bonesfrom this site have been dated with radiometrictechnique,mostof themgiving opendates.Most of our samplesgaveages>40kyr BP (seeFigure 1), suggestinggood performanceof the adaptedmethods,exceptfor onesamplepreparedwith simpleLongin method.The latter sampleappearedto be contaminatedwith ca 0.6 percentof moderncarbon.For routinepreparationof bones we chose the Longin method with additional alkalitreatment.

Additionally we producedgraphitetargetsfrom two collagensamples(named

Dw) extracted with simple Longin method (L), that yielded too little material tobe dated by GPC technique. Both Dw samples gave comparable and consistentwith expected ages.

Figure 1. Results of dating of investigated samples.

References

Goslar, T. & Czernik, J. 2000. Sample preparation in the Gliwice RadiocarbonLaboratory for AMS 14C dating of sediments. Geochronometria 18: 1-8.Gurfinkel, D. M. 1987. Comparative study of the radiocarbon dating of differentbone collagen preparations. Radiocarbon 29(1), 45-52.Hedges, R. E. M. & van Klinken, G. J. 1992. A review of current approaches inthe pretreatment of bone for radiocarbon dating by AMS. Radiocarbon 34(3),279-291.Nelson, D. E. 1991. A new method for carbon isotopic analysis of protein.Science 251, 552-554.

LA LB N

GPC

AMS

L

Preparation method

44000

40000

36000

32000

28000

24000

Rad

ioca

rbo

n a

ge

[yea

rs B

P]

AMS

GPC

LB N L

Magurska I/2 Magurska I/7

LA

Measurements of 137Cs in cultivated soil and itspotential to use as a soil erosion indicator

Grzegorz Por� ba1 and Andrzej Bluszcz1

1Radiocarbon Laboratory, Instytute of Physics, Silesian University of Technology,Gliwice, Poland, grzegorz.poreba@radiocarbon.gliwice.pl.

137Cs is radioactive isotope which get to atmosphereasresultsof nuclear

weaponstests. The highest intensity of the nuclearweaponstests assumedbetween1956 and 1965. After this period the fallout of 137Cs is decreasing.In 1986 Czernobylaccidentincreaseddepositionrateof caesiumbut now valueof caesiumdeposition is again at the level before the Czernobylaccident.Caesiumis strongly absorbed to soil particles, escpeciallyon the colloidalfraction.

Here we presentpreliminary resultsof activity 137Cs measurmentsin BiałaPrudnicka andOdonówareas.Thesamplesof soil weretaken in May 2001inBiała Prudnicka (a village nearPrudnik)andin July 2001in Odonów(a villagenearKazimierzaWielka). Both of this areasare cultivatedsoil. Biała Prudnickais locatedin theareawhere larger 137Cs concentrationcausedby theCzernobylaccident maybe expected.

Caesiumconcentrations weremeasuredby meansof a gammaspectrometerwith HPGe detector manufacturedby Canberrain Marinelli geometry (0,5 lcapacity). Calculationsof caesiumactivity in soil wereperformedwith aid ofsoftware GENIE PC.

Figure 1. Results of measurments of 137Cs in soil in Biała Prudnicka

Higherconcentrationsof 137Csin soil in Biala arefoundbetween0 and40cm.Likewise in profiles in Odonówhigherconcentrationsof 137Cs in soil arefoundbetween0 and 15-30cm. The rangeof higer caesiumactivities consent withploughdepth. Activity of 137Csin thoseareasarebetween26,1and49,5Bq/kg.

0

5

10

15

20

25

30

35

40

45

50

0 20 40 60 80 100 120 140 160

depth, cm

caes

ium

-137

acti

vity

,B

q/k

g

Below this depth activity of 137Cs drasticalydecreasesto the value below1 Bq/kg. This meansthat vertical migration of caesiumin soil is verylimitied. (e.g.,bioturbationor washingout of 137Cs aremediocre). Thereforeredistributionof 137Cs is only a resultof soil erosion and may be used forestimation of soil erosion.

Figure 2. Results of measurements of 137Cs in soil in Odonów area (profile 2a)

Figure 3. Results of measurements of 137Cs in soil in Odonów area (profile 2b)

0 10 20 30 40depth, cm

0

10

20

30

40

50ca

esiu

m-1

37ac

tivity

,Bq/

kg

0 10 20 30 40depth, cm

0

10

20

30

40

50

caes

ium

-137

activ

ity,B

q/kg

References

Davis J.J. 1963. Cesium and its relationship to potassium in ecology.Radioecology.ShultzV., Klement Jr. A. W. (red.) Reinhold,New York; 539-556.StachA. 1996. Mo � liwo � ci I ograniczeniazastosowaniacezu-137do badaniaerozji gleb na obszarze Polski. Materiały Ogólnopolskiego SympozjumNaukowego:OchronaAgroekosystemówzagro� onych erozj� . Puławy, 11-13wrze� nia 1996, 203-226.Strzelecki R., Wołkowicz S. and Lewandowski P. 1994. Koncentracja cezu wPolsce. Przegl� d Geologiczny 1 (42);3-8.

Palaeoenvironmental interpretation of isotopeand pollen data from marl sections of some

Estonian lakes

J.- M. Punning1 , T. Martma2, T. Koff1

1 Institute of Ecology at Tallinn Pedagogical University, Tallinn, Estonia,mati@eco.edu.ee, koff@eco.edu.ee; 2Institute of Geology at Tallinn Technical University,Tallinn, Estonia, martma@gi.ee

Coherentstableisotopeandpollenanalysesconductedat fine-resolutionscalefrom lake marl sedimentsformed during the Preborealand Boreal climaticperiodswerestudied.During this interval thedevelopmentof climatic conditionsin Northern Europeand particularly in Estoniawas greatly influencedby theregionalpecularitiesof deglaciationand landscapedevelopmentprocesses.Asthe authigenic calcite precipitatesduring the spring/summerphotosyntheticbloom, the isotopic recordsreflect the equilibrium conditions(temperatureandisotopicratio) in lakewater,whenlocal evaporationanddirectprecipitationhavetheir strongestisotopic effects. The pollen spectra,however, reflect mainlyintegratedlong-term changesin the forest compositionand thus the trendsofmeanclimatic variablesin a certainarea.Thusby combiningbothapproaches,itis possibleto studythedynamicsof differentenvironmentalprocessesin theareasurrounding a lake.

Differences in δ18O and δ13C values for layers accumulatedduring thePreboreal and Boreal are significant and are causedpartly by the changingclimatic conditionsaroundthe Ancylus Lake stagein the developmentof theBaltic Sea.The obtainedisotopeandpollen datafor studiedsitesshowthat thepalaeoclimaticconditionson thewhole transectfrom north to southwereduringthe Preborealclimatic period rather similar and the isotopic content of themeteoricwaterandprecipitatedmarl wasnearlysameastoday(about-12‰ inthesurfacemarl in theL.Sinijärv) andcarbonateprecipitationtook part in nearlyequilibriumconditions.Therole of evaporationin studiedlakesin this time wasnot essential.Though there are fluctuations in some δ18O isotoperecord, thegeneraltrend demonstratesratherstabile climatic conditionsup to the end ofBoreal period.

The covariancebetweenδ13C and δ18O valuesas well changesin the pollenspectraarea reflectionof climatically controlleddynamicswherethe residencetime evolutionplaysa significantrole. Most significantis thesharpshift of δ13Ctowardsnegativevaluesup to 3‰ in themarl accumulatedduringsome100-300yearsshortlybefore8000BP is mostprobablyconnectedwith soil development.Almost at the sametime alsoan increasein the δ18O valuestook place,whichshowsa rise in the temperatureof the water in the lake. Thesechangesare

accompaniedwith notableimprovementof climatic conditionsand changesinthevegetation(changesin thecontentof Betula andPinus pollenandanincreasein broad-leaved trees).

Essentialchangesin the carbonisotopecontentwereestablishedby us earlierin manysitesin Estonia;they havebeenfixed alsoin SouthFinland.Accordingto pollenstratigraphythey took placein theBoreal.In L. Ilmjärv we establishedtheageof this eventas8000BP by usingAMS 14C datingfrom macrofossils.Afixed sharpincreasein δ13C andδ18O valuesin manylakemarl profiles in UpperEstonia and South Finland is rather close in time and might be used as astratigraphical stratum which delineates a certain stage in soil development.

Enrichment of 13C by chemical exchange betweenCO2 and amine carbamate in nonaqueous solvent

Paula Raica1, D. Axente2

1Technical University of Cluj-Napoca, Dpt. of Automation, 3400 Cluj-Napoca, Romania;2National Institute for R. & D. of Isotopic & Molecular Technologies,3400 Cluj-Napoca,Romania, e-mail: axente@s6.itim-cj.ro

Enrichmentof 13C by chemicalexchangebetweenCO2 andaminecarbamateinnonaqueous solvents has been mathematically modelled in two ways.

Theheightequivalentto a theoreticalplateandsteady-stateseparation,basedon the two models,havebeenobtained.If only the isotopic exchangebetweenCO2 gasandaminecarbamateis considered,themodelcanestimatethe processperformancefor pressurescloseto the atmosphericone and room temperature.For processanalysis at pressureshigher than atmosphericone and lowertemperatures, a two-steps model has been used. Using two models the effects of pressures have been studied.

References

DroncaS.,AxenteD., BâldeaA., Teac� C. 2000.Studyof the13Cseparationbyisotopic exchange13C/12C in CO2-Di-n- butylaminocarbamatein methanol.Rev. Chim., 51, 1, 65 – 72.Agrawal J. T. 1971.Enrichmentof carbon-13by chemicalexchangeof carbondioxidewith aminecarbamatesin nonaqueoussolvent.SeparationScience,6, 6,831 – 839.Agrawal J. T. 1971. Fractionationof oxygen-18and carbon-13isotopesbychemicalexchangeof carbondioxidewith aminecarbamates.SeparationScience,6, 6, 819 – 829.TkeshitaK. andKitamotoA. 1989.Relationbetweenseparationfactorof carbonisotopeand chemical reactionof CO2 with amine in nonaqueoussolvent. J.Chem. Eng. Japan, 22, 5, 447 – 454.Kitamoto A., TakeshitaK. 1992.A two stepsmodel for advancedseparationof13C by chemical exchangemethod betweenCO2 and amine in nonaqueoussolvent. Proc. Intern. Symp. on isotope separationand chemical exchangeuranium enrichment. Tokyo, T.I.T. 376 – 385.DroncaS., Axente D., BâldeaA., AbrudeanM. 1998. Absorption of CO2 insolutions of Di–n–butylamine in methanol. Rev. Chim. 49, 11, 775 – 780.

Sulfur isotopic composition of H2S and SO42-

from mineral springs in the Polish Carpathians

Rajchel L.1, Rajchel J.2, Szaran J.3 and Halas S.3

1Academy of Mining and Metallurgy, Chair of Stratigraphy and Regional Geology, 30-059 Krakow, Poland; E-mail: rajchel@geolog.geol.agh.edu.pl; 2Academy of Mining andMetallurgy, Department of General and Mathematical Geology, 30-059 Krakow, Poland;3Institute of Physics, Maria Curie-Sklodowska University, 20-031 Lublin, Poland; E-mail: jszaran@tytan.umcs.lublin.pl; halas@tytan.umcs.lublin.pl

A number of springs in Carpathian Mts. contain dissolved H2S and SO42- in

concentrations above 10mg/L. In this study we have selected 10 springs (Rajchel2000) for sulfur isotope analysis from the area of flysh Carpathian, which arelocalized along of tectonic dislocations. It is believed that a fraction of suchsprings may carry extremely deep sulfur (mantle origin) which is subjected toSO4

2--H2S isotope exchange in high temperatures and bacterial reduction intemperatures below 100oC.

In order to distinguish the sulfur of mantle origin we investigated δ34S ofdissolved sulfide and sulfate and on the basis of known concentrations wecalculated δ34S of total dissolved sulfur (TDS). Also the isotope fractionationbetween sulfate and sulfide may be indicative in selection of deep origin sulfur.These data are collected in Table 1.

It is seen that most springs have δ34S of TDS close to zero while SO42--H2S

fractionation varies from 8 to 61 per mil. Thus 103lnα is less indicative thanisotope composition of TDS itself. However it may be informative on theconditions of sulfur transport and on pollution by sulfur from other sources.

H2S was precipitated in form of CdS which subsequently was converted toAg2S, while SO4

2- ion was precipitated as BaSO4.Sulfur isotope composition of collected samples was investigated with a

modified MI-1305 spectrometer in form of sulfur dioxide. Sulfur from bariumsulfate samples was converted to SO2 in vacuum line at 800oC (Halas andSzaran,). Silver sulfide samples were prepared to sulfur dioxide in vacuum line at850oC with the aid of Cu2O. Precision of δ34S measurements is 0.05 per mil.

References

Halas S. and Szaran J. 2001. Improved thermal decomposition of sulfates to SO2

and mass spectrometric determination of δ34S of IAEA SO-5, IAEA SO-6 andNBS-127 sulfate standards. Rapid Commun. Mass Spectrom.15: 1618-1620.Rajchel L. 2000. Springs of sulphurous waters in the Polish Carpathians.Geologia (Geological Quarterly AGH) 26/3:309-373.

Table 1. Sulfur chemistry and isotope data.

No

Spring Samplingdate

H2S SO42- TDS

mmol/dm3

δ34SV-

CDT(‰)

mmol/dm3

δ34SV-

CDT(‰)mmol/dm3

δ34SV-

CDT(‰)

103lnα

1. Polichty Pawe"

18.10.2001

0.464 -41.9 0.559 18.30 1.023 -9.00 60.9

2. Polichty Jacek"

18.122001

1.270 -14.89* 0.389 23.00 1.659 -6.00 37.7

3. Rytro Katarzyna"

19.10.2001

0.292 -15.93 0.268 2.91 0.560 -6.91 19.0

4 Szaflary "Bachledów"

20.10.2001

0.715 -24.78 0.413 27.12 1.128 -5.78 51.9

5 Lipnica Jacek"

20.10.2001

0.101 -18.48 0.370 -7.51 0.471 -9.86 11.1

6. Lipnica "Wawrzyniec"

20.10.2001

0.392 -6.68 0.240 1.48 0.632 -3.58 8.2

7. Nieborów Balneologów"

18.10.2001

0.875 -15.99 0.414 12.00 1.289 -7.00 28.0

8. Szklary Katarzyna"

18.10.2001

0.917 -39.94 0.702 -5.65 1.619 -25.07 35.1

9. Nowy Scz Wspomnienie"

19.10.2001

1.710 -16.64 0.757 29.32 2.467 -2.54 45.7

10.

Lipnica-KiczorySiary"

20.10.2001

0.188 -11.16 0.129 17.29 0.317 0.42 28.4

Measurement of δ13C and δ18O Isotopic Ratios OfCaCO3 by Thermoquest-Finnigan GasBench II andDelta Plus XL Continuous Flow Isotope Ratio MassSpectrometer with Application to Devils Hole Core

DH-11 calcite.

Kinga Revesz and Jurate M. Landwehr

U.S.Geological Survey, 431 National Center, Reston VA, 20192, USAkrevesz@usgs.gov; jmlandwe@usgs.gov

A new method was developed to analyze the stable carbon and oxygen isotoperatios of small samples (0.4mg) of calcium carbonate. This new methodstreamlines the classical H3PO4-CaCO3 reaction method by making use of aThermoquest-Finnigan GasBench II preparation device and a Delta Plus XLcontinuous flow isotope ratio mass spectrometer. To obtain reproducible andaccurate results, optimal conditions for the phosphoric acid-calcite reaction hadto be determined. Using temperature close to that the factory suggested (65 oC)for the acid-carbonate reaction even the shortest reaction time possible using asingle arm robot, the precision of oxygen isotope ratio results was unacceptable,probably due to a secondary reaction. When the acid-carbonate reactiontemperature was lowered (to 26 °C), and the reaction time was increased to 24hours, and screening rules for sample analysis quality were put in place, theoxygen and carbon isotope ratio precision of duplicate analyses improved to 0.2and 0.1 per mil, respectively.

The technique was tested by analyzing Devils Hole calcite, which precipitatedfrom ground water onto the walls of a sub-aqueous cavern during the last500,000 years. Isotope ratio values for Devils Hole core DH-11 had previouslybeen obtained by the classical method and is reported by Landwehr and others(1997). The DH-11 core was resampled and isotope-ratio values were obtainedusing the new method. The results were comparable to those obtained by theclassical method (Figure 1).

Indeed, the consistency of the isotopic results is such that an alignment offsetcould be identified. This cutting error was later independently confirmed. Thereproducibility of the isotopic values (correlation, after correcting for alignmentoffset, is approximately 0.96 for both carbon and oxygen, Figure 2) shows thatthe new method is a viable alternative to the classical method. In particular, thenew method requires less sample material and allows automation of someprocesses, so it is superior to the classical method when sample amount islimited and/or finer resolution is desirable.

Figure 1. Stable carbon and oxygen ratio data obtained by GasBench II method and a continuousflow isotope ratio mass spectrometer (filled symbols) for calcite from resampled materialrelative to isotope trace of original sample data analyzed using the classical method and

a dual inlet isotope ratio mass spectrometer (open symbols)(Landwehr and others, 1997).δ13C values are in per mil, reported relative to VPDB [Vienna Peedee belemnite, define by

δ13CNBS19/VPDB= +1.95 per mil (Hut, 1987)], and δ18O reported relative toVSMOW [Vienna standard Mean Ocean Water] on a scale normalized to

δ18O of SLAP [Standard Light Antarctic Precipitation] = -55.5 per mil (Coplen, 1988).

Figure 2. Stable carbon and oxygen ratio data traces for the two separate DH-11 coressamples shown in Figure 1, but with an appropriate depth correction applied to the

resampled data set. Data analyzed by GasBench II (filled symbol) and classical methods(open symbol) (Landwehr and others, 1997) produce highly correlated data traces

(s=0.96) for both isotopes. Isotope values are reported as in Figure 1.

References

Landwehr, J.M, Coplen, T.B., Ludwig, K.R., Winograd, I.J., and Riggs, A.C.1997. Data for Devils Hole Core DH-11: U.S. Geological Survey Open-FileReport 97-792, 8pp.Hut, G. 1987. Consultant Group Meeting on Stable Isotope Reference Samplesfor Geochemical and Hydrological Investigations, Vienna, 16 to 18 September1985. Report to Director General, International Atomic Energy Agency, Vienna,42 p. Coplen. 1988. Chemical Geology, v.72, 293.

Interpretation of isotope records in large riversystems using neural networks approach

K. Rozanski1, M. Zimnoch1, M. Mikolajczak1, D. Rank2

1) University of Mining and Metallurgy, Faculty of Physics and Nuclear Techniques,Krakow, Poland2) Österreichisches Forschungs- und Prüfzentrum Arsenal GmbH, Vienna, Austria

River systemsconstitutean importantpart of the hydrologicalcycle. On onehand,they remainthe basicsourceof potablewater for humanpopulation.Onthe otherhand,they aresubjectof dramaticimpactof man'sactivitiesin a formof massive and widespreadpollution. In many instancesnatural cleaningcapabilitiesof thosesystemswere surpassedwith the resulting conversionofnumerousrivers into biologically deadsewagechannels.In this context,betterunderstandingof the dynamicsof river systemson a catchmentscaleand theirinteraction with groundwater becomes an urgent task.

Environmentalisotopessuchas tritium, deuteriumand oxygen-18are wellrecognizedtools for studyingdynamicsof hydrologicalcycleon differentspatialand temporalscales.In river systems,18O and 2H have beenusedmostly insmall-scaleinvestigationsfor separatingdifferent flow components(hydrographseparation).Tritium wasusedto derive informationon the meantransit time ofwater on a catchmentscale. Long-term, systematicobservationsof isotopiccompositionof rivers exist for severallargerivers in the United States(3H) andfor the Danube river in Europe (3H, 18O).

An attemptwasmadeto apply the neuralnetworksformalismto describethetransportof environmentalisotopetracers(18O, 3H) throughcatchmentsof largeriver systemsin order to gain a better insight into the dynamicsof water flowwithin suchsystems.Theavailabletime seriesof oxygen-18andtritium contentin the Danuberiver were used for this purpose.In parallel with the neuralnetworksmodelling of the Danubedata,also the lump-parametermodelswereused to derive information on the mean transit time of water in the studiedcatchment. Comparison of the modelling results obtained by these twocompletely different approachessuggest that neural networks representapotentiallyattractivealternativefor themodellingof waterflow in suchcomplexsystemsascatchmentsof largerivers.The neuralnetworkmodellingyields thetransit time distributionfunction for the studiedsystem,whereasthe box-modelapproach is capable to deliver only the mean value of the transit time.

Whole-rock stable carbon and oxygen isotopestratigraphy of the type Wenlock Series (Silurian),

Welsh Borderland, UK

Sarah-Jane Schmidt1, Richard. M. Corfield2 Derek. J. Siveter3

Department of Earth Sciences, University of Oxford, Parks Road, Oxford, OX1 3PR, UK.1(sarahjs@earth.ox.ac.uk), 2(richard.corfield@earth.ox.ac.uk),3(derek.siveter@earth.ox.ac.uk)

A completestablecarbonisotopestratigraphyis presentedfor the WenlockSeriesof the type areain the Welsh Borderland,UK. The isotopecurvesareconstructedfrom whole rock samplesfrom outcrop localities and boreholesamples.The Wenlock Seriesin the type areais predominantlya sequenceofsilty carbonate mudstones, the Apedale Member of the CoalbrookadaleFormation,depositedon thenorthernpartof theNE-SWtrendingstableshelfofthe Midland Platform.Purerlimestonehorizonsof the BuildwasFormationandthe Much Wenlock limestoneFormationoccurat the bottomandthe top of theseries respectively (Holland & Bassett 1989, Aldridge et al. 2000).

The compositewhole-rockcarbonisotopestratigraphyof the Wenlockof thetype areashowstwo major positiveδ13C excursionsthat areassociatedwith theperiodsof increasedcarbonatedepositionin the early and late Wenlock. Theearlier,BuildwasFormationpeakhasvaluesof around3.5 ‰. ThelateWenlockpeakcomprisestwo positiveexcursions,oneat thebaseof theFarleyMemberoftheCoalbrookdaleFormationto ~ 2.75‰, andonein thelower partof thereefalMuch WenlockLimestoneFormationto ~ 2.5 ‰. The lower Wenlockpositiveexcursionpeakswithin the centrifugusbiozoneand declinessharply to valuesnear to 0 ‰ throughout the murchisoni biozone. The two upper Wenlockexcursions occur in the nassa and ludensis biozones respectively.

Thereturnto lower valuesfollowing themajorpositiveisotopeexcursionsmaybe correlatedwith timesof increasedoceanventilationin the centrifugus, nassaandludensisbiozones(Kemp 1991,Corfield et al 1992).Thereis only a broadcorrelation with published sea-level curves (Lloydell 1999),

The carbon (and oxygen) isotope curves obtainedfor the Wenlock (andLudlow) Seriesof the Anglo-Welsh areaare similar to thosethat have beenproducedfor the same parts of the Silurian sequenceof the Baltic Basin(Samtlebenet al. 1996, Bickert et al. 1997, Kaljo et al 1997, Wenzel &dJoachimski 1996).

Stablecarbonisotopework may proveto be a useful tool to correlateacrossdifferent lithofacies (Corfield et al. 1992), or palaeo-continents,as well asprovide information on palaeoclimatology and palaeoceanography.

References

Aldridge, R.J.,Siveter,David J., Siveter,DerekJ., Lane,P.D., Palmer,D. andWoodcock, N.H. 2000. British Silurian Stratigraphy.Bassett, M. G. 1989. The Wenlock Series in the Wenlock area. In: Holland, C. H.and Basset,M. G., (eds).A global standardfor the Silurian System.Nationalmuseum of Wales, Cardiff, Geological series No. 10. Bickert, T., Pätzhold, J., Samtleben, C, Munnecke, A. 1997. Palaeoen-vironmentalchangesin the Silurian indicatedby stableisotopesin brachiopodshellsfrom Gotland,Sweden.Geochimicaet CosmochimicaActa, 61, No. 13,pp. 2717-2730.Corfield, M., Siveter,D. J., Cartlidge,J. E., andMckerrow,W. S. 1992.Carbonisotopeexcursionnear the Wenlock-Ludlow(Silurian) boundaryin the anglo-welsh area. Geology, 20, 371-374.Kaljo, D., Kiipli, T., Martma,T. 1997.CarbonisotopeeventmarkersthroughtheWenlock-Pridoli sequence at Ohesaare (Estonia) and Priekule (Latvia).Palaeogeography, Palaeoclimatology, Palaeoecology, 132, pp. 211-223.Kemp.E.S. 1991. Mid-Silurian pelagic and hemipelagic sedimentationandpalaeoceanography.In: Basset,M.G., Lane, P.D. & Edwards,D. (eds) TheMurchison symposium: Proceedingsof an international conferenceon theSilurian system. Special Papers in Palaeontology, 44, 261-299.Jeppsson,L., Aldridge, R. J. 2000.Ludlow (late Silurian) oceanicepisodesandevents, Journal of the Geological Society, London, 157, pp. 1137-1148.Loydell. D. 1999.Early Siluriam sea-levelchanges.GeologicalMagazine.135.(4). pp. 447-471.Samtleben,C., Munnecke,A., Bickert, T., Pätzhold,J. 1996. The Silurian ofGotland(Sweden):faciesinterpretationbasedon stableisotopesof brachiopodsshells. Geologisches Rundschau, 85, pp. 278-292.Wenzel,B., Joachimski,M. M. 1996.CarbonandOxygenisotopiccompositionof Silurian Brachiopods(Gotland/Sweden):palaeoceanographicimplications.Palaeogeography, Palaeoclimatology, Palaeoecology 122, pp143-166.

Molecular and isotopic biogeochemical changesduring prograde metamorphism of a black shale

formation, Swiss Alps

Valérie Schwab, Jorge E. Spangenberg and Johannes Hunziker

Institut de Minéralogie et Géochimie, Université de Lausanne, Switzerland,Valrie.Schwab@img.unil.ch, Jorge.Spangenberg@img.unil.ch

Carbonaceousrocks in high temperaturemetamorphicsystemscontaintraceamounts of petroleum-like hydrocarbons.An ongoing study in a progrademetamorphicLiassic black shaleformation in the CentralSwissAlps aims tocharacterizethe origin and transformationof these hydrocarbonsby usingisotopic (C, N, H) and molecular methods. The studied samples includenonmetamorphosed(~100°C) sedimentsof the Tabular-Jura(Frick) up to lowamphibolite facies in the helvetic nappes (Frey 1978). In this sequence Hoefs andFrey (1976) described a 13C-enrichment (up to 11‰) in bulk carbonaceous matterwith increasingmetamorphism.In this communicationwe summarizethe firstisotopic biogeochemical data from this sequence.

The δ13C valuesof the carbonatesand kerogens(insoluble organic matter)showthesametrendsobservedby HoefsandFrey(1976),with a 13C-enrichmentof the total organiccarbonat >350°C.However,theδ13C valuesof theextractedn-alkanesincreaseprogressivelywith metamorphictemperatures>200°C (Fig.1). We recognizethe following trends:(1) In the unmetamorphosedsediments(δ13Cker = -27.5 ± 0.7‰, δ15Nker = 2.1± 1.8‰), the δ13C valuesof n-alkanesandthe moleculardistribution of biomarkersreflect the elevatedmaturationof themarine kerogen. The n-alkanes from montmorillonite-rich sediments areenrichedin 13C (up to 2‰), probablydueto the clays-catalyzedcrackingof thehydrocarbons.(2) At metamorphictemperaturesof 200 to 250°C (δ13Cker =

-25.9± 0.6‰, δ15Nker = 2.9± 5.0‰), theC<15 n-alkanesareenrichedin 13C (up to5), indicating the loss of 13C-depletedmoietiesduring crackingof longer-chainhomologues.(3) At ~350°C(δ13Cker = -26.3 ± 1.2‰, δ15Nker = 1.9 ± 1.6‰), the

uniform morepositiveδ13C valuesof then-alkanesmayindicatea steadystateofthe thermalbreakdownsof the 12C-12C and 12C-13C in the C15 to C25 range.(4)

Above450°C(δ13Cker = -12.4± 2.4‰, δ15Nker = -3.5 ± 1.5‰), the δ13C valuesofthen-alkaneshavean invertedL distribution,which reflectstwo processes:(i) a13C-enrichment(up to 1.5‰) of theC>19 n-alkanesformedby furthercrackingof

longer C-chains,and (ii) a 13C-depletion(up to 4.5‰) of the C<17 n-alkanes,which suggestsa distinct sourceof isotopically light n-alkanes.Thesemayoriginate from lipids, which have preservedthe original biogenic C-skeleton.Alkylcyclohexaneswith a primary 18 C-atomsstructuremay be formed from

fatty acidsretainedin the aluminosilicatestructure(Rubinsteinet al. 1979).Thestudiedsedimentsfrom theSwissAlps containalkycyclohexanesin therangeC11

to C27. We suggestthat the isotopically light C<17 n-alkanesobservedin thesedimentsfrom Lukmanierarea( 400-450ºC)were formed by ring-openingofthe alkylcyclohexanesat elevatedtemperatures.The carbonisotopicanalysesofthesecyclic compoundswill further the understandingof this process.The 15Nvaluesof thekerogensfrom low amphibolitefaciessedimentsaredistinctly morenegative (up to 6). This mayberelatedto thebreakdownof ammoniumretainedin micasandfeldspars,and incorporationof the releasedisotopically lighter N2

in organic compounds. Furthermore,the changesin the distribution of alkenesand alkanoic acids

during progrademetamorphismindicate increasingO2 fugacity in the water-hydrocarbons-rocksystem. Price & DeWitt (2001) interpret similar hydro-carbonsdistributionsin samplesform the samemetamorphicsequenceasproofof hydrolytic disproportionation of organic matter during metamorphism.

Our first data show that combinedmolecularand isotopic studiesservetoexplore the relative importance of the mechanisms(cracking, hydrolyticdisproportionation) responsible for the transformation of individualhydrocarbons during prograde metamorphism.

Figure 1. 13C ranges of n-alkanes from extracts of Liassic black shalemetamorphic sequence, Central Swiss Alps.

References

Frey, M. 1978. Progressive low-grade metamorphism of a black shale formation,Central Swiss Alps, with special reference to pyrophyllite and margarite bearingassemblages. Journal of Petrology, 19, 93-135.

Hoefs, J. & Frey, M. 1976. The isotopic composition of carbonaceous matter in ametamorphic profile from the Swiss Alps. Geochim. Cosmochim. Acta, 40,945-951.Price , C. L. & DeWitt, E. 2001. Evidence and characteristics of hydrolyticdisproportionation of organic matter during metasomatic processes. Geochim.Cosmochim. Acta, 65, 3791-3826.Rubinstein, I. & Strausz, O. P. 1979. Geochemistry of the thiourea adductfraction from an Alberta petroleum, Geochim. Cosmochim. Acta, 43, 1387-1392.

Antiphase hydrogen and oxygen isotope periodicityin chert nodules from Holy Cross Mtns, Poland

Zachary Sharp1, Tomasz Durakiewicz 2,3, Zdzisław M. Migaszewski 4,5, Viorel Atudorei1

1Dept. of Earth and Planetary Sci., Univ. of New Mexico, Albuquerque, NM 87131, USA,zsharp@unm.edu, 2Los Alamos National Laboratory, Condensed Matter & ThermalPhysics Group, Mailstop K764, NM 87545, USA, 3Institute of Physics, Maria Curie-Sklodowska University, 20-031 Lublin, Poland, 4Department of Environmental Geology,Polish Geological Institute, 00-975 Warsaw, Poland, 5Geochemistry and the EnvironmentDivision, Pedagogical University, 25-020 Kielce, Poland

Most chertexposedon land todayformedin broadepicontinentalseas.Chertformssoonafterdepositionof thecarbonatematrix, within oneor two metersofthe sediment/waterinterfacethrough the simultaneousdissolutionof siliceousfossilsand reprecipitation. As such,they are diageneticfeaturesby definition,but their chemistry may still reflect near-primaryconditions. Oxygen andhydrogenisotopeanalyseswere madeof Jurassic-agechert nodulesfrom theHoly Cross Mountains, SE Poland along radial transectsat high spatialresolution. The goal of this work was to extracttemperature-timeinformationduringnoduleformation. Periodicityin bothδD andδ18O valuesasa functionofdistancefrom the centerof the noduleis clear in the largernodule,Ozarów1b(Fig. 1). Similar variationsare seenin second,smaller nodule (1a), but theradiusof the noduleis too small to seea full cycle. A numberof observationscan be made from the measured data.•Theδ18O valuesof 31 to 34 ‰ aretypical of shallowseacherts,andlower thanthe ~33 to 36 ‰ range reported for deep-sea cherts.•TheδD - δ18O valuesof sample1ahavea δD/δ18O slopeof –8, identicalto thatfor chertsequilibratedwith marinewater. Temperatureestimatesfluctuateover10°C (~40 – 50°C).•Oxygenandhydrogenisotopedataareperiodic. The period length is nearly

constant, but slightly shorter close to the center of the nodule.•Oxygen and hydrogen isotope data are perfectly out of phase(perfectly

anticorrelated) with each other.•The δ18O andδD valuesof the minima andmaximaarerelatively constantin

each transect, but decrease slightly towards the edge of the nodule. •There is no correlation between the dark and light bands and isotopic

composition.Periodicity for a 100-120 mm diameternodule is approximately16 mm,

increasingslightly towardsthe rim, with amplitudesapproaching20‰ and3‰for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotopedatafor one nodulefall on a publishedcurve for chert forming in equilibrium

with seawater;datafor a secondchertfall on a sub-parallelδD-δ18O line with δDvaluesthatarealmost50‰ lower. The δD-δ18O patternsfor the nodulescannotbe explained by periodic mixing of meteoric and ocean water becausethehydrogenandoxygenisotopedataareout of phase. Two possibleexplanationsfor the antiphaseperiodicity are 1) cyclical temperaturevariations, perhapsrelated to an unstable convection system (e.g., Bolton et al., Am. J. Sci.299,1999)and2) self-organizingcatalyticprecipitation(e.g.,WangandMerino,GCA 54,1990). The systematicisotopic variationsare difficult to explain bydiagenesis,and strongly suggest that primary isotopic compositions arepreserved. The isotopic data provide important information on the thermalhistory of the sedimentarybasin,if temperaturevariationsare the causeof theisotopic periodicity.

Fig. 1. δD and δ18Ο variations in chert nodule as a function of distance from center.Solid line is a best fit of the form y=sin√x, where x is the distance from center;

the dashed line is a fit of the equation of Wang and Merino (1990).

210Pb in deposits of dammed lake in Kozłowa Góra

Jarosław Sikorski

Department of Radioisotopes, Institute of Physics, Silesian University of Technology,Bolesława Krzywoustego 2, 44-100 Gliwice, Poland, e-mail: js@zeus.polsl.gliwice.pl

Measurementsof 210Pb havebeenwidely usedfor dating young sediments,mostlyin naturallakes.Thesemeasurementsareusuallybasedondetectionof � -radioactivity of 210Po, being in equilibrium with 210Pb in sediments.In ourlaboratorythe sedimentis dried, polonium is extractedand depositedas a thinlayer on a silver disc. Radioactivityof 210Po is measuredwith a silicon surfacebarrier semiconductor detector.

Specific activity of 210Pb can be determinedwith an uncertaintyof a fewmBq/g. The reliability of our techniquehasbeenconfirmedby the analysesof210Pb concentration in the sediments of Lake Go

�ci ��� .

Herewe presentpreliminary210Pbmeasurementsin sedimentsof a dammed–lake in Kozłowa Góra,Upper Silesia.This lake was built on Brynica River in1934,andsincethen hasservedas the reservoirof water for the populationofUpper Silesia.Thereforethe contentof heavymetals(Fe, Mn, Pb) in the lakewater was monitored in the past, more or less continuously.

For 210Pb measurements,the coresof sedimentshavebeencollectedfrom 13sites,6 of themalongthe dam. Thicknessof sedimentsvariesgreatlybetweensites, probably due to sedimentoutwashcausedby opening the dam duringseverefloods. We hope,knowing maximumpossibleageof the sediments,todetectsucheventsin theprofilesof 210Pbof particularcores.Thetotal amountof210Pbin thelakesedimentsprofileswill alsobecomparedwith thatof thesoilsinthenearbyforest.Correlationof Fecontentandthe rateof 210Pbscavengingwillbe searched for, too.

Total 210Pb in sedimentconsistsof autigenic210Pbcomingfrom decayof 226Racontainedin the sediment,and allochtonous210Pb, airborne in the main partproducedby subsequentdecayof gaseous222Rn. 210Pb getsto sedimenttogetherwith precipitation,or boundto particlesof aerosols[seeFig.1.].Concentrationofautigenic210Pb doesnot changewith time, becauseradioactivedecayof 210Pb iscompensatedthrough its production from 226Ra. Allochtonous 210Pb is notgenetically connectedwith radium in the sediment, and its concentrationdecreaseswith time. For this reasonmeasurementsof 210Pb can be used todeterminethe age of sediments.Due to the short half-life time of 210Pb (22years), the range of the method is limited to 100-150 years.

Fig.1. 210Pb in sediment sources.

References

Tomasz Goslar, Małgorzata Ganowicz, Jarosław Sikorski. 2000. Firstmeasurements of natural radioactivities of 210Pb in the Institute of Physics,Silesian University of Technology. Geochronometria vol. 18: 29-34.

222Rn—>210Pb

222Rn

210Pb

Seasonal Variation of Oxygen-18 inPrecipitation in Finland

E. Sonninen

Dating Laboratory, University of Helsinki, Finland, eloni.sonninen@helsinki.fi

The δ18O values of monthly precipitation for the period 1989-1998arepresented.The Finnish EnvironmentInstitute collectedsamplesfrom sites oftheir network, which was constructedto collect precipitationsamplesfor theirchemicalanalyses.For isotopeanalyses11 siteswereselectedto coverthe areaof Finlandfrom south60°N to north70°N,andfrom west20°Eto east31°E.Thealtitudes of the sites are below 500 m a.s.l..

The δ18O valuesof precipitation follow the generally found progressivelydecreasingtrendwith increasinglatitudeanddecreasingsurfaceair temperature.The differencein the δ18O valuesbetweenwinter (December– February)andsummer(June– August)increasesfrom about4 ‰ in thesouthto about7 ‰ inthe north.

The seasonalδ18O – temperaturedependenceat individual sitesderivedfromthe averagemonthly mean δ18O values and correspondingaveragemonthlysurfaceair temperaturesrangesfrom 0.22 to 0.35 ‰ °C-1. Thesevalues arecomparable to those found for European low elevation stations.

Isotopic evidence for Mississippi Valley-type zinc-lead mineralization at Topla (Slovenia)

Jorge E. Spangenberg1 and Uroš Herlec2

1 Institut de Minéralogie et Géochimie, Université de Lausanne, Switzerland,Jorge.Spangenberg@img.unil.ch; 2 Department of Geology, University of Ljubljana,Slovenia, uros.herlec@ntfgeo.uni-lj.si

The Topla deposit(53 km N-E of Ljubljana) is oneof the strataboundZn-Pbdepositshostedby Middle Triassiccarbonaterocks in the NorthernKaravankeMts., EasternAlps. This small deposit(250,148tonnesore of 10 wt.% Zn and3.3wt.% Pb)wassetapartfrom theAlpine MississippiValley-type(MVT) zinc-lead ore deposits (Bleiberg-Kreuth, Mežica, Raibl) due to ore textures of“unmistakable” sedimentary origin and “distinct” stable and lead isotopesignatures(Štrucl1974,Köppel1983,Drovenik& Pungartnik1987).Usingnewlithogeochemical,isotopic (C, O, N), and biogeochemicaldata of the Anisiancarbonate host rocks a new look has been taken at the origin of Topla deposit.

The uniform REE patterns,lack of Ce-anomaly,and marine carbonisotopecomposition(2.3 ± 0.6 ‰) of the hostandganguecarbonatesis similar to thoseof other Alpine MVT deposits,and indicate that Topla host rocks were notinvaded/recrystallisedby deep(magmatic)hydrothermalsolutions.The isotopecompositionsof thekerogens(δ13Cker = –29.4to –25.0‰, δ15Nker = –13.6to 6.8‰) indicate contributions of continental organic matter to the marinealgal/bacterialsourceof thecarbonaceousmatter.On averagethekerogensfrommineralisedsamplesaredepletedin 13C (up to 3.5 ‰) andenrichedin 15N (up to4.3‰) comparedto thebarrensamples.Thesignificantscatterof thevalues(4.4‰ δ13C, 20.6‰ δ15N) may be attributedto compositionalvariability of organicmatterin theore-bearingbeds(e.g.,marine:δ15N ≈ 8 ‰; terrestrial:δ15N ≈ 0 ‰),combinedto differentdegreeof alterationof thekerogensduringore formation.The oxidative/bacterialdegradationof the sedimentaryorganic matter duringinteractionwith the mineralizingdiagenetic/hydrothermalfluids is in line withthe petrographicstudiesindicating that Topla ore hadundergoneseveralstagesof recrystallizationandremobilizationof ore andgangueminerals(Drovenik &Pungartnik 1987).

Topla rocks contain low to moderateconcentrationsof bitumen (solublepetroleum-like organic matter). The differences between the δ13C of thebitumensand the associatedkerogensvary largely from –2 to +5 ‰. Thisindicates that the bitumens contain variable amounts of (locally migrated)hydrocarbonsof different δ13C values. This is attributedto different degreeofmaturation and alteration of the bitumens during multiple hydrothermalalterations. The small intra-samplesδ13C-variability (± 0.5 ‰) of the individualn-alkanes(Fig. 1), and the inter-samplesuniform distribution of the biomarker

hydrocarbonsexcludethemixing of hydrocarbonsfrom differentsources.Then-alkanes and isoprenoids were enriched in 13C by up to 2.5 ‰ duringmineralization.The “open L-shaped”trendof δ13C values(Fig. 1) is dueto 13C-enrichmentof short-chainn-alkanesduring preferentialbreakdown of 12C-12Cbondsand lossof 12CH2-moietiesof longerchainhomologues.We believethatthe bitumensin Topla host-rocksare indigenousand formed by thermal andoxidative degradation(hydrolytic disproportionation;Helgesonet al. 1993) oflocal organic matter.

In general,the inorganicandorganicgeochemistryof Topla is similar to thoseof other MVT deposits, which have great diversity of geological andgeochemicalcharacteristicsat both district anddepositscale(e.g.,Spangenberget al. 1999,Leachet al. 2001).Therefore,the new datasuggestthat Topla is anintegral part of the Alpine Mississippi Valley-type district.

Figure 1. Carbon isotope composition of n-alkanes from Topla samples.

References

Drovenik,M. & Pungartnik,M. 1987.Origin of the zinc-leadore depositToplaand its particularities. Geologija, 30, 245-314.Helgeson,H. C., Knox, A. M., Owens,C. E. & Shock,E. 1993.Petroleum,oilfield waters, and authigenic mineral assemblages:Are they in metastableequilibrium in hydrocarbonreservoirs?Geochim.Cosmochim.Acta, 57, 3295-3339.Köppel,V. 1983.Summaryof leadisotopedatafrom oredepositsof theEasternand Southern Alps: some metallogeneticand geotectonic implications. InMineral depositsof theAlps andof theAlpine epochin Europe(Scheneider,H.-J., ed.), pp. 162-168. Springer, Berlin-Heidelberg.LeachD. L., Bradley,D., Lewchuk,M. T., Symons,D. T. A., Marsily. G. de,Brannons,J.2001.MississippiValley-typelead-zincdepositsthroughgeologicaltime: implications from recent age-dating research. Min. Deposita, 36, 711-740.Spangenberg,J. E., Fontboté,L. & Macko, S. A. 1999. An evaluationof the

inorganicandorganicgeochemistryof the SanVicenteMississippiValley-typezinc-leaddistrict, central Peru: implications for ore fluid composition,mixingprocesses and sulfate reduction. Econ. Geol., 94, 1067-1092.Štrucl, I. 1974. Die Entstehungenbedingungender Karbonatgesteineund Blei-Zinkvererzungen in den Anisschichten von Topla. Geologija, 17, 383-399.

Organic Geochemistry of Organic-RichCretaceous Carbonates of the Outer Dinarides

(Dalmatia, South Croatia)

D. Spanic, T. Troskot-Corbic, I. Stankovic, V. Culjak

INA-Division Of Strategic Development, Research and Investment, Research andLaboratory Testing Department, Geochemical Laboratory, 10002 Zagreb, Lovinciceva 1,Croatia;e-mail: darko.spanic@ina.hr; tamara.troskot-corbic@ina.hr;irenka.stankovic@ina.hr; veronika.culjak@ina.hr

The outcrop samplesof the organic-rich Cretaceouscarbonatesfrom 20localities in the OuterDinarides(Dalmatia,SouthCroatia)weregeochemicallyinvestigated.

The objectiveof this study is detail geochemicalcharacterizationof typesoforganic matter, their origin and genetic correlation, as well as hydrocarbonpotential.

The resultsof the analysesshowthepresenceof thekerogentype I-II in fine-grained, laminated limestones, which means the samples investigated areconsideredas sourcerocks of very high generativepotential (HI= 660-810).Microscopic examinationsof kerogen revealed its amorphousappearance,without any tracesof discreteorganic components.Greyish-browncolour intransmitted light and bright green-yellow fluorescenceindicates algal andbacterialorigin of kerogen.Enrichmentin heavy13C isotope(δ13CPDB= -18 to -23‰) establishalgal precursorsof organic matter,as well as anoxic depositionconditions.

Somesamplesare dolomitesand fosiliferous limestoneswith pores,fissuresand cavities filled with migrated bitumen. High content of sulphur andenrichmentin 13C isotope(δ13CPDB= -22 to -25 ‰), as well asprominentn-C17,indicatethat analysedbitumensoriginatefrom algal-derivedkerogen,and thusevidence their origin from organic-rich, laminated, fine-grained limestones.Thosebitumensare productof the early generationfrom the abovementionedsource rocks. In the absenceof cap rocks, bitumen was surface exposed,degraded and transformed from primary viscous liquid into solid bitumen.

Key words: Cretaceouscarbonates,Outer Dinarides, Dalmatia, source rock,bitumen, stable carbon isotope

Carbon isotope application on genetic relationshipbetween kerogens, bitumens and oils (marginal part

of Pannonian Basin-Croatia)

Irenka Stankovic; Veronika Culjak; Darko Spanic

INA-Division Of Strategic Development, Research And Investment, Research AndLaboratory Testing Department, Geochemical Laboratory, 10002 Zagreb, Lovinciceva 1,Croatia: e-mail: irenka.stankovic@ina.hr; veronika.culjak@ina.hr; darko.spanic@ina.hr

Stable carbon isotopesare primarily used in petroleum geochemistrytoestimateorigin of organic matter, but also to trace geneticrelationsbetweenhydrocarbons and their precursors.

Geochemicalanalysesof kerogen,bitumenand oil from nine wells in threeDepressionsof the PannonianBasin havebeenrevealed.Geneticrelationshipsbetween them were evaluated regarding mostly their carbon isotopiccomposition.

Carbonisotopicdatafrom kerogens(–23.0;-25.6 δ13C‰) andtheir associatedbitumens(-24.4; -26.5 δ13C‰) from Bjelovar Depressionshow a consistentdepletion of 13C in the bitumen in comparisonto the associatedkerogen.Bitumensfrom SavaDepressionarealso indigenousto the kerogens,accordingto their lower δ13C valuesof about 0,6‰ to the origin organic matter in thesediment.

Carbon isotope compositionsof oils (-25.5; -26.7 δ13C‰) from BjelovarDepressionrelated to kerogensare enriched in 12C and were supposedlygeneratedfrom thesekerogens.Carbonisotoperangesbetweenkerogensandoilsfrom Drava Depressionare less than 1,85 ‰, what supposesgood correlationbetweenthem. The lighter isotopic valuesfor oils are result of oil generationoccurring primarily from kerogen enriched in the isotopically lighter lipidfraction.Oils from SavaDepressionareisotopicallydifferent from theotheroils(-24.0; -24.3 δ13C‰), and are negativelly correlated to the bitumens andkerogens(-25.5; -26.2 δ13C‰) what suggeststhat oils are not originatedfromdeterminated source rocks.

Kerogensfrom four wells in Bjelovar Depressionwere analysedby opticalmethods and determinatedas marine originated amorphous,algal-bacterialkerogen.However the aberrationin their carbonisotopevalues(from -23.1 to-25.3‰) werenoted.Carbonisotopicvariationsof kerogengenerallyreflect thevariouscontributionsof organicinputsbut arenot causedonly by differencesintheir composition but also by heterogeneity of the kerogen matter.

Key words: kerogen, bitumen, oil, stable isotope, genetic relationship

Table 1: Stable carbon isotope composition of kerogens, bitumens and oilsin the Pannonian Basin Croatia

Sampl e Depthm

Kerogenδ13C‰ (PDB)

Bitumenδ13C‰ (PDB)

Oilδ13C‰ (PDB)

VC-2 - - - -26,7

VC-2 2406-2412 -23.0 -24.4 -VC-2 2412-2419 -24.0 -24.4 -SA-2 - - - -25.5SA-1Da 1220-1225 -25.6 -25.9 -SA-1Da 1250-1256 -23.7 -25.4 -BL-75 1488,5-1491,5 -25.3 -26.5 -BL-75 2631-2633 -25.1 -26.0 -BL-79 2324-2325 -23.8 -25.1 -LUK-1 2006-2010 -26.2 -26.9 -LUK-1 1270-1299 - -24.5 -24.3AND-1J 2050-2053 -25.5 -26.1 -24.0OB-5 2174-2177 -25.2 - -27.0CR-17 2597-2620 -25.1 - -25.6CR-13 2571-2592 -25.8 - -26.0

The C-Isotope Fractionation as an Indicatorfor the Degradation of Chlorinated

Hydrocarbons in Groundwater Aquifers

G. Strauch, J. Müller*), J. Dermietzel, W. Gläßer, P. Kowski,H.H. Richnow, A. Vieth

UFZ Centre for Environmental Research Leipzig-Halle Ltd, Departments ofHydrogeology and Remediation Research, Theodor-Lieser Str. 4, D-06120 Halle*)Staatliches Umweltfachamt Leipzig, Bautzner Str., D-04318 Leipzig

The evaluationof large scalecontaminationsby organic compoundsin agroundwateraquifersis evidently for remediationmeasuresbecausemicrobialinducednaturaldegradationprocessesoftenareableto diminishthegroundwatercontamination.Typical contaminantsare chlorinated aliphatic and aromatichydrocarbonsoriginatedfrom local cleanersandchemicalplants.In additiontothe hydrochemicalmonitoringof the contaminationplume,its distribution,age,andcompositionisotopetechniqueis increasinglyusedto assessthedegradationstageof the pollutants.Hereby, the carbon isotope signatureof the organicpollutants can be used as an indicator for the degradationof those organiccompounds.During microbial anaerobicdegradationof chlorinatedaliphatichydrocarbonsthe 13C/12C is stepwise fractionated from the higher stage ofchlorinationto thelower one.Investigationsof Hunkeler(1999)andBloum et al.(2000)reportedenrichmentfactorsε from +2 to +26‰ for themicrobial induceddegradationstepsbetweenperchlor-ethylene(PCE),trichlor-ethylene(TCE),cis-dichlor-ethylene (c-DCE), vinylchloride, and ethylene.

We presentfirst resultsof the carbonisotopefractionationof PCEandTCEdueto microbial degradationin a contaminatedQuaternaryandTertiary aquiferdownstream of a former cleaner plant located in the northern part of Leipzig.

For the degradationof the chlorinatedcompoundsPCE and TCE in theQuaternaryaquiferwe measureda rangeof the C-isotopefractionationbetween0.7 to 4.6‰ which correlatesto the resultsof Hunkeler(1999).Thedegradationof thoseboth compoundsPCE and TCE seemsto be to small in the Tertiaryaquiferin relationto the Quaternarygroundwater.Although high concentrationswereobservedin the centreof the contaminationsite the degradationprocessisobviously limited by a lack of electron donors.

UsingtheRayleighfractionationconceptandtheδ13C valuesof PCEaswell asthedecreaseof measuredconcentrationsof PCEandTCE in thegroundwaterwecalculatedthe degradationof PCE along the contaminationplume to be in therangeof about 99%. The C-isotopefractionationof the field experimentsinrelation to the experimentsof Hunkeler et al. (1999) was used to assessthemicrobial induceddegradationof PCE which gave reasonableresultsfor thatcontamination site.

At least,theresultsshowthat thePCEdegradationprocesscanbedescribedin

a good correlation with the Rayleigh equations despite the limiting conditions ofthe Rayleigh model. Moreover, the concept of microbial degradation is supportedby the δ13C of dissolved inorganic carbon.

References

Hunkeler, D., Aravena, R., Butler, B.J., Environ. Sci. Technol. 33. 1999. 2733-2738Bloum, Y., Aravena, R., Hunkeler, D., Edwards, E., Frape, S. K., Environ. Sci.Technol. 34. 2000. 2768-2772

Chemical and isotopic studies around a near surfaceradioactive waste disposal

Zs. Szántó1, É. Svingor, I. Futó, L. Palcsu, M. Molnár

1 Institute of Nuclear Research of the Hungarian Academy of Sciences, Debrecen,Hungary, aszanto@moon.atomki.hu

Within theframeworkof theHungariansafetyassessmentprogramfor thenearsurfaceradioactivewastedisposalfacility at Püspökszilágy,water quality andstableisotopeinvestigationshavebeencarriedout. In this paperthemainresultsof the site characterizationprogrammehavebeenpresented,which servedto abetter understandingof the groundwatergeochemistryof the site implyingknowledge of mixing condition, residence time and origin of groundwater.

The Püspökszilágyfacility is locatedon the crestof a NW/SE trendingridge.The ridge is boundedto the SW by the Némedistreamand to the NE by theSzilágyi stream.The depthsof the observationwells drilled on the site variedbetween7-60 m. Beneaththe disposal,groundwaterflow direction at shallowdepthis towardsthe Szilágyi stream.On the crestof the ridge nearthe facility,groundwater level is approximately 20-24 m below ground surface. Themeasurement data are summarized in Table 1.:

Table 1. Mean stable isotope values and tritium concentrations measuredin the observation wells and streams

Sample � 18OSMOW(‰) � DSMOW (‰) � 34SCD (‰) 3H conc. (TU)

O1 -11.20±0.05 -82.2±0.3 -7.8±0.08 0.06±0.01O2 -11.63±0.04 -83.4±0.3 -9.2±0.04 0.19±0.02

Psz 20 -8.62±0.04 -63.3±0.2 -10.76±0.07 0.36±0.02Psz 51 -8.78±0.04 -64.7±0.3 -3.79±0.07 1.33±0.05Psz 54 -8.70±0.04 -62.6±0.3 -0.67±0.02 18.3±0.5Psz 56 -8.62±0.02 -59.7±0.2 -4.49±0.07 1.18±0.05Psz 57 -9.93±0.04 -70.2±0.3 -12.39±0.08 1.83±0.02Psz 58 -10.36±0.04 -73.2±0.3 -13.72±0.08 0.29±0.01Psz 59 -9.09±0.06 -65.2±0.4 -6.21±0.03 5.66±0.03Psz 63 -9.26±0.05 -68. 8±0.4 -4.12±0.06 11.4±0.2Psz 65 -9.21±0.04 -67.1±0.2 -10.16±0.09 0.18±0.01Psz 70 -8.99±0.05 -68.4±0.3 1.35±0.07 1.15±0.03

Némedi stream -8.61±0.03 -63.6±0.4 - 7.77±0.04Szilágyi stream -9.02±0.07 -66.9±0.3 - 7.07±0.04

As we canseein Figure1., thereis a largerangein thecalculatedages.On theNémedisideof thehill, thegroundwaterappearsto beold, while on the top andon theSzilágyi sideof thehill, youngvirtual agesaredominant.Thequestionis

that this differencereflectsdifferent origins or different mixing ratesof the twowater bodies.

Figure 1. Distribution of calculated 14C ages

Correlationcan be seenbetweenthe radiocarboncontent,water chemistry,stableisotopeand tritium data.The water in wells with low 14C concentrationcontainslargeamountof sulphate,HCO3, Mg, andtheir conductivityis high.The

negativeδ34S valuesof the sulphatein thesewells canbe explainedby their oldageaswell (their sulphatecontentwasdissolvedfrom sedimentaryrocks).Thesewells areon theNémedisideof thehill. Thewells on thetop andon theSzilágyiside of the hill are characterized by higher 14C concentrations, smaller amounts ofsulphate,HCO3, Mg, low conductivityandpositiveδ34S values.The differencessuggestdifferent origins for the two waterbodies.Wells O1 andO2 screeningthe Oligoceneare apart from all the other wells: contain typical Na-Cl typewaterswith old agesand low tritium content.δ18O and δD databoth manifestdepletedsignaturesand low valuesof deuteriumexcess,indicating that a largeportion of the groundwaterwas rechargedduring a cooler climate such as aglacial epoch.

Carbon isotope composition in carbonatesfrom Tertiary basaltic rocks and olivine xenoliths

(SW Poland): Mantle CO2 or crustal contamination?

Anna Szynkiewicz, Maciej Górka and Mariusz O. J� drysek

Laboratory of Isotope Geology and Geoecology, University of Wrocław, Cybulskiego 30,50-205 Wrocław, POLAND, AS szyna@ing.uni.wroc.pl, MG gurcyt@ing.uni.wroc.pl,MOJ morion@ing.uni.wroc.pl

IntroductionCarbonandoxygenisotopeanalysisof calcitefrom theTertiarybasalticrocks

(SW Poland)and from olivine-pyroxenitexenolithsin thesebasalts,havebeencarriedout. Theserocksbelongto the volcanicbelt, which extendsfrom Polandto GermanyandFrance.Thecalciteformsscatteredfine-grainedmineralization,difficult to determinateunder the microscope.Samplesanalysedhave beencollectedin four different outcrops200 km apart.The basaltsfrom Trupie� (T)and Wilcza Góra (WG) cut the Cretaceousand Permiansedimentarycover(limestones,marbles,sandstones),and the basaltsfrom Luba� (Lb) cuts thePaleozoicsedimentaryrocks (sandstones)while basaltsfrom Lutynia cuts theProterozoic crystalline rocks (mainly different types of gneisses).

The mainaim of this work is to considerthe role of carbonassimilationfromthe neighbouringlimestonesandto pay attentionto the role of CO2 degassationandpH variationduring volcanicactivity (including mixing of groundwaterandhydrothermal water). These processesmay involve strong carbon isotopevariations in precipitated carbonates.

ResultsDue to low concentrationof carbonates,the carbon and oxygen isotope

analysiswaspossiblein thesebasaltsonly, which cut the sedimentarycover(T,WG andLb). Theotherbasaltse.g.from Lutynia, containnanomoleamountsofcarbonatesonly. Thecarbonatematerielanalysedyield very wide rangesof δ13Candδ18O values(-8.42to –24.16‰ and15.37to 34.31‰, respectively- Fig. 1,2).Generally, following observations in basalts can be done:1) the basaltsandolivine xenolithsfrom T andWG showhigherδ13C values(-7.86 to –19.93 ‰) than these from Lb (-12.45 to –24.16 ‰) (Fig. 1);2) δ13C valueshowsrathernarrowrangesin basalts(-7.86to –12.13‰ in T, WGand –15.86‰ to –21.54‰ in Lb) and the wider rangesin respectiveolivinexenoliths (-8.42 to –19.93 ‰ in T, WG and –12.45 to –24.16 ‰ in Lb) (Fig. 1);

3) all basaltsshowshigherδ18O values(23.48to 34.31‰) thanolivine xenoliths(15.37 to 25.03 ‰) (Fig. 2);

Fig. 1. The carbon isotope composition of carbonates in basalts and their olivine xenoliths.

4) both the basaltsand olivine xenolithsshow an increaseof δ18O value withincreasing degree of weathering of the rock, especially olivine xenoliths (Fig. 3);5) the carbonatesstudied,group in two ∆13C(xen-bas) - ∆18O(xen-bas) areas(Fig. 4) –this may suggest presence of two carbon generations of carbonates;6) δ13C value of limestones from the carbonateplatform of T and WGcharacterisehigher valuesof δ13C (-1.03 to 2.06 ‰) than the basaltsand theirolivine xenoliths (Fig. 2)

Fig. 2. The carbon and oxygen isotope composition of carbonates from Wilcza Góra,Trupie� and Luba� .

Fig. 3. The oxygen isotope composition of carbonates in basalts and their olivine xenoliths.

Fig. 4. ∆13C(xen-bas) - ∆18O(xen-bas) variations in basalts and olivine xenoliths from SW Poland.

DiscussionCarbon isotopes

In general,thecalcitecontentin thebasaltsandxenolithsanalysedis very low(c.a. 1 wt %). This may suggestthat the primary basalticmelt was poor incarbon.Also, theδ13C valueanalysedis lower thanthat in themantle(Taylor etal. 1967,Keller andHoefs1995),(Fig. 1). On the otherhand,the calciteunder

studyoccursonly in theseplaceswherethebasaltscut the limestones.Thus,webelieve that the main portion of carbon was derived from groundwatersinfiltrating through the sedimentarycarbonatecovers.This thesis apparentlycontradictsto isotope ratios, as the averageδ13C value of calcite from thelimestonesof T andWG areais 1.16‰ andtheδ13C valuesin basaltsaremuchlower (see above). Therefore, to accept this thesis, the potential isotope effect hasto be elucidated.

PresentlymeasuredpH of waterinfiltrating throughtheT andWG limestonesis about8. In suchconditionsthe HCO3

- andCO2(aq) contentis 97.7 and2.3 %

respectively. Likewise, it can be estimated that δ13C value of dissolvedcarbonatesin this water is near–1.44‰. Nevertheless,volcanic solutionscanrapidly changepH of groundwatersbecausethey show high concentrationofHCl, SO2, H2S andHF. Hence,typically thepH of low temperaturehydrothermalsolutionsin basaltsis about5 (Capassoet al. (1997).On theotherhand,it is wellknown that the CO2(aq)/HCO3

-/CO32- ratio in water largely dependson the pH

value.Basingon Mook et al. (1974),Vogel etal. (1970)andBottinga(1968)onemayestimatethatat 20 °C andlow pH = 5 (CO2 dominatestheDIC system)the

δ13C(CO2) valueof dissolvedT andWG carbonatescanreachabout–11.04‰.Consequently,similar dramaticchangeof pH, in the areaunder study, couldpotentiallyshift theδ13C of groundwatersinfiltrated in limestonesfrom –1.44to–11.04‰. Further13C-depletionof residualcarbonatewasprobablyresultedbysimultaneousCO2 degassation.It may be estimated,from Reyleighdistillationmodel,that in suchconditionsabout90 % of CO2 wereprobablyremovedfromthesystem(thetemperaturewasprobablymuchlower than122.5°C - crossovertemperature).Finally, this processcould result in precipitation of 13C-depletedcarbonates in the basalts under study.Oxygen isotopes

In therocksunderstudyanincreaseof δ18O valueof carbonatescorrespondstoincreasingdegreeof rocksweathering,especiallythe olivine xenoliths(Fig. 3).This mayreflect(i) retrogradeoxygenisotopeexchangebetweencarbonatesandsilicaterock (the samepostmagmaticfluid circulationprobablyalsocausedtheserpentinizationof olivine); (ii) decreaseof temperatureduring precipitationofthe carbonates;(iii) variations in the % ratios between the potential twogenerations of carbonates formed in different temperatures.

Conclusion1. The main sourceof carbon in the tertiary basaltsfrom Sudety Mts. wasneighbouringlimestones.The precipitationof 13C-depletedcarbonatesin basaltsresultedfrom decreasein pH and degassationof up to 90 % of CO2 from thesystem.2. The oxygenisotopecompositionof carbonatesprobably reflectsan isotopeexchange between carbonates – postmagmatic/surficial fluids – rock system.

Acknowledgements: This studyhasbeensupportedby and"S” and“W" grantsatthe University of Wrocław and IAI.

References

BOTTINGA, Y. 1969.Carbonisotopefractionationbetweengraphite,diamondand carbon dioxide. Earth Planet Sci Lett 5, 301-307.CAPASSO,G. FAVARA, R. INGUAGGIATO, S. 1997Chemicalfeaturesandisotopic composition of gaseousmanifestationson Volcano Island, AeolianIslands, Italy: An interpretative model of fluid circulation. Geochim.Cosmochim. Acta 61, 3425-3440.KELLER, J. HOEFS, J. 1995. Stable isotope characteristicsof recentnatrocarbonatitesfrom Oldoinyo Lengai. (edit. Bell, K. Keller, J.) CarbonatiteVolcanism: Oldoinyo Lengai and the Petrogenesisof Natrocarbonatites.Springer, Berlin, 113-123.MOOK, W.G. BOMMERSON,J.C.STAVERMAN, W.H. 1974.Carbonisotopefractionationbetweendissolvedbicarbonateand gaseouscarbondioxide. EarthPlanet. Sci. Let. 22/2, 169-176.TAYLOR, H.P.FRECHEN,J.DEGENS,E.T. 1967.Oxygenandcarbonisotopestudiesof carbonatitesfrom the LaacherSeeDistrict, West Germanyand theAlno District Sweden. Geochim. Cosmochim. Acta 31, 407-430.VOGEL, J.C. GROOTES, P.M. MOOK, W.G. 1970. Isotope fractionationbetween gaseous and dissolved carbon dioxide. Z. Phys. 230, 255-258.

Sulphur and oxygen isotopic composition ofsulphates in springs feeding the Wieprz river and

other springs of Lublin Uppland and Roztocze

Andrzej Trembaczowski1 and Andrzej �wieca2

1 Mass Spectrometry Laboratory, Institute of Physics, Maria Curie-SklodowskaUniversity, 20-031 Lublin, Poland, e-mail: atrem@tytan.umcs.lublin.pl;2Department of Regional Geography, Maria Curie-Sklodowska University, 20-033Lublin, Poland, e-mail: aswieca@biotop.umcs.lublin.pl.

Startingfrom 2001the waterof four springsfeedingthe upperWieprz havebeenstudied.In this paperisotopic and chemicaldata are comparedwith theresultsobtainedpreviously,alsowith dataof analysesobtainedfor otherspringson Roztoczeand Lublin Uppland regions.The resultsof studiesallow us todistinguish five types of groundwaters( � wieca 2000). Thesedifferention arecausedby different litology; opokas,gaizes,sandy-silty-claydepositts,sandswith shell sandstones,marly opokas,marly limestonesand soft limestonesofchalk type.

Thegroundwatersof theNał � czów Plateauaresituatedinto different rocksofupperCretaceouscoveredthick layersof loess.Thesegroundwatershavehightotal mineralizationca. 400 mg/L and high total hardnessca. 6 mval/L. Theconcentrationof sulphatesin thesewatersis high, rangingfrom 35 to 40 mg/L.These sulphateshave the most negative δ34S values, up to –20 per mill(Trembaczowski 1991).

The groundwatersof Chełm Hills regionhavehigh total mineralization(340mg/L) and high total hardness(5.8 mval/L) too, but the concentrationofsulphatesin thesegroundwatersis only 18 mg/L. Their δ34S valuesrange,from+2 to - 4 per mil.

The watersfrom springssituatedon Roztoczeare more differentiated.Thehighestmineralizationhavesprigsin WesternRoztocze,ca.315 mg/L, the totalhardnessof thesewatersis ca. 5.4 mval/L. The concentrationof sulphatesissmall,15 mg/L, while the springsof EsternRoztoczehavelower mineralization(300 mg/L), lower total hardness(5.2 mval/L) and higher concentrationofsulphates,ca. 30 mg/L. The aquifer rocks are the opokascoveredby Tertiarylimestones.The springs of Midle Roztocze region have the lowest totalmineralization(of 216 mg/L) and the lowest total hardness,of 4.4 mval/L. Thesulphateconcentrationin thesegroundwatersis 25 mg/L.The aquifer of thesewaters is in the complex of opakas and gaizes of upper Cretaceous.

Theisotopiccompositionof sulphatesletsusdistinguishthewaterswhich haveless34S (morenegativevaluesof δ34S), thanshallowgroundwaters(Trembac-zowski 1991).

The upperWieprz is fed by 27 springs,the biggestof which aresituatednear

the river bed. The biggest springs are situated near the following villages:Krasnobród,Hutki, StokowaGóraandObrocz.NearKrasnobród,on theleft sideof the Wieprz river, aretwo springs.The wateroutflow andthe temperatureofthe water vary more than in the other springs.The largestwater outflow wasnoticedin 1988(Michalczyk,Wilgat 1996)wasabout100L/s, while from 1989to 1992 the springsdisappeared.Bigger springsare in Hutki, whereundertheslopenearthe left bankof the Wieprz river the water flows out of six springs.The maximal observedoutflow was 250 L/s. The springs of the highestproductivityaresituatedin StokowaGóra,on theright sideof theWieprz,whereunderthe rocky wall water flows out through18 holesand forms two streams.Theyield of springwaterrangesfrom 100L/s to 180L/s. Thespringsin Obroczareon theleft sideof theWieprz,partly neartheriverside,partly in theriver. Allthesespringshada higherconcentrationof sulphatesthan the river water.Thehighestconcentrationof thesulphateion wasfound in thespringsin Obrocz(17mg/L – 40 mg/L), while the lowestconcentrationin the springin Krasnobród(7mg/L – 16 mg/L). All these springs containedsulphatesdepletedin heavysulphur isotope,it is typical for the groundwatersdissolvinglimestones.Morenegativeδ34S valueswere found in springslocatedin the lower sectionof theWieprz river valley, (as Obrocz) in comparisonto the springssituatedhigher(like Krasnobród).

Theseasonalvariationsof the isotopiccompositionandsulphateconcentrationareobserved.The recordedvariationsweresimultaneousandsimilar in all thesesprings.It canbe observedthat when the concentrationof sulphatesincreases,δ34S increases,too. Thesevariationswereprobablycausedby the admixtureofsulphates which come from shallow water layers or leached from soil.

Acknowledgement

This research was supported by KBN project Nr 6PO4E01920.

References

Michalczyk Z., Wilgat T. 1996.Watercondition in the Lublin District. UMCSLublin (in Polish)�wieca A. 2000.Spatialvariabilityof chemicaldenudationinthe uplandpart of

theVistula andBug interfluve.Karstandspeleology,T. 1). (XIX), Katowice,inPolish. TrembaczowskiA. 1991.Sulphurandoxygenisotopesbehaviourin sulphatesofatmosphericgroundwatersystem,observationandmodel.Nordic Hydrology,22,49-66.

Variations of compound specific stablecarbon isotope compositions of peat sediments

in China for the last 3,500 years

Masao Uchida1,2, Yasuyuki Shibata1, Hong Yetang3, Qinghua Lin3

1 Institute of Low Temperature Sciences, Hokkaido University; uchidama@jamstec.go.jp;2 National Institute for Environmental Studies (NIES), Tsukuba, Japan; 3 Institute ofGeochemistry, Chinese Academy of Science, China.

We will report here compound specific stable carbon isotope composition of n-alkanes and radiocarbon of organic compounds (OCs, biomarker) from peatsediment collected in the Tibetan plateau in west China, in order to elucidatehigh resolution rhythm for temperature, humid, atmospheric CO2 concentrationin late holocene. Our peat samples have high time resolution which is corres-ponding to about 20 years or shorter times for each layer. So the molecular-isotopic stratigraphy of sedimentary lipids in peat samples with independentpaleoecological data will be useful information for reconstraction of millenial tocerenial climate changes, as well as the glacial to interglacial changes in carboncycling within the peat environment.

Peat samples were collected from Chengdu in Sichuan Province near N30,which is located along with south branch of west Wind Zone and is also Indiamonsoon zone. The individual organic molecules in peat sediment underspecific climate condition were derived not only from terrestrial higher plant, butalso aquatic plants and micro-organisms. So far the bulk isotope signal of OCsin sediments reflects a diverse array of carbon sources. Compound-specificisotope analysis now permits the measurement of δ13C for individual OCs withdifferent sources, thereby minimizing the overprint of specific inputs.

Palaeogroundwater of glacial origin in theCambrian-Vendian aquifer of northern Estonia

Rein Vaikmäe1, Jüri Ivask1, Enn Kaup1, Andres Marandi1 , Tõnu Martma1,Valle Raidla1, Leo Vallner2, H. Hugo Loosli3, Petra Blaser3

1Institute of Geology at Tallinn Technical University, Tallinn, Estonia,Rein.Vaikmae@gi.ee, Jyri.Ivask@gi.ee, Enn.Kaup@gi.ee, marandi@ut.ee,Tonu.Martma@gi.ee, Valle.Raidla@gi.ee; 2Estonian Geological Survey, Tallinn,Estonia,vallner@egk.ee; 3Climate and Environmental Physics Institute, University ofBern, Bern, Switzerland, loosli@climate.unibe.ch, petra.blaser@bluewin.ch.

Most of Europe’sgroundwaterresourcesare found in sedimentarybasinsranging from Mesozoic to Quaternaryage. Throughoutgeological time thesehavebeensubjectto flushing andreplenishmentwith fresh (or saline)water inresponseto changesin hydraulicgradientsbroughtaboutby tectonicmovement,sealevel changesor otherprocesses.Most recentlythedirectandindirecteffectsof glaciation,notably ice cover,permafrostand sealevel changehaveinducedchangesin hydraulicheadandpatternsof groundwaterflow both in coastalandadjacent inland areas.

Strongly depletedstable isotope composition, absenceof 3H and lowradiocarbon concentration are the main indicators of glacial origin ofgroundwater in the Cambrian-Vendian aquifer in northern Estonia. The noble gasanalysesallowed to conclude,that palaeorechargetook place at temperaturesaroundthe freezingpoint. In somewells unexpectedlyhigh gasconcentrationshavebeenfound.Excessair up to about50 % is common,but factors2 to 5 fortheoversaturationarevery unusualandneedspecialprocessesandexplanations.Oneexplanationcould be, that oversaturationindicatesthe rechargein the highpressure conditions, e.g. by subglacial meltwater recharge through aquifers.

Analysesof the gascompositionin somegroundwatersamplesshowedalsoaratherhigh concentrationof methane.This is indicatingtheinfluenceof biogenicreactionsin the subsurface,which could causethe rathernegativeδ13C values.Resultsof δ13C analysesin two methanesamplesalsoshow,thatthemethanehasmost probably biogenic origin.

Basedon theisotopedata,on theresultsof noblegasanalyses,andconsideringthepalaeoclimaticandpalaeoenvironmentalsituation in Estonia during the lateWeichseliantime, the conclusionwasmade,that palaeorechargeof Cambrian-Vendianaquifermostprobablyoccurredduring the last glaciationpreferablybysubglacial drainage through the tunnel valleys.

C-H-O isotopy of the methane-water system in thedeep aquifers of the Pannonian basin, SE-Hungary

Vetö, I. 1, Futó, I.2, Horváth, I.1, Szántó, Zs.2

1 Geological Institute of Hungary, Budapest, Stefánia út 14., H-1142, e-mail:vetoi@mafi.hu/c2 Institute of Nuclear Research, Hungarian Academy of Sciences, Debrecen, Bem tér 18/c,H-4026

Geochemistryof HC-gasesin deepaquifers,not relatedto oil andgaspoolsisvery poorly studied.Hencetheherereportedmethaneδ13C, δD valuesmeasuredfrom 25 watersrepresentingdeepaquifers(0.5 – 2.2 km) of SE-Hungaryarescientific novelties.Aquifers have beendepositedin the brackish PannonianLake and on floodplain areas surrounding it. Waters are of sodiumhydrogencarbonatetype, thebulk of the inorganiccarbonhasbeenproducedbybacterial and early thermal degradationof the sedimentaryorganic matter.Isotopicallyheavywaters(δ18O > –4 ‰ andδD > -45 ‰) inheritedfrom thelakeare of importancebut their mixing with and replacementby isotopically lightmeteoricwater(δ18O < -11 ‰ andδD < -85 ‰) infiltrated duringthelastglacialare common phenomena.These processesare confirmed by chloride andbromide content data, too.

While headspacestudiesrevealedthatearly thermalgasgenerationis in workin the aquitardsbelow 0.7 – 1.3 km, all but two of the studiedaquiferscontainpredominantlybacterialmethane(δ13C < -50 ‰) evenat 2.2 km depth.Methaneδ13C showsa greatscatterand a downwardincreaseup to 1 km depththen itdisplaysa reversedtrendreachingvaluesas low as–70 ‰ in the 1.5 – 2.2 kmdepthinterval. Themajority of thesamples,characterisedby methaneδD valuesless negativethan -260 ‰ contain methanegeneratedmostly via carbonatereduction. This assumptionis supportedby the finding that the differencebetweenhydrogenisotoperatios of methaneand co-producedwater is mostlycloseto –160‰, thevalueexpectedin caseof carbonatereduction.Somewatersproducedmostly from below 1.5 km containmethanewith δD below -290 ‰,suggesting the predominance of acetate fermentation.

Methanecontentof the connatewatercanbe ashigh as20 mol/m3 while themaximumamountof methanein watersinfiltrated during the last glacial is 8mol/m3. This latter abundancemeans that the rate of bacterial methanegeneration can reach 0.1 mol/ m3/ky in the crossflowing meteoric waters.

Influence of Oil dump remediation on δ34S ofdissolved sulfate in a Llobregat creek

(Catalonia, NE Spain)

E. Viñals1, A. Canals1, A. Soler1, P. Teixidor2

1 Dpt. Cristal·lografia, Mineralogia i Dipòsits Minerals, University of Barcelona,Barcelona, Spain; angels@natura.geo.ub.es; 2 Serveis Cientificotècnics, University ofBarcelona, Barcelona, Spain, teixidor@giga.sct.ub.es

TheLlobregatis a typical Mediterraneanriver locatedin theNE of Spain,witha length of 156.5km,drainageareaof 4948.4km2, and a meandischargeof100m3/s.Thechemicalcompositionsof mostLlobregatstreamwatersaremainlycontrolled by the weatheringof chemical sedimentsof Tertiary basin. Theconcentrationon sulfate in Llobregatwatersrangefrom 26 to 870 ppm. Thelowestvaluecorrespondsto the headwatersamplewith a δ34S of 8.4‰,andthehighestfor a samplewith a δ34S compositionof 12.2‰nearthe outlet.Most ofthe � 34S values of dissolvedsulfate in the Llobregat basin are positive butsignificantly lower than sulfatesfrom the bedrocksindicating a changeof thesulfur isotopic composition induced by pollution (Soler et al., 2002).

Figure 1. Calders creek water composition and δ34SSO4= values.

Only in two smallcreeks,calledCaldersandCastellolí,negativevalues,up to-13.7‰,of δ34SSO4= weremeasured,despiteboth creeksare hostedin the samebedrocks, mean values of � 34SSO4= in Castellolí are always more negative, three orfour units permil. Occasionallyoil dumpshave occurredupstreamof Calderscreek,the last one took placeon May 98 and the remediationconsistedin oildepressionusing Na-Cl brines. In order to elucidateif sulfateof thesecreeksderived from natural sources by oxidation of H2S of the bedrocks oranthropogenicorganicsulfur couldbeinvokedto explaintheselow values,high-resolutionsamplinghasbeendone.Herewe reportchemistryandisotopicdata

of nineteenmonthly samplingof one samplelocatedat the confluenceof theCalderscreekwith the main Llobregatflow, andone samplingof eight waterscollected upstream. In addition data of the site of oil dump is also displayed.

Chemistryof surficial watersusingStiff diagramsareshownin figure 1, C6 isthe site of oil dump and is possible to recognize a change from Ca-Mgbicarbonateto Na-Chlorinetypewaters.Castellolíwaterchemistryaresimilar toC7 or C3 points but with ten times more sulfate. Theanalysisof theextractableorganicmatterof a watersamplecollectedat siteC6 (31 monthsafteroil dump)still revealthe traceof contaminatingmineraloil.It is remarkablethe presenceof organic sulphur species(S6-S8) and a hydro-carbon distribution (C15-C31, without even/odd predominance).

Valuesof δ34SSO4= arealsoreportedon figure 1, note the valuesfor point C6

and for point C3 with δ34SSO4= values of +20.5‰ and -7.2‰ respectively. The lastone representsthe naturalvalue of sulfatewhereasthe first is consequenceofsulfato reductiondue to the oil dump.Note the decreaseof the δ34SSO4= down-waters due to introduction of natural sulfate with negativevalues. Figure 2representsthe isotopic time evolution for sampleC1 during nineteenmonths,from June 97 to January 99, together with dissolved oxygen, the BO5D and COD.It is remarkablethe abruptchangeon theseparametersdue to oil dischargeonMay 98. It is alsoimportantto noticetheprogressiveincreaseof theδ34SSO4=evenfifteen months latter.

Figure 2. Time evolution of dissolved oxygen (in ppm),BO5D, COD and δ34SSO4= (‰ VCDT) for sample C1.

References

Soler, A., Canals, A., Goldstein, S.R., Otero, N., Antich, N. and Spangenberg, J.2002. Sulfur and Strontium isotope composition of the Llobregat river (NESpain): tracers of natural and anthropogenic chemicals in stream waters. Water,Air and Soil Pollution, in press.

Isotope and tracer techniques in studies ofconstructed wetlands: The PRIMROSE project

example.

Przemysław Wachniew, Piotr Czupry� ski, Kazimierz Ró� a� ski

University of Mining and Metallurgy, Kraków, Poland, wachniew@agh.edu.pl

Constructedwetlandsarewetlandspurposelyconstructedto useaquaticplantsandanimalsfor the treatmentof wastewaters.This rapidly world-wide growingtechnology is used for treatmentof wastewaterand runoff from domestic,agriculturaland industrial sources.Constructedwetlandsare lessexpensivetobuild than other options, their operation and maintenanceare simple andinexpensive.Additionally they providenumerousenvironmentalbenefitsandasan environmentallysensitiveapproachare viewed with favour by the generalpublic.

Knowledgeof hydraulic propertiesconstitutesa crucial factor in designandanalysisof constructedwetlandsbecausetreatmentefficiency dependson timescale of contact betweenwastewaterand microbiologically active surfaces.Overall hydrauliccharacteristicsof a constructedwetland(actualwatervolume,mean detention time) can be inferred from residence time distributionsobtainableby meansof tracertests.The optimal useof the wetlandrequirestheconsiderationof processeslike dispersion,existenceof heterogeneities(yieldchannelling effects or multiflow), existenceof zones with stagnantwater,diffusive exchangeof solutesbetweenmobile and stagnantzonesand/or thesaturation stage of the wetland with a waste.

Influenceof hydraulic phenomenaon constructedwetlandsperformanceisaddressedin thePRIMROSEproject(http://primrose.jordforsk.no) within the 5th

Framework Programmeof the EU. The project entitled “PRocess basedIntegratedManagementof constructedand Riverine wetlands for Optimalcontrol of wastewaterat catchmentScalE in boreal sub-basins“deals withvarious tools for the design and management of constructed wetlands.

The posterpresentsmethodologyof tracer testswith tritium and KBr andresultsobtainedfor two Polishwetlands.Potentialuseof stableisotopesof water(18O and 2H) as natural tracersin studiesof water flow dynamicsin large freewater flow constructed wetlands is discussed.

3He/3H dating of strongly benzene-contaminatedgroundwaters

Stephan M. Weise1, Stefan Gödeke2, Mario Schirmer3, Rolf Trettin1

1 UFZ Centre for Environmental Research, Isotope Hydrology Group, Halle, Germany,weise@halle.ufz.de, trettin@halle.ufz.de; 2 UFZ-Interdisciplinary Department ofIndustrial and Mining Landscapes, Leipzig, Germany, goedeke@pro.ufz.de; 3 UFZ-Department of Hydrogeology, Halle, Germany, schirmer@pro.ufz.de.

Tritium (3H; radioactive)is mainly releasedby bombteststill theearlysixtiesinto atmosphereand is – thougha quite imprecisetool – very commonastimemarkerin groundwaterinvestigations.Combiningfor datingpurposesthe parent3H with its daughter3He, the stableproduct of decay,improvesstrongly thedetermination of simple apparent groundwater ages (e.g. Weise & Moser 1987).

The test field is locatedon the site of a former hydrogenationplant in Zeitz(Saxonia-Anhalt,Germany).The upperaquifer is a 5-10 m layer of sandyandclayey depositsfrom the PleistoceneElster-glacial.The groundwatertable issituated8 to 10 m below surface.The Tertiary aquifer is composedof graveldepositedby an Eoceneriver, partly overlainby a lignite seamor silt andclaylayer of Tertiary age. Both aquifers are partly connectedhydraulically. Thegeneral groundwater flow direction in aquifer I is to the North, in aquifer II to theNorth-East.

From 1963 till 1990 in the easternpart of hydrogenationplant a benzeneproduction plant producedmore than 750,000 t of benzenewith maximumproductionrate in 1979 (79,000 t per year). Leaks and productionaccidentscontaminated groundwater.

The prevailing contaminantsof aquifer I are BTEX, dominatedby highbenzeneconcentrationsup to 500mg L-1. BTEX-concentrationsin theaquiferofTertiary age are considerablylower (100 mg L -1), and benzeneis again thedominant pollutant.

At threepositions,in 2000groundwatersamplesfor tritium and 3He analysesweretakenfrom both aquiferstrying to matchbeginning,centre,andendof thecontaminationplume. Samplesexhibit tritium contentsof about 10 TU, thegroundwaterfrom deepestwell 11.7 TU. Tritiugenic 3He contentsare in theupperaquiferbetween0 and3.3TUequivalent(1 TUequivalentis the 3He contentyieldedby the decayof 1 TU tritium) correspondingto 3He/tritium ratios of 0.31 andless,whereasin thedeeperaquifertritiugenic 3He wasfoundbetween19 and37TUequivalent, i.e. 3He/tritium varies in flow direction from 2.0 to 3.1. In termsofapparentgroundwateragesthesecontentscorrespondto 3 – 5 yearsin theupperand10 – 25 yearsin thedeeperaquifer(comp.figure 1). In caseof samplesfromthe deeper aquifer even increasing ‘ages’ in flow direction might be evident.

Theupperaquiferis phreatic,andtherefore3He contentstheremaybeaffectedby diffusive losses.However,tritium contentsin bothaquifersindicate‘ages’of

less than 15 years.The confinementof the deeperaquifer probablypreservesmost of tritiugenic 3He. Apparent groundwaterages in figure 1 indicate arechargein 1975 or younger.Thus, it is probablethat at least in the deeperaquifer the contaminant plume does not ‘flow’ together with the groundwater.

Figure 1. 3He/tritium ratios of groundwater samples and correlated apparent groundwater ages.The extreme situations piston flow and exponential mixing were assumed as flow conditions.

References

Weise,S. M. & Moser,H. 1987.Groundwaterdatingwith helium isotopes.InIsotope Techniquesin Water ResourcesDevelopment(International AtomicEnergy Agency IAEA, ed.), 105-126, International Atomic Energy AgencyIAEA, Vienna.

Oxygen and Hydrogen Isotopic Measurements forFood Authentication

Ryszard Wierzchnicki1, Nada Miljevic2, Andrzej G. Chmielewski1

1 Institute of Nuclear Chemistry and Technology, Warsaw, Poland,rwierzch@orange.ichtj.waw.pl; 2 Vinca Institute of Nuclear Sciences, Belgrade,Yugoslavia,

The stable isotope compositions of food are typical for its geographical originand place of manufacturing. This is the reason that they have been widely usedfor verification of food authenticity. The information about food origin is veryimportant because price of food is strongly connected with their origin.

Present-day methods of food adulteration are very sophisticated; therefore westill need new, more efficient and sensitive methods for their detection. Hydro-gen, oxygen, nitrogen and carbon compositions have been tested in many sorts offruits, vegetables and beverages. The collected data give a possibility to find therelationship between time and place of origin and sort of plants or foodstuff.

Hydrogen and oxygen composition are particularly interesting probes forgeographical origin and authenticity identification. The 18O/16O and D/1H isotoperatios of water from plants give interesting information about the environmentalconditions during their growing.

The aim of the study was to explore the relationship between isotopecompositions some kinds of food and its origin. The other aim was imple-mentation of new methods of measurements and sample preparation for labora-tory practice. It was especially interesting to look for relationship between theresults of measurements and food origin.

In this study, we have investigated many commercially available samples ofwine, juice and other beverages. Two different uncomplicated procedures usingcommercial available sample preparation apparatus H/Device and Gasbench wasemployed. The δ18O and δD contents of wine samples were determined using thenew techniques of gas sample preparation. During the study many data of winesmeasurement were stored. Exemplary data are presented to demonstrate theusefulness of the methods for food authenticity control. Mathematical correlationbetween stable isotope content δ18O and δD for analyzed wines was found. Therelationship between the δ18O analysed wines and geographical origin arediscussed.

The methods used provide two advantages: simple sample preparation and nottime-consuming. All processes are automatic and computer controlled. Theyshowed that could be applied to the analyses of other foodstuff. In summary, theimportance and usefulness of the IRMS technique associated with a samplepreparation unit GasbenchII, H/Device was demonstrated. Good precision ofmeasurements and proficiency of laboratory work were achieved.

Is quartz in Karkonosze granite postmagmaticallyreworked? Cathodoluminescence observations andoxygen isotopic signals of quartz from the Łomnica

granite

Andrzej Wilamowski1

1Institute of Geological Sciences, Polish Academy of Sciences, ul. Twarda 51/55, 00-818Warszawa, Poland, awilamow@twarda.pan.pl.

Granitecoresamplesfrom the 500 m deepboreholein the easternpart of theKarkonoszegranite(Poland)revealvaryingextentof thechloritizationof biotite,recordedalso in isotopic data.Unalteredbiotites haveδ18O and δD of about5and -85 ‰, respectively,while the highly chloritized samples2.8 and -50 ‰(Wilamowski, 2002).Chlorite geothermometersshowedtemperaturesfrom 315to 335°C. The verification of the temperatureof chlorite formation could beprovidedby theO-isotopegeothermometerinvolving two mineralphases,whichequilibrated isotopically and preservedthe attained isotopic signals. Besidechlorite, the choiceof the secondphasewasdifficult. Nevertheless,18 analysesof oxygenisotopesin quartzrevealedthespreadof δ18O valuesfrom 9.8 to 10.9‰. Fourteenquartzsampleshadδ18O 9.8 - 10.2‰ andthe remainingfour wereisotopically heavier.Cathodoluminescenceobservationsof quartz phenocrystsshowedtheir complexstructure(Figs 1, 2). Mostly abundantareround internalzones.Thesezonesaredarkerthanthesurroundingpartsof thequartzcrystal.Inthe quartz sample showing the isotopically heaviestoxygen, dimensionsofinternal zonesare small, as presentedin the Fig. 1a. Roughly estimated,darkzonesin this sampleconstituteup to 10%of thebulk quartzvolume.Thezoningmay be attributedeither to magmaticor to postmagmaticphenomena.In myinterpretation,dark zones are remnantsof the quartz not affected by thehydrothermalactivity. The round shapeof internal zones could be due torecrystallization,which proceededfrom theboundaryto the centreof the quartzgrain. It might be accompaniedby diffusion, as the bordersare not sharp.Thezoningmight also representthe varying conditionsof the quartzcrystallizationfrom the magma.However, the occurrenceof one dark zone commonfor anaggregateof phenocrystsof quartz(Fig. 1b) might indicateratherthe processofquartzgrainrecrystallizationstartingfrom theboundaryof theaggregatethantheprocessof crystallizationfrom the magma.As it is seenin Figs 1 and 2, thereoccuralsomorecomplexpatternsof zoning,which cannotbeeasilyinterpreted.The heaviest isotopic signal recorded, δ18O=10.9 ‰, was taken for thetemperatureestimationaccordingto Sharpand Kirschner(1994) and Cole andRipley (1999). It yieldedT = 297 °C by the fractionationvalue8.1, what is infair agreement with the results from the chlorite geothermometer.

Fig. 1abc (from the left). Corresponding images of the quartz phenocrysts of the size 3×2 mmtaken in CCL (upper row, computer-enhanced) and TLM.

Fig. 2abc. Continuation of figure 1.

References

Cole,D. R. & Ripley,E. M. 1999.Oxygenisotopefractionationbetweenchloriteandwaterfrom 170to 350degreesC: A preliminaryassessmentbasedon partialexchange and fluid rock experiments. Geochim. Cosmochim. Acta, 63, 449-457.Sharp, Z. D. & Kirschner, D. L. 1994. Quartz-calcite oxygen isotopethermometry: a calibration based on natural isotopic variations. Geochim.Cosmochim. Acta, 58, 4491-4501.Wilamowski, A. 2002. Chloritization and polytypism of biotite in the omnicagranite, KarkonoszeMassif, Sudetes,Poland:stable isotopeevidence.Chem.Geol., 182, 529-547.

Isotopic composition of minerals of native copperdeposits and occurrences of Ukraine

V.Zagnitko1, I.Kvasnytsya2, A.Senkevich3

1Institute of Geochemistry, Mineralogy and Ore Formation of NAS of Ukraine, Kyiv,Ukraine, igmof@mail.kar.net; 2Kyiv National University, Kyiv, Ukraine,irenek@bigmir.net; 3Institute of Metal Physics of NAS of Ukraine, Kyiv, Ukraine,senk@imp.kiev.ua

Severaldepositsandoccurrencesof nativecopperareknownon theterritory ofUkraine; their genesis is in discussion (Kvasnytsya et. al, 2001).

The Volynian depositsandoccurrenceshavebeendiscoveredin the Vendiantrappeanformation (Volyn'-Podolian plate). Thicknessof the copper-bearingeffusive-pyroclasticrocks (basaltsand their tuffs) is up to 450 meters.Nativecopperhas beenfound in massivebasalts,in hydrothermallyalteredmassivebasalts,in amygdaloidalbasalts,in lavabreccias,tuff brecciasandbasaltictuffs,andalsoin quartzveins.Nativecopperoccurswith chlorite,quartz,chalcedony,analcime,calcite, zeolites,barite,native silver, cuprite,malachite,and azurite.Native copper is representedby xenomorphicgrains and small crystals.Thecopperof the Volyn’ is very pure (up to 99.8%of Cu). It containsonly minorimpuritiesof Fe,Ag andsometimes,Au. The isotopiccompositionof oxygeninquartzis 11.66÷ 18.04‰,SMOW. The temperatureof formationof this quartzis 100-283oC. Thecalculationof isotopiccompositionof oxygenin water(δ18O= -3.17 ÷ -4.4‰, SMOW) equilibratedwith the quartzof such temperaturesindicatesthe essentialinfluence of meteoric waters on the formation of thecopper deposits. Isotopic composition of native copper differs on 9% incomparisonwith standardfor theseassociations.The isotopic compositionofcalcite from thesedepositsvaries within the limits of 19.31 ÷ 28.82‰ (δ18O,SMOW) and -0.31 ÷ -11.46‰ (δ13C, PDB).

Native copper,connectedwith strongly low-temperaturealteredmicaceousperidotites,hasbeenfound in Zhdanivintrusionon the southwesternpart of theBerdychiv block of the Ukrainian shield. Ultramafites consist of olivine,bronzite,phlogopite,hornblendeandchromspinels.Increasedcontentsof nativecopper,Au and Ag have beenconnectedwith hydrothermalalterationof theperidotites(silicification, carbonatizationand sulphidization).Native copperisrepresentedby micro dendrites,often in intergrowthswith hematite.The cubicform of growth prevailson dendrites.Compositionof nativecopperis 99.9%ofCu, 0.1%of Fe, tracesof Ag, Pt andNi. Theageof theZhdanivintrusionis notknown.It is suggestedto becompatiblewith alkali-ultramaficrocks(about2000Ma) on adjacentBug-Dnisterblock. The ageof later hydrothermalalterationofultramafites is not defined.

Table. Isotopic composition in quartz, calcite and water

Mineral δ18O δ13C δ18OH2ORock, mineral assemblage

Volynian deposits and occurrencesQuartz 13.46 Basalt with native copperQuartz 11.66 Tuff breccia with native copperQuartz 16.99 Quartz thread from basaltQuartz 18.04 Quartz thread from basaltQuartz 18.02 Quartz thread from basaltQuartz 13.83 Quartz thread from basaltQuartz 16.60 -4.4 Quartz vein with native copperQuartz 17.03 -4.4 Quartz vein with native copperQuartz 17.83 -3.17 quartz vein with native copperQuartz 17.53 -3.5 Quartz vein with native copperCalcite 21.20 -11.13 Tuff breccia with native copperCalcite 19.31 -8.70 Tuff breccia without native copperCalcite 22.78 -11.46 Tuff brecciaCalcite 28.82 -0.31 Carbonate breccia

Zhdaniv occurrenceCalcite 25.52 -10.54 UltrabasiteCalcite 25.52 -10.54 Ultrabasite

TheKurchytsioccurrenceof nativecoppermineralizationhasbeendiscoveredin polymetallic ores of Precambrianmetamorphizedcarbonaterocks of theVolyn’ megablock(the Ukrainian shield). Veinlet-disseminatedpolymetallicmineralizationhasbeenfound in dolomite-calcitemarbleandcalciphyre.Rock-forming minerals of ore zones are representedby diopside, forsterite,hornblende,phlogopite, serpentine,calcite and dolomite. Assemblageof oremineralsconsistsof galena,sphalerite,native copper,native lead, pyrrhotite,pyrite,chalcocite,chalcopyrite,greenockite,covellineandbornite.Copperformsxenomorphicgrains.Copperis very pureandcontainsonly minor impuritiesofAg, Pt, Sb and S. The lead-modelageof galenafrom Kurchytsi occurrenceis1890±70Ma. The isotopiccompositionof carbonin calciteis -3.0‰ of 13C andisotopiccompositionof oxygenin calciteis +26.5‰of 18O. The lower valueof13C and isotopic-heavy composition of oxygen suggests influence ofsedimentary-diagenetic processes on carbon isotopic composition.

Reference

Kvasnytsya,V.M., Zagnitko, V.M. and Kvasnytsya,I.V. 2001. Native copperoccurrencesof the West Ukraine. In Mineral Depositsat the Beginningof the21st century (Piestrzynski, A., ed.), pp. 595-597. Balkema, The Netherlands.