The Cryosphere Discussions www.the-cryosphere-discuss.net 1994-0432 1994-0440 4 3 2010 10.5194/tcd-4-1561-2010 http://www.the-cryosphere-discuss.net/4/1561/2010/ http://www.the-cryosphere-discuss.net/4/1561/2010/tcd-4-1561-2010.html http://www.the-cryosphere-discuss.net/4/1561/2010/tcd-4-1561-2010.pdf 1561 1591 2010-09-02 Glaciochemical investigations on the subterranean ice deposit of Vukušić Ice Cave, Velebit Mountain, Croatia Z. Kern kern@geochem.hu I. Fórizs N. Horvatinčić É. Széles N. Bočić B. Nagy Institute for Geochemical Research, Hungarian Academy of Sciences, Budapest, Hungary Laboratory for Measurements of Low-level Radioactivity, Ruđer Bošković Institute, Zagreb, Croatia Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary Department of Geography, Faculty of Science, University of Zagreb, Zagreb, Croatia Department of Physical Geography, Eötvös Loránd University, Budapest, Hungary The ³H activity, ¹⁸O/¹⁶O and ²H/¹H ratio and concentration of 33 metals and metalloids have been analysed on ice core samples from the perennial subterranean cave ice deposit of Vukušić Ice Cave, Velebit Mt. The tritium data suggested that the ice deposition at 2–2.4 m depth is build from precipitation fallen ~45 years before sampling and the uppermost ice layer could be estimated between early 1970s and early 1980s or between ~1954 and 1960. Both the fluctuation range of stable water isotopes and the derived isotopic waterline of the ice agree reasonably well with the corresponding data of the local precipitation. This fact predicts that the potential of Vukušić Ice Cave's ice deposit is superior for paleoclimatological studies to the nearby Ledena Pit. Principal component analysis helped to select three groups of elements. The Ca-Mg governed group (PC1) encompasses the bedrock related components; hence the fluctuation of these elements might reflect the past intensities of the dissolution process of the adjacent epikarst. The Zn governed group (PC2) preserves probably an atmospheric deposition signal and related to the emission of regional non-ferrous metallurgy. PC3 is governed by Al and Fe. This probably carries the distal, non-karstic crustal signal hence might be related to the past atmospheric circulation (i.e. wind direction and speed). Barbante, C., Schwikowski, M., Doring, T., Gäggeler, H. W., Schotterer, U., Tobler, L., van de Velde, K., Ferrari, C., Cozzi, G., Turetta, A., Rosman, K., Bolshov, M., Capodaglio, G., Cescon, P., and Boutron, C: Historical record of European emissions of heavy metals to the atmosphere since the 1650s from Alpine snow/ice cores drilled near Monte Rosa, Environ. Sci. Technol., 38, 4085–4090, 2004. Belmonte Ribas, A. B. and Marcén, C. S.: First data from a Pyrenean ice cave (A294 cave, Cotiella massif, Spain), in: 4th~International Workshop on Ice Caves, edited by: Spötl, C., Luetscher, M., and Rittig, P., Volume of Abstracts, 7, 2010. Boutron, C. F. and Batifol, F. M.: Assessing laboratory procedures for the decontamination of polar snow or ice samples for the analysis of toxic metals and metalloids, Ann. Glaciol., 7, 7–11, 1985. Bronk Ramsey, C.: Development of the Radiocarbon Program OxCal, Radiocarbon, 43(2A), 355–363, 2001. Chueca, J., Julián, A., Saz, M. A., Creus, J., and López-Moreno, J. I.: Responses to climatic changes since the Little Ice Age on Maladeta Glacier (Central Pyrenees), Geomorphology, 68, 167–182, 2005. Citterio, M., Diolaiuti, G., Smiraglia, C., D'Agata, C., Carnielli, T., Stella, G., and Siletto, G. B.: The Fluctuations of Italian Glaciers during the Last Century: A Contribution to Knowledge about Alpine Glacier Changes, Geogr. Ann A, 89, 167–184, 2007. Citterio, M., Turri, S., Bini, A., Maggi, V., Pelfini, M., Pini, R., Ravazzi, C., Santillini, M., Stenni, B., and Udisti, R.: Multidisciplinary approach to the study of the LoLc~1650 "Abisso sul margine dell'Alto Bregai" ice cave (Lecco, Italy), Theor. Appl. Karst., 17, 27–44, 2004a. Citterio, M., Turri, S., Bini, A., and Maggi, V.: Observed trends in the chemical composition, $\delta^18$O and crystal sizes vs depth in the first core from the LoLc~1650 "Abisso sul margine dell'Alto Bregai" ice cave (Lecco, Italy), Theor. Appl. Karst., 17, 45–50, 2004b. Clausen, H. B., Vrana, K., Hansen, S. B., Larsen, L. B., Baker, J., Siggaard-Andersen, M.-L., Sjolte, J., and Lundholm, S. C.: Continental ice body in Dobšiná Ice Cave (Slovakia) – part~II. – Results of chemical and isotopic study, in: Proceedings of the 2nd~International Workshop on Ice Caves Liptovsky Mikulás, edited by: Zelinka, J., 29–37, 2007. Craig, H.: Isotopic variations in meteoric waters, Science, 133, 1702–1703, 1961. Curie, L. A.: Nomenclature in evaluation of analytical methods including detection and quantification capabilities, IUPAC Recommendation~1995, Pure Appl. Chem., 67, 1699–1723, 1995. Dansgaard, W.: Stable isotopes in precipitation, Tellus, 16/4, 436–468, 1964. D'Orefice, M., Pecci, M., Smiraglia, C., and Ventura, R.: Retreat of Mediterranean glaciers since the Little Ice Age: case study of Ghiacciao del Calderone, Central Apennines, Italy, Arct. Antarct. Alp. Res., 32/2, 197–201, 2000. Eichler, A., Schwikowski, M., and Gaggeler, H. W.: Meltwater-induced relocation of chemical species in Alpine firn, Tellus~B, 53(2), 192–203, 2001. EMEP: http://tarantula.nilu.no/projects/ccc/sitedescriptions/hr/index.html, last access: 12~July~2010. Epstein, S. and Mayeda, T.: Variation of $^18$O content of waters from natural sources, Geochim. Cosmochim. Acta, 4, 89–103, 1953. Eriksson, E.: An account of the major pulses of tritium and their effects in the atmosphere, Tellus, 17, 118–130, 1965. Fairchild, I. J. and Treble, P. C.: Trace elements in speleothems as recorders of environmental change, Quaternary Sci. Rev., 28, 449–468, doi:10.1016/j.quascirev.2008.11.007, 2009. Fórizs, I.: Processes behind the isotopic water line: water cycle and climate, Stud. Univ. Babes-Bolyai, Physica, 50/3, 138–146, 2005. Gabrielli, P., Cozzi, G., Torcini, S., Cesconi, P., and Barbante, C.: Trace elements in winter snow of the Dolomites (Italy): a statistical study of natural and anthropogenic contributions, Chemosphere, 72, 1504–1509, 2008. Gabrovec, M.: Triglavski ledenik med letoma 1986 in 1998 [The Triglav glacier between 1986 and 1998], Geogr. Zbornik, 38, 89–105, 1998. González Trueba, J. J., Martín Moreno, R., Martínez de Pisón, E., and Serrano, E.: "Little Ice Age" glaciation and current glaciers in the Iberian Peninsula, Holocene, 18(4), 551–568, 2008. Grünewald, K., Weber, C., Scheithauer, J., and Haubold, F.: Mikrogletscher im Piringebirge (Bulgarien), Z. Gletscherkd. Glazialgeol., 39, 99–114, 2006. Grünewald, K. and Scheithauer, J.: Bohrung in einen Mikrogletscher, Z. Gletscherkd. Glazialgeol., 42(1), 3–18, 2008. Grünewald, K. and Scheithauer, J.: Europe's southernmost galciers: response and adaptation to climate change, J. Glaciol., 195, 129–142, 2010. He, Y., Tandong, Y., Guodong, C., and Meixue, Y.: Climatic records in a firn core from an Alpine temperate glacier on Mt Yulong, southeastern part of the Tibetan Plateau, Episodes, 24, 13–18, 2001. Horvatinči\'c, N.: Isotopic measurement in ice, Ledenica Cave, Velebit, Croatia, in: Proceedings of the third symposium of the Croatian Radiation Protection Association, edited by: Kubelka, D. and Kovač, J., Zagreb, 297–302, 1996. Horvatinči\'c, N., Bareši\'c, J., Krajcar Broni\'c, I., and Obeli\'c, B.: Measurement of low $^14$C activities in liquid scintillation counter in the Zagreb Radiocarbon Laboratory, Radiocarbon, 46, 105–116, 2004. Horvatinči\'c, N., Krajcar Broni\'c, I., Bareši\'c, J., Obeli\'c, B., and Vidič, S.: Tritium and stable isotope distribution in the atmosphere at the coastal region of Croatia, in: Isotopic composition of precipitation in the Mediterranean Basin in relation to air circulation patterns and climate, edited by: Gourcy, L., IAEA-TECDOC-1453, 37–50, 2005. Hughes, P. D.: Recent behaviour of the Debeli Namet glacier, Durmitor, Montenegro, Earth Surf. Proc. Land., 32(10), 1593–1602, 2007. Hughes, P. D.: Response of a Montenegro glacier to extreme summer heatwaves in 2003 and 2007, Geogr. Ann A, 90(4), 259–267, 2008. Hughes, P. D.: Twenty-first century glaciers and climate in the Prokletije Mountains, Albania, Arct., Antarct. Alp. Res., 41(4), 455–459, 2009. IAEA 2004: Isotope Hydrology Information System, The ISOHIS Database, http://isohis.iaea.org, last access: 17~March~2010. Jeleni\'c, I., Horvatinči\'c, N., and Boži\'c, V.: Ledena Jama (The Ice Pit) in Lomska Duliba, Senjski zbornik, 28, 5–20, 2001. Jolliffe, I. T.: Principal component analysis, second edition, Springer-Verlag New York, Inc., New York, 2002. Kern, Z., Surányi, G., Molnár, M., Nagy, B., and Balogh, D.: Investigation of natural perennial ice deposits of Durmitor Mts, Montenegro, in: Proceedings of the 2nd International Workshop on Ice Caves, edited by: Zelinka, J., Liptovsk\'y Mikuláš, 70–73, 2007. Kern, Z., Boči\'c, N., Horvatinči\'c, N., Fórizs, I., Nagy, B., and László, P.: Palaeoenvironmental records from ice caves of Velebit Mountains – Ledena Pit and Vukuši\'c Ice Cave, Croatia, in: 3rd~International Workshop on Ice Caves Proceedings, edited by: Kadebskaya, O., Mavlyudov, B. R., and Pyatunin, M., Kungur, 108–113, 2008. Kern, Z., Fórizs, I., Perşoiu, A. and Nagy B.: Stable isotope study of water sources and of an ice core from the Bortig Ice Cave, Romania, Data Glac. Stud. (Materialy Glyatsiologicheskikh Issledovaniy), 107, 175–182, 2009. Kuhta, M.: Inventarizacija speleoloških objekata na području Nacionalnog parka "Sjeverni Velebit", Inventarisation of the speleological features in the area of the National part "Sjeverni Velebit", Speleološki klub Željezničar Speleological club Željezničar, Zagreb, 52~pp., 2002. Lacelle, D., Lauriol, B., and Clark, I. D.: Formation of seasonal cave ice and associated cryogenic carbonates in Caverne de l'Ours, Québec, Canada, Kinetic isotope effects and pseudo-biogenic crystal structures, J. Cave Karst Stud., 71, 48–62, 2009. Lucas, L. L. and Unterweger, M. P.: Comprehensive review and critical evaluation of the half-life of tritium, J. Res. Natl. Inst. Stan., 105, 541–549, 2000. Luetscher, M.: Process in ice caves and their significance for paleoenvironmental reconstructions, PhD thesis, SISKA, Switzerland, 51~pp., 2005. Luetscher, M. and Jeannin, P.: A process-based classification of alpine ice caves, Theor. Appl. Karst., 17, 5–10, 2004. Luetscher, M., Bolius, D., Schwikowski, M., Schotterer, U., and Smart, P. L.: Comparison of techniques for dating of subsurface ice from Monlesi ice cave, Switzerland, J. Glaciol., 53/182, 374–384, 2007. Mavlyudov, B. R.: Snow and ice formations in caves and their regime, in: Proceeding of the 10th~International Congress of Speleology, Budapest, 295–297, 1989. Mavlyudov, B. R.: Oledenie pescher (Caves glaciation: in Russian) Russian Academy of Sciences, Moscow, Russia, 2008. McKinney, C. R., McCrea, J. M., Epstein, S., Allen, A., and Urey, H. C.: Improvements in mass spectrometers for the measurement of small differences in isotope abundance ratios, Rev. Sci. Instrum., 21, 724–730, 1950. Mihevc, A.: Ice change in the caves of Slovenia shown by the old literature, Data Glac. Stud. (Materialy Glyatsiologicheskikh Issledovaniy), 107, 107–174, 2009. Paul, D., Skrzypek, G., and Fórizs, I.: Normalization of measured stable isotopic compositions to isotope reference scales – a review, Rapid Commun. Mass Sp., 21(18), 3006–3014, doi:10.1002/rcm.3185, 2007. Paterson, W. S. B.: The physiscs of glaciers, Pergamon, Oxford, 1994. Perşoiu, A.: Ice speleothemes in Scãrişoara Cave: dynamics and controllers, Theor. Appl. Karst., 17, 71–76, 2004. Perşoiu, A., Bojar, A.-V., and Onac, B. P.: Stable isotopes in cave ice: what do they tell us?, Stud Univ Babeş-Bolyai, Geologia, 52/1, 59–62, 2007. Poljanac, M., Svedek, I., and Kos, R.: Republic of Croatia informative inventory report to LRTAP convention for 2008, Submission to the Convention on Long-range Transboundary Air Pollution, EKONERG Ltd, Zagreb, 172~pp., 2010. Pavšek, M.: Ledenik pod Skuto kot pokazatelj podnebnih sprememb v slovenskem delu Alp, The Skuta Glacier as an Indicator of Climate Changes in Slovenian Part of the Alps, Dela, 28, 207–219, 2007. Pavšek, M.: Ledeniki, Vzajemna, 2, 10–15, 2010. Prosser, S. J. and Scrimgeour, C. M.: High-precision determination of ²H/$^1$H in H₂ and H₂O by continuous-flow isotope ratio mass spectrometry, Anal. Chem., 67, 1992–1997, 1995. Reimer, P. J., Baillie, M. G. L., Bard, E., Bayliss, A., Beck, J. W., Bertrand, C., Blackwell, P. G., Buck, C. E., Burr, G., Cutler, K. B., Damon, P. E., Edwards, R. L., Fairbanks, R. G., Friedrich, M., Guilderson, T. P., Hughen, K. A., Kromer, B., McCormac, F. G., Manning, S., Bronk Ramsey, C., Reimer, R. W., Remmele, S., Southon, J. R., Stuiver, M., Talamo, S., Taylor, F. W., van der Plicht, J., and Weyhenmeyer, C. E.: IntCal04 terrestrial radiocarbon age calibration, 0–26 cal kyr BP, Radiocarbon, 46, 1029–1058, 2004. Roether, W.: Estimating the tritium input to groundwater from wine samples: ground-water and direct run-off contribution to central European surface waters, in: Proceedings of IAEA Conference on Isotopes in Hydrology, IAEA, Vienna, 73–90, 1967. Rozanski, K., Araguás-Araguás, L., and Gonfiantini, R.: Isotopic patterns in modern global precipitation in.: Climate change in continental isotopic records, Geophys. Monogr., 78, 1–36, 1993. Saaroni, H., Ziv, B., Edelson, J., and Alpert, P.: Long-term variations in summer temperatures over the Eastern Mediterranean, Geophys. Res. Lett., 30, 1946, doi:10.1029/2003GL017742, 2003. Sarıkaya, M. A., Zreda, M., amd Çiner, A.: Glaciations and paleoclimate of Mount Erciyes, central Turkey, since the Last Glacial Maximum, inferred from $^36$Cl cosmogenic dating and glacier modelling, Quaternary Sci. Rev., 28, 2326–2341, doi:10.1016/j.quascirev.2009.04.015, 2009. Schwikowski, M.: Reconstruction of European Air Pollution from Alpine Ice Cores, in: Earth Paleoenvironments: Records Preserved in Mid- and Low-Latitude Glaciers, edited by: Cecil, J. R. G. and Thompson, L. G., Kluwer Academic Publishers, Dordrecht, 95–119, 2004. SDH: Speleološki objekti na karti 1:50 000 Senj~1, Speleological features on the map 1:50 000 Senj~1, Speleološko društvo Hrvatske, Croatian speleological society, Zagreb, 18~pp., 1962. Špoler Čani\'c, K., Vidič, S., and Klai\'c Z. B.: Precipitation chemistry in Croatia during the period 1981–2006, J. Environ. Monitor., 11, 839–851, doi:10.1039/b816432k, 2009. Thompson, L. G.: Ice core studies from Mt Kenya, Africa, and their relationship to other tropical ice core studies, in: Proc of Sea Level, Ice and Climatic Change, edited by: Allison, I., International Association of Hydrological Sciences Publ No 131, 55–62, 1980. Tošič, I.: Spatial and temporal variability of winter and summer precipitation over Serbia and Montenegro, Theor. Appl. Climatol., 77, 47–56, 2004. Vreèa, P., Krajcar Broni\'c, I., Horvatinči\'c, N., and Barešic, J.: Isotopic characteristics of precipitation in Slovenia and Croatia: Comparison of continental and maritime stations, J. Hydrol., 330, 457–469, 2006. Xoplaki, E., González-Rouco, J. F., Luterbacher, J., and Wanner, H.: Mediterranean summer air temperature variability and its connection to the large-scale atmospheric circulation and SSTs, Clim. Dynam., 20, 723–739, doi:10.1007/s00382-003-0304-x, 2003.