An optimized thermal extraction system for preparation of water from fluid inclusions in speleothems.

Authors

  • E. CABALLERO Instituto Andaluz de Ciencias de la Tierra, CSIC. Fuentenueva 18071 Granada, Spain.
  • J.A. VERA departamento de estratigrafía y Paleontología, Facultad de Ciencias, Universidad de Granada. Fuentenueva 18071 Granada, Spain.
  • B. ANDREO departamento de Geología, Facultad de Ciencias, Universidad de Málaga. Campus de Teatinos E-29071 Málaga, Spain.

DOI:

https://doi.org/10.1344/105.000001646

Keywords:

Fluid inclusions, Speleothems, Paleoclimate, Stable isotopes

Abstract

The fluid inclusions present in speleothems (secondary mineral deposits formed in caves) are a relict sample of the parent seepage water from which the speleothem was deposited and determination of their composition can solve the palaeotemperature equation for the precipitation of speleothem carbonate. We have extracted fluid inclusions using a newly-designed thermal vacuum extraction method in stalagmites and stalactites from Nerja Cave, Southern Spain. Optimal conditions were found to involve heating samples crushed to 0.8-2mm for 3 hours at 300-400ºC. Waters extracted from modern aragonitic speleothem samples produced results on the Meteoric Water Line defined by modern infiltration and other waters associated with the cave and hence demonstrate an absence of fractionation effects. This successfully demonstrates the utility of the method.

References

Andreo, B., Liñán, C., Carrasco, F., Jiménez de Cisneros, C., Caballero, E., Mudry, J., 2004 Influence of rainfall quantity on the isotopic composition (18O and 2 H) of water in mountainous areas. Application for groundwater research in the Yunquera-Nieves karst aquifers (S Spain). Applied Geochemistry, 19, 561-574.

Bar-Matthews, M., Ayalon, A., Kaufman, A., Wasserburg, G.J., 1999. The Eastern Mediterranean paleoclimate as a reflection of regional events: Soreq Cave, Israel. Earth and Planetary Science Letters, 166, 85-95.

Caballero, E., Jiménez de Cisneros, C., Reyes, E. 1996. A stable isotope study of cave seepage waters. Applied Geochemistry, 11, 583-587.

Craig, H., 1961. Isotopic variations in meteoric waters. Science, 133, 1708-1708.

Dennis, P.F., Rowe, P.J., Atkinson, T.C., 1996. Isotopic composition of paleoprecipitation and paleogroundwaters from speleothem fluid inclusions. Whiteknights (United Kingdom), J.N. Andrews Memorial Meeting, University of Reading, 15-16.

Dennis, P.F., Rowe, P.J., Atkinson, T.C., 1998. Stable isotope composition of paleoprecipitation and paleogroundwaters from speleothem fluid inclusions. In: International Atomic Energy Agency (eds.). Isotope Techniques in the Study of Environmental Change. Vienna, 663-671.

Dennis, P.F., Rowe, P.J., Atkinson, T.C., 2001. The recovery and isotopic measurement of water from fluid inclusions in speleothems. Geochimica et Cosmochimica Acta, 65(6), 871-884.

Drysdale, R.N., Zanchetta, G., Hellstrom, J.C., Fallick, A.E., Zhao, J., Isola, I., Bruschi, G., 2004. Palaeoclimatic implications of the growth history and stable isotope (δ18O and δ13C) geochemistry of a Middle to Late Pleistocene stalagmite from central-western Italy. Earth and Planetary Science Letters, 227, 215-229

Durán, J.J., Grün, R., Ford, D.C., 1993. Dataciones geocronológicas absolutas (Métodos E.S.R. y Series de Uranio) en la Cueva de Nerja y su entorno. Implicaciones evolutivas, paleoclimáticas y neosintectónicas. In: Carrasco, F. (ed.). Trabajos sobre la Cueva de Nerja. Málaga, Patronato de la Cueva de Nerja 3, 233-248.

Epstein, S., Mayeda, T., 1953. Variations of 18O content of waters from natural sources. Geochimica et Cosmochimica Acta, 4, 213-224.

Fairchild, I.J., Borsato, A., Tooth, A.F., Frisia, S., Hawkesworth, C.J., Huang, Y., McDermott, F, Spiro, B., 2000. Controls on trace element (Sr-Mg) compositions of carbonate cave waters: implications for speleothem climatic records. Chemical Geology, 166, 255-269.

Fairchild, I.J., Smith, C.L., Baker, A., Fuller, L., Spötl, C., Mattey, D., McDermott, F., 2006. Modification and preservation of environmental signals in speleothems. Earth Science Reviews, 75, 105-153.

Folk, R.L., Assereto, R., 1976. Comparative fabrics of lenghtslow and lenght-fast calcite and calcitized aragonite in a Holocene speleothem. Carlsbad Caverns, New Mexico. Journal Sedimentary Petrology, 46, 486-496.

Friedman, I., O’Neil, J.R., 1977. Compilation of stable isotope fractionation factors of geochemical interest. In: Fleischer, M. (ed.). Data of Geochemistry, sixth edition, United States. Geological Survey, Washington DC, Chapter KK(Professional Paper), 440-KK.

Frisia, S., Borsato, A., Fairchild, I., McDermott, F., 2000. Calcite fabrics, growth mechanismsand environments of formation in speleothems from the Italian Alps and Southwestern Ireland. Journal Sedimentary Research, 70(5), 1183-1196.

Frumkin, A., Ford, D.C., Schwarcz, H.P., 1999. Continental oxygen isotopic record of the last 170,000 years in Jerusalem. Quaternary Research, 51, 317-327.

Gascoyne, M., Ford, D.C., Schwarcz, H.P., 1981. Late Pleistocene chronology and paleoclimate of Vancouver Island determined from cave deposits. Canadian Journal of Earth Science, 18, 1643-1652.

Gat, J.R., 1980. The isotopes of hydrogen and oxygen in precipitation. In: Fritz, P., Fontes, G. (eds.). Handbook of Environmental Isotope Geochemistry. Amsterdam/Oxford/New York, Elsevier, 1, 21-47.

Gat, J.R., Carmi, I., 1987. Effect of climate changes on the precipitation patterns and isotopic composition of water in a climate transition zone: case of the Eastern Mediterranean Sea area. The influence of Climate Change and Climatic Variability on the hydrologic Regime and Water Resources. Proceedings of the Vancouver Symposium. International

Association Hydrological Sciences Publication, 168, 513-523.

Genty, D., Plagnes, V., Causse, Ch., Cattani, O., Stievenard, M., Falourd, S., Blamart, D., Ouahdi, R., Van-Exter, S., 2002. Fossil water in large stalagmite voids as a tool for paleoprecipitation stable isotope composition reconstitution and paleotemperature calculation. Chemical Geology, 184, 83-95.

Goede, A., Green, D.C., Harmon, R.S., 1986 Late Pleistocene palaeotemperature record from a Tasmanian speleothem. Australian Journal Earth Science, 33, 333-342.

Goede, A., Veeh, H.H., Aycliffe, L.K., 1990. Late Quaternary paleotemperature records for two Tasmanian speleothems. Australian Journal Earth Science, 37, 267-278.

González, L.A., Carpenter, S.J., Lohmann K.C., 1992. Inorganic calcite morphology: roles of fluid flow. Journal Sedimentary Petrology, 62, 383-399.

González, L.A., Carpenter, S.J., Lohmann K.C., 1993a. Columnar calcite speleothems: reply. Journal Sedimentary Petrology, 63, 553-556.

González, L.A., Carpenter, S.J., Lohmann K.C., 1993b. Inorganic calcite morphology: roles of fluid chemistry and fluid flowreply. Journal Sedimentary Petrology, 63, 562-563.

Grossman, E.L., Ku, T.L., 1986. Oxygen and carbon isotope fractionation in biogenic aragonite: temperature effect. Chemical Geology, 59, 59-74.

Harmon, R.S., Schwarcz, H.P., O’Neil, J.R., 1979. D/H ratios in speleothem fluid inclusions: A guide to variations in the isotopic composition of meteoric precipitation? Earth and Planetary Science Letters, 42, 254-266.

Hendy, C.H., Wilson, A.T., 1968. Paleoclimatic data from speleothems. Nature, 219, 48-51.

Hendy, C.H., 1971. The isotopic geochemistry of speleothems. I. The calculation of the effect of different modes of formation on the isotopic composition of speleothems and their applicability as paleoclimatic indicators. Geochimica et Cosmochimica Acta, 35, 807-824.

Holmgren, K., Karlen, W., Lauritzen, S.E., Lee Thorp, J.A., Partridge, T.C., Piketh, S., Repinski, P., Stevenson, C., Svanered, O., Tyson, P.D., 1999. A 3000-year high-resolution stalagmite-based record of palaeoclimate for North-eastern South Africa. Holocene, 9, 295-309.

Ivanovich, M., Harmon, R.S., 1992 Uranium-series disequilibrium. Application to Earth, Marine and Environmental Sciences. 2nd edition, Clarendon Press, Oxford Science, 910pp.

Jiménez de Cisneros, C., Caballero, E., Vera, J.A., Durán, J.J., Juliá, R., 2003. A record of Pleistocene climate from a stalactite, Nerja Cave, southern Spain. Palaeogeography, Palaeoclimatology, Palaeoecology, 189, 1-10.

Kendall, A.C., Brougton, P., 1978. Origin of fabrics in speleothems composed of columnar calcite crystals. Journal Sedimentary Petrology, 48, 519-538.

Kendall, A.C., Brougton, P., 1993. Columnar calcite speleothems: discussion. Journal Sedimentary Petrology, 63, 550-552.

Matthews, A., Ayalon, A., Bar-Matthews, M., 2000. D/H ratios of fluid inclusions of Soreq cave (Israel) speleothems as a guide to the Eastern Mediterranean Meteoric Line relationship in the last 120 ky. Chemical Geology, 166, 183-191.

McDermott, F., 2004. Palaeoclimate reconstruction from stable isotope variations in speleothems: a review. Quaternary Science Review, 23, 901-918.

McDermott, F., Mattey, D.P., Hawkesworth, C., 2001. Centennialscale Holocene climate variability revealed by a high-resolution speleothem δ18O record from SW Ireland. Science, 292(5545), 1328-1331.

McDermott, F., Schwarcz, H.P., Rowe, P.J., 2006. Isotopes in speleothems. In: Leng, M.J. (ed.). Isotopes in Palaeoenvironmental Research. Dordrecht (The Netherlands), Springer, 185-226.

McGarry, S., Bar-Matthews, M., Matthews, A., Vaks, A., Schilman, B., Ayalon, A., 2004. Constraints on hydrological and paleotemperature variations in the Eastern Mediterranean region in the last 140ka given by the δD values of speleothem fluid inclusions. Quaternary Science Reviews, 23, 919-934.

Morrison, J., Brockwell, T., Merren, T., Fourel, F., Phillips, A.M., 2001. On-line high-precision stable hydrogen isotopic analyses on nanoliter water samples. Analytical Chemistry, 73(15), 3570-3575.

Nelson, S.T., 2000. A simple, practical methodology for routine VSMOW/SLAP normalization of water samples analyzed by continuous flow methods. Rapid Communications in Mass Spectrometry, 14(12), 1044-1046.

Nelson, S.T., Dettman, D., 2001. Improving hydrogen isotope ratio measurements for on-line chromium reduction systems. Rapid Communications in Mass Spectrometry, 15(23), 2301-2306.

O’Neil, J.R., Clayton, R.N., Mayeda, T.K., 1969 Oxygen isotope fractionation in divalent metal carbonates. Journal Chemical Physics, 51, 5547-5558.

Rozanski, K., Dulinski, M., 1987. Deuterium content of European paleowaters as inferred from the isotopic composition of fluid inclusions trapped in carbonate cave deposits. Vienna, International Atomic Energy Agency (IAEA), SM-299/99, 565-578.

Rowe, P.J., Dennis, P.F., Atkinson, T.C., Lauritzen, S.E., Lundberg, J., 1998. High resolution deuterium record from fluid inclusion in a Late Holocene speleothem from SW Britain. Past Global Changes and their Significance for the Future. London, First International Geophere Biosphere Programme, Past Global Changes (IGBP PAGES), Open Science Meeting, 112.

Schwarcz, H.P., Yonge, C., 1983. Isotopic composition of paleowaters as inferred from speleothem and its fluid inclusions. In: Gonfiantini, R. (ed.). Paleoclimates and Paleowaters: A collection of Environmental Isotope Studies. International Atomic Energy Agency (IAEA), STI/PUB/621, 115-133.

Schwarcz, H.P., Harmon, R.S., Thompson, P., Ford, D.C., 1976. Stable isotope studies of fluid inclusions in speleothems and their paleoclimatic significance. Geochimica et Cosmochimica Acta, 40, 657-665.

Siklosy, Z., Demeny, A., Vennemann, T.W., Kramers, J., Lauritzen, S.E., Lee-Ossy, S.Z., 2007. Middle bronze age climate change recorded in a Hungarian stalagmite: triggering by volcanic activity? Geophysical Research Abstracts, 9, 1607-7962/gra/EGU2007-A-00777.

Tămaş, T., Onac, B.P., Bojar, A., 2005. Late glacial-Middle Holocene stable isotope records in two coeval stalagmites from the Bihor Mountains, NW Romania. Geological Quarterly, 49(2), 185-194.

Treble, P.C., Chappell, J., Gagan, M.K., McKeegan, K.D., Harrison, T.M., 2005. In situ measurement of seasonal δ18O variations and analysis of isotopic trends in a modern speleothem from southwest Australia. Earth Planetary Science Letters, 233, 17-32.

Verheyden, S., Genty, D., Cattani, O., Van Breukelen, M.R., 2008. Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions. Chemical Geology, 247, 266-281.

Vonhof, H.B., Van Breukelen, M.R., Postma, O., Rowe, P.J., Atkinson, T.C., Kroon, D., 2006. A continuous-flow crushing device for on-line δ2 H analysis of fluid inclusion water in speleothems. Rapid Communications in Mass Spectrometry, 20, 2553-2558.

Wang, Y.J., Cheng, H., Edwards, R.L., An, Z.S., Wu, J.Y., Shen, C.C., Dorale, J.A. 2001. A High-Resolution Absolute-Dated Late Pleistocene Monsoon Record from Hulu Cave, China. Science, 294, 2345.

Wilburn, F.W., Sharp, J.H., 1993. The bed-depth effect in the thermal decomposition of carbonates. Journal Thermal Analysis, 40, 133-140.

Yonge, C.J., 1982. Stable isotope studies of water extracted from speleothems. Doctoral Thesis. Canada, McMaster University, Hamilton, Ontario, 298pp.

Yonge, C.J., Ford, D.C., Gray, J., Schwarcz, H.P., 1985. Stable isotope studies of cave seepage water. Chemical Geology (Isotope Geosc. Section), 58, 97-105.

Yonge, C.J., 1981. Fluid inclusions in speleothems as palaeoclimatic indicators. In: Beck, BF. (ed.). Proceedings of the 8th International Congress of Speleology. Bowling Green (Kentucky), International Union of Speleology, 1, 301-304.

Zhang, R., Schwarcz, H.P., Ford, D.C., Schroeder, F.S., Beddows, P.A., 2008. An absolute paleotemperature record from 10 to 6Ka inferred from fluid inclusion D/H ratios of a stalagmite from Vancouver Island, British Columbia, Canada. Geochimica et Cosmochimica Acta, 72, 1014-1026.

Downloads

Published

2011-07-14

Issue

Section

Articles