The isotopic geochemistry of speleothems--I. The calculation of the effects of different modes of formation on the isotopic composition of speleothems and their applicability as palaeoclimatic indicators

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The effects of different modes of formation on the isotopic composition of speleothems has been examined to delineate the conditions under which they may be used to give palaeo-climatic data. The modes of deposition considered were: equilibrium loss of CO 2 , kinetic loss of CO 2 , and evaporation of water. If isotopic equilibrium is maintained between HCO 3 - and CO 2(aq) the calcite precipitated will be in isotopic equilibrium with the water and variations in 18 O / 16 O will depend on climate alone, variations in 13 C / 12 C will be independent of climate. This will occur if the loss of CO 2 from solution is slow. If loss of CO 2 is rapid a kinetic fractionation will occur between HCO 3 - and CO 2(aq) and the calcite precipitated will show a simultaneous enrichment in 13 C and 18 O. If evaporation of water occurs the calcite precipitated will be enriched in 18 O and will be close to 13 C and 14 C equilibrium with the cave atmosphere. Speleothems deposited under conditions of kinetic loss of CO 2 or evaporation of water cannot be used to give palaeoclimate data.

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