J. A. Cruz

Trace Elements in Speleothems as Indicators of Past Climate and Karst Hydrochemistry: A Case Study from Kaite Cave (N Spain)

A stalagmite that grew during the Holocene (between 4.9 and 0.9 ka BP) in Kaite Cave (Ojo Guarena Karst Complex, Burgos, N Spain) has been analyzed by Laser-Induced Breakdown Spectroscopy (LIBS) with the aim of reconstructing secular variations in the hydrochemistry of the karst system, in turn related to changes in the environment outside the cave. LIBS analyses yield significant changes in Mg/Ca and Sr/Ca intensity ratios through the stalagmite, which reveal consistent trends and patterns at decadal to centennial scales. The origin of the observed changes in Mg/Ca and Sr/Ca ratios is discussed in the framework of the cave system and the regional climatic variability, particularly the changes in precipitation.

Vaterite Stability in the Presence of Chromate

ABSTRACT Vaterite aggregates grown in Cr(VI)-bearing silica gel were studied by combining scanning electron microscopy and Raman spectroscopy. All the vaterite samples were spherical aggregates consisting of lens-shaped individuals, and their morphology was distinctive for vaterite. Raman spectra corresponding to the aggregates grown in gels containing high Cr(VI) concentrations showed the typical bands of vaterite. However, in contrast to their morphology, the Raman spectra of the aggregates grown in the presence of lower Cr(VI) concentrations exclusively showed bands characteristic of calcite. These aggregates are interpreted as calcite pseudomorphs formed after vaterite through a replacement process. The replacement involves the interface coupling of the dissolution of vaterite and the precipitation of the stable polymorph calcite. The fact that only those vaterite aggregates formed in the presence of low Cr(VI) concentrations transformed into calcite indicates the presence of high Cr(VI) concentrations in the growth medium contributes to stabilize vaterite and prevents its transformation into calcite in the short term.