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Helictites—an enigmatic type of mineral structure occurring in some caves—differ from classical speleothems as they develop with orientations that defy gravity. While theories for helictite formation have been forwarded, their genesis remains equivocal. Here, we show that a remarkable suite of helictites occurring in Asperge Cave (France) are formed by biologically-mediated processes, rather than abiotic processes as had hitherto been proposed. Morphological and petro-physical properties are inconsistent with mineral precipitation under purely physico-chemical control.
Instead, microanalysis and molecular-biological investigation reveals the presence of a prokaryotic biofilm intimately associated with the mineral structures. We propose that microbially-influenced mineralization proceeds within a gliding biofilm which serves as a nucleation site for CaCO3, and where chemotaxis influences the trajectory of mineral growth, determining the macroscopic morphology of the speleothems. The influence of biofilms may explain the occurrence of similar speleothems in other caves worldwide, and sheds light on novel biomineralization processes.
Calcite spar (crystals >1 cm in diameter) are common in limestone and dolostone terrains. In the Guadalupe Mountains, New Mexico and west Texas, calcite spar is abundant and lines small geode-like caves. Determining the depth and timing of formation of these large scalenohedral calcite crystals is critical in linking the growth of spar with landscape evolution. In this study, we show that large euhedral calcite crystals precipitate deep in the phreatic zone (400–800 m) in these small geode-like caves (spar caves), and we propose both are the result of properties of supercritical CO2 at that depth. U-Pb dating of spar crystals shows that they formed primarily between 36 and 28 Ma. The 87Sr/86Sr values of the euhedral calcite spar show that the spar has a signifi cantly higher 87Sr/86Sr (0.710–0.716) than the host Permian limestone (0.706–0.709). This indicates the spar formed from waters that are mixed with, or formed entirely from, a source other than the surrounding bedrock aquifer, and this is consistent with hypogene speleogenesis at signifi cant depth. In addition, we conducted highly precise measurements of the variation in nonradiogenic isotopes of strontium, 88Sr/86Sr, expressed as 88Sr, the variation of which has previously been shown to depend on temperature of precipitation. Our preliminary 88Sr results from the spar calcite are consistent with formation at 50–70 °C. Our fi rst U-Pb results show that the spar was precipitated during the beginning of Basin and Range tectonism in a late Eocene to early Oligocene episode, which was coeval with two major magmatic periods at 36–33 Ma and 32–28 Ma. A novel speleogenetic process that includes both the dissolution of the spar caves and precipitation of the spar by the same speleogenetic event is proposed and supports the formation of the spar at 400–800 m depth, where the transition from supercritical to subcritical CO2 drives both dissolution of limestone during the main speleogenetic event and precipitation of calcite at the terminal phase of speleogenesis. We suggest that CO2 is derived from contemporaneous igneous activity. This proposed model suggests that calcite spar can be used for reconstruction of landscape evolution
Calcited issolution and gypsum precipitation is expected to occur when injecting CO2 in a limestone reservoir with sulfate - rich resident brine. If the reservoir is fractured, These reactions will take place mainly in the fractures, which serve as preferential paths for fluid flow. As a consequence, the geometry of the fractures will vary leading to changes in their hydraulic and transport properties. In this study, a set of percolation experiments which consisted of injecting CO 2 - rich solutions through fractured limestone cores were performed under P = 150 bar and T = 60 ºC . Flow rate s ranging from 0.2 to 60 mL/ h and sulfate - rich and sulfate - free solutions were used. Variation in fracture volume induced by calcite dissolution and gypsum precipitation was measured by X - ray computed microtomography (XCMT) and aqueous chemistry. An increase in flow rate led to an increase in volume of dissolved limestone per unit of time , which indicated that the calcite dissolution rate in the fracture was transport controlled. Moreover, the dissolution pattern varied from face dissolution to wormhole formation and uniform dissolution by increasing the flow rate (i.e., Pefrom 1 to 346 ). Fracture permeability always increased and depended on the type of dissolution pattern.
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