Modelling of dripwater hydrology and hydrogeochemistry in a weakly karstified aquifer : Implications for climate change studies

A better knowledge of dripwater hydrology in karst systems is needed to understand the palaeoclimate implications of temporal variations in Mg/Ca and Sr/Ca of calcareous cave deposits. Quantitative modelling of drip hydrology and hydrochemistry was undertaken at a disused limestone mine (Brown's Folly Mine) in SW England overlain by 15 m of poorly karstified Jurassic limestones, with sub-vertical fracturing enhanced by proximity to an escarpment. Discharge was monitored at 15 sites intermittently from the beginning of 1996, and every 10-20 days from later 1996 to early 1998. Samples for hydrochemical parameters (pH, alkalinity, cations, anions, fluorescence) were taken corresponding to a sub-set of these data and supplernented by bedrock and soil sampling, limited continuously logged discharge, and soil water observations. Three sites, covering the range of discharge (approximately 1 mu L s(-1) to 1 ml s(-1) maximum discharge) and hydrochemical behaviours, were studied in more detail. A quantitative flow model was constructed, based on two parallel unit hydrographs: responsive and relatively unresponsive to discharge events, respectively. The linear response and conservative mixing assumptions of the model were tested with hydrogeochemical data. Dripwaters at many of sites are characterized by evidence of prior calcite precipitation in the flowpath above the mine, which in the higher discharging sites diminishes at high flow. Also at low flow rates, dripwaters may access seepage reservoirs enriched in Mg and/or Sr, dependent on the site. The discharge at all three sites can be approximated by the flow model, but in each case, hydrochemical data show violations of the model assumptions. All sites show evidence of non-conservative mixing, and there are temporal discontinuities in behaviour, which may be stimulated by airlocks generated at low flow. Enhanced Mg/Ca and Sr/Ca often do relate to low-flow conditions, but the relationships between climate and hydrogeochemical response are non-linear. (c) 2005 Elsevier B.V. All rights reserved.