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Water quality at many karst springs undergoes very high amplitude but relatively brief degradation following influxes of runoff. Accurately recording transient variations requires more rigorous sampling strategies than traditional methods. A pilot study to determine the usefulness of high‐frequency, flow‐dependent sampling strategies, combined with coincidental quantitative dye tracer tests, was implemented in the Big Spring Ground‐Water Basin in Mammoth Cave National Park, Kentucky. Data recorded following two separate runoff events showed that the concentrations of two nonpoint source pollutants, fecal coliform bacteria and suspended sediment, greatly exceeded prerunoff event values for very short periods of time. A phreatic conduit segment, calculated at 17 million liters in volume, instantaneously propagated head changes, caused by direct runoff entering the aquifer, from the ground‐water inputs to Big Spring. A significant delay between the initial increases in discharge and the arrival of direct runoff, as indicated by a steady decrease in specific conductance, represented the time required to displace this volume of phreatic water. The delay showed that sampling a karst spring only during peak discharge would be an unreliable sampling method. Runoff from two different subcatchments was tagged with tracer dye and the timing of the passage of the resultant dye clouds through Big Spring were compared to water quality variations. Distinct lag times between the arrival of direct runoff at Big Spring and the bacteria and suspended sediment waveforms were shown through the concurrent quantitative tracer tests to be related to the areal distribution of land‐cover type within the basin.

Abstract:High-resolution measurements of rainfall, water level, pH, conductivity, temperature and carbonate chemistry parameters of groundwater at two adjacent locations within the peak cluster karst of the Guilin Karst Experimental Site in Guangxi Province, China, were made with different types of multiparameter sonde. The data were stored using data loggers recording with 2 min or 15 min resolution. Waters from a large, perennial spring represent the exit for the aquifer's conduit flow, and a nearby well measures water in the conduit-adjacent, fractured media. During flood pulses, the pH of the conduit flow water rises as the conductivity falls. In contrast, and at the same time, the pH of groundwater in the fractures drops, as conductivity rises. As Ca 2C and HCO 3 were the dominant (>90%) ions, we developed linear relationships (both r 2 > 0Ð91) between conductivity and those ions, respectively, and in turn calculated variations in the calcite saturation index SI C and CO 2 partial pressure P CO 2 of water during flood pulses. Results indicate that the P CO 2 of fracture water during flood periods is higher than that at lower flows, and its SI C is lower. Simultaneously, P CO 2 of conduit water during the flood period is lower than that at lower flows, and its SI C also is lower. From these results we conclude that at least two key processes are controlling hydrochemical variations during flood periods: (i) dilution by precipitation and (ii) water-rock-gas interactions. To explain hydrochemical variations in the fracture water, the water-rock-gas interactions may be more important. For example, during flood periods, soil gas with high CO 2 concentrations dissolves in water and enters the fracture system, the water, which in turn has become more highly undersaturated, dissolves more limestone, and the conductivity increases. Dilution of rainfall is more important in controlling hydrochemical variations of conduit water, because rainfall with higher pH (in this area apparently owing to interaction with limestone dust in the lower atmosphere) and low conductivity travels through the conduit system rapidly. These results illustrate that to understand the hydrochemical variations in karst systems, considering only water-rock interactions is not sufficient, and the variable effects of CO 2 on the system should be evaluated. Consideration of water-rock-gas interactions is thus a must in understanding variations in karst hydrochemistry.

The peak cluster and peak forest karst regions of Southeast Asia form one of the earth's most extensive karst regions. Although there exists a rich, descriptive tradition of geomorphic work performed there, little quantitative study has been made of carbonate hydrochemistry and related aquifer/landscape behavior and evolution. In this paper, high-resolution measurements of ground water carbonate chemistry and flow were made and analyzed at two adjacent locations within the subtropical peak cluster karst of the Guilin Karst Experimental Site in Guangxi Province, China. While waters from a large, perennial spring represent the exit for the 2 km2 catchment's conduit flow, a nearby well (within 5 m) measures water in the conduit-adjacent, fractured media. Results indicate that within peak cluster karst aquifer flow systems, spatially heterogeneous flow conditions can exist with respect to timing, magnitude, and, in some cases, direction of responses, as different controls can operate in the different flow system components. Storm-scale chemical responses are controlled by dilution from rapid infiltration of rain water, CO2 gas sources and sinks, and water-carbonate rock interactions. At this particular location, there is also an influence from high pH recharge, apparently buffered by atmospheric limestone dust. An example of the varying controls on storm-scale responses within the flow system is that within the fractured medium, variations in the ground water calcite saturation index, a key parameter influencing rates of aquifer/landscape evolution, are small and controlled by CO2 gas, while in the conduit they are more significant and dominated instead by dilution with rain water.

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