Formation of phreatic caves in an eogenetic karst aquifer by CO2 enrichment at lower water tables and subsequent flooding by sea level rise

Formation of extensive phreatic caves in eogenetic karst aquifers is widely believed to require mixing of fresh and saltwater. Extensive phreatic caves also occur, however, in eogenetic karst aquifers where fresh and saltwater do not mix, for example in the upper Floridan aquifer. These caves are thought to have formed in their modern settings by dissolution from sinking streams or by convergence of groundwater flow paths on springs. Alternatively, these caves have been hypothesized to have formed at lower water tables during sea level low‐stands. These hypotheses have not previously been tested against one another. Analyzing morphological data and water chemistry from caves in the Suwannee River Basin in north‐central Florida and water chemistry from wells in the central Florida carbonate platform indicates that phreatic caves within the Suwannee River Basin most likely formed at lower water tables during lower sea levels. Consideration of the hydrological and geochemical constraints posed by the upper Floridan aquifer leads to the conclusion that cave formation was most likely driven by dissolution of vadose CO₂ gas into the groundwater. Sea level rise and a wetter climate during the mid‐Holocene lifted the water table above the elevation of the caves and placed the caves tens of meters below the modern water table. When rising water tables reached the land surface, surface streams formed. Incision of surface streams breached the pre‐existing caves to form modern springs, which provide access to the phreatic caves. Phreatic caves in the Suwannee River Basin are thus relict and have no causal relationship with modern surficial drainage systems. Neither mixing dissolution nor sinking streams are necessary to form laterally extensive phreatic caves in eogenetic karst aquifers. Dissolution at water tables, potentially driven by vadose CO₂ gas, offers an underappreciated mechanism to form cavernous porosity in eogenetic carbonate rocks. Copyright © 2012 John Wiley & Sons, Ltd.     

Line-source multi-tracer test for assessing high groundwater velocity

Segmented line-source multi-tracer injection is suggested as an effective method for assessing groundwater velocities and flow directions in subsurfaces characterized by high water flux. Modifying the common techniques of injecting a tracer into a well became necessary after point-source natural and forced gradient tracer tests ended with no reliable information on the local groundwater flow. The tracer's line-source increases the likelihood of success of the test and could provide additional information regarding the lateral heterogeneity of the aquifer. In a field experiment conducted in the northwestern part on the Dead Sea coast, tracers were injected into an 8-m-long line injection system perpendicular to the assumed flow direction. The injection system was divided into four separate segments with four different tracers. An array of five boreholes located within a 10 × 10 m area downstream was used for monitoring the tracers' transport. Two dye tracers (uranine and Na naphthionate) were injected in a long pulse of several hours into two of the injection pipe segments. Two other tracers (Rhenium oxide and Gd-DTPA) were instantaneously injected into the other two segments. The tracers were detected 0.7 to 2.3 h after injection in four of the five observation wells, located 2.3 to 10 m away from the injection system. The groundwater velocity was determined to be ～80 to 170 m/d, based on the recoveries of the tracers. The groundwater flow direction was derived based on the arrival of the tracers and was found to be quite consistent with the apparent direction of the hydraulic gradient.     

Field Tracer Tests to Evaluate Transport Properties of Tryptophan and Humic Acid in Karst

The monitoring of water quality, especially of karst springs, requires methods for rapidly estimating and quantifying parameters that indicate contamination. In the last few years, fluorescence-based measurements of tryptophan and humic acid have become a promising tool to assess water quality in near real-time. In this study, we conducted comparative tracer tests in a karst experimental site to investigate the transport properties and behavior of tryptophan and humic acid in a natural karst aquifer. These two tracers were compared with the conservative tracer uranine. Fluorescence measurements were conducted with an online field fluorometer and in the laboratory. The obtained breakthrough curves (BTCs) and the modeling results demonstrate that (1) the online field fluorometer is suitable for real-time fluorescence measurements of all three tracers; (2) the transport parameters obtained for uranine, tryptophan, and humic acid are comparable in the fast flow areas of the karst system; (3) the transport velocities of humic acid are slower and the resulting residence times are accordingly higher, compared to uranine and tryptophan, in the slower and longer flow paths; (4) the obtained BTCs reveal additional information about the investigated karst system. As a conclusion, the experiments show that the transport properties of tryptophan are similar to those of uranine while humic acid is partly transported slower and with retardation. These findings allow a better and quantitative interpretation of the results when these substances are used as natural fecal and contamination indicators.     

Assessment of groundwater recharge processes through karst vadose zone by cave percolation monitoring

Recharge processes of karst aquifers are difficult to assess given their strong heterogeneity and the poorly known effect of vadose zone on infiltration. However, recharge assessment is crucial for the evaluation of groundwater resources. Moreover, the vulnerability of karst aquifers depends on vadose zone behaviour because it is the place where most contamination takes place. In this work, an in situ experimental approach was performed to identify and quantify flow and storage processes occurring in karst vadose zone. Cave percolation monitoring and dye tracing were used to investigate unsaturated zone hydrological processes. Two flow components (diffuse and quick) were identified and, respectively, account for 66% and 34% of the recharge. Quickflow was found to be the result of bypass phenomenon in vadose zone related to water saturation. We identify the role of epikarst as a shunting area, most of the storage in the vadose zone occurring via the diffuse flow component in low permeability zones. Relationship between rainfall intensity and transit velocity was demonstrated, with 5 times higher velocities for the quick recharge mode than the diffuse mode. Modelling approach with KarstMod software allowed to simulate the hybrid recharge through vadose zone and shows promising chances to properly assess the recharge processes in karst aquifer based on simple physical models.     

Tracer tests in fractured rocks with a new fluorescent dye—pyrene-1,3,6,8-tetra sulphonic acid (PTS) / Tests de traçage en roches fracturées avec un nouveau produit fluorescent—l'acide pyrène 1.3.6.8 tétra sulfonique (PTS)

Abstract

Two multi-tracer tests were performed in fissured rocks accessible in underground laboratories to examine a new fluorescent dye: pyrene-1,3,6,8-tetra sulphonic acid (PTS). The first test was carried out at the Lindau Rock Laboratory (LRL), Germany, in a highly permeable ore dike, and the second, at the Grimsel Test Site (GTS), Switzerland, in a heterogeneous granite fault zone (AU 126). At the LRL new tracer was injected together with uranine in a convergent flow field (monopole test), and slightly different tracer breakthrough curves were observed according to different diffusion coefficients of both tracers. The matrix porosity calculated with the aid of the one-dimensional (1-D) single-fissure dispersion model (SFDM) agrees well with that found in earlier tracer tests and with measurements performed on core samples. At the GTS, the PTS tracer was applied together with pyranine in two-well injection–withdrawal (dipole) tests. Both tracers yielded identical tracer concentration curves, which confirm their conservative behaviour. Mathematical simulations performed with the aid of a 3-D numerical model (FRAC3DVS) yielded equally good fits for different sets of parameters, independent of whether matrix porosity was included or neglected. That lack of unique solution and the difficulty in observing the influence of matrix diffusion result from a wide distribution of the transit times of particular streamlines, which is characteristic for injection–withdrawal tests. However, both tracer tests clearly indicated that the new tracer (PTS) behaves conservatively at high pH values and can be successfully used for groundwater labelling.     

Coastal and inland karst morphologies driven by sea level stands: a GIS based method for their evaluation

Sea level is the base level for groundwater circulation in coastal aquifers. The evolution of karst surface landforms and subsurface drainage systems in these aquifers has been conditioned in geological time by tectonics and glacio‐eustatic sea‐level changes. Present morpho‐structural settings and the type/distribution of karst surface and subsurface forms have developed in different carbonate formations according to differences in lithology, climate and exposure time, all driving the intensity of morphologic and karst processes. The repeated and significant changes of groundwater level linked to ‘sea‐level changes’ have had the most important role in driving the continuous evolution of karstic drainage systems, and has resulted in most cases in a multiphase karst. This study aims at defining a general method for identifying, in karst coastal settings, the elevations of flat or low topographic gradient surfaces (using morphometric analysis of Digital Elevation Models (DEMs) and geographical information systems (GISs), and their comparison with elevations of distinctive karstic levels (passages, lateral solution cavities) observed in vertical shafts and horizontal caves. Of the elevations of flat or low topographic gradient surfaces only those agreeing, within ±10 m or ±20 m, with elevation ranges marked by the high frequency of distinctive karst levels were considered as representative of the more probable past sea‐level stands. The method is applied to a regional coastal carbonate formation in southern Italy, by using a 10 m DEM and information on 140 complex caves and 85 shafts. Of the 15 elevations indicated by DEM analysis [620, 600, 470, 450, 425, 385, 355, 315, 270, 250, 205, 180, 150, 110, and 70 m above sea level (a.s.l.)], 13 match clearly those highlighted by significant frequencies of distinctive karstic levels. These elevations are validated by comparison to the elevation of terraces and karst plains indicated in the literature. Copyright © 2012 John Wiley & Sons, Ltd.     

Differential Transport of Escherichia coli Isolates Compared to Abiotic Tracers in a Karst Aquifer

Lack of filtration and rapid transport of groundwater and particulate matter make karst aquifers susceptible to bacterial contamination. This study utilized quantitative polymerase chain reaction (qPCR) to examine the transport and attenuation of two nonvirulent isolates of Escherichia coli (E. coli) in relation to traditional groundwater tracers (rhodamine WT dye and 1-µm diameter latex microspheres) in a karst-conduit aquifer in central Kentucky. Bacterial isolates were labeled with stable isotopes (¹⁵N and ¹³C). All tracers were detected more than 6 km downstream from the injection site and demonstrated overlapping breakthrough curves, with differential transport observed between the two bacterial strains. The E. coli isolate containing the kps gene (low attachment) arrived at sampling sites 1.25 to 36 h prior to the bacterial isolate containing the iha gene (high attachment) and was detected in samples collected following storm events in which the iha isolate was not detected. The storage potential of contaminants within karst systems was demonstrated by the remobilization of all tracers during storm events more than 1 month after injection. Bacteria-sized microspheres were more easily remobilized during periods of increased discharge compared to other tracers. The study demonstrated that molecular biology techniques such as qPCR can be utilized as a sensitive analysis of bacterial tracers in karst aquifers and may prove to be a more sensitive analytical technique than stable isotope analysis for field-scale traces.     

Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.     

Solute and colloid transport in karst conduits under low- and high-flow conditions

Solute and colloid transport in karst aquifers under low and high flows was investigated by tracer tests using fluorescent dyes (uranine) and microspheres of the size of pathogenic bacteria (1 microm) and Cryptosporidium cysts (5 microm), which were injected into a cave stream and sampled at a spring 2.5 km away. The two types of microspheres were analyzed using an epifluorescence microscope or a novel fluorescence particle counter, respectively. Uranine breakthrough curves (BTCs) were regular shaped and recovery approached 100%. Microsphere recoveries ranged between 27% and 75%. During low flow, the 1-microm spheres displayed an irregular BTC preceding the uranine peak. Only a very few 5-microm spheres were recovered. During high flow, the 1-microm-sphere BTC was regular and more similar to the uranine curve. BTCs were modeled analytically with CXTFIT using a conventional advection dispersion model (ADM) and a two-region nonequilibrium model (2RNE). The results show that (1) colloids travel at higher velocities than solutes during low flow; (2) colloids and solutes travel at similar velocities during high flow; (3) higher maximum concentrations occur during high flow; and (4) the 2RNE achieves a better fit, while the ADM is more robust, as it requires less parameters.     

Multitracer test approach to characterize reactive transport in karst aquifers

A method to estimate reactive transport parameters as well as geometric conduit parameters from a multitracer test in a karst aquifer is provided. For this purpose, a calibration strategy was developed applying the two-region nonequilibrium model CXTFIT. The ambiguity of the model calibration was reduced by first calibrating the model with respect to conservative tracer breakthrough and later transferring conservative transport parameters to the reactive model calibration. The reactive transport parameters were only allowed to be within a defined sensible range to get reasonable calibration values. This calibration strategy was applied to breakthrough curves obtained from a large-scale multitracer test, which was performed in a karst aquifer of the Swabian Alb, Germany. The multitracer test was conducted by the simultaneous injection of uranine, sulforhodamine G, and tinopal CBS-X. The model succeeds to represent the tracer breakthrough curves (TBCs) of uranine and sulforhodamine G and verifies that tracer-rock interactions preferably occur in the immobile fluid region, although the fraction of this region amounts to only 3.5% of the total water. However, the model failed to account for the long tailing observed in the TBC of tinopal CBS-X. Sensitivity analyses reveal that model results for the conservative tracer transport are most sensitive to average velocity and volume fraction of the mobile fluid region, while dispersion and mass transfer coefficients are least influential. Consequently, reactive tracer calibration allows the determination of sorption sites in the mobile and immobile fluid region at small retardation coefficients.     

The role of antecedent groundwater heads in controlling transient aquifer storage and flood peak attenuation in karst watersheds

Transient storage of floodwaters in aquifers is known to attenuate peak flows in rivers and drive subsurface dissolution. Transient aquifer storage could be enhanced in watersheds overlying karst aquifers where caves facilitate surface and groundwater exchange. Few studies, however, have examined controls on, or magnitudes of, transient aquifer storage or flood peak attenuation in karstic watersheds. Here we evaluate flood peak attenuation with multiple linear regression analyses of 10 years of river and groundwater data from the Suwannee River, which flows over the karstic upper Floridan aquifer in north-central Florida and experiences frequent flooding. Regressions show antecedent river stage exerts the dominant control on magnitudes of transient aquifer storage, with recharge and time to peak having secondary controls. Specifically, low antecedent stages result in larger magnitudes of transient aquifer storage and thus greater flood attenuation than conditions of elevated antecedent stage. These findings suggest subsurface weathering, including cave formation and enlargement, caused by transient aquifer storage could occur on a more frequent basis in aquifers where groundwater table elevation is lowered due to anthropogenic or climatic influences. Our work also shows that measures of groundwater table elevation prior to an event could be used to improve predictive flood models. © 2018 John Wiley & Sons, Ltd.     

Heterogeneous distributions of CO2 may be more important for dissolution and karstification in coastal eogenetic limestone than mixing dissolution

Mixing dissolution, a process whereby mixtures of two waters with different chemical compositions drive undersaturation with respect to carbonate minerals, is commonly considered to form cavernous macroporosity (e.g. flank margin caves and banana holes) in eogenetic karst aquifers. On small islands, macroporosity commonly originates when focused dissolution forms globular chambers lacking entrances to the surface, suggesting that dissolution processes are decoupled from surface hydrology. Mixing dissolution has been thought to be the primary dissolution process because meteoric water would equilibrate rapidly with calcium carbonate as it infiltrates through matrix porosity and because pCO₂ was assumed to be homogeneously distributed within the phreatic zone. Here, we report data from two abandoned well fields in an eogenetic karst aquifer on San Salvador Island, Bahamas, that demonstrate pCO₂ in the phreatic zone is distributed heterogeneously. The pCO₂ varied from less than log ?2.0 to more than log ?1.0 atm over distances of less than 30 m, generating dissolution in the subsurface where water flows from regions of low to high pCO₂ and cementation where water flows from regions of high to low pCO_2. Using simple geochemical models, we show dissolution caused by heterogeneously distributed pCO₂ can dissolve 2.5 to 10 times more calcite than the maximum amount possible by mixing of freshwater and seawater. Dissolution resulting from spatial variability in pCO₂ forms isolated, globular chambers lacking initial entrances to the surface, a morphology that is characteristic of flank margin caves and banana holes, both of which have entrances that form by erosion or collapse after cave formation. Our results indicate that heterogeneous pCO₂, rather than mixing dissolution, may be the dominant mechanism for observed spatial distribution of dissolution, cementation and macroporosity generation in eogenetic karst aquifers and for landscape development in these settings. Copyright © 2015 John Wiley & Sons, Ltd.     

Groundwater mixing between different aquifer types in a complex structural setting discerned by elemental and stable isotope geochemistry

Karst aquifers are well known for their intricate stratigraphy and geologic structures, which make groundwater characterization challenging because flowpaths and recharge sources are complex and difficult to evaluate. Geochemical data, collected from ten closely spaced production wells constructed in two karst aquifers (Bangor Limestone (Mb) and Tuscumbia Limestone/Fort Payne Chert (Mftp)) in Trussville, north‐central Alabama, illustrate two distinctive groundwater end‐members: (1) higher major ion, dissolved inorganic carbon, conductivity, alkalinity concentrations, heavier δ¹³C ratios (max: −10.2 ± 0.2‰ Vienna Pee Dee Belemnite (PDB)) and lower residence times (mean: 19.5 ± 2 years, n = 2) of groundwater in the Mb aquifer and (2) lower constituent concentrations, lighter δ¹³C ratios (min: −13.4 ± 0.2‰ PDB) and longer residence times of groundwater (mean: 23.6 ± 2 years, n = 4) in the Mftp aquifer. Summer and fall data and the binary mixing model show aquifer inter‐flow mixing along solution fractures and confirms the distinctive groundwater geochemistry of the two aquifers. Lowering of static water levels over the summer (drawdown from 2 to 5.2 m) leads to more reducing groundwater conditions (lower Eh values) and slightly enriched δ¹⁸O and δD ratios during the fall [δ¹⁸O: −4.8 ± 0.1 to −5.4 ± 0.1‰ Vienna Standard Mean Oceanic Water (VSMOW), n = 9; δD: −25.4 ± 1 to −27.4 ± 1‰ VSMOW, n = 9] when compared with summer season samples (δ¹⁸O: −5.1 ± 0.1 to −5.7 ± 0.1‰ VSMOW, n = 11; δD: −25.0 ± 1 to −30.6 ± 1‰ VSMOW, n = 11). GIS analyses confirm the localized origin of recharge to the investigated aquifers. The combination of GIS, field parameters and geochemistry analyses can be successfully used to identify recharge sources, evaluate groundwater flow and transport pathways and to improve understanding of how groundwater withdrawals impact the sustainability and susceptibility to contamination of karst aquifers. Copyright © 2015 John Wiley & Sons, Ltd.     

Transport and Variability of Fecal Bacteria in Carbonate Conglomerate Aquifers

Clastic sedimentary rocks are generally considered non‐karstifiable and thus less vulnerable to pathogen contamination than karst aquifers. However, dissolution phenomena have been observed in clastic carbonate conglomerates of the Subalpine Molasse zone of the northern Alps and other regions of Europe, indicating karstification and high vulnerability, which is currently not considered for source protection zoning. Therefore, a research program was established at the Hochgrat site (Austria/Germany), as a demonstration that karst‐like characteristics, flow behavior, and high vulnerability to microbial contamination are possible in this type of aquifer. The study included geomorphologic mapping, comparative multi‐tracer tests with fluorescent dyes and bacteria‐sized fluorescent microspheres, and analyses of fecal indicator bacteria (FIB) in spring waters during different seasons. Results demonstrate that (1) flow velocities in carbonate conglomerates are similar as in typical karst aquifers, often exceeding 100 m/h; (2) microbial contaminants are rapidly transported toward springs; and (3) the magnitude and seasonal pattern of FIB variability depends on the land use in the spring catchment and its altitude. Different groundwater protection strategies that currently applied are consequently required in regions formed by karstified carbonatic clastic rocks, taking into account their high degree of heterogeneity and vulnerability.     

Comparison of the results of quantitative and non-quantitative tracer tests for determination of Karst conduit networks: An example from the Traligill Basin,Scotland

The relative advantages of fluorescent dyes and Lycopodium spores as tracers are discussed. The major advantage of fluorescent dyes is that they may be detected quantitatively. Thus, in combination with discharge measurements, a dye mass balance can be prepared for tracer tests in karst conduits, which permits elucidation of the underground network. The advantages of this procedure are illustrated by comparison of the networks derived from non-quantitative (Lycopodium and dye) and quantitative (fluorescent dye) tracer methods in the Traligill Basin, Scotland. These tests also suggest that Lycopodium does not give a true indication of travel time, due to sedimentation underground. This could also cause contamination problems in later tests. For non-quantitative tracer tests, sensitive methods are necessary if incorrect inferences on conduit networks are to be avoided. In general, however, quantitative tests give much less ambiguous results, and are therefore to be preferred.     

Water and air dynamics within a deep vadose zone of a karst massif: Observations from the Lukina jama–Trojama cave system (−1,431 m) in Dinaric karst (Croatia)

Extreme heterogeneity of karst systems makes them very challenging to study. Various processes within the system affect its global response, usually measured at karst springs. Research conducted in caves provides a unique opportunity for in situ analysis of separate processes in karst underground. The aim of the present study was to research the water and air dynamics within a deep karst system. Air and water basic physical parameters across the Lukina jama–Trojama cave system (?1,431 m) were continuously monitored during a 1‐year period. Recorded hydrograph of the siphon lake at the bottom of the cave was used to interpret the characteristics of an unexplored phreatic/epiphreatic conduit network. Water origin in the siphon was determined based on temperature and electrical conductivity. Air temperature and humidity monitoring revealed a strong inflow of air of sub‐zero temperature into the upper portion of the cave during winter. Cave passage morphology was interpreted as the main determinant of air dynamics, which caused ice to accumulate extensively in the upper portions of the cave and caused the temperature on the top of the homothermic zone to be significantly below the mean outside temperature. Air dynamics also lowered the temperature of water flowing through the cave vadose zone and feeding the phreatic zone of the massif. The pronounced temperature difference between the phreatic zone and the top of the homothermic zone probably contributed to the thermal gradient observed in the cave, which is steeper than in ice‐free caves in the area. Our results enabled the development of a conceptual model that describes coupling between air and water dynamics in the cave system and its surroundings.     

Modifications to the Conduit Flow Process Mode 2 for MODFLOW-2005

As a result of rock dissolution processes, karst aquifers exhibit highly conductive features such as caves and conduits. Within these structures, groundwater flow can become turbulent and therefore be described by nonlinear gradient functions. Some numerical groundwater flow models explicitly account for pipe hydraulics by coupling the continuum model with a pipe network that represents the conduit system. In contrast, the Conduit Flow Process Mode 2 (CFPM2) for MODFLOW-2005 approximates turbulent flow by reducing the hydraulic conductivity within the existing linear head gradient of the MODFLOW continuum model. This approach reduces the practical as well as numerical efforts for simulating turbulence. The original formulation was for large pore aquifers where the onset of turbulence is at low Reynolds numbers (1 to 100) and not for conduits or pipes. In addition, the existing code requires multiple time steps for convergence due to iterative adjustment of the hydraulic conductivity. Modifications to the existing CFPM2 were made by implementing a generalized power function with a user-defined exponent. This allows for matching turbulence in porous media or pipes and eliminates the time steps required for iterative adjustment of hydraulic conductivity. The modified CFPM2 successfully replicated simple benchmark test problems.     

Tracking Groundwater Discharge to a Large River using Tracers and Geophysics

Few studies have investigated large reaches of rivers in which multiple sources of groundwater are responsible for maintaining baseflow. This paper builds upon previous work undertaken along the Fitzroy River, one of the largest perennial river systems in north‐western Australia. Synoptic regional‐scale sampling of both river water and groundwater for a suite of environmental tracers (⁴He, ⁸⁷Sr/⁸⁶Sr, ²²²Rn and major ions), and subsequent modeling of tracer behavior in the river, has enabled definition and quantification of groundwater input from at least three different sources. We show unambiguous evidence of both shallow “local” groundwater, possibly recharged to alluvial aquifers beneath the adjacent floodplain during recent high‐flow events, and old “regional” groundwater introduced via artesian flow from deep confined aquifers. We also invoke hyporheic exchange and either bank return flow or parafluvial flow to account for background ²²²Rn activities and anomalous chloride trends along river reaches where there is no evidence of the local or regional groundwater inputs. Vertical conductivity sections acquired through an airborne electromagnetic (AEM) survey provide insights to the architecture of the aquifers associated with these sources and general groundwater quality characteristics. These data indicate fresh groundwater from about 300 m below ground preferentially discharging to the river, at locations consistent with those inferred from tracer data. The results demonstrate how sampling rivers for multiple environmental tracers of different types—including stable and radioactive isotopes, dissolved gases and major ions—can significantly improve conceptualization of groundwater—surface water interaction processes, particularly when coupled with geophysical techniques in complex hydrogeological settings.     

Using nitrate to quantify quick flow in a karst aquifer

In karst aquifers, contaminated recharge can degrade spring water quality, but quantifying the rapid recharge (quick flow) component of spring flow is challenging because of its temporal variability. Here, we investigate the use of nitrate in a two-endmember mixing model to quantify quick flow in Barton Springs, Austin, Texas. Historical nitrate data from recharging creeks and Barton Springs were evaluated to determine a representative nitrate concentration for the aquifer water endmember (1.5 mg/L) and the quick flow endmember (0.17 mg/L for nonstormflow conditions and 0.25 mg/L for stormflow conditions). Under nonstormflow conditions for 1990 to 2005, model results indicated that quick flow contributed from 0% to 55% of spring flow. The nitrate-based two-endmember model was applied to the response of Barton Springs to a storm and results compared to those produced using the same model with δ¹⁸O and specific conductance (SC) as tracers. Additionally, the mixing model was modified to allow endmember quick flow values to vary over time. Of the three tracers, nitrate appears to be the most advantageous because it is conservative and because the difference between the concentrations in the two endmembers is large relative to their variance. The δ¹⁸O-based model was very sensitive to variability within the quick flow endmember, and SC was not conservative over the timescale of the storm response. We conclude that a nitrate-based two-endmember mixing model might provide a useful approach for quantifying the temporally variable quick flow component of spring flow in some karst systems.     

Effects of Alkali and Alkaline‐earth Cations on the Removal of Reactive Dyes with Cucurbituril

The sorption of reactive (textile) dyes onto cucurbituril, a cyclic polymer with hydrophobic cavity, was studied. Dye sorption is strongly enhanced by Ca²⁺ or Sr²⁺ concentrations up to 100 mmol/L for all studied dyes. Mg²⁺ and alkaline ions had similar effects for only one dye (Reactive Red 120), and only at higher concentrations. Concentrations above 100 mmol/L – depending on cation and dye – dissolve cucurbituril and prevent dye removal. As shown in previous studies by our group loadings obtained under suitable conditions (calcium concentration between 2 and 100 mmol/L, total salt concentration not exceeding 100 mmol/L) are 1 to 1.7 mol/mol or 0.9 to 1.8 g/g. The chemical mechanism responsible for the ionic influences is still under investigation. Generally, cucurbituril is a potent sorbent for reactive dyes. However, the technical application is still limited by the lack of a support material that would allow use in fixed bed filters.