沉积物和悬浮颗粒物在岩溶水系统污染物衰减与运移中的作用

本文讨论了沉积物和悬浮颗粒物/胶体在岩溶水系统污染物衰减与运移中的作用,介绍了关于瑞士某岩溶水系统内颗粒物与微生物污染间关系的实验结果。该实验场包括一个接纳农田排水的落水洞及与其相连的两个泉,其中一个泉是供水水源地。利用便携式粒子计实时监测泉水中颗粒分布的变化情况,同时对浊度、总有机碳和其它参数进行连续监测;并对水中E型大肠菌群进行了分析。在暴雨过后,观测到了浊度的两种不同表现:即泉排泄量增加时,浊度最初表现为脉状水动力条件下岩溶系统内沉积物的二次运移;几天后观测到的浊度则表明水已从落水洞到了泉口,常常具有高的总有机碳、硝酸盐及E型大肠菌群。颗粒分布分析结果差异更大:早期的浊度是不同粒径颗粒物的混合,而后期的浊度更多是由较细颗粒构成,因为大颗粒物已沉积在落水洞到泉口之间的岩溶系统内。E型大肠菌群与0.9～1.5 μm颗粒物之间具有很好的相关性。因而较细颗粒的相对增加可应用于微生物污染 “早期预报系统”。除了水污染,颗粒分还可以帮助我们研究岩溶环境的其它问题,如土壤侵蚀。      

Microbial communities in karst groundwater and their potential use for biomonitoring

The structure, diversity and dynamics of microbial communities from a swallow hole draining agricultural land and two connected karst springs (Switzerland) were studied using molecular microbiological methods and related to hydrological and physicochemical parameters. Storm responses and an annual hydrological cycle were monitored to determine the short- and long-term variability, respectively, of bacterial communities. Statistical analysis of bacterial genetic fingerprints (16S rDNA PCR-DGGE) of spring water samples revealed several clusters that corresponded well with different levels of the allochthonous swallow hole contribution. Microbial communities in spring water samples highly affected by the swallow hole showed low similarities among them, reflecting the high temporal variability of the bacterial communities infiltrating at the swallow hole. Conversely, high similarities among samples with low allochthonous contribution provided evidence for a stable autochthonous endokarst microbial community. Three spring samples, representative for low, medium and high swallow hole contribution, were analysed by cloning/sequencing in order to identify the major bacterial groups in the communities. The autochthonous endokarst microbial community was mainly characterized of δ-Proteobacteria, Acidobacteria and Nitrospira species. A high percentage of unknown sequences suggested further that many karst aquifer bacteria are still undiscovered. Finally, the potential use of groundwater biomonitoring using microbial communities is discussed.     

Analysis of karst hydrodynamics through comparison of dissolved and suspended solids' transport

In karst systems, rain events often result in a decrease of the conductivity (a tracer of dissolved phase transport) and an increase in turbidity (a tracer of suspended solids transport) at wells and springs. This study shows that the comparison of suspended solids and solute transport by the coupled approach of $T\text{–}C$ curves (Turbidity–Conductivity) and autocorrelations gives evidence of the transport processes in the karst network and allows understanding the karst hydrodynamics. To cite this article: D. Valdes et al., C. R. Geoscience 337 (2005).     

Dynamics and interaction of organic carbon, turbidity and bacteria in a karst aquifer system

The dynamics of organic carbon (OC), turbidity, faecal indicator bacteria and physicochemical parameters was studied in a karst system near Yverdon, Switzerland. Online measurements and sampling were done at a swallow hole draining an agricultural surface (the input), and two groups of springs (the outputs) that often show bacterial contamination. A fluorescent tracer that was injected into the swallow hole during low-flow conditions first arrived at the springs 10–12 days after injection; the total recovery rate was 29%. Previous tracer tests during high-flow conditions gave shorter travel times. After a major rainfall event, a primary turbidity peak was observed at the springs. It coincides with the rising limb of the hydrograph, indicating remobilisation of autochthonous particles from the aquifer. A secondary turbidity peak occurs several days later, suggesting the arrival of allochthonous particles from the swallow hole. Wider peaks of OC and bacteria were observed simultaneously. Applying methods from molecular microbiology (PCR-DGGE) allowed characterisation of the bacterial communities at the swallow hole and the springs. The results demonstrate that the swallow hole is an important source of groundwater contamination, while its contribution to aquifer recharge is insignificant. OC appears to be a better indicator for bacterial contamination than turbidity.     

Water quality deterioration at a karst spring (Gallusquelle,Germany) due to combined sewer overflow: evidence of bacterial and micro-pollutant contamination

The concurrent use of karst aquifers as drinking water resources and receptors of combined sewer overflow lacking appropriate pre-treatment may cause conflicts between drinking water supply and storm water management. A storm water tank (SWT) for combined wastewater is identified as the source of sporadic contamination of a karst spring (Gallusquelle, “Schwäbische Alb”, SW Germany) used for public water supply. Spring water quality was examined by routine and event sampling and by evaluating physicochemical and microbiological parameters. The total number of microbial colonies growing at 20°C and the number of Escherichia coli colonies rose to values up to four orders of magnitude higher than background, 2–5 days after overflow of the SWT. High concentrations of chloride, sodium, and total organic carbon (TOC) and high values of turbidity coincide with this increase. However, high bacterial contamination is also observed while turbidity and TOC are low. Several wastewater-related organic micro-pollutants such as chlorinated and non-chlorinated organophosphates were detected in the SWT and, depending on their K_ow values and their biodegradability, in lower concentrations at the spring.     

The study of hydrodynamic behaviour of a complex karst system under low-flow conditions using natural and artificial tracers (the catchment of the Unica River,SW Slovenia)

In this study a multi-tracer test with fluorescent tracers was combined with time series analyses of natural tracers to characterize the dynamics of the solute transport through different recharge pathways and to study hydraulic behaviour of a binary karst system under low-flow conditions. Fluorescent tracer testing included the introduction of uranine, amidorhodamine G, or naphthionate at three injection points. Sampling and monitoring took place at two karst springs (Malenščica, Unica) and at two underground rivers (Pivka, Rak) recharging the Unica River at the Polje of Planina, SW Slovenia. Other monitored parameters included precipitation, spring or underground river discharge, water temperature, and electrical conductivity. Water samples were collected and analyzed for total organic carbon, Mg²⁺, SO₄ ²⁻, and NO₃ ⁻ in the laboratory. In the study area, results of the tracer test suggest that contaminant transport in karst may be retarded for several weeks during low-flow conditions followed by increases in contaminant concentrations after subsequent rainfall events. Based on interpretation of tracer concentration breakthrough curves, low apparent dominant flow velocities (i.e., between 5.8 and 22.8 m/h through the well developed karst conduits, and 3.6 m/h through the prevailing vadose zone with a dominant influence of a diffuse recharge) were obtained. Together with analyses of hydro-chemographs the artificial tracing identified different origins of water recharging the studied aquifer. During prolonged low-water conditions the Malenščica spring is mainly recharged from the karst aquifer and the Unica spring by the sinking Pivka River. After more intensive rainfall events allogenic recharge from Cerknica prevails in the Malenščica spring, while the Unica spring drains mainly the allogenic water from the Pivka Valley. These findings of alternating hydraulic connections and drainage areas due to respective hydrological conditions are important and should be considered when monitoring water quality, implementing groundwater protection measures, and optimizing future water exploitation.     

Contamination risk of the Alburni Karst System (Southern Italy)

The Alburni massif (1742m a.s.l.) stretches NW–SE, about 23km long and 9–10km wide, covering 246km² with an average elevation of about 940m a.s.l. This massif, with more than 500 caves, is the most important karst area in southern Italy. The karst channel network is hierarchically organized: some channels feed a major spring (1m³/s) with a very short transit time while others communicate directly with the basal water table related to other springs (Q > 3m³/s).There are several dolines and swallow holes just above the basal water table and in the urbanized areas; for years a swallow hole directly transferred pollutants into the aquifer. The contamination vulnerability map shows that the prevalent vulnerability degree ranges from high to very high, due to the widespread karstification of the area and to the presence, on the plateau, of large vegetated areas with gentle slopes favouring fast infiltration.Hence it is important to ascertain the human impact on the area and the consequent contamination risk of the aquifer of the Alburni karst area. Three main layers were created to assess groundwater contamination risk: the vulnerability map, the hazard map, and the value map.The groundwater contamination risk map stresses the importance in a park area of aquifer vulnerability, which strongly influences the risk: indeed, the prevalent moderate degree of risk in the final map depends on the high vulnerability and the low hazard degree. However, in the future it is crucial to take into account the nature of the agricultural land use allowed in the park, which could increase the hazard degree and consequently the risk degree.     

Proposed method for groundwater vulnerability mapping in carbonate (karstic) aquifers: the COP method

The ‘COP method’ has been developed for the assessment of intrinsic vulnerability of carbonate aquifers in the frame of the European COST Action 620. This method uses the properties of overlying layers above the water table (O factor), the concentration of flow (C factor) and precipitation (P factor) over the aquifer, as the parameters to assess the intrinsic vulnerability of groundwater. This method considers karst characteristics, such as the presence of swallow holes (C factor) and their catchment areas as well as karstic landforms, as factors which decrease the natural protection provided by overlying layers (O factor). The P factor allows for consideration of the spatial and temporal variability of precipitation, which is considered the transport agent of contamination. Two carbonate aquifers in the South of Spain, Sierra de Líbar (a conduit flow system) and Torremolinos (a diffuse flow system), have been selected for the application and validation of the method and the results have been compared with three methods widely applied in different aquifers around the world (AVI, GOD and DRASTIC). Comparisons with these methods and validation tools (hydrogeological data and tracer test) show the advantages of the COP method in the assessment of vulnerability of karstic groundwaters.     

Geochemical and boron,oxygen and hydrogen isotopic constraints on the origin of salinity in groundwaters from the crystalline basement of the Alpine Foreland

The B isotopic composition, in combination with O and H isotopes and hydrochemical tracers, is utilized to constrain the evolution of basement-hosted groundwaters via water–rock interactions and fluid infiltration from external (sedimentary) reservoirs. Two distinct groundwater types have been identified in the Central European crystalline basement (N Switzerland–SW Germany): (1) fresh groundwaters characterized by low values of δ¹¹B (−3.5 to −0.6‰), δ¹⁸O (−12.0 to −10.0‰), and δD (−86.8 to −71.9‰), and (2) brackish groundwaters with distinctly heavier B, O, and H isotopic compositions (δ¹¹B=+6.4 to +17.6‰, δ¹⁸O=−9.4 to −5.6‰, δD=−67.6 to −60.8‰). Fresh groundwaters show a systematic decrease in δ¹¹B, related to an increase in B concentrations (and degree of total mineralization), along the pathway of groundwater migration which can only be interpreted in terms of leaching of crystalline host rocks. A δ¹¹B value of −3.3‰ is inferred for the crustal B source (mainly Hercynian granites) involved in the leaching process, in agreement with the known δ¹¹B range of granitic rocks. The evolution of brackish groundwaters, derived from crystalline basement reservoirs with little water circulation, is more complex. As indicated by B–O–H stable isotope and hydrochemical (e.g. B/Cl, Na/Cl, and Br/Cl) constraints, brackish groundwaters from the study area are influenced by admixture of sediment-derived fluids which infiltrated from Late Paleozoic (Permo-Carboniferous) and Early Mesozoic (Lower Triassic) sedimentary strata. The data presented show that B isotopes are sensitive to mixing processes of fluids derived from different crustal reservoirs and, hence, may be utilized as a tracer for constraining the internal (autochthonous) vs external (allochthonous) origin of salinity in basement-hosted groundwaters.     

Dynamics and anthropogenic impacts of multiple karst flow systems in a mountainous area of South China

The Xiangxi River basin, South China, is a steep terrane with well-developed karst features and an important Cambrian-Ordovician aquifer. Meteoric water in this mountainous area features a mean δ¹⁸O elevation gradient of –2.4?‰/km. This gradient was used to estimate mean recharge elevations of 760 m for Shuimoxi (SMX) spring, 1,060 m for Xiangshuidong (XSD) spring, and 1,430 m for drill hole ZK03, indicating multiple flow paths in the Cambrian-Ordovician karst aquifer. Mean residence times of 230 and 320 days and ～2 years were estimated for these features, respectively, using the damped running average model that predicts the isotopic variations in groundwater from those in precipitation. Groundwater in the regional karst flow system has the longest residence time, the highest recharge elevation, the longest flow paths, the lowest addition of anthropogenic components, and the greatest amount of water–rock interaction as indicated by its higher dissolved solids, Mg²⁺ concentrations and Mg/Ca ratios than the springs. In contrast, the local and shallow karst flow systems respond rapidly to recharge events. Artificial tracer tests prove that these shallow karst systems can also quickly transmit anthropogenic contaminants, indicating that they are highly vulnerable to human impacts, which include the enrichment of NO₃ ^–. The intensity of water–rock interaction and groundwater vulnerability are mainly determined by the structure and dynamics of the multiple karst flow systems.     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.     

Hydrogeological characterization and environmental effects of the deteriorating urban karst groundwater in a karst trough valley: Nanshan,SW China

The unique hydrogeology of karst makes the associated groundwater respond quickly to rainfall events and vulnerable to anthropogenic pollutions. In this study, high-frequency monitoring of spring discharge, temperature, electrical conductivity (EC) and pH, along with monthly hydrochemical and microbial analyses, was undertaken at the outlet of Laolondong karst underground river in Nanshan, southwestern China. The aim was to explore the environmental effects of the catchment’s urban area on the karst groundwater resources. The monitoring data of a tracer test and the response of discharge to rainfall events demonstrate that conduits and narrow fissures coexist in the Laolongdong karst aquifer. The EC, Na⁺, Cl^? and SO₄^2? values (840 μS/cm, 33.7, 38.6 and 137.2 μg/L, respectively), along with high concentrations of fecal coliform bacteria, at the outlet indicate considerable urban pollution in this area. The contaminants sulfate and nitrate showed different relationships with discharge and EC in different stages of a rainfall event. This behavior provided information about aquifer structure and the influence of transport properties. Meanwhile, the hydrological processes of groundwater flow could be modified by urbanization and result in increasing magnitude of urban floods in the underground river. In addition, sulfuric and nitric acids introduced by urbanization not only impact the karst groundwater quality, but also result in a significant perturbation to the carbon cycling system in the karst area.     

Sources and transports of organochlorine pesticides in the Nanshan underground river,China

Karst areas have much higher ecological vulnerability and are prone to be contaminated. Organochlorine pesticides (OCPs) were detected in waters and sediment from the two sites of the karst Nanshan underground river system, China, to understand the sources and transport of OCPs in the underground river systems. Obviously, seasonal variations were found both in the waters and the sediments. Detected OCPs ranged from 61 to 936 ng L^?1 in the groundwaters and 51–3,842.0 ng g^?1 in the underground sediments, respectively. OCPs in groundwaters were mixture of younger and older residues from commercial sources. The maximum OCPs in the sediments of the underground river were historically older residues from commercial sources. The sources of OCPs in the waters and sediments of the underground river indicated that the surface systems play an important role in OCPs transport and pollution in the underground river. Karst features were liable for the transport behavior.     

Evaluation of ionic strength and salinity of groundwaters: effect of the ionic composition

An improved method has been used for rapid determination of the ionic strength (I) and the salinity of Apulian groundwaters. The parameters required are the electrolytic conductivity (EC) and the total solute concentration (C_T) of the solutions. A simple empirical relation between I, EC and C_T is presented. The relation holds over a wide concentration and composition range. The combined use of C_T and of the ratio $\text{I}\text{C}{}_{\mathrm{T}}$ is shown to be effective in defining the salinity of groundwaters.     

Characterisation of the physicochemical qualities of a typical rural-based river: ecological and public health implications

The physicochemical qualities of a typical rural-based river were assessed over a 12-month period from August 2010 to July 2011 spanning the spring, summer, autumn and winter seasons. Water samples were collected from six sampling sites along Tyume River and analysed for total nitrogen, orthophosphate, biochemical oxygen demand (BOD), temperature, pH, dissolved oxygen (DO), electrical conductivity (EC), total dissolved solids (TDS) and turbidity. BOD regimes did not differ significantly between seasons and between sampling points and ranged from 0.78 to 2.76 mg/L across seasons and sampling points, while temperature ranged significantly (P < 0.05) between 6 and 28 °C. Turbidity varied significantly (P < 0.05) from 6 to 281 nephelometric turbidity units while TDS (range 24–209 ppm) and conductivity (range 47.6–408 mg/L) also varied significantly (P < 0.05) across sampling points with a remarkable similarity in their trends. Orthophosphate concentrations varied from 0.06 to 2.72 mg/L across seasons and sampling points. Negative correlations were noted between temperature and the nutrients, DO and temperature (r = ?0.56), and TDS and DO (r = ?0.33). Positive correlations were noted between TDS and temperature (r = 0.41), EC and temperature (r = 0.15), and DO and pH (r = 0.55). All nutrients were positively correlated to each other. Most measured parameters were within prescribed safety guidelines. However, the general trend was that water quality tended to deteriorate as the river flows through settlements, moreso in rainy seasons.     

Environmental geochemistry and sources of potentially toxic elements in thermal springs in the Sabalan volcanic field,NW Iran

Thermal springs are attractive geological features interesting for tourists because of their balneological and therapeutic applications. In Iran, the thermal springs surrounding Mount Sabalan are famous and unique in this regard. Two clusters of thermal springs consisting of 16 springs and mostly used as spas occur in Neer and Meshkinshahr areas. In order to investigate the seasonal changes of field and chemical parameters and to trace element concentrations in dry and wet seasons, springs were sampled twice in May and November. Field data including T, EC, pH and Q were measured on-site and major cations and anions were analysed in the laboratory along with 72 trace elements. Cations show the following order of abundance: Na ? Ca ≥ K > Mg and anions follow the order of Cl > HCO₃ > SO₄. Trace element concentrations indicate that most of the elements show concentrations well beyond the standard guideline values for drinking water. pH, T, spring discharge and elevation are not correlated with each other and with other parameters, indicating that they have had no role on concentrating or depleting trace elements in spring waters. While the two sets of samples were taken within a 6 month interval, the elements and parameters show slight or no variation from the first period to the second and in some cases, they show less than 5 % decrease or increase in the second sampling period. Correlation coefficient and principal component analysis of analytical data indicate that EC, K, Cl, HCO₃, As, B, Ba, Br, Li, Na, Rb, Sr and V show very strong mutual correlation coefficients implying their relationship and common source and fate in the hydrothermal fluid that carries them out of the geothermal system. Moreover, they all fall in the component 1 of PCA. This group of elements is supposed to be derived from the magmatic-hydrothermal system through the interaction of hydrothermal fluids with the rocks they have passed through. The mean As value is 160-fold higher than the guideline values (10 μg/l) and Mn and Sb shows an exceedance of 12- and 11.5-fold, respectively. Arsenic shows a variation of 5–5,834 μg/l. Hence, it is supposed that potentially toxic elements may have adverse effects on tourists using the springs as a treatment or recreation. Indeed, the discharge of springs with high values of As and other elements represents a threat for downstream water uses. The higher concentrations of most elements including As, Pb, S, Cl and Sb and the higher pH values found in Neer area springs seem to be more related to an older hydrothermal system present in this area than the Meshkinshahr system that is still active today.     

Comparison of age distributions estimated from environmental tracers by using binary-dilution and numerical models of fractured and folded karst: Shenandoah Valley of Virginia and West Virginia, USA

Measured concentrations of environmental tracers in spring discharge from a karst aquifer in the Shenandoah Valley, USA, were used to refine a numerical groundwater flow model. The karst aquifer is folded and faulted carbonate bedrock dominated by diffuse flow along fractures. The numerical model represented bedrock structure and discrete features (fault zones and springs). Concentrations of ³H, ³He, ⁴He, and CFC-113 in spring discharge were interpreted as binary dilutions of young (0–8  years) water and old (tracer-free) water. Simulated mixtures of groundwater are derived from young water flowing along shallow paths, with the addition of old water flowing along deeper paths through the model domain that discharge to springs along fault zones. The simulated median age of young water discharged from springs (5.7  years) is slightly older than the median age estimated from ³H/³He data (4.4  years). The numerical model predicted a fraction of old water in spring discharge (0.07) that was half that determined by the binary-dilution model using the ³H/³He apparent age and ³H and CFC-113 data (0.14). This difference suggests that faults and lineaments are more numerous or extensive than those mapped and included in the numerical model.     

Assessment of key transport parameters in a karst system under different dynamic conditions based on tracer experiments: the Jeita karst system,Lebanon

Artificial tracer experiments were conducted in the mature karst system of Jeita (Lebanon) under various flow conditions using surface and subsurface tracer injection points, to determine the variation of transport parameters (attenuation of peak concentration, velocity, transit times, dispersivity, and proportion of immobile and mobile regions) along fast and slow flow pathways. Tracer breakthrough curves (TBCs) observed at the karst spring were interpreted using a two-region nonequilibrium approach (2RNEM) to account for the skewness in the TBCs’ long tailings. The conduit test results revealed a discharge threshold in the system dynamics, beyond which the transport parameters vary significantly. The polynomial relationship between transport velocity and discharge can be related to the variation of the conduit’s cross-sectional area. Longitudinal dispersivity in the conduit system is not a constant value (α?=?7–10 m) and decreases linearly with increasing flow rate because of dilution effects. Additionally, the proportion of immobile regions (arising from conduit irregularities) increases with decreasing water level in the conduit system. From tracer tests with injection at the surface, longitudinal dispersivity values are found to be large (8–27 m). The tailing observed in some TBCs is generated in the unsaturated zone before the tracer actually arrives at the major subsurface conduit draining the system. This work allows the estimation and prediction of the key transport parameters in karst aquifers. It shows that these parameters vary with time and flow dynamics, and they reflect the geometry of the flow pathway and the origin of infiltrating (potentially contaminated) recharge.     

Flow and solute transport monitoring in the karst aquifer in SW Slovenia

The role of the unsaturated zone in the karst aquifer hydraulic behaviour was brought into focus in these studies of the catchment of the Hubelj spring (SW Slovenia). The variations of natural tracers in precipitation and in groundwater during a summer storm event made it possible to trace local flow and solute transport in the observed aquifer. The results produced data on the aquifer recharge, storage and discharge processes, as well as on mechanisms that affected them, which reflects a karst groundwater dynamics also at a regional scale. They point out the significance of effects of the fast preferential flow—epiflow that is the main factor controlling solute/contaminant transport towards the aquifer saturated zone. Numerous arguments indicate that the karst aquifer flow and solute transport mechanisms depend on the hydraulic behaviour of the epikarst zone.     

Quantifying stream-loss recovery in a spring using dual-tracer injections in the Snake Creek drainage,Great Basin National Park,Nevada, USA

Simultaneous short-pulse injections of two tracers (sodium bromide [Br^–] and fluorescein dye) were made in a losing reach of Snake Creek in Great Basin National Park, Nevada, USA, to evaluate the quantity of stream loss through permeable carbonates that resurfaces at a spring approximately 10 km down drainage. A revised hydrogeologic cross section for a possible flow path of the infiltrated Snake Creek water is presented, and the results may inform water management in the region. First arrival and peak concentration of the two tracers occurred at 9.5 and 12.7 days after injection, respectively. Fracture transport simulations indicate that Br^– preferentially diffuses into immobile regions of the aquifer, and this diffusive flux is likely responsible for the major differences in the breakthrough curves. When considering the diffusive tracer flux, total apparent Br^– and fluorescein dye recoveries were 16.9–22.1% and 21.7–24.3%, respectively. These findings imply that consideration of diffusive flux and long-term monitoring in fracture-dominated flow may support accurate quantification of tracer recovery. In addition, the apparent power law slopes of the breakthrough tails for both tracers were steeper at early times than have been attributed to heterogeneous advection or channeling in meter-scale tests, but the late-time Br^– power law slope becomes less steep than has been attributed to diffusive exchange. These deviations may reflect fracture transport patterns that occur at larger scales.