Dual-domain transport is an alternative conceptual and mathematical paradigm to advection-dispersion for describing the movement of dissolved constituents in groundwater. Here we test the use of a dual-domain algorithm combined with advective pathline tracking to help reconcile environmental tracer concentrations measured in springs within the Shenandoah Valley, USA. The approach also allows for the estimation of the three dual-domain parameters: mobile porosity, immobile porosity, and a domain exchange rate constant. Concentrations of CFC-113, SF6, H-3, and He-3 were measured at 28 springs emanating from carbonate rocks. The different tracers give three different mean composite piston-flow ages for all the springs that vary from 5 to 18 years. Here we compare four algorithms that interpret the tracer concentrations in terms of groundwater age: piston flow, old-fraction mixing, advective-flow path modeling, and dual-domain modeling. Whereas the second two algorithms made slight improvements over piston flow at reconciling the disparate piston-flow age estimates, the dual-domain algorithm gave a very marked improvement. Optimal values for the three transport parameters were also obtained, although the immobile porosity value was not well constrained. Parameter correlation and sensitivities were calculated to help quantify the uncertainty. Although some correlation exists between the three parameters being estimated, a watershed simulation of a pollutant breakthrough to a local stream illustrates that the estimated transport parameters can still substantially help to constrain and predict the nature and timing of solute transport. The combined use of multiple environmental tracers with this dual-domain approach could be applicable in a wide variety of fractured-rock settings.Plain Language Summary The movement of dissolved chemicals, such as pollutants, underground has been notoriously difficult to predict in terrains composed of fractured rock because of the complex way in which the chemicals mix between fractures and the host rock. One evidence for this has been that when different atmospheric-derived tracers are measured in springs in karst terrains they give different apparent times of travel between the land surface and the spring. The authors of this paper have presented a new approach that can both partially characterize the nature of how such chemicals are mixing underground and reconcile the difference in apparent times of travel. The authors took a widely used model that can simulate the flow of groundwater and transport of chemicals without mixing, and applied it the upper Potomac River Basin where they had tracer data from 28 springs. They wrote a new routine that calculates the mixing of the chemicals in transit and added it to the flow lines predicted by the simulation model. They were able to reproduce the tracer concentrations in the springs, partially constrain the amount of void space in both the fractures and solid rock, and estimate the rate at which chemicals exchange between these two.

Numerous methods have been proposed to estimate the pre-nuclear-detonation C-14 content of dissolved inorganic carbon (DIC) recharged to groundwater that has been corrected/adjusted for geochemical processes in the absence of radioactive decay (C-14(0)) - a quantity that is essential for estimation of radiocarbon age of DIC in groundwater. The models/approaches most commonly used are grouped as follows: (1) single-sample based models, (2) a statistical approach based on the observed (curved) relationship between C-14 and delta C-13 data for the aquifer, and (3) the geochemical mass-balance approach that constructs adjustment models accounting for all the geochemical reactions known to occur along a groundwater flow path. This review discusses first the geochemical processes behind each of the single-sample-based models, followed by discussions of the statistical approach and the geochemical mass-balance approach. Finally, the applications, advantages and limitations of the three groups of models/approaches are discussed.The single-sample-based models constitute the prevailing use of C-14 data in hydrogeology and hydrological studies. This is in part because the models are applied to an individual water sample to estimate the C-14 age, therefore the measurement data are easily available. These models have been shown to provide realistic radiocarbon ages in many studies. However, they usually are limited to simple carbonate aquifers and selection of model may have significant effects on C-14(0) often resulting in a wide range of estimates of C-14 ages.Of the single-sample-based models, four are recommended for the estimation of C-14(0) of DIC in groundwater: Pearson's model, (Ingerson and Pearson, 1964; Pearson and White, 1967), Han & Plummer's model (Han and Plummer, 2013), the IAEA model (Gonfiantini, 1972; Salem et al., 1980), and Oeschger's model (Geyh, 2000). These four models include all processes considered in single-sample-based models, and can be used in different ranges of C-13 values.In contrast to the single-sample-based models, the extended Gonfiantini & Zuppi model (Gonfiantini and Zuppi, 2003; Han et al., 2014) is a statistical approach. This approach can be used to estimate C-14 ages when a curved relationship between the C-14 and C-13 values of the DIC data is observed. In addition to estimation of groundwater ages, the relationship between C-14 and delta C-13 data can be used to interpret hydrogeological characteristics of the aquifer, e.g. estimating apparent rates of geochemical reactions and revealing the complexity of the geochemical environment, and identify samples that are not affected by the same set of reactions/processes as the rest of the dataset. The investigated water samples may have a wide range of ages, and for waters with very low values of C-14, the model based on statistics may give more reliable age estimates than those obtained from single sample-based models. In the extended Gonfiantini & Zuppi model, a representative system-wide value of the initial C-14 content is derived from the C-14 and delta C-13 data of DIC and can differ from that used in single-sample-based models. Therefore, the extended Gonfiantini & Zuppi model usually avoids the effect of modern water components which might retain 'bomb' pulse signatures.The geochemical mass-balance approach constructs an adjustment model that accounts for all the geochemical reactions known to occur along an aquifer flow path (Plummer et al., 1983; Wigley et al., 1978; Plummer et al., 1994; Plummer and Glynn, 2013), and includes, in addition to DIC, dissolved organic carbon (DOC) and methane (CH4). If sufficient chemical, mineralogical and isotopic data are available, the geochemical mass-balance method can yield the most accurate estimates of the adjusted radiocarbon age. The main limitation of this approach is that complete information is necessary on chemical, mineralogical and isotopic data and these data are often limited. Failure to recognize the limitations and underlying assumptions on which the various models and approaches are based can result in a wide range of estimates of C-14(0) and limit the usefulness of radiocarbon as a dating tool for groundwater. In each of the three generalized approaches (single-sample-based models, statistical approach, and geochemical mass-balance approach), successful application depends on scrutiny of the isotopic (C-14 and C-13) and chemical data to conceptualize the reactions and processes that affect the C-14 content of DIC in aquifers. The recently developed graphical analysis method is shown to aid in determining which approach is most appropriate for the isotopic and chemical data from a groundwater system. (C) 2015 Elsevier B.V. All rights reserved.

A new analytical method using gas chromatography with an atomic emission detector (GC–AED) was developed for measurement of ambient concentrations of hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) in soil, air, and groundwater, with the goal of determining their utility as groundwater age tracers. The analytical detection limits of HCFC-22 (difluorochloromethane, CHClF2) and HFC-134a (1,2,2,2-tetrafluoroethane, C2H2F4) in 1L groundwater samples are 4.3×10−1 and 2.1×10−1pmolkg−1, respectively, corresponding to equilibrium gas-phase mixing ratios of approximately 5–6 parts per trillion by volume (pptv). Under optimal conditions, post-1960 (HCFC-22) and post-1995 (HFC-134a) recharge could be identified using these tracers in stable, unmixed groundwater samples. Ambient concentrations of HCFC-22 and HFC-134a were measured in 50 groundwater samples from 27 locations in northern and western parts of Virginia, Tennessee, and North Carolina (USA), and 3 unsaturated-zone profiles were collected in northern Virginia. Mixing ratios of both HCFC-22 and HFC-134a decrease with depth in unsaturated-zone gas profiles with an accompanying increase in CO2 and loss of O2. Apparently, ambient concentrations of HCFC-22 and HFC-134a are readily consumed by methanotrophic bacteria under aerobic conditions in the unsaturated zone. The results of this study indicate that soils are a sink for these two greenhouse gases. These observations contradict the previously reported results from microcosm experiments that found that degradation was limited above-ambient HFC-134a. The groundwater HFC and HCFC concentrations were compared with concentrations of chlorofluorocarbons (CFCs, CFC-11, CFC-12, CFC-113) and sulfur hexafluoride (SF6). Nearly all samples had measured HCFC-22 or HFC-134a that were below concentrations predicted by the CFCs and SF6, with many samples showing a complete loss of HCFC-22 and HFC-134a. This study indicates that HCFC-22 and HFC-134a are not conservative as environmental tracers and leaves in question the usefulness of other HCFCs and HFCs as candidate age tracers.

Determination of the C-14 content of dissolved inorganic carbon (DIC) is useful for dating of groundwater. However, in addition to radioactive decay, the C-14 content in DIC (C-14(DIC)) can be affected by many geochemical and physical processes and numerous models have been proposed to refine radiocarbon ages of DIC in groundwater systems.Changes in the delta C-13 content of DIC (delta C-13(DIC)) often can be used to deduce the processes that affect the carbon isotopic composition of DIC and the C-14 value during the chemical evolution of groundwater. This paper shows that a curved relationship of C-14(DIC) vs.delta C-13(DIC) will be observed for groundwater systems if (1) the change in delta C-13 value in DIC is caused by a first-order or pseudo-first-order process, e.g.isotopic exchange between DIC and solid carbonate, (2) the reaction/process progresses with the ageing of the groundwater, i.e.with decay of C-14 in DIC, and (3) the magnitude of the rate of change in delta C-13 of DIC is comparable with that of C-14 decay.In this paper,we use a lumped parameter method to derive a model based on the curved relationship between C-14(DIC) and delta C-13(DIC).The derived model, if used for isotopic exchange between DIC and solid carbonate, is identical to that derived by Gonfiantini and Zuppi (2003).The curved relationship of C-14(DIC) vs. delta C-13(DIC) can be applied to interpret the age of the DIC in groundwater.Results of age calculations using the Method discussed in this paper are compared with those obtained by using other methods that calculate the age of DIC based on adjusted initial radiocarbon values for individual samples.This paper shows that in addition to groundwater age interpretation,the lumped parameter method presented here also provides a useful tool for geochemical interpretations, e.g.estimation of apparent rates of geochemical reactions and revealing the complexity of the geochemical environment. (C) 2014 Elsevier B.V.All rights reserved.

A 17-year record (1995–2012) of a suite of environmental tracer concentrations in discharge from 34 springs located along the crest of the Blue Ridge Mountains in Shenandoah National Park (SNP), Virginia, USA, reveals patterns and trends that can be related to climatic and environmental conditions. These data include a 12-year time series of monthly sampling at five springs, with measurements of temperature, specific conductance, pH, and discharge recorded at 30-min intervals. The monthly measurements include age tracers (CFC-11, CFC-12, CFC-113, CFC-13, SF6, and SF5CF3), dissolved gases (N2, O2, Ar, CO2, and CH4), stable isotopes of water, and major and trace inorganic constituents. The chlorofluorocarbon (CFC) and sulfur hexafluoride (SF6) concentrations (in pptv) in spring discharge closely follow the concurrent monthly measurements of their atmospheric mixing ratios measured at the Air Monitoring Station at Big Meadows, SNP, indicating waters 0–3 years in age. A 2-year (2001–2003) record of unsaturated zone air displayed seasonal deviations from North American Air of ±10 % for CFC-11 and CFC-113, with excess CFC-11 and CFC-113 in peak summer and depletion in peak winter. The pattern in unsaturated zone soil CFCs is a function of gas solubility in soil water and seasonal unsaturated zone temperatures. Using the increase in the SF6 atmospheric mixing ratio, the apparent (piston flow) SF6 age of the water varied seasonally between about 0 (modern) in January and up to 3 years in July–August. The SF6 concentration and concentrations of dissolved solutes (SiO2, Ca2+, Mg2+, Na+, Cl−, and HCO3 −) in spring discharge demonstrate a fraction of recent recharge following large precipitation events. The output of solutes in the discharge of springs minus the input from atmospheric deposition per hectare of watershed area (mol ha−1 a−1) were approximately twofold greater in watersheds draining the regolith of Catoctin metabasalts than that of granitic gneisses and granitoid crystalline rocks. The stable isotopic composition of water in spring discharge broadly correlates with the Oceanic Niño Index. Below normal precipitation and enriched stable isotopic composition were observed during El Niño years.

During October 1995 through March 2014, the U.S. Geological Survey in cooperation with the National Park Service, Luray, Virginia Station collected and analyzed samples of selected springs, air and unsaturated-zone gases in Shenandoah National Park, Virginia. The 19-year record of measurements of chemical and isotopic composition of water discharging from 34 springs located along the crest of the Blue Ridge Mountains in Shenandoah National Park, Virginia, is reported. These data include field measurements of water temperature, specific conductance, concentrations of dissolved oxygen (O2), and pH. Laboratory measurements included major-, minor-, and trace-element chemistry; concentrations of dissolved gases (nitrogen, [N2] argon [Ar], oxygen, and carbon dioxide [CO2]); concentrations of dissolved trace atmospheric gases, including trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), and trichlorotrifluoroethane (CFC-113) and sulfur hexafluoride (SF6); and hydrogen stable isotopic composition (δ2H) and oxygen isotopic composition (δ18O) of water. The data include an up to 14-year time series record of monthly sampling at five springs collected between 1995 and 2013. The measurements included temperature, specific conductance, pH, and discharge recorded at 30-minute intervals. Atmospheric mixing ratios of CFC-11, CFC-12, CFC-113, trifluorobromomethane (CF3Br), SF6, and trifluoromethyl sulfur pentafluoride (SF5CF3) in air from the Big Meadows Air Monitoring Station, Shenandoah National Park, were measured at approximately weekly intervals from September 1995 through March 2014. Additional data include monthly (between May 2001 and August 2003) measurements of temperature, N2, O2, Ar, CO2, CFC-12, CFC-11, CFC-113, and SF6 concentrations in unsaturated-zone air from seven multilevel piezometers in Shenandoah National Park and at the U.S. Geological Survey National Center in Reston, Virginia. All samples were analyzed at the U.S. Geological Survey Laboratories in Reston, Virginia.

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from H-3/He-3 and SF6 data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC-ECD) exceeded that possible for air-water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg(-1)), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The H-3/He-3 groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003-2004), and ages in the range of 4-7 a in periods of more average precipitation (2008-2009). The SF6 and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities. Published by Elsevier Ltd.

This book investigates applications of selected chemical and isotopic substances that can be used to recognize and interpret age information pertaining to 'old' groundwater (defined as water that was recharged on a timescale from approximately 1000 to more than 1 000 000 a). However, as discussed below, only estimates of the 'age' of water extracted from wells can be inferred. These groundwater age estimates are interpreted from measured concentrations of chemical and isotopic substances in the groundwater. Even then, there are many complicating factors, as discussed in this book. In spite of these limitations, much can be learned about the physics of groundwater flow and about the temporal aspects of groundwater systems from age interpretations of measured concentrations of environmental tracers in groundwater systems. This chapter puts the concept of 'age' into context, including its meaning and interpretation, and attempts to provide a unifying usage for the rest of the book.

The widely applied model for groundwater dating using 14C proposed by Fontes and Garnier (F&G) (Fontes and Garnier, 1979) estimates the initial 14C content in waters from carbonate-rock aquifers affected by isotopic exchange. Usually, the model of F&G is applied in one of two ways: (1) using a single 13C fractionation factor of gaseous CO2 with respect to a solid carbonate mineral, εg/s, regardless of whether the carbon isotopic exchange is controlled by soil CO2 in the unsaturated zone, or by solid carbonate mineral in the saturated zone; or (2) using different fractionation factors if the exchange process is dominated by soil CO2 gas as opposed to solid carbonate mineral (typically calcite). An analysis of the F&G model shows an inadequate conceptualization, resulting in underestimation of the initial 14C values (14C0) for groundwater systems that have undergone isotopic exchange. The degree to which the 14C0 is underestimated increases with the extent of isotopic exchange. Examples show that in extreme cases, the error in calculated adjusted initial 14C values can be more than 20% modern carbon (pmc). A model is derived that revises the mass balance method of F&G by using a modified model conceptualization. The derivation yields a “global” model both for carbon isotopic exchange dominated by gaseous CO2 in the unsaturated zone, and for carbon isotopic exchange dominated by solid carbonate mineral in the saturated zone. However, the revised model requires different parameters for exchange dominated by gaseous CO2 as opposed to exchange dominated by solid carbonate minerals. The revised model for exchange dominated by gaseous CO2 is shown to be identical to the model of Mook (Mook, 1976). For groundwater systems where exchange occurs both in the unsaturated zone and saturated zone, the revised model can still be used; however, 14C0 will be slightly underestimated. Finally, in carbonate systems undergoing complex geochemical reactions, such as oxidation of organic carbon, radiocarbon ages are best estimated by inverse geochemical modeling techniques.

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.

We compile a unique 13-year record of groundwater age for 11 springs in Sagehen basin, a watershed in the Sierra Nevada Mountains of California, USA. Chlorofluorocarbon (CFC), sulfur hexafluoride (SF6), and tritium (H-3) data collected in prior studies from 1997 to 2003 are re-interpreted and combined with new data collected in 2009 and 2010. The age record is analyzed to explore the potential value of groundwater age monitoring for (1) providing additional constraints on the age distribution in mixed-age samples, and (2) identifying temporal changes in groundwater recharge. Motivation for this study is provided by a lack of knowledge of how groundwater recharge and discharge (stream baseflow) in mountain watersheds might respond to climate change, and a resulting need to better understand mountain aquifer residence times, storage, and recharge. Piston-flow ages for the springs generally range from 10 to 50 yr. The plausibility of different age mixing models is tested by comparing observed temporal variations in age with those simulated using simple numerical models, and by examining plots comparing the concentrations of different age tracers. We find that most spring waters are best characterized by a bimodal mixing model consisting of a new (<1 yr old) fraction and a fraction that is older, but still modern (recharged after 1950). Identification of this mixing model would not have been possible without data from multiple age tracers and data from multiple years. Computed mean ages vary substantially (often by 3-7 yr) between sampling events for most springs, including those with ages of 20-50 yr. Mean age variations are likely controlled by variations in the magnitude of the new fraction, which is positively correlated with annual snowpack water content. Most springs show overall upward trends in mean age for the sampling period, consistent with decreasing recharge rates in response to diminishing snowpack. Groundwater age monitoring appears to be a potentially valuable tool for both constraining the age distribution in sampled waters and investigating recharge transients. Published by Elsevier B.V.

Apparent groundwater ages along two flow paths in the upper Patapsco aquifer of the Maryland Atlantic Coastal Plain, USA, were estimated using 14C, 36Cl and 4He data. Most of the ages range from modern to about 500 ka, with one sample at 117 km downgradient from the recharge area dated by radiogenic 4He accumulation at more than one Ma. Last glacial maximum (LGM) water was located about 20 km downgradient on the northern flow path, where the radiocarbon age was 21.5 ka, paleorecharge temperatures were 0.5–1.5  °C (a maximum cooling of about 12 °C relative to the modern mean annual temperature of 13 °C), and Cl–, Cl/Br, and stable isotopes of water were minimum. Low recharge temperatures (typically 5–7 °C) indicate that recharge occurred predominantly during glacial periods when coastal heads were lowest due to low sea-level stand. Flow velocities averaged about 1.0 m a–1 in upgradient parts of the upper Patapsco aquifer and decreased from 0.13 to 0.04 m a–1 at 40 and 80 km further downgradient, respectively. This study demonstrates that most water in the upper Patapsco aquifer is non-renewable on human timescales under natural gradients, thus highlighting the importance of effective water-supply management to prolong the resource.

A graphical method is described for identifying geochemical reactions needed in the interpretation of radiocarbon age in groundwater systems. Graphs are constructed by plotting the measured 14C, δ13C, and concentration of dissolved inorganic carbon and are interpreted according to specific criteria to recognize water samples that are consistent with a wide range of processes, including geochemical reactions, carbon isotopic exchange, 14C decay, and mixing of waters. The graphs are used to provide a qualitative estimate of radiocarbon age, to deduce the hydrochemical complexity of a groundwater system, and to compare samples from different groundwater systems. Graphs of chemical and isotopic data from a series of previously-published groundwater studies are used to demonstrate the utility of the approach. Ultimately, the information derived from the graphs is used to improve geochemical models for adjustment of radiocarbon ages in groundwater systems.

This report documents selected age data interpreted from measured concentrations of environmental tracers in groundwater from 1,399 National Water-Quality Assessment (NAWQA) Program groundwater sites across the United States. The tracers of interest were chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), and tritium/helium-3 (3H/3He).Tracer data compiled for this analysis primarily were from wells representing two types of NAWQA groundwater studies—Land-Use Studies (shallow wells, usually monitoring wells, in recharge areas under dominant land-use settings) and Major-Aquifer Studies (wells, usually domestic supply wells, in principal aquifers and representing the shallow, used resource). Reference wells (wells representing groundwater minimally impacted by anthropogenic activities) associated with Land-Use Studies also were included. Tracer samples were collected between 1992 and 2005, although two networks sampled from 2006 to 2007 were included because of network-specific needs. Tracer data from other NAWQA Program components (Flow System Studies, which are assessments of processes and trends along groundwater flow paths, and various topical studies) were not compiled herein.Tracer data from NAWQA Land-Use Studies and Major-Aquifer Studies that previously had been interpreted and published are compiled herein (as piston-flow ages), but have not been reinterpreted. Tracer data that previously had not been interpreted and published are evaluated using documented methods and compiled with aqueous concentrations, equivalent atmospheric concentrations (for CFCs and SF6), estimates of tracer-based piston-flow ages, and selected ancillary data, such as redox indicators, well construction, and major dissolved gases (N2, O2, Ar, CH4, and CO2).Tracer-based piston-flow ages documented in this report are simplistic representations of the tracer data. Tracer-based piston-flow ages are a convenient means of conceptualizing groundwater age. However, the piston-flow model is based on the potentially limiting assumptions that tracer transport is advective and that no mixing occurs. Additional uncertainties can arise from tracer degradation, sorption, contamination, or fractionation; terrigenic (natural) sources of tracers; spatially variable atmospheric tracer concentrations; and incomplete understanding of mechanisms of recharge or of the conditions under which atmospheric tracers were partitioned to recharge. The effects of some of these uncertainties are considered herein. For example, degradation, contamination, or fractionation often can be identified or inferred. However, detailed analysis of the effects of such uncertainties on the tracer-based piston-flow ages is constrained by sparse data and an absence of complementary lines of evidence, such as detailed solute transport simulations. Thus, the tracer-based piston-flow ages compiled in this report represent only an initial interpretation of the tracer data.