A detailed local-scale monitoring network was used to assess CFC distribution in an unconfined sand aquifer in southwestern Ontario where the zone of 1–5-year-old groundwater was known with certainty because of prior use of a bromide tracer. Groundwater ⩽5 years old was confined to an aerobic zone at ⩽5m depth and had CFC concentrations consistent with modern atmospheric mixing ratios at recharge temperatures of 7–11°C, as was observed in the 3-m thick vadose zone at the site. At depths below 6m, the groundwater became progressively more reducing, however, with a denitrifying horizon at 6–7m depth, and a Mn and Fe reducing zone below 7m depth. In the anaerobic zone, 3H/3He ratios indicated that groundwater-age continued to increase uniformly with depth, to a maximum value of 27 years at 13m depth. CFC concentrations, however, decreased abruptly within the denitrifying zone, leading to substantial age overestimation compared to the 3H/3He ages. Noble gas data indicated that the apparent CFC mass loss was not likely the result of gas stripping from possible bubble formation; thus, CFC degradation was indicated in the anoxic zone. The field data are consistent with first-order degradation rates of 0.3yr−1 for CFC-12, 0.7yr−1 for CFC-11, and 1.6yr−1 for CFC-113. CFC attenuation at this site coincides with a zone where reduced S (pyrite) is actively oxidized by NO3 and dissolved oxygen (DO). Similar behavior has been observed at other sites [Tesoriero, A.J., Liebscher, H., Cox, S.E., 2000. Mechanism and rate of denitrification in an agricultural watershed: electron and mass balance along groundwater flow path. Water Resour. Res. 36 (6), 1545–1559; Hinsby, K., Hojberg, A.L., Engesgaard, P., Jensen, K.H., Larsen, F., Plummer, L.N., Busenberg, E., Accepted for publication. Transport and degradation of chlorofluorocarbons (CFCs) in a pyritic aquifer, Rabis Creek, Denmark. Water Resour. Res.], further demonstrating that the use of CFCs for age-dating anaerobic groundwater should be approached with caution, particularly if the sediment contains pyrite.

Vertical profiles of the chlorofluorocarbons CFC‐11, CFC‐12, and CFC‐113 penetrating aerobic and anaerobic parts of a shallow sandy aquifer show that the CFC gases are degraded in the <1 m thick transition zone from aerobic to anaerobic groundwater in a pyritic sand aquifer at Rabis Creek, Denmark. Two‐dimensional solute transport simulations with either zero‐order or first‐order degradation in the anaerobic zone corroborate this interpretation. The transport model was previously calibrated against detailed tritium profiles in the same wells. First‐order degradation is found to best match the observed CFC profiles yielding an approximate half‐life of a few months for CFC‐11. Degradation is not as clearly recognized for CFC‐12 and CFC‐113, but it may occur with rates corresponding to a half‐life of a few years or more. Data indicate a geochemical control of the CFC concentration gradient at the redox front and that denitrification and denitrifiers are not of major importance for the observed CFC degradation. The responsible mechanism behind the observed degradation is not known but we suggest that reductive dehalogenation by surface‐bound Fe(II) on pyrite possibly enhanced by the presence of Fe(III)‐bearing weathering products (green rust) may be a plausible mechanism. The observed data and the performed simulations confirm the potential application of the CFC gases as age‐dating tools in the aerobic part of the investigated aquifer, but also that CFC data must be analyzed carefully before it is used as a dating tool in reducing aquifers because degradation may have occurred. The use of multiple or alternative tracers should be considered in anaerobic environments.

Transport of chlorofluorocarbon (CFC) gases through the unsaturated zone to the water table is affected by gas diffusion, air–water exchange (solubility), sorption to the soil matrix, advective–dispersive transport in the water phase, and, in some cases, anaerobic degradation. In deep unsaturated zones, this may lead to a time lag between entry of gases at the land surface and recharge to groundwater. Data from a Danish field site were used to investigate how time lag is affected by variations in water content and to explore the use of simple analytical solutions to calculate time lag. Numerical simulations demonstrate that either degradation or sorption of CFC‐11 takes place, whereas CFC‐12 and CFC‐113 are nonreactive. Water flow did not appreciably affect transport. An analytical solution for the period with a linear increase in atmospheric CFC concentrations (approximately early 1970s to early 1990s) was used to calculate CFC profiles and time lags. We compared the analytical results with numerical simulations. The time lags in the 15‐m‐deep unsaturated zone increase from 4.2 to between 5.2 and 6.1 yr and from 3.4 to 3.9 yr for CFC‐11 and CFC‐12, respectively, when simulations change from use of an exponential to a linear increase in atmospheric concentrations. The CFC concentrations at the water table before the early 1990s can be estimated by displacing the atmospheric input function by these fixed time lags. A sensitivity study demonstrates conditions under which a time lag in the unsaturated zone becomes important. The most critical parameter is the tortuosity coefficient. The analytical approach is valid for the low range of tortuosity coefficients (τ = 0.1–0.4) and unsaturated zones greater than approximately 20 m in thickness. In these cases the CFC distribution may still be from either the exponential or linear phase. In other cases, the use of numerical models, as described in our work and elsewhere, is an option.

Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl4), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl4, chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6.7% of the CCl4 and PCE detections, respectively, in pre-1940 water, and 68% and 62% of the CCl4 and PCE detections, respectively, in water recharged in 2000 exceed solubility equilibrium with average atmospheric concentrations. These exceedences can be attributed to local atmospheric enrichment or direct contaminant input to ground-water flow systems. The detection of VOCs at concentrations indicative of atmospheric sources in 100% of the samples indicates that untreated drinking water from ground-water sources in the US recharged within the past 60 years has been affected by anthropogenic activity. Additional inputs from a variety of sources such as spills, underground injections and leaking landfills or storage tanks increasingly are providing additional sources of contamination to ground water used as drinking-water sources.

Model ground water ages based on chlorofluorocarbons (CFCs) and tritium/helium-3 (H-3/He-3) data were obtained from two arrays of nested piezometers located on the north limb of an anticline in fractured sedimentary rocks in the Valley and Ridge geologic province of Pennsylvania. The fracture geometry of the gently east plunging fold is very regular and consists predominately of south dipping to subhorizontal to north dipping bedding-plane parting and east striking, steeply dipping axial-plane spaced cleavage. In the area of the piezometer arrays, which trend north-south on the north limb of the fold, north dipping bedding-plane parting is a more dominant fracture set than is steeply south dipping axial-plane cleavage. The dating of ground water from the piezometer arrays reveals that ground water traveling along paths parallel to the dip direction of bedding-plane parting has younger H-3/He-3 and CFC model ages, or a greater component of young water, than does ground water traveling along paths opposite to the dip direction. In predominantly unmixed samples there is a strong positive correlation between age of the young fraction of water and dissolved sodium concentration. The travel times inferred from the model ages are significantly longer than those previously calculated by a ground water flow model, which assumed isotropically fractured layers parallel to topography. A revised model factors in the directional anisotropy to produce longer travel times. Ground water travel times in the watershed therefore appear to be more influenced by anisotropic fracture geometry than previously realized. This could have significant implications for ground water models in other areas underlain by similarly tilted or folded sedimentary rock, such as elsewhere in the Valley and Ridge or the early Mesozoic basins.

Recent studies have suggested that DIC in cold groundwaters may represent a significant fraction of global volcanic carbon emissions. Big Springs, in eastern California, has a flow rate of 9 x 10(4) m(3)/d and forms the headwaters of the Owens River. Its total DIC discharge is 10.1 t/d (as CO2) with a C-14 of 41.5 pmC. Tritium and SF6 indicate an average flow time of < 50 years, so the depletion in C-14 from 117 pmC results from an input of 6.5 t/d of dead carbon. The springs issue from volcanic rocks filling the floor of the 760-ka Long Valley caldera but also drain areas of marine meta-sediments, which could provide dead carbon. Various tracers, both natural ((3) He) and anthropogenic (Cl-, NO3-), suggest that the dead carbon is magmatic and mostly sourced from Mammoth Mountain volcano, the locus of strong CO2 emissions 15 km to the SW.

Chemical and isotopic properties of water discharging from springs and wells in Shenandoah National Park (SNP), near the crest of the Blue Ridge Mountains, VA, USA were monitored to obtain information on groundwater residence times. Investigated time scales included seasonal (wet season, April, 1996; dry season, August–September, 1997), monthly (March through September, 1999) and hourly (30-min interval recording of specific conductance and temperature, March, 1999 through February, 2000). Multiple environmental tracers, including tritium/helium-3 (3H/3He), chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), sulfur-35 (35S), and stable isotopes (δ18O and δ2H) of water, were used to estimate the residence times of shallow groundwater discharging from 34 springs and 15 wells. The most reliable ages of water from springs appear to be based on SF6 and 3H/3He, with most ages in the range of 0–3 years. This range is consistent with apparent ages estimated from concentrations of CFCs; however, CFC-based ages have large uncertainties owing to the post-1995 leveling-off of the CFC atmospheric growth curves. Somewhat higher apparent ages are indicated by 35S (>1.5 years) and seasonal variation of δ18O (mean residence time of 5 years) for spring discharge. The higher ages indicated by the 35S and δ18O data reflect travel times through the unsaturated zone and, in the case of 35S, possible sorption and exchange of S with soils or biomass. In springs sampled in April, 1996, apparent ages derived from the 3H/3He data (median age of 0.2 years) are lower than those obtained from SF6 (median age of 4.3 years), and in contrast to median ages from 3H/3He (0.3 years) and SF6 (0.7 years) obtained during the late summer dry season of 1997. Monthly samples from 1999 at four springs in SNP had SF6 apparent ages of only 1.2 to 2.5±0.8 years, and were consistent with the 1997 SF6 data. Water from springs has low excess air (0–1 cm3 kg−1) and N2–Ar temperatures that vary seasonally. Concentrations of He and Ne in excess of solubility equilibrium indicate that the dissolved gases are not fractionated. The seasonal variations in N2–Ar temperatures suggest shallow, seasonal recharge, and the excess He and Ne data suggest waters mostly confined to gas exchange in the shallow, mountain-slope, water-table spring systems. Water from wells in the fractured rock contains up to 8 cm3 kg−1 of excess air with ages in the range of 0–25 years. Transient responses in specific conductance and temperature were observed in spring discharge within several hours of large precipitation events in September, 1999; both parameters increased initially, then decreased to values below pre-storm base-flow values. The groundwater residence times indicate that flushing rates of mobile atmospheric constituents through groundwater to streams draining the higher elevations in SNP average less than 3 years in base-flow conditions.

Sulfur hexafluoride (SF6) is primarily of anthropogenic origin but also occurs naturally. The troposphere concentration of SF6 has increased from a steady state value of 0.054±0.009 to more than 4 parts per trillion volume during the past 40 years. An analytical procedure was developed for measuring concentrations of SF6 to less than 0.01 fmol/L in water. Groundwater can be dated with SF6 if it is in equilibrium with atmospheric SF6 at the time of recharge and does not contain significant SF6 from other sources. The dating range of SF6 is currently 0 to 30 years. The tracer was successfully used to date shallow groundwater of the Atlantic Coastal Plain sand aquifers of the United States and springs issuing near the top of the Blue Ridge Mountains of Virginia. Significant concentrations of naturally occurring SF6 were found in some igneous, volcanic, and sedimentary rocks and in some hydrothermal fluids.

Interpretation of CFC analyses in groundwater samples from fractured rock aquifers is complicated due to mixing of water within the aquifer and during borehole sampling. Recharge dates derived directly from atmospheric CFC master curves are meaningless, since samples contain water from a range of flow paths in different proportions. Additional tracers, with appropriate input functions need to be used to quantify these effects. Groundwater from the fractured Table Mountain Group produced a range of inconsistent C-14 ages, tritium ages and CFC recharge dates when interpreted as unmixed, piston-flow water samples. Plots of the tracer concentrations against each other were compared to that of tracer input curves. They demonstrate mixing between a young and an old component that is consistent with the flow patterns established earlier. This approach offers possibilities to use CFC analyses in mixed-water aquifers containing significant amounts of water recharged during the last few decades.

Stable isotope data (2H and 18O) were used in conjunction with chlorofluorocarbon (CFC) and tritium/helium‐3 (3H/3He) data to determine the fraction and age of irrigation water in ground water mixtures from farmed parts of the Eastern Snake River Plain (ESRP) Aquifer in south‐central Idaho. Two groups of waters were recognized: (1) regional background water, unaffected by irrigation and fertilizer application, and (2) mixtures of irrigation water from the Snake River with regional background water. New data are presented comparing CFC and 3H/3He dating of water recharged through deep fractured basalt, and dating of young fractions in ground water mixtures. The 3H/3He ages of irrigation water in most mixtures ranged from about zero to eight years. The CFC ages of irrigation water in mixtures ranged from values near those based on 3H/3He dating to values biased older than the 3H/3He ages by as much as eight to 10 years. Unsaturated zone air had CFC‐12 and CFC‐113 concentrations that were 60% to 95%, and 50% to 90%, respectively, of modern air concentrations and were consistently contaminated with CFC‐11. Irrigation water diverted from the Snake River was contaminated with CFC‐11 but near solubility equilibrium with CFC‐12 and CFC‐113. The dating indicates ground water velocities of 5 to 8 m/d for water along the top of the ESRP Aquifer near the southwestern boundary of the Idaho National Engineering and Environmental Laboratory (INEEL). Many of the regional background waters contain excess terrigenic helium with a 3He/4He isotope ratio of 7 × 10−6 to 11 × 10−6 (R/Ra= 5 to 8) and could not be dated. Ratios of CFC data indicate that some rangeland water may contain as much as 5% to 30% young water (ages of less than or equal to two to 11.5 years) mixed with old regional background water. The relatively low residence times of ground water in irrigated parts of the ESRP Aquifer and the dilution with low‐NO3 irrigation water from the Snake River lower the potential for NO3 contamination in agricultural areas.

The impact on ground water quality from increasing fertilizer application rates over the past 40 years is evaluated within a glacial aquifer system beneath a thick unsaturated zone. Ground water ages within the aquifer could not be accurately determined from the measured distribution of 3H and as a result, chlorofluorocarbon (CFC) and 3H/3He dating techniques were applied. Beneath a 25 m thick unsaturated zone, ground water ages based on CFC‐11 concentrations were greater than 3H/3He ground water ages by 6 to 10 years, due to the time lag associated with the diffusion of CFCs through the unsaturated zone. Using the corrected CFC‐11 and 3H/3He ground water ages and the estimated travel time of 3H within the unsaturated zone, the approximate position of ground water recharged since the mid‐1960s was determined. Nitrate concentrations within post mid‐1960s recharge were generally elevated and near or above the drinking water limit of 10 mg‐N/L. In comparison, pre mid‐1960s recharge had nitrate concentrations <2.5 mg‐N/L. The elevated NO3− concentrations in post mid‐1960s recharge are attributed mainly to increasing fertilizer application rates between 1970 and the mid‐ to late 1980s. Anaerobic conditions suitable for denitrifkation are present within pre mid‐1960s recharge indicating that removal of DO is a slow process taking tens of years. Over the next 10 to 20 years, nitrate concentrations at municipal well fields that are currently capturing aerobic ground water recharged near the mid‐1960s are expected to increase because of the higher fertilizer application rates beginning in the 1970s and 1980s.

Tritium/helium-3 (H-3/He-3) and chlorofluorocarbon (CFCs, CFC-11, CFC-12, CFC-113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources - the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The H-3/He-3 age is independent of the extent of dilution with older (H-3-free and 3He(trit)-free) water. The groundwater mixtures are designated as Type-1 for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl- and delta(18)O data for water from the Upper Floridan aquifer at Valdosta, Georgia.The chlorofluorocarbons CFC-11 and CFC-113 are removed by microbial degradation and/or sorption processes in most anaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-1 water. CFC-12 persists in both SO4-reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg(-1)) permitted CFC-11 and CFC-12 dating of the fraction of regional infiltration water in Type-1 mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water samples obtained from the Upper Floridan aquifer have CFC-12-based ages of the young fraction that are consistent with the H-3 concentration of the groundwater. Because of uncertainties associated with very low H-3 and He-3 content in dilute mixtures, H-3/He-3 dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10% river water. Of the 41 water samples measured for H-3/He-3 dating, dilution of H-3 and low He-3 concentration limited H-3/He-3 dating to 16 mixtures in which H-3/He-3 ages are defined with errors ranging from +/- 2 to +/- 7.5 a (1 sigma). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC-12 ages agree with H-3/He-3 ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures.Tritium data and dating based on both CFC-11 and CFC-12 in Type-1 mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and H-3/He-3 dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.3 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10000 - a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River. (C) 1998 Elsevier Science Ltd. All rights reserved.

Boreholes open to the unsaturated zone at the crest of Yucca Mountain, Nevada, were variously sampled for CO2 (including 13C and 14C), CH4, N2, O2, Ar, CFC‐11, CFC‐12, and CFC‐113 from 1986 to 1993. Air enters the mountain in outcrops, principally on the eastern slope, is enriched in CO2 by mixing with soil gas, and is advected to the mountain crest, where it returns to the atmosphere. The CFC data indicate that travel times of the advecting gas in the shallow Tiva Canyon hydrogeologic unit are ≤5 years. The 14C activities are postbomb to depths of 100 m, indicating little retardation of 14CO2 in the shallow flow systems. The 14C activities from 168 to 404 m in the Topopah Spring hydrogeologic unit are 85–90 pMC at borehole USW‐UZ6. The CFC data show that the drilling of USW‐UZ6 in 1984 has altered the natural system by providing a conduit through the Paintbrush Nonwelded unit, allowing flow from Topopah Spring outcrops in Solitario Canyon on the west to USW‐UZ6, upward in the borehole through the Paintbrush, to the shallow Tiva Canyon flow systems, and out of the mountain.

The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl−, 3H, tritiogenic helium-3 (3He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O2 (DO), H2S, CH4, δ18O, δD, and 14C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl−, δ18O, δD, CFC-12, and the quantity (3H+3He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H2S, CH4, 14C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl− and δ18O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ18O=−2.5±0.3‰, Cl−=12.2±2 mg/l), (2) regional infiltration water (δ18O=−4.2±0.1‰, Cl−=2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ18O=−3.4±0.1‰, Cl−=2.6±0.1 mg/l) (uncertainties are ±1σ). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer.

Groundwater dating studies have supported the concept that aquifers with low coefficients of dispersion may contain coherent records of past conditions in recharge areas. Groundwater records can provide unique information about natural or anthropogenic changes in the atmosphere and hydrosphere where long-term monitoring data are not available. Here we describe a 40-year record of halocarbon contamination in the Danube River that was retrieved from a shallow aquifer in northwest Hungary. The time scale is based on H-3 and He isotope dating of groundwaters that were recharged by the Danube River and moved horizontally away from the river in a surficial gravel aquifer with minor dispersion at a maximum rate of at least 500 m/yr. Analyses of dated groundwaters along a flow path indicate that the river loads of selected compounds (including CFC-12, CFC-113, and trichloroethane) were negligible before about 1950, rose rapidly to peak values in the 1960s and 1970s, and then decreased by varying degrees to the present. Peak concentrations are tentatively attributed to point sources in upstream urban-industrial centers; while recent decreases presumably resulted from declining manufacturing rates and(or) improvements in control of urban-industrial runoff and sewage effluent entering the river in upstream areas.

The Ridge and Valley Province of eastern Tennessee is characterized by (1) substantial topographic relief, (2) folded and highly fractured rocks of various lithologies that have low primary permeability and porosity, and (3) a shallow residuum of medium permeability and high total porosity. Conceptual models of shallow groundwater flow and solute transport in this system have been developed but are difficult to evaluate using physical characterization or short‐term tracer methods due to extreme spatial variability in hydraulic properties. In this paper we describe how chlorofluorocarbon 12, 3H, and 3He were used to infer groundwater flow and solute transport in saprolite and fractured rock near Oak Ridge, Tennessee. In the shallow residuum, fracture spacings are <0.05 m, suggesting that concentrations of these tracers in fractures and in the matrix have time to diffusionally equilibrate. The relatively smooth nature of tracer concentrations with depth in the residuum is consistent with this model and quantitatively suggests recharge fluxes of 0.2 to 0.4 m yr−1. In contrast, groundwater flow within the unweathered rock appears to be controlled by fractures with spacings of the order of 2 to 5 m, and diffusional equilibration of fractures and matrix has not occurred. For this reason, vertical fluid fluxes in the unweathered rock cannot be estimated from the tracer data.

Groundwater age dating through the combination of transient tracer methods (chlorofluorocarbons (CFCs) and tritium/helium 3 ( 3 H/ 3 He)) and groundwater flow path analysis is useful for investigating groundwater travel times, flow patterns, and recharge rates, as demonstrated by this study of the homogeneous shallow, unconfined Kirkwood‐Cohansey aquifer system in the southern New Jersey coastal plain. Water samples for age dating were collected from three sets of nested observation wells (10 wells) with 1.5‐m‐long screens located near groundwater divides. Three steady state finite difference groundwater flow models were calibrated by adjusting horizontal and vertical hydraulic conductivities to match measured heads and head differences (range, 0.002–0.23 m) among the nested wells, with a uniform recharge rate of 0.46 m per year and porosities of 0.35 (sand) and 0.45 (silt) that were assumed constant for all model simulations and travel time calculations. The simulated groundwater travel times increase with depth in the aquifer, ranging from about 1.5 to 6.5 years for the shallow wells (screen bottoms 3–4 m below the water table), from about 10 to 25 years for the medium‐depth wells (screen bottoms 8–19 m below the water table), and from about 30 to more than 40 years for the deep wells (screen bottoms 24–26 m below the water table). Apparent groundwater ages based on CFC‐ and 3 H/ 3 He‐dating techniques and model‐based travel times could not be statistically differentiated, and all were strongly correlated with depth. Confinement of 3He was high because of the rapid vertical flow velocity (of the order of 1 m/yr), resulting in clear delineation of groundwater travel times based on the 3 H/ 3 He‐dating technique. The correspondence between the 3 H/ 3 He and CFC ages indicates that dispersion has had a minimal effect on the tracer‐based ages of water in this aquifer. Differences between the tracer‐based apparent ages for seven of the 10 samples were smaller than the error values. A slight bias toward older apparent ages, found not to be statistically significant, was noted for the 3 H/ 3 He‐dating technique relative to the CFC‐dating technique. This result may be caused by enrichment of local air in CFC‐Il and CFC‐12 from urban and industrial sources in the northeastern United States and minor contamination from sampling equipment. The demonstrated validity of the combined tracer‐dating techniques to determine the age of water in the Kirkwood‐Cohansey aquifer system indicates that groundwater flow models can be refined when apparent ages based on 3 H/ 3 He‐ and CFC‐ dating are used as calibration targets.

Detailed depth profiles of chlorofluorocarbons CFC-11 (CFCl3), CFC-12 (CF2Cl2) and CFC-113 (C2F3Cl3) have been obtained from a well-characterized field site in central Ontario. Aquifer materials comprise predominantly silty sands, with a mean organic carbon content of 0.03%. Nearly one-dimensional flow exists at this site, and the vertical migration of a well-defined H-3 peak has been tracked through time. Detailed vertical sampling has allowed CFC tracer velocities to be estimated to within 10%. Comparison with H-3 profiles enables estimation of chlorofluorocarbon transport parameters. CFC-12 appears to be the most conservative of the CFCs measured. Sorption at this site is low (K-d < 0.03), and degradation does not appear to be important. CFC-113 is retarded both with respect to CFC-12 and with respect to H-3 (K-d = 0.09-0.14). CFC-11 appears to be degraded both in the highly organic unsaturated zone and below 3.5 m depth in the aquifer, where dissolved oxygen concentrations decrease to below 0.5 mg L(-1). The half-life for CFC-11 degradation below 3.5 m depth is less than 2 years. While apparent CFC-12 ages match hydraulic ages to within 20% (up to 30 years), apparent CFC-11 and CFC-113 ages significantly overestimate hydraulic ages at our field site.

Leakage from sinkhole lakes significantly influences recharge to the Upper Floridan aquifer in poorly confined sediments in northern Florida. Environmental isotopes (oxygen 18, deuterium, and tritium), chlorofluorocarbons (CFCs: CFC‐11, CCl3F; CFC‐12, CCl2F2; and CFC‐113, C2Cl3F3), and solute tracers were used to investigate groundwater flow patterns near Lake Barco, a seepage lake in a mantled karst setting in northern Florida. Stable isotope data indicated that the groundwater downgradient from the lake contained 11–67% lake water leakage, with a limit of detection of lake water in groundwater of 4.3%. The mixing fractions of lake water leakage, which passed through organic‐rich sediments in the lake bottom, were directly proportional to the observed methane concentrations and increased with depth in the groundwater flow system. In aerobic groundwater upgradient from Lake Barco, CFC‐modeled recharge dates ranged from 1987 near the water table to the mid 1970s for water collected at a depth of 30 m below the water table. CFC‐modeled recharge dates (based on CFC‐12) for anaerobic groundwater downgradient from the lake ranged from the late 1950s to the mid 1970s and were consistent with tritium data. CFC‐modeled recharge dates based on CFC‐11 indicated preferential microbial degradation in anoxic waters. Vertical hydraulic conductivities, calculated using CFC‐12 modeled recharge dates and Darcy's law, were 0.17, 0.033, and 0.019 m/d for the surficial aquifer, intermediate confining unit, and lake sediments, respectively. These conductivities agreed closely with those used in the calibration of a three‐dimensional groundwater flow model for transient and steady state flow conditions.

This paper describes a direct comparison of apparent ages derived from H-3/He-3, chlorofluorocarbons (CCl3F and CCl2F2), and Kr-85 measurements in shallow groundwater. Wells chosen for this study are completed in the unconfined surficial aquifers in late Cenozoic Atlantic Coastal Plain sediments of the Delmarva Peninsula, on the east coast of the United States. Most of the apparent tracer ages agree within 2 years of each other for recharge dates between 1965 and 1990. Discrepancies in apparent tracer ages usually can be explained by hydrological processes such as mixing in a discharge area. Recharge rate calculations based on apparent tracer age gradients at multilevel well locations agree with previous recharge estimates. High recharge rates on the Delmarva Peninsula result in nearly complete dissolved-gas confinement in the groundwater. The remarkable agreement between the different tracer ages indicates negligible mixing of waters of different ages, insignificant dispersion, minimal gas loss to the atmosphere, and insignificant sorption-desorption processes at this location.