Analytical Method for Measuring Cosmogenic (35)S in Natural Waters.

Cosmogenic sulfur-35 in water as dissolved sulfate ((35)SO4) has successfully been used as an intrinsic hydrologic tracer in low-SO4, high-elevation basins. Its application in environmental waters containing high SO4 concentrations has been limited because only small amounts of SO4 can be analyzed using current liquid scintillation counting (LSC) techniques. We present a new analytical method for analyzing large amounts of BaSO4 for (35)S. We quantify efficiency gains when suspending BaSO4 precipitate in Inta-Gel Plus cocktail, purify BaSO4 precipitate to remove dissolved organic matter, mitigate interference of radium-226 and its daughter products by selection of high purity barium chloride, and optimize LSC counting parameters for (35)S determination in larger masses of BaSO4. Using this improved procedure, we achieved counting efficiencies that are comparable to published LSC techniques despite a 10-fold increase in the SO4 sample load. (35)SO4 was successfully measured in high SO4 surface waters and groundwaters containing low ratios of (35)S activity to SO4 mass demonstrating that this new analytical method expands the analytical range of (35)SO4 and broadens the utility of (35)SO4 as an intrinsic tracer in hydrologic settings.

Short-lived natural radionuclides as tracers in hydrogeological studies - A review.

Fundamental approaches to the study of groundwater rely on investigating the spatial and temporal distribution of stable and radioactive isotopes and other anthropogenic compounds in natural waterbodies. The most often used tracers for estimating groundwater flow paths and residence times, groundwater/surface water interaction as well as tracing chemical (contamination) sources include stable isotopes of water (δ 18O and δ 2H), radiocarbon (14C; t1/2 = 5730 a), tritium (3H; t1/2 = 12.43 a) as well as unreactive fluorine-containing gases (e.g., chlorofluorocarbons CCl3F or CFC-11; CCl2F3 or CFC-12; C2Cl3F3 or CFC-113; and SF6). While gas tracers are usually referred to as transient tracers and are appropriate for investigating modern flow systems, the isotopic tracers are often used to investigated paleo or regional flow systems. Stable isotopes of water can also be used to investigate groundwater/surface water interactions. Another, thus far been less frequently used group of groundwater tracers, are cosmo- and geo- genic short-lived radioisotopes. These isotopes are uniquely suited for studying a wide range of groundwater problems that have short time scales including high aquifer vulnerability to quantitative and qualitative impacts and groundwater discharge to surface waters. Here, we discuss and compare the applications of radio­sulphur (35S; half-life t1/2 = 87 d), radio­beryllium (7Be; t1/2 = 53 d), radio­phosphorus (32/33P; combined t1/2 = 33 d), natural tritium (3H; t1/2 = 12.43 a), radon (222Rn; t1/2 = 3.8 d) and short-lived radium (224/223Ra; combined t1/2 = 5.2 d). The paper discusses the principles of the individual tracer methods, focusing on the isotopes' input functions or values, on sampling techniques, and on methods of analyses. Case studies that applied a combined use of the tracers are referred to for readers who wish to learn more about the application of the so far underused cosmo- and geo- genic radioisotopes as aquatic tracers.

Sulfur Hexafluoride and Potassium Bromide as Groundwater Tracers for Managed Aquifer Recharge.

Sulfur hexafluoride (SF6 ) is an established tracer for use in managed aquifer recharge projects. SF6 exsolves from groundwater when it encounters trapped air according to Henry's law. This results in its retardation relative to groundwater flow, which can help determine porous media saturation and flow dynamics. SF6 and the conservative, nonpartitioning tracer, bromide (Br- added as KBr), were introduced to recharge water infiltrated into stacked glacial aquifers in Thurston County, Washington, providing the opportunity to observe SF6 partitioning. Br- , which is assumed to travel at the same velocity as the groundwater, precedes SF6 at most monitoring wells (MWs). Average groundwater velocity in the unconfined aquifer in the study area ranges from 3.9 to 40 m/d, except in the southwestern corner where it is slower. SF6 in the shallow aquifer exhibits an average retardation factor of 2.5 ± 3.8, suggesting an air-to-water ratio on the order of 10-3 to 10-2 in the pore space. Notable differences in tracer arrival times at adjacent wells indicate very heterogeneous conductivity. One MW exhibits double peaks in concentrations of both tracers with different degrees of retardation for the first and second peaks. This suggests multiple flowpaths to the well with variable saturation. The confining layer between the upper two aquifers appears to allow intermittent connection between aquifers but serves as an aquitard in most areas. This study demonstrates the utility of SF6 partitioning for evaluating hydrologic conditions at prospective recharge sites.

Use of tracers to quantify subsurface flow through a mining pit.

Three independent tracer experiments were conducted to quantify the through-flow of water from Herman Pit, an abandoned mercury (Hg) mine pit adjacent to Clear Lake, California, USA. The tracers used were Rhodamine-WT, sulfur hexafluoride, and a mixture of sulfur hexafluoride and neon-22. The tracers were injected into Herman Pit, a generally well-mixed water body of approximately 81,000 m2, and the concentrations were monitored in the mine pit, observation wells, and the lake for 2-3 months following each injection. The results for all three experiments showed that the tracer arrived at certain observation wells within days of injection. Comparing all the well data showed a highly heterogeneous response, with a small number of wells showing this near-instantaneous response and others taking months before the tracer was detectable. Tracer was also found in the lake on four occasions over a one-month period, too few to infer any pattern but sufficient to confirm the connection of the two water bodies. Using a simple mass balance model it was possible to determine the effective loss rate through advection for each of the tracers and with this to estimate the through-flow rate. The through-flow rate for all three experiments was approximately 630 L/s, at least 1-2 orders of magnitude larger than previous estimates, all of which had been based on geochemical inferences or other indirect measures of the pit through-flow.

Mechanisms of contaminant transport in a multi-basin lake.

Tracer studies are combined with a three-dimensional (3-D) numerical modeling study to provide a robust description of hydrodynamic and particle transport in Clear Lake, a multi-basin, polymictic lake in northern California, USA. The focus is on the mechanisms of transport of contaminants away from the vicinity of the Sulphur Bank Mercury Mine and out of the Oaks Arm to the rest of the lake and the hydraulic connection existing among the sub-basins of the lake. Under stratified conditions, the rate of spreading of the tracer was found to be large. In less than a week the tracer spread from the eastern end of the Oaks Arm to the other basins. Under non-stratified conditions, the tracer spread more slowly and had a concentration that gradually diminished with distance from the injection location. The numerical results showed that the mechanisms accounting for these observed patterns occur in pulses, with maximum rates coinciding with the stratified periods. Stratification acts first to enhance the currents by inhibiting vertical momentum mixing and decoupling the surface currents from bottom friction. The diversity of the flow structures that results from the interaction of the wind and the density fields in the lake is responsible for the high dispersion rates. Contaminants originating in the Oaks Arm are shown to be transported into the Lower Arm following the surface currents and into the Upper Arm mainly through the bottom currents. It was also shown that, under stratified conditions, both the baroclinic (density driven) gradients and the wind forcing act jointly to exacerbate the interbasin exchange.

Geochemical imaging of flow near an artificial recharge facility, Orange County, California.

Critical for the management of artificial recharge operations is detailed knowledge of ground water dynamics near spreading areas. Geochemical tracer techniques including stable isotopes of water, tritium/helium-3 (T/3He) dating, and deliberate gas tracer experiments are ideally suited for these investigations. These tracers were used to evaluate flow near an artificial recharge site in northern Orange County, California, where approximately 2.5 x 10(8) m3 (200,000 acre-feet) of water are recharged annually. T/3He ages show that most of the relatively shallow ground water within 3 km of the recharge facilities have apparent ages < 2 years; further downgradient apparent ages increase, reaching > 20 years at approximately 6 km. Gas tracer experiments using sulfur hexafluoride and xenon isotopes were conducted from the Santa Ana River and two spreading basins. These tracers were followed in the ground water for more than two years, allowing subsurface flow patterns and flow times to be quantified. Results demonstrate that mean horizontal ground water velocities range from < 1 to > 4 km/year. The leading edges of the tracer patch moved at velocities about twice as fast as the center of mass. Leading edge velocities are important when considering the potential transport of microbes and other "time sensitive" contaminants and cannot be determined easily with other methods. T/3He apparent ages and tracer travel times agreed within the analytical uncertainty at 16 of 19 narrow screened monitoring wells. By combining these techniques, ground water flow was imaged with time scales on the order of weeks to decades.

Gas transport below artificial recharge ponds: insights from dissolved noble gases and a dual gas (SF6 and 3He) tracer experiment.

A dual gas tracer experiment using sulfur hexafluoride (SF6) and an isotope of helium (3He) and measurements of dissolved noble gases was performed at the El Rio spreading grounds to examine gas transport and trapped air below an artificial recharge pond with a very high recharge rate (approximately 4 m day(-1)). Noble gas concentrations in the groundwater were greater than in surface water due to excess air formation showing that trapped air exists below the pond. Breakthrough curves of SF6 and 3He at two nearby production wells were very similar and suggest that nonequilibrium gas transfer was occurring between the percolating water and the trapped air. At one well screened between 50 and 90 m below ground, both tracers were detected after 5 days and reached a maximum at approximately 24 days. Despite the potential dilution caused by mixing within the production well, the maximum concentration was approximately 25% of the mean pond concentration. More than 50% of the SF6 recharged was recovered by the production wells during the 18 month long experiment. Our results demonstrate that at artificial recharge sites with high infiltration rates and moderately deep water tables, transport times between recharge locations and wells determined with gas tracer experiments are reliable.