Geology topics

Eurybiades Busenberg

Publications and source records attributed to Eurybiades Busenberg.

At least 19 recordsLinked to original sources

USGS2021

DGMETA (version 1)—Dissolved gas modeling and environmental tracer analysis computer program

DGMETA (Dissolved Gas Modeling and Environmental Tracer Analysis) is a Microsoft Excel-based computer program that is used for modeling air-water equilibrium conditions from measurements of dissolved gases and for computing concentrations of environmental tracers that rely on air-water equilibrium model results. DGMETA can solve for the temperature, salinity, excess air, fractionation of gases, or pressure/elevation of water when it is equilibrated with the atmosphere. Models are calibrated inversely using one or more measurements of dissolved gases such as helium, neon, argon, krypton, xenon, and nitrogen. Excess nitrogen gas, originating from denitrification or other sources, also can be included as a fitted parameter or as a separate calculation from the dissolved gas modeling results. DGMETA uses the air-water equilibrium models to separate measured concentrations of gases and isotopes of gases into components that are used for tracing water in the environment. DGMETA calculates atmospheric dry-air mole fractions (mixing ratios) for transient atmospheric gas tracers such as chlorofluorocarbons, sulfur hexafluoride, and bromotrifluoromethane (Halon-1301); and concentrations of tritiogenic helium-3 and radiogenic helium-4, which accumulate from the decay of tritium in water and the decay of uranium and thorium in rocks, respectively. Sample data can be graphed to identify applicable models of excess air, samples that contain excess nitrogen gas, or samples that have partially degassed, for example. Monte Carlo analysis of errors associated with dissolved gas equilibrium model results can be carried through computations of environmental tracer concentrations to provide robust estimates of error. In addition, graphical routines for separating helium sources using helium isotopes are included to refine estimates of tritiogenic helium-3 when terrigenic helium from mantle or crustal sources is present in samples. Environmental tracer concentrations and their errors computed from DGMETA can be used with other programs, such as TracerLPM (Jurgens and others, 2012), to determine groundwater ages and biogeochemical reaction rates. DGMETA also produces output files in a format that meets the U.S. Geological Survey open data requirements for documentation of model inputs and outputs. DGMETA is a versatile and adaptable program that allows users to add solubility data for new gases, modify the existing set of gas solubility data, modify the default set of gases used for modeling, choose calculations based on real (non-ideal) gas behavior, and select various concentration units for data entry and results to match laboratory reports and study objectives. DGMETA comes with a set of gases widely used in hydrology and oceanography and many gases include multiple solubilities from previous work. Seventeen dissolved gases are included in the default version of the program: noble gases (helium, neon, argon, krypton, and xenon), reactive gases (nitrogen, oxygen, methane, carbon dioxide, carbon monoxide, hydrogen, and nitrous oxide), and environmental tracers (chlorofluorocarbon-11, chlorofluorocarbon-12, chlorofluorocarbon-113, sulfur hexafluoride, and Halon-1301).

Techniques and Methods↗

USGS2014

Groundwater Dating with Atmospheric Halogenated Compounds

"Atmospheric environmental releases refer to the emission of stable, long-lived compounds of solely anthropogenic origin into the atmosphere and the use of the compounds to estimate dates of their incorporation into groundwater."

Book chapter↗

USGS2014

Measurements of HFC-134a and HCFC-22 in groundwater and unsaturated-zone air: implications for HFCs and HCFCs as dating tracers

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, CHClF 2 ) and HFC-134a (1,2,2,2-tetrafluoroethane, C 2 H 2 F 4 ) in 1 L groundwater samples are 4.3 × 10 − 1 and 2.1 × 10 − 1 pmol kg − 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 CO 2 and loss of O 2 . 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 (SF 6 ). 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.

North Carolina, Tennessee, Virginia↗

USGS2014

Integration of stable carbon isotope, microbial community, dissolved hydrogen gas, and 2 H H 2 O tracer data to assess bioaugmentation for chlorinated ethene degradation in fractured rocks

An in situ bioaugmentation (BA) experiment was conducted to understand processes controlling microbial dechlorination of trichloroethene (TCE) in groundwater at the Naval Air Warfare Center (NAWC), West Trenton, NJ. In the BA experiment, an electron donor (emulsified vegetable oil and sodium lactate) and a chloro-respiring microbial consortium were injected into a well in fractured mudstone of Triassic age. Water enriched in 2 H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ 13 C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ 2 H of water; changes in the abundance of the microbial communities; and the concentration of dissolved H2 gas compared to pre- test conditions, provided multiple lines of evidence that enhanced biodegradation occurred in the injection well and in two downgradient wells. For those wells where the biodegradation was stimulated intensively, the sum of the molar chlorinated ethene (CE) concentrations in post-BA water was higher than that of the sum of the pre-BA background molar CE concentrations. The concentration ratios of TCE/(cis-DCE + VC) indicated that the increase in molar CE concentration may result from additional TCE mobilized from the rock matrix in response to the oil injection or due to desorption/diffusion. The stable carbon isotope mass-balance calculations show that the weighted average 13 C isotope of the CEs was enriched for around a year compared to the background value in a two year monitoring period, an effective indication that dechlorination of VC was occurring. Insights gained from this study can be applied to efforts to use BA in other fractured rock systems. The study demonstrates that a BA approach can substantially enhance in situ bioremediation not only in fractures connected to the injection well, but also in the rock matrix around the well due to processes such as diffusion and desorption. Because the effect of the BA was intensive only in wells where an amendment was distributed during injection, it is necessary to adequately distribute the amendments throughout the fractured rock to achieve substantial bioremediation. The slowdown in BA effect after a year is due to some extend to the decrease abundant of appropriate microbes, but more likely the decreased concentration of electron donor.

New Jersey↗

USGS2014

A 19-year record of chemical and isotopic composition of water from springs of the Shenandoah National Park, Virginia, 1995-2014

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 (O 2 ), and pH. Laboratory measurements included major-, minor-, and trace-element chemistry; concentrations of dissolved gases (nitrogen, [N 2 ] argon [Ar], oxygen, and carbon dioxide [CO 2 ]); concentrations of dissolved trace atmospheric gases, including trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), and trichlorotrifluoroethane (CFC-113) and sulfur hexafluoride (SF 6 ); and hydrogen stable isotopic composition (δ 2 H) and oxygen isotopic composition (δ 18 O) 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 (CF 3 Br), SF 6 , and trifluoromethyl sulfur pentafluoride (SF 5 CF 3 ) 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, N 2 , O 2 , Ar, CO 2 , CFC-12, CFC-11, CFC-113, and SF 6 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.

Virginia↗

USGS2013

A 17-year record of environmental tracers in spring discharge, Shenandoah National Park, Virginia, USA: use of climatic data and environmental conditions to interpret discharge, dissolved solutes, and tracer concentrations

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, SF 6 , and SF 5 CF 3 ), dissolved gases (N 2 , O 2 , Ar, CO 2 , and CH 4 ), stable isotopes of water, and major and trace inorganic constituents. The chlorofluorocarbon (CFC) and sulfur hexafluoride (SF 6 ) 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 SF 6 atmospheric mixing ratio, the apparent (piston flow) SF 6 age of the water varied seasonally between about 0 (modern) in January and up to 3 years in July–August. The SF 6 concentration and concentrations of dissolved solutes (SiO 2 , Ca 2+ , Mg 2+ , Na + , Cl − , and HCO 3 − ) 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.

Virginia↗

USGS2013

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer, Leetown Science Center, West Virginia, USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from 3 H/ 3 He and SF 6 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 3 H/ 3 He 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 SF 6 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.

West Virginia↗

USGS2012

Estimates of tracer-based piston-flow ages of groundwater from selected sites: National Water-Quality Assessment Program, 2006-2010

Piston-flow age dates were interpreted from measured concentrations of environmental tracers from 812 National Water-Quality Assessment (NAWQA) Program groundwater sites from 27 Study Units across the United States. The tracers of interest include chlorofluorocarbons (CFCs), sulfur hexafluoride (SF 6 ), and tritium/helium-3 ( 3 H/ 3 He). Tracer data compiled for this analysis were collected from 2006 to 2010 from groundwater wells in NAWQA studies, including: * Land-Use Studies (LUS, shallow wells, usually monitoring wells, located in recharge areas under dominant land-use settings), * Major-Aquifer Studies (MAS, wells, usually domestic supply wells, located in principal aquifers and representing the shallow drinking water supply), * Flow System Studies (FSS, networks of clustered wells located along a flowpath extending from a recharge zone to a discharge zone, preferably a shallow stream) associated with Land-Use Studies, and * Reference wells (wells representing groundwater minimally impacted by anthropogenic activities) also associated with Land-Use Studies. Tracer data were evaluated using documented methods and are presented as aqueous concentrations, equivalent atmospheric concentrations (for CFCs and SF 6 ), and tracer-based piston-flow ages. Selected ancillary data, such as redox data, well-construction data, and major dissolved-gas (N 2 , O 2 , Ar, CH 4 , and CO 2 ) data, also are presented. Recharge temperature was inferred using climate data (approximated by mean annual air temperature plus 1°C [MAAT +1°C]) as well as major dissolved-gas data (N 2 -Ar-based) where available. The N 2 -Ar-based temperatures showed significantly more variation than the climate-based data, as well as the effects of denitrification and degassing resulting from reducing conditions. The N 2 -Ar-based temperatures were colder than the climate-based temperatures in networks where recharge was limited to the winter months when evapotranspiration was reduced. The tracer-based piston-flow ages compiled in this report are provided as a consistent means of reporting the tracer data. The tracer-based piston-flow ages may provide an initial interpretation of age in cases in which mixing is minimal and may aid in developing a basic conceptualization of groundwater age in an aquifer. These interpretations are based on the assumption that tracer transport is by advection only and that no mixing occurs. In addition, it is assumed that other uncertainties are minimized, including tracer degradation, sorption, contamination, or fractionation, and that terrigenic (natural) sources of tracers, and spatially variable atmospheric tracer concentrations are constrained.

Scientific Investigations Report↗

USGS2011

Estimates of tracer-based piston-flow ages of groundwater from selected sites: National Water-Quality Assessment Program, 1992–2005

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 (SF 6 ), and tritium/helium-3 ( 3 H/ 3 He). 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 SF 6 ), estimates of tracer-based piston-flow ages, and selected ancillary data, such as redox indicators, well construction, and major dissolved gases (N 2 , O 2 , Ar, CH 4 , and CO 2 ). 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.

Scientific Investigations Report↗

USGS2010

A rapid method for the measurement of sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), and Halon 1211 (CF2ClBr) in hydrologic tracer studies

A rapid headspace method for the simultaneous laboratory determination of intentionally introduced hydrologic tracers, sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), Halon 1211 (CF2ClBr), and other halocarbons in water and gases is described. The high sensitivity of the procedure allows for introduction of minimal tracer mass (a few grams) into hydrologic systems with a large dynamic range of analytical detection (dilutions to 1:108). Analysis times by gas chromatography with electron capture detector are less than 1 min for SF6; about 2 min for SF6 and SF5CF3; and 4 min for SF6, SF5CF3, and Halon 1211. Many samples can be rapidly collected, preserved in stoppered septum bottles, and analyzed at a later time in the laboratory. Examples are provided showing the effectiveness of the gas tracer test studies in varied hydrogeological settings.

Geochemistry, Geophysics, Geosystems↗

USGS2010

Use of chlorofluorocarbons (CCl3F and CCl2F2) as hydrologic tracers and age‐dating tools: The alluvium and terrace system of central Oklahoma

The use of Chlorofluorocarbons (CFCs) as an age‐dating tool and tracer in shallow groundwaters has been investigated. New methodology for field sampling and preserving groundwaters containing parts per trillion concentrations of the CFCs, F‐1l and F‐12, is presented. Samples are analyzed by purge‐and‐trap gas chromatography with an electron capture detector. Physical and chemical processes that can alter natural concentrations (air‐water equilibrium) of CFCs were investigated to assess dating uncertainties. CFC model recharge ages appear to be defined within 2 years under optimum conditions. The method was applied to central Oklahoma to demonstrate the usefulness of CFCs as (1) an age‐dating tool of shallow groundwaters, (2) a tracer of sewage effluent in surface and shallow groundwaters, and (3) a tracer of shallow groundwater. Results of dating indicate two primary recharge periods in central Oklahoma over the past 45 years that correspond to the wet periods 1945–1960 and 1967–1975.

Water Resources Research↗

USGS2010

The use of simulation and multiple environmental tracers to quantify groundwater flow in a shallow aquifer

Measurements of the concentrations of chlorofluorocarbons (CFCs), tritium, and other environmental tracers can be used to calculate recharge ages of shallow groundwater and estimate rates of groundwater movement. Numerical simulation also provides quantitative estimates of flow rates, flow paths, and mixing properties of the groundwater system. The environmental tracer techniques and the hydraulic analyses each contribute to the understanding and quantification of the flow of shallow groundwater. However, when combined, the two methods provide feedback that improves the quantification of the flow system and provides insight into the processes that are the most uncertain. A case study near Locust Grove, Maryland, is used to investigate the utility of combining groundwater age dating, based on CFCs and tritium, and hydraulic analyses using numerical simulation techniques. The results of the feedback between an advective transport model and the estimates of groundwater ages determined by the CFCs improve a quantitative description of the system by refining the system conceptualization and estimating system parameters. The plausible system developed with this feedback between the advective flow model and the CFC ages is further tested using a solute transport simulation to reproduce the observed tritium distribution in the groundwater. The solute transport simulation corroborates the plausible system developed and also indicates that, for the system under investigation with the data obtained from 0.9-m-long (3-foot-long) well screens, the hydrodynamic dispersion is negligible. Together the two methods enable a coherent explanation of the flow paths and rates of movement while indicating weaknesses in the understanding of the system that will require future data collection and conceptual refinement of the groundwater system.

Water Resources Research↗

USGS2010

Dating of shallow groundwater: Comparison of the transient tracers 3H/3He, chlorofluorocarbons, and 85Kr

This paper describes a direct comparison of apparent ages derived from 3 H/ 3 He, chlorofluorocarbons (CCl 3 F and CCl 2 F 2 ), and 85 Kr 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.

Water Resources Research↗

USGS2010

Chemical evolution of groundwater near a sinkhole lake, northern Florida: 2. Chemical patterns, mass-transfer modeling, and rates of chemical reactions

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO 2 ), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13 C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO 2 reduction pathway based on the isotopic composition of hydrogen (δ 2 H(CH 4 ) = −186 to −234‰) and carbon (δ 13 C(CH 4 ) = −65.7 to −72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L −1 yr −1 for groundwater downgradient from the lake.

Water Resources Research↗

USGS2010

Chemical evolution of groundwater near a sinkhole lake, northern Florida: 1. Flow patterns, age of groundwater, and influence of lakewater leakage

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, CCl 3 F; CFC-12, CCl 2 F 2 ; and CFC-113, C 2 Cl 3 F 3 ), 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.

Florida↗

USGS2010

Testing mixing models of old and young groundwater in a tropical lowland rain forest with environmental tracers

We tested three models of mixing between old interbasin groundwater flow (IGF) and young, locally derived groundwater in a lowland rain forest in Costa Rica using a large suite of environmental tracers. We focus on the young fraction of water using the transient tracers CFC‐11, CFC‐12, CFC‐113, SF 6 , 3 H, and bomb 14 C. We measured 3 He, but 3 H/ 3 He dating is generally problematic due to the presence of mantle 3 He. Because of their unique concentration histories in the atmosphere, combinations of transient tracers are sensitive not only to subsurface travel times but also to mixing between waters having different travel times. Samples fall into three distinct categories: (1) young waters that plot along a piston flow line, (2) old samples that have near‐zero concentrations of the transient tracers, and (3) mixtures of 1 and 2. We have modeled the concentrations of the transient tracers using (1) a binary mixing model (BMM) of old and young water with the young fraction transported via piston flow, (2) an exponential mixing model (EMM) with a distribution of groundwater travel times characterized by a mean value, and (3) an exponential mixing model for the young fraction followed by binary mixing with an old fraction (EMM/BMM). In spite of the mathematical differences in the mixing models, they all lead to a similar conceptual model of young (0 to 10 year) groundwater that is locally derived mixing with old (>1000 years) groundwater that is recharged beyond the surface water boundary of the system.

Water Resources Research↗

USGS2009

A simple technique for continuous measurement of time-variable gas transfer in surface waters

Mass balance models of dissolved gases in streams, lakes, and rivers serve as the basis for estimating wholeecosystem rates for various biogeochemical processes. Rates of gas exchange between water and the atmosphere are important and error-prone components of these models. Here we present a simple and efficient modification of the SF6 gas tracer approach that can be used concurrently while collecting other dissolved gas samples for dissolved gas mass balance studies in streams. It consists of continuously metering SF6-saturated water directly into the stream at a low rate of flow. This approach has advantages over pulse injection of aqueous solutions or bubbling large amounts of SF6 into the stream. By adding the SF6 as a saturated solution, we minimize the possibility that other dissolved gas measurements are affected by sparging and/or bubble injecta. Because the SF6 is added continuously we have a record of changing gas transfer velocity (GTV) that is contemporaneous with the sampling of other nonconservative ambient dissolved gases. Over a single diel period, a 30% variation in GTV was observed in a second-order stream (Sugar Creek, Indiana, USA). The changing GTV could be attributed in part to changes in temperature and windspeed that occurred on hourly to diel timescales.

Limnology and Oceanography: Methods↗

USGS2007

Evidence of CFC degradation in groundwater under pyrite-oxidizing conditions

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 ⩽5 m 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 6 m, the groundwater became progressively more reducing, however, with a denitrifying horizon at 6–7 m depth, and a Mn and Fe reducing zone below 7 m depth. In the anaerobic zone, 3 H/ 3 He ratios indicated that groundwater-age continued to increase uniformly with depth, to a maximum value of 27 years at 13 m depth. CFC concentrations, however, decreased abruptly within the denitrifying zone, leading to substantial age overestimation compared to the 3 H/ 3 He 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 0.3 yr −1 for CFC-12, 0.7 yr −1 for CFC-11, and 1.6 yr −1 for CFC-113. CFC attenuation at this site coincides with a zone where reduced S (pyrite) is actively oxidized by NO 3 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.

Journal of Hydrology↗