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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.

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.

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 2H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ13C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ2H 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 13C 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.

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 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.

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, SF6, 3H, and bomb 14C. We measured 3He, but 3H/3He dating is generally problematic due to the presence of mantle 3He. 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.

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.

Mass balance models of dissolved gases in streams, lakes, and rivers serve as the basis for estimating whole‐ecosystem 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.

A new groundwater dating procedure using the transient atmospheric signal of the environmental tracers SF5CF3, CFC‐13, SF6, and CFC‐12 was developed. The analytical procedure determines concentrations of the four tracers in air and water samples. SF5CF3 and CFC‐13 can be used to date groundwaters in some environments where the CFCs and SF6 have previously failed because these new tracers have increasing atmospheric input functions, no known terrigenic source, and are believed to be stable under reducing conditions. SF5CF3 has a dating range from 1970 to modern; the mixing ratio (mole fraction) in North American air has increased from the detection limit of 0.005 parts per trillion (ppt) to the 2006 mole fraction of about 0.16 ppt. No evidence was found for degradation of SF5CF3 in laboratory anaerobic systems. The solubility of SF5CF3 was measured in water from 1 to 35°C. Groundwater samples that contained large amounts of terrigenic SF6 did not contain terrigenic SF5CF3. CFC‐13 is a trace atmospheric gas with a dating range in groundwater of about 1965 to modern. CFC‐13 has been used primarily in very low‐temperature refrigeration; thus groundwater environments are less likely to be contaminated with nonatmospheric sources as compared to other widely used CFCs. Because of the low solubility of SF5CF3 and CFC‐13 in water, an excess air correction must be applied to the apparent ages. The new dating procedure was tested in water samples from wells and springs from Maryland, Virginia, and West Virginia.

Concentrations of halogenated volatile organic compounds (VOCs) were determined by gas chromatography (GC) with an electron-capture detector (GC-ECD) and by gas chromatography with mass spectrometry (GC-MS) in 109 groundwater samples from five study areas in the United States. In each case, the untreated water sample was used for drinking-water purposes or was from a monitoring well in an area near a drinking-water source. The minimum detection levels (MDLs) for 25 VOCs that were identified in GC-ECD chromatograms, typically, were two to more than four orders of magnitude below the GC-MS MDLs. At least six halogenated VOCs were detected in all of the water samples analyzed by GC-ECD, although one or more VOCs were detected in only 43% of the water samples analyzed by GC-MS. In nearly all of the samples, VOC concentrations were very low and presented no known health risk. Most of the low-level VOC detections indicated post-1940s recharge, or mixtures of recharge that contained a fraction of post-1940s water. Concentrations of selected halogenated VOCs in groundwater from natural and anthropogenic atmospheric sources were estimated and used to recognize water samples that are being impacted by nonatmospheric sources. A classification is presented to perform vulnerability assessments at the scale of individual wells using the number of halogenated VOC detections and total dissolved VOC concentrations in samples of untreated drinking water. The low-level VOC detections are useful in vulnerability assessments, particularly for samples in which no VOCs are detected by GC-MS analysis.

Measurements of the concentrations of dichlorodifluoromethane (CFC-12), tritium (3H), and sulfur hexafluoride (SF6) in groundwater from basaltic aquifers in Jeju Island, Korea, demonstrate a terrigenic source of SF6. Using a lumped-parameter dispersion model, groundwater was identified as young water (<15 years), old water with negligible CFC-12 and 3H, and binary mixtures of the two. Model calculations using dispersion models and binary mixing based on 3H and CFC-12 concentrations demonstrate a non-atmospheric excess of SF6 relative to CFC-12 and 3H concentrations for more than half of the samples. The non-atmospheric excess SF6 may have originated from terrigenic sources in relict volcanic fluids, which could have acquired SF6 from granites and basement rocks of the island during volcanic activity. Local excess anthropogenic sources of SF6 are unlikely. The SF6 age is biased young relative to the CFC-12 age, typically up to 20 years and as high as 30 years. This age bias is more pronounced in samples of groundwater older than 15 years. The presence of terrigenic SF6 can affect the entire dating range for groundwater in mixtures that contain a fraction of old water.

Tritium/helium-3 (3H/3He) and chlorofluorocarbons (CFCs) were investigated as environmental tracers in ground water from Jeju Island (Republic of Korea), a basaltic volcanic island. Ground-water mixing was evaluated by comparing 3H and CFC-12 concentrations with lumped-parameter dispersion models, which distinguished old water recharged before the 1950s with negligible 3H and CFC-12 from younger water. Low 3H levels in a considerable number of samples cannot be explained by the mixing models, and were interpreted as binary mixing of old and younger water; a process also identified in alkalinity and pH of ground water. The ground-water CFC-12 age is much older in water from wells completed in confined zones of the hydro-volcanic Seogwipo Formation in coastal areas than in water from the basaltic aquifer. Major cation concentrations are much higher in young water with high nitrate than those in uncontaminated old water. Chemical evolution of ground water resulting from silicate weathering in basaltic rocks reaches the zeolite–smectite phase boundary. The calcite saturation state of ground water increases with the CFC-12 apparent (piston flow) age. In agricultural areas, the temporal trend of nitrate concentration in ground water is consistent with the known history of chemical fertilizer use on the island, but increase of nitrate concentration in ground water is more abrupt after the late 1970s compared with the exponential growth of nitrogen inputs.

Multiply By To obtain Cubic centimeters (cm 3 ) 0.06102 Cubic inch Gram (g) 0.03527 Ounce Kilogram (kg) 2.205 Pound Milligram (mg) 0.001 Gram Picogram (pg) 1x10 -12 Gram Femtogram (fg) 1x10 -15 Gram For temperature, degrees Celsius ( o C) can be converted to degrees Fahrenheit ( o F) by using the formula F=(1.8)( o C) + 32.Abbreviated units used in report: L (liter), mL (milliliter), kg (kilogram), pg (picogram), mol (mole), mol (micromole), fmol (femtomol), fg (femtogram), pptv (parts per trillion by volume), mg/L (milligrams per liter), g/L (micrograms per liter).

Chemical and isotopic data for groundwater from the Middle Rio Grande Basin, New Mexico, were used to (l) delineate hydrochemical zones and their source area to the basin, (2) evaluate paleo-recharge conditions, including recharge from the Rio Grande and mountain fronts, and (3) calibrate a basin-scale groundwater model. Twelve sources of recharge and one zone of groundwater discharge were identified and traced throughout the basin. Geochemical mass-balance calculations, accounting for mixing of surface-water and groundwater sources, evapotranspiration/dilution processes, and water-rock reaction, led to well-defined radiocarbon ages that range from modern to more than 30 ka B.P. in the Santa Fe Group aquifer system. Recharge rates determined from the groundwater model were appreciably lower than previous estimates based on a rainfall-runoff model, but in agreement with recharge estimates determined from a previous investigation using the chloride mass-balance method. The groundwater model reproduces key features of the groundwater-flow system, including a trough in the water-table surface in the central part ofthe basin, and accounts for the observation ofa substantial quantity of paleo Rio Grande water in the aquifer. Results from a 30,000year transient simulation suggest that recharge at the Last Glacial Maximum (LGM) may have been ten times the modern rate, but that recharge following the LGM was about 60 percent of the modern rate. Over the past 30 ka, 62H of Rio Grande water was maximum in the present and at about 15 ka, and minimum at approximately 5 ka and 22 ka, before present. Seasonal shifts in the timing of peak discharge of the Rio Grande andlor changes in the amounts of low-altitude