Geology topics

Niel Plummer

Publications and source records attributed to Niel Plummer.

At least 55 records · Page 3Linked to original sources

USGS2008

Dating groundwater with trifluoromethyl sulfurpentafluoride (SF 5CF3), sulfur hexafluoride (SF6), CF 3Cl (CFC-13), and CF2Cl2 (CFC-12)

[1] 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. SF 5CF3 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 SF 5CF3. CFC-13 is a trace atmospheric gas with a dating range in groundwater of about 1965 to modem. 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.

Water Resources Research↗

USGS2008

Low-Level detections of halogenated volatile organic compounds in groundwater: Use in vulnerability assessments

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.

Journal of Hydrologic Engineering↗

USGS2007

Transport and degradation of chlorofluorocarbons (CFCs) in the pyritic Rabis Creek aquifer, Denmark

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.

Rabis Creek aquifer↗

USGS2007

Origin of halite brine in the Onondaga Trough near Syracuse, New York State, USA: Modeling geochemistry and variable-density flow

Halite brine (saturation ranging from 45 to 80%) lies within glacial sediments that fill the Onondaga Trough, a bedrock valley deepened by Pleistocene glaciation near Syracuse, New York State, USA. The most concentrated brine occupies the northern end of the trough, about 10 km downgradient of the northern limit of halite beds in the Silurian Salina Group, the assumed source of salt. The chemical composition of the brine and its radiocarbon age suggest that the brine originally formed about 16,700 years ago through dissolution of halite by glacial melt water and later mixed with saline bedrock water. Two hypotheses regarding the formation of the brine pool were tested through variable-density flow simulations using SEAWAT. Simulation results supported the first hypothesis that the brine pool was derived from a source in the glacial sediments and then migrated to its current position, where it has persisted for over 16,000 years. A second hypothesis that the brine pool formed through steady accumulation of brine from upward flow of a source in the underlying bedrock was not supported by simulation results, because the simulated age distribution was much younger than the age estimated from geochemical modeling.

New York↗

USGS2007

Evidence for terrigenic SF6 in groundwater from basaltic aquifers, Jeju Island, Korea: Implications for groundwater dating

Measurements of the concentrations of dichlorodifluoromethane (CFC-12), tritium ( 3 H), and sulfur hexafluoride (SF 6 ) in groundwater from basaltic aquifers in Jeju Island, Korea, demonstrate a terrigenic source of SF 6 . Using a lumped-parameter dispersion model, groundwater was identified as young water (<15 years), old water with negligible CFC-12 and 3 H, and binary mixtures of the two. Model calculations using dispersion models and binary mixing based on 3 H and CFC-12 concentrations demonstrate a non-atmospheric excess of SF 6 relative to CFC-12 and 3 H concentrations for more than half of the samples. The non-atmospheric excess SF 6 may have originated from terrigenic sources in relict volcanic fluids, which could have acquired SF 6 from granites and basement rocks of the island during volcanic activity. Local excess anthropogenic sources of SF 6 are unlikely. The SF 6 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 SF 6 can affect the entire dating range for groundwater in mixtures that contain a fraction of old water.

Jeju Island↗

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↗

USGS2007

Recharge area, base-flow and quick-flow discharge rates and ages, and general water quality of Big Spring in Carter County, Missouri, 2000-04

Exploration for lead deposits has occurred in a mature karst area of southeast Missouri that is highly valued for its scenic beauty and recreational opportunities. The area contains the two largest springs in Missouri (Big Spring and Greer Spring), both of which flow into federally designated scenic rivers. Concerns about potential mining effects on the area ground water and aquatic biota prompted an investigation of Big Spring. Water-level measurements made during 2000 helped define the recharge area of Big Spring, Greer Spring, Mammoth Spring, and Boze Mill Spring. The data infer two distinct potentiometric surfaces. The shallow potentiometric surface, where the depth-to-water is less than about 250 feet, tends to mimic topographic features and is strongly controlled by streams. The deep potentiometric surface, where the depth-to-water is greater than about 250 feet represents ground-water hydraulic heads within the more mature karst areas. A highly permeable zone extends about 20 mile west of Big Spring toward the upper Hurricane Creek Basin. Deeper flowing water in the Big Spring recharge area is directed toward this permeable zone. The estimated sizes of the spring recharge areas are 426 square miles for Big Spring, 352 square miles for Greer Spring, 290 square miles for Mammoth Spring, and 54 square miles for Boze Mill Spring. A discharge accumulation curve using Big Spring daily mean discharge data shows no substantial change in the discharge pattern of Big Spring during the period of record (water years 1922 through 2004). The extended periods when the spring flow deviated from the trend line can be attributed to prolonged departures from normal precipitation. The maximum possible instantaneous flow from Big Spring has not been adequately defined because of backwater effects from the Current River during high-flow conditions. Physical constraints within the spring conduit system may restrict its maximum flow. The largest discharge measured at Big Spring during the period of record (water years 1922 through 2004) was 1,170 cubic feet per second on December 7, 1982. The daily mean water temperature of Big Spring was monitored during water years 2001 through 2004 and showed little variability, ranging from 13 to 15° C (degree Celsius). Water temperatures generally vary less than 1° C throughout the year. The warmest temperatures occur during October and November and decrease until April, indicating Big Spring water temperature does show a slight seasonal variation. The use of the traditional hydrograph separation program HYSEP to determine the base flow and quick flow or runoff components at Big Spring failed to yield base-flow and quick-flow discharge curves that matched observations of spring characteristics. Big Spring discharge data were used in combination with specific conductance data to develop an improved hydrograph separation method for the spring. The estimated annual mean quick flow ranged from 15 to 48 cubic feet per second for the HYSEP analysis and ranged from 26 to 154 cubic feet per second for the discharge and specific conductance method for water years 2001 to 2004. Using the discharge and specific conductance method, the estimated base-flow component rises abruptly as the spring hydrograph rises, attains a peak value on the same day as the discharge peak, and then declines abruptly from its peak value. Several days later, base flow begins to increase again at an approximately linear trend, coinciding with the time at which the percentage of quick flow has reached a maximum after each recharge-induced discharge peak. The interval between the discharge peak and the peak in percentage quick flow ranges from 8 to 11 days for seven hydrograph peaks, consistent with quick-flow traveltime estimates by dye-trace tests from the mature karst Hurricane Creek Basin in the central part of the recharge area. Concentrations of environmental tracers chlorofluorocarbons (CFCs: CFC-11, CFC-12, CFC-113), and sulfur hexafluoride in discharge from Big Spring vary approximately linearly with percent quick flow from about 5 to 45 percent of discharge. Linear extrapolation to 100 percent quick flow implies CFC and SF 6 concentrations nearly identical to those in the 2002 atmosphere and indicates a modern age for the quick-flow component. Tracer concentrations for less than about 5 percent quick flow are increasingly lower than those expected from linear extrapolation to zero percent quick flow, indicating that the reservoir of older water in the Big Spring watershed may be a series of water mixtures with piston-flow ages greater than those obtained by extrapolation to zero percent quick flow. Each sample point with a low percentage of quick flow (less than 5 percent) may be a unique mixture. Environmental tracer data from Big Spring plot intermediate to the simple binary mixing of modern and old, pre-tracer water and results from the exponential mixture model. The mean ages of waters in the base-flow component approximately range from 30 to 200 years. The mean age of the base-flow component is youngest (30 to 40 years) in samples containing the highest quick-flow component (45 percent quick flow) and increases to 200 years or more as the fraction of quick flow decreases to less than 5 percent. Tritium data are consistent with a model of dilution of a modern component with an old, pre-tracer component and indicates that the old fraction is mostly pre-1960s in age with mean residence time of more than several hundred years. All of the samples from Big Spring and Greer Spring have water temperatures warmer than their nitrogen-argon recharge temperature, which range from approximately 10.5 to 14° C, suggesting recharge to the Big Spring watershed occurs primarily in late winter to early spring. The water temperatures at Big Spring are consistent with relatively shallow circulation (less than about 600 feet), and the water does not appear to be warmed by deep circulation along a geothermal gradient. Specific conductance values and concentrations of most inorganic constituents in water samples from Big Spring generally decrease with increasing discharge because of dilution with quick-flow water of lower ionic strength. Concentrations of some constituents such as chloride and nitrite plus nitrate, and fecal coliform densities, however, did not decrease with increasing discharge, indicating that quick flow probably is a more important source of these constituents compared to base flow. Water samples from Big Spring plot along the line of dolomite dissolution by carbonic acid, are at equilibrium with dolomite and calcite, and have a molar ratio of Ca:Mg of near 1, indicating dissolution of the mineral dolomite as the primary control on concentrations of calcium, magnesium, and bicarbonate. The flux of calcium and magnesium from Big Spring represents the dissolution of about 1,950 cubic feet of dolomite per day. The suspended sediment load of Big Spring was estimated to range from about 1 to about 70 tons per day, and the sediment load during base-flow periods ranged from about 1 to about 7 tons per day.

Missouri↗

USGS2007

Halite brine in the Onondaga Trough near Syracuse, New York: Characterization and simulation of variable-density flow

Halite brine (saturation ranging from 45 to 80 percent) lies within glacial-drift deposits that fill the Onondaga Trough, a 40-km long bedrock valley deepened by Pleistocene ice near Syracuse, N.Y. The most concentrated brine occupies the northern end of the trough, more than 15 kilometers (km) beyond the northern limit of halite beds in the Silurian Salina Group, the assumed source of salt. The chemical composition of the brine and its radiocarbon age estimated from geochemical modeling with NETPATH suggest that the brine formed through dissolution of halite by glacial melt water, and later mixed with saline bedrock water about 16,500 years ago. Transient variable-density flow simulations were conducted with SEAWAT to assess current (2005) ground-water flow conditions within the glacial drift. A transient three-dimensional (3D) model using a grid spacing of 100 meters (m) and maximum layer spacing of 30 m was used to simulate a 215-year period from 1790 to 2005. The model was calibrated to observations of water levels, chloride concentrations, and discharges of water and chloride. The model produced an acceptable match to the measured data and provided a reasonable representation of the density distribution within the brine pool. The simulated mass of chloride in storage declined steadily during the 215-year period; however, the decline was mainly due to dispersion, which is probably overestimated because of the large layer spacing. Model results suggest that saline water from waste-disposal operations associated with a chemical plant has migrated beneath the western shore of Onondaga Lake. Two-dimensional (2D) cross-sectional models of the aquifer system within the Onondaga Trough were prepared to test the plausibility of a hypothesis that the brine was derived from a relict source of halite that was dissolved by glacial melt water. The 2D models used parameter estimates obtained with the calibrated 3D model. Model results indicated the brine could have migrated from the bedded-halite subcrop area and remained in the glacial sediments at the northern end of trough for over 16,000 years, as suggested by radiocarbon dating. The 2D models also indicated that slow dissipation of brine occurs through a mixing zone formed by upward flow of freshwater over the southern end of the brine pool. The simulated depletion rate is controlled by the rate of mixing, which is limited by the specified grid resolution and the accuracy of the numerical method used to solve the advection-dispersion equation. A numerical solution obtained by using an implicit finite-difference method with upstream weighting and a 2D grid containing a column and layer spacing of 76 m and 3 m, respectively, provided an acceptable match to chloride concentration profiles measured at three locations within the Onondaga Trough.

New York↗

USGS2006

The geochemical evolution of riparian ground water in a forested piedmont catchment

The principal weathering reactions and their rates in riparian ground water were determined at the Panola Mountain Research Watershed (PMRW) near Atlanta, Georgia. Concentrations of major solutes were measured in ground water samples from 19 shallow wells completed in the riparian (saprolite) aquifer and in one borehole completed in granite, and the apparent age of each sample was calculated from chloroflourocarbons and tritium/helium-3 data. Concentrations of SiO 2 , Na + , and Ca 2+ generally increased downvalley and were highest in the borehole near the watershed outlet. Strong positive correlations were found between the concentrations of these solutes and the apparent age of ground water that was modern (zero to one year) in the headwaters, six to seven years midway down the valley, and 26 to 27 years in the borehole, located ∼500 m downstream from the headwaters. Mass-balance modeling of chemical evolution showed that the downstream changes in ground water chemistry could be largely explained by weathering of plagioclase to kaolinite, with possible contributions from weathering of K-feldspar, biotite, hornblende, and calcite. The in situ rates of weathering reactions were estimated by combining the ground water age dates with geochemical mass-balance modeling results. The weathering rate was highest for plagioclase (∼6.4 μmol/L/year), but could not be easily compared with most other published results for feldspar weathering at PMRW and elsewhere because the mineral-surface area to which ground water was exposed during geochemical evolution could not be estimated. However, a preliminary estimate of the mineral-surface area that would have contacted the ground water to provide the observed solute concentrations suggests that the plagioclase weathering rate calculated in this study is similar to the rate calculated in a previous study at PMRW, and three to four orders of magnitude slower than those published in previous laboratory studies of feldspar weathering. An accurate model of the geochemical evolution of riparian ground water is necessary to accurately model the geochemical evolution of stream water at PMRW.

Groundwater↗

USGS2006

Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO 4 - ) concentrations of 0.12−1.8 μg/L. Because the water samples are mostly preanthropogenic in age (0−28 000 years) and there are no industrial sources in the study area, a natural source of the ClO 4 - is likely. Most of the samples have Br - , Cl - , and SO 4 2 - concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7−40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The NO 3 - /Cl - and ClO 4 - /Cl - ratios are more variable than those of Br - /Cl - or SO 4 2 - /Cl - . Samples thought to have recharged under the most arid conditions in the Holocene have relatively high NO 3 - /Cl - ratios and low δ 15 N values (+1 per mil (‰)) similar to those of modern bulk atmospheric N deposition. The δ 18 O values of the NO 3 - (−4 to 0 ‰) indicate that atmospheric NO 3 - was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric NO 3 - /Cl - ratios have relatively high ClO 4 - concentrations (1.0−1.8 μg/L) with a nearly constant ClO 4 - /Cl - mole ratio of (1.4 ± 0.1) × 10 - 4 , which would be consistent with an average ClO 4 - concentration of 0.093 ± 0.005 μg/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged under wetter conditions have higher δ 15 N values (+3 to +8 ‰), lower NO 3 - /Cl - ratios, and lower ClO 4 - /Cl - ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO 3 - also may have depleted ClO 4 - to varying degrees prior to recharge. If these interpretations are correct, then ClO 4 - concentrations of atmospheric origin as high as 4 μg/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher ClO 4 - concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO 4 - exist.

Environmental Science & Technology↗

USGS2006

Application of environmental tracers to mixing, evolution, and nitrate contamination of ground water in Jeju Island, Korea

Tritium/helium-3 ( 3 H/ 3 He) 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 3 H and CFC-12 concentrations with lumped-parameter dispersion models, which distinguished old water recharged before the 1950s with negligible 3 H and CFC-12 from younger water. Low 3 H 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.

Jeju Island↗

USGS2005

Influence of fracture anisotropy on ground water ages and chemistry, Valley and Ridge province, Pennsylvania

Model ground water ages based on chlorofluorocarbons (CFCs) and tritium/helium-3 (3H/3He) 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 3H/3He 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.

Pennsylvania↗

USGS2005

Ground water age and nitrate distribution within a glacial aquifer beneath a thick unsaturated zone

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 3 H and as a result, chlorofluorocarbon (CFC) and 3 H/ 3 He dating techniques were applied. Beneath a 25 m thick unsaturated zone, ground water ages based on CFC‐11 concentrations were greater than 3 H/ 3 He 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 3 H/ 3 He 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 NO 3 − 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.

Groundwater↗

USGS2005

Age of irrigation water in ground water from the Eastern Snake River Plain Aquifer, south-central Idaho

Stable isotope data ( 2 H and 18 O) were used in conjunction with chlorofluorocarbon (CFC) and tritium/helium-3 ( 3 H/ 3 He) 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 3 H/ 3 He dating of water recharged through deep fractured basalt, and dating of young fractions in ground water mixtures. The 3 H/ 3 He 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 3 H/ 3 He dating to values biased older than the 3 H/ 3 He 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 3 He/ 4 He isotope ratio of 7 x 10-6 to 11 x 10-6 (R/R a = 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-NO 3 irrigation water from the Snake River lower the potential for NO 3 contamination in agricultural areas.

Ground Water↗

USGS2005

Geochemistry and the understanding of ground-water systems

Geochemistry has contributed significantly to the understanding of ground-water systems over the last 50 years. Historic advances include development of the hydrochemical facies concept, application of equilibrium theory, investigation of redox processes, and radiocarbon dating. Other hydrochemical concepts, tools, and techniques have helped elucidate mechanisms of flow and transport in ground-water systems, and have helped unlock an archive of paleoenvironmental information. Hydrochemical and isotopic information can be used to interpret the origin and mode of ground-water recharge, refine estimates of time scales of recharge and ground-water flow, decipher reactive processes, provide paleohydrological information, and calibrate ground-water flow models. Progress needs to be made in obtaining representative samples. Improvements are needed in the interpretation of the information obtained, and in the construction and interpretation of numerical models utilizing hydrochemical data. The best approach will ensure an optimized iterative process between field data collection and analysis, interpretation, and the application of forward, inverse, and statistical modeling tools. Advances are anticipated from microbiological investigations, the characterization of natural organics, isotopic fingerprinting, applications of dissolved gas measurements, and the fields of reaction kinetics and coupled processes. A thermodynamic perspective is offered that could facilitate the comparison and understanding of the multiple physical, chemical, and biological processes affecting ground-water systems.

Hydrogeology Journal↗

USGS2005

The stability of chlorofluorocarbons (CFCs) in ground-water samples archived in borosilicate ampoules

The U.S. Geological Survey (USGS) Chlorofluorocarbon (CFC) Laboratory in Reston, Va., has been measuring concentrations of CFCs in ground-water samples since 1989 to estimate the year that a water sample was recharged to a ground-water flow system. The water samples have been collected in flame-sealed borosilicate ampoules. Typically for each site, three samples were analyzed within days to a few months after collection, and additional samples were archived for extended periods of time (up to four years). The stability of CFC concentrations in the archived water samples from the USGS CFC Laboratory was investigated by analyzing the CFC concentrations in archived water samples and comparing them with the CFC concentrations that were obtained soon after the samples were collected. The archived samples selected for analysis were chosen from sites with a wide variety of hydrogeologic and geochemical conditions. For CFC-11 and CFC-12 concentrations, approximately 14% and 10.5%, respectively, of the archived samples were statistically different (both higher and lower) from the concentrations obtained from analyses conducted soon after the sample collection. Most of the extraneous values were attributed to natural variability of CFC concentrations originally in the water discharged from wells, rather than to microbial degradation within the ampoule on storage.

Virginia↗

USGS2004

Hydrochemical tracers in the middle Rio Grande Basin, USA: 1. Conceptualization of groundwater flow

Chemical and isotopic data for groundwater from throughout the Middle Rio Grande Basin, central New Mexico, USA, were used to identify and map groundwater flow from 12 sources of water to the basin, evaluate radiocarbon ages, and refine the conceptual model of the Santa Fe Group aquifer system. Hydrochemical zones, representing groundwater flow over thousands to tens of thousands of years, can be traced over large distances through the primarily siliciclastic aquifer system. The locations of the hydrochemical zones mostly reflect the “modern” predevelopment hydraulic-head distribution, but are inconsistent with a trough in predevelopment water levels in the west-central part of the basin, indicating that this trough is a transient rather than a long-term feature of the aquifer system. Radiocarbon ages adjusted for geochemical reactions, mixing, and evapotranspiration/dilution processes in the aquifer system were nearly identical to the unadjusted radiocarbon ages, and ranged from modern to more than 30 ka. Age gradients from piezometer nests ranged from 0.1 to 2 year cm –1 and indicate a recharge rate of about 3 cm year –1 for recharge along the eastern mountain front and infiltration from the Rio Grande near Albuquerque. There has been appreciably less recharge along the eastern mountain front north and south of Albuquerque.

Rio Grande Basin↗

USGS2004

Hydrochemical tracers in the middle Rio Grande Basin, USA: 2. Calibration of a groundwater-flow model

The calibration of a groundwater model with the aid of hydrochemical data has demonstrated that low recharge rates in the Middle Rio Grande Basin may be responsible for a groundwater trough in the center of the basin and for a substantial amount of Rio Grande water in the regional flow system. Earlier models of the basin had difficulty reproducing these features without any hydrochemical data to constrain the rates and distribution of recharge. The objective of this study was to use the large quantity of available hydrochemical data to help calibrate the model parameters, including the recharge rates. The model was constructed using the US Geological Survey's software MODFLOW, MODPATH, and UCODE, and calibrated using 14C activities and the positions of certain flow zones defined by the hydrochemical data. Parameter estimation was performed using a combination of nonlinear regression techniques and a manual search for the minimum difference between field and simulated observations. The calibrated recharge values were substantially smaller than those used in previous models. Results from a 30,000-year transient simulation suggest that recharge was at a maximum about 20,000 years ago and at a minimum about 10,000 years ago.

Rio Grande Basin↗