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At least 1,243 records · Page 69Linked to original sources

Transport of chromium and selenium in the suboxic zone of a shallow aquifer: Influence of redox and adsorption reactions

Breakthrough of Cr(VI) (chromate), Se(VI) (selenate), and O 2 (dissolved oxygen) was observed in tracer tests conducted in a shallow, sand and gravel aquifer with mildly reducing conditions. Loss of Cr, probably due to reduction of Cr(VI) to Cr(III) and irreversible sorption of Cr(III), occurred along with slight retardation of Cr(VI), owing to reversible sorption. Reduction of Se(VI) and O 2 was thermodynamically feasible but did not occur, indicating conditions, were unfavorable to microbial reduction. Cr(VI) reduction by constituents of aquifer sediments did not achieve local equilibrium during transport. The reduction rate was probably limited by incomplete contact between Cr(VI) transported along predominant flow paths and reductants located in regions within aquifer sediments of comparatively low permeability. Scatter in the amount of Cr reduction calculated from individual breakthrough curves at identical distances downgradient probably resulted from heterogeneities in the distribution of reductants in the sediments. Predictive modeling of the transport and fate of redox-sensitive solutes cannot be based strictly on thermodynamic considerations; knowledge of reaction rates is critical. Potentially important mass transfer rate limitations between solutes and reactants in sediments as well as heterogeneities in the distribution of redox properties in aquifers complicate determination of limiting rates for use in predictive simulations of the transport of redox-sensitive contaminants in groundwater.

Water Resources Research↗

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↗

Marginal bed load transport in a gravel bed stream, Sagehen Creek, California

Marginal bed load transport describes the condition when relatively few bed particles are moving at any time. Bed particles resting in the shallowest bed pockets will move when the dimensionless shear stress т * exceeds a value of about 0.020. As т * increases, the number of bed particles moving increases. Significant motion of bed particles, i.e., when a substantial fraction of the bed particles are moving, occurs when т * exceeds a value of about 0.060. Thus marginal bed load transport occurs over the domain 0.020 < т * < 0.060. Marginal bed load transport rates and associated hydraulic characteristics of Sagehen Creek, a small mountain gravel bed stream, were measured on 55 days at discharges ranging from slightly less than one half of the bank-full discharge to more than 4 times the bank-full discharge. Dimensionless shear stress varied from 0.032 to 0.042, and bed particles as large as the 80th percentile of the bed surface were transported. The relation between reference dimensionless shear stress and relative particle protrusion for Sagehen Creek was determined by varying т * ri to obtain the best fit of the Parker bed load function to the measured transport rates. During the period of record (water years 1954–1991), the mean annual quantity of bed load transported past the Sagehen Creek gage was 24.7 tons. Forty-seven percent of all bed load transported during the 38 years of record occurred in just 6 years. During 10 of the 38 years of record, essentially no bed load was transported. The median diameter of bed load was 26 mm, compared to 58 mm in the surface bed material.

California↗

Climate, soil water storage, and the average annual water balance

This paper describes the development and testing of the hypothesis that the long-term water balance is determined only by the local interaction of fluctuating water supply (precipitation) and demand (potential evapotranspiration), mediated by water storage in the soil. Adoption of this hypothesis, together with idealized representations of relevant input variabilities in time and space, yields a simple model of the water balance of a finite area having a uniform climate. The partitioning of average annual precipitation into evapotranspiration and runoff depends on seven dimensionless numbers: the ratio of average annual potential evapotranspiration to average annual precipitation (index of dryness); the ratio of the spatial average plant-available water-holding capacity of the soil to the annual average precipitation amount; the mean number of precipitation events per year; the shape parameter of the gamma distribution describing spatial variability of storage capacity; and simple measures of the seasonality of mean precipitation intensity, storm arrival rate, and potential evapotranspiration. The hypothesis is tested in an application of the model to the United States east of the Rocky Mountains, with no calibration. Study area averages of runoff and evapotranspiration, based on observations, are 263 mm and 728 mm, respectively; the model yields corresponding estimates of 250 mm and 741 mm, respectively, and explains 88% of the geographical variance of observed runoff within the study region. The differences between modeled and observed runoff can be explained by uncertainties in the model inputs and in the observed runoff. In the humid (index of dryness <1) parts of the study area, the dominant factor producing runoff is the excess of annual precipitation over annual potential evapotranspiration, but runoff caused by variability of supply and demand over time is also significant; in the arid (index of dryness >1) parts, all of the runoff is caused by variability of forcing over time. Contributions to model runoff attributable to small-scale spatial variability of storage capacity are insignificant throughout the study area. The consistency of the model with observational data is supportive of the supply-demand-storage hypothesis, which neglects infiltration excess runoff and other finite-permeability effects on the soil water balance.

Water Resources Research↗

Reply to “Comment on ‘An efficient numerical solution of the transient storage equations for solute transport in small streams" by R. L. Runkel and S. C. Chapra

We thank Dawes and Short [this issue] for presenting an alternate technique for the efficient solution of the transient storage solute transport equations. After reading their comment, it is clear that several points in our original manuscript are in need of clarification. In this reply we provide additional information on our solution technique and comment briefly on the alternate scheme of Dawes and Short.

Water Resources Research↗

Flow path studies in forested watersheds of headwater tributaries of Brush Brook, Vermont

An investigation was undertaken into how headwater tributaries of Brush Brook, Vermont, could have average p H differences of almost two units (4.75 and 6.7). Sampling along four tributaries revealed that most of one tributary, below an area of seeps, had consistently higher p H, Ca 2+ , Mg 2+ , and K + , and lower Al than other sites. Bedrock mapping showed numerous fractures in vicinity of the seeps. A portion of this tributary's watershed and a portion of an acid tributary's watershed were intensively mapped for soil depth. Sampling showed the widespread existence of dense basal till in the watershed of the acid tributary but none in that of the near-neutral stream. Lateral flow, found above the dense till, was chemically similar to that of the acid tributary and to solutions sampled from soil B horizons. There were no differences in the average p H of nonseep soils sampled from either watershed. Flow paths are hypothesized to be through the B horizons in the acid tributaries and from below the soil profile in the near-neutral tributary. The acid catchment should be more sensitive to environmental change.

Vermont↗

Characterization of a high-transmissivity zone by well test analysis: Steady state case

A method is developed to analyze steady horizontal flow to a well pumped from a confined aquifer composed of two homogeneous zones with contrasting transmissivities. Zone 1 is laterally unbounded and encloses zone 2, which is elliptical in shape and is several orders of magnitude more transmissive than zone 1. The solution for head is obtained by the boundary integral equation method. Nonlinear least squares regression is used to estimate the model parameters, which include the transmissivity of zone 1, and the location, size, and orientation of zone 2. The method is applied to a hypothetical aquifer where zone 2 is a long and narrow zone of vertical fractures. Synthetic data are generated from three different well patterns, representing different areal coverage and proximity to the fracture zone. When zone 1 of the hypothetical aquifer is homogeneous, the method correctly estimates all model parameters. When zone 1 is a randomly heterogeneous transmissivity field, some parameter estimates, especially the length of zone 2, become highly uncertain. To reduce uncertainty, the pumped well should be close to the fracture zone, and surrounding observation wells should cover an area similar in dimension to the length of the fracture zone. Some prior knowledge of the fracture zone, such as that gained from a surface geophysical survey, would greatly aid in designing the well test.

Water Resources Research↗

Influence of diurnal variations in stream temperature on streamflow loss and groundwater recharge

We demonstrate that for losing reaches with significant diurnal variations in stream temperature, the effect of stream temperature on streambed seepage is a major factor contributing to reduced afternoon streamflows. An explanation is based on the effect of stream temperature on the hydraulic conductivity of the streambed, which can be expected to double in the 0° to 25°C temperature range. Results are presented for field experiments in which stream discharge and temperature were continuously measured for several days over losing reaches at St. Kevin Gulch, Colorado, and Tijeras Arroyo, New Mexico. At St. Kevin Gulch in July 1991, the diurnal stream temperature in the 160-m study reach ranged from about 4° to 18°C, discharges ranged from 10 to 18 L/s, and streamflow loss in the study reach ranged from 2.7 to 3.7 L/s. On the basis of measured stream temperature variations, the predicted change in conductivity was about 38%; the measured change in stream loss was about 26%, suggesting that streambed temperature varied less than the stream temperature. At Tijeras Arroyo in May 1992, diurnal stream temperature in the 655-m study reach ranged from about 10° to 25°C and discharge ranged from 25 to 55 L/s. Streamflow loss was converted to infiltration rates by factoring in the changing stream reach surface area and streamflow losses due to evaporation rates as measured in a hemispherical evaporation chamber. Infiltration rates ranged from about 0.7 to 2.0 m/d, depending on time and location. Based on measured stream temperature variations, the predicted change in conductivity was 29%; the measured change in infiltration was also about 27%. This suggests that high infiltration rates cause rapid convection of heat to the streambed. Evapotranspiration losses were estimated for the reach and adjacent flood plain within the arroyo. On the basis of these estimates, only about 5% of flow loss was consumed via stream evaporation and stream-side evapotranspiration, indicating that 95% of the loss within the study reach represented groundwater recharge.

Water Resources Research↗

Long-term hydrologic and biogeochemical responses of a soft water seepage lake in north central Wisconsin

Hydrologic and chemical budgets were determined for the period October 1980 through September 1988 for Vandercook Lake, a 43-ha soft water seepage lake located in predominantly sandy outwash in northern Wisconsin. The 1951–1980 mean annual precipitation for the lake, based on nearby National Weather Service (NWS) stations, was 825 mm; volume-weighted p H of bulk atmospheric deposition during the 8-year study averaged 4.7. From October 1980 through September 1983, annual precipitation was 108% of the 30-year NWS average, annual recharge was 144% of the 8-year study period average, and annual groundwater inflow to the lake ranged from 5 to 9% of the total inflow. From October 1986 through September 1988, annual precipitation was 90% of the NWS average, annual recharge was 30% of the study period average, and the lake received no groundwater inflow. During the study, the lake changed from a system whose buffering mechanism was significantly influenced by mineral weathering in inflowing groundwater to one dominated by in-lake sulfate reduction. The functional differences exhibited by this lake during the 8 years of study demonstrate the tenuousness with which conclusions based on shorter-term studies of similar systems must be considered.

Wisconsin↗

An updated model of induced airflow in the unsaturated zone

Simulation of induced movement of air in the unsaturated zone provides a method to determine permeability and to design vapor extraction remediation systems. A previously published solution to the airflow equation for the case in which the unsaturated zone is separated from the atmosphere by a layer of lower permeability (such as a clay layer) has been superseded. The new solution simulates airflow through the layer of lower permeability more rigorously by defining the leakage in terms of the upper boundary condition rather than by adding a leakage term to the governing airflow equation. This note presents the derivation of the new solution. Formulas for steady state pressure, specific discharge, and mass flow in the domain are obtained for the new model and for the case in which the unsaturated zone is in direct contact with the atmosphere.

Water Resources Research↗

Deducing the distribution of terminal electron-accepting processes in hydrologically diverse groundwater systems

The distribution of microbially mediated terminal electron-accepting processes (TEAPs( was investigated in four hydrologically diverse groundwater systems by considering patterns of electron acceptor (nitrate, sulfate) consumption, intermediate product (hydrogen (H 2 )) concentrations, and final product (ferrous iron, sulfide, and methane) production. In each hydrologic system a determination of predominant TEAPs could be arrived at, but the level of confidence appropriate for each determination differed. In a portion of the lacustrine aquifer of the San Joaquin Valley, for example, all three indicators (sulfate concentrations decreasing, H 2 concentrations in the 1–2 nmol range, and sulfide concentrations increasing along flow paths identified sulfate reduction as the predominant TEAP, leading to a high degree of confidence in the determination. In portions of the Floridan aquifer and a petroleum hydrocarbon-contaminated aquifer, sulfate reduction and methanogenesis are indicated by production of sulfide and methane, and hydrogen oncentrations in the 1–4 nmol and 5–14 nmol range, respectively. However, because electron acceptor consumption could not be documented in these systems, less confidence is warranted in the TEAP determination. In the Black Creek aquifer, no pattern of sulfate consumption and sulfide production were observed, but H2 concentrations indicated sulfate reduction as the predominant TEAP. In this case, where just a single line of evidence is available, the least confidence in the TEAP diagnosis is justified. Because this methodology is based on measurable water chemistry parameters and upon the physiology of microbial electron transfer processes, it provides a better description of predominant redox processes in groundwater systems than more traditional Eh-based methods.

Water Resources Research↗

Chlorofluorocarbons as tracers of groundwater transport processes in a shallow, silty sand aquifer

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

Water Resources Research↗

Evaluation of 11 equations for determining evaporation for a small lake in the North Central United States

Eleven equations for calculating evaporation were compared with evaporation determined by the energy budget method for Williams Lake, Minnesota. Data were obtained from instruments on a raft, on land near the lake, and at a weather station 60 km south of the lake. The comparisons were based on monthly values for the open-water periods of 5 years, a total of 22 months. A modified DeBruin-Keijman, Priestley-Taylor, and a modified Penman equation resulted in monthly evaporation values that agreed most closely with energy budget values. To use these equations, net radiation, air temperature, wind speed, and relative humidity need to be measured near the lake. In addition, thermal surveys need to be made to determine change in heat stored in the lake. If data from distant climate stations are the only data available, and they include solar radiation, the Jensen-Haise and Makkink equations resulted in monthly evaporation values that agreed reasonably well with energy budget values.

Minnesota↗

Modeling the effects of variable groundwater chemistry on adsorption of molybdate

Laboratory experiments were used to identify and quantify processes having a significant effect on molybdate (MoO 4 2− ) adsorption in a shallow alluvial aquifer on Cape Cod, assachusetts. Aqueous chemistry in the aquifer changes as a result of treated sewage effluent mixing with groundwater. Molybdate adsorption decreased as p H, ionic strength, and the concentration of competing anions increased. A diffuse-layer surface complexation model was used to simulate adsorption of MoO 4 2− , phosphate (PO 4 3− ), and sulfate (SO 4 2− ) on aquifer sediment. Equilibrium constants for the model were calculated by calibration to data from batch experiments. The model was then used in a one-dimensional solute transport program to successfully simulate initial breakthrough of MoO 4 2− from column experiments. A shortcoming of the solute transport program was the inability to account for kinetics of physical and chemical processes. This resulted in a failure of the model to predict the slow rate of desorption of MoO 4 2− from the columns. The mobility of MoO 4 2− ncreased with ionic strength and with the formation of aqueous complexes with calcium, magnesium, and sodium. Failure to account for MoO 4 2− speciation and ionic strength in the model resulted in overpredicting MoO 4 2− adsorption. Qualitatively, the laboratory data predicted the observed behavior of MoO 4 2− in the aquifer, where retardation of MoO 4 2− was greatest in uncontaminated roundwater having low p H, low ionic strength, and low concentrations of PO 4 3− and SO 4 2− .

Water Resources Research↗

Transport of chromium and selenium in a pristine sand and gravel aquifer: Role of adsorption processes

Field transport experiments were conducted in an oxic sand and gravel aquifer using Br (bromide ion), Cr (chromium, injected as Cr(VI)), Se (selenium, injected as Se(VI)), and other tracers. The aquifer has mildly acidic p H values and low concentrations of dissolved salts. Within analytical errors, all mobile Cr was present as Cr(VI). All mobile Se was probably present as Se(VI). Adsorption of Cr and Se onto aquifer sediments caused retardation of both tracers. Breakthrough curves for Cr and Se had extensive tails, which caused large decreases in their maximum concentrations relative to the nonreactive Br tracer after only 2.0 m of transport. A surface complexation model was applied to the results of laboratory studies of Cr(VI) adsorption on aquifer solids from the site based on adsorption onto hydrous ferric oxide. The modeling results suggested that the dominant adsorbents in the aquifer solids have lower affinities for anion adsorption than pure hydrous ferric oxide. The steep rising limbs and extensive tails observed in most of the breakthrough curves are qualitatively consistent with the equilibrium surface complexation model; however, slow rates of adsorption and desorption may have contributed to these features. Variations during transport in the concentrations of Cr, Se, and other anions competing for adsorption sites likely gave rise to variations in the extent of adsorption. Adequate description of the observed retardation of Cr and Se would require a coupled transport-adsorption model that can account for these effects. Companion experiments in the mildly reducing zone of the aquifer (Kent et al., 1994) showed a loss of Cr mass, probably resulting from reduction to Cr(III), and little retardation of mobile Cr and Se during transport; this contrast illustrates the influence of aquifer chemistry on the transport of redox-sensitive solutes.

Water Resources Research↗

Effects of carbon and nitrate on denitrification in bottom sediments of an effluent-dominated river

Nitrogen and carbon limitation of denitrification in the bed sediments of an effluent-dominated stream were investigated by quantifying the effects of nitrate and glucose additions on the rate of sediment N 2 O production. Bed sediment samples were collected from a 30-km stretch of the South Platte River where up to 95% of the base flow discharge consists of effluent from a water treatment plant in Denver, Colorado. The rate of denitrification in upstream sediment samples incubated under in situ nitrate and carbon conditions was primarily limited by nitrate supply. The stimulatory effect of nitrate additions on the rate of bed sediment denitrification decreased with increasing distance downstream of the treatment plant. Approximately 35 km downstream of the treatment plant, denitrification in the bed sediment samples was carbon limited. The observed decreases in the concentration of total inorganic nitrogen (as NH 4 + NO 3 ) dissolved in the river and the organic carbon content of the bed sediments with increasing distance downstream of the treatment plant suggest that bed sediment denitrification is a significant sink for nitrogen in this stretch of the river.

Colorado↗

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↗

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↗