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At least 1,315 records · Page 73Linked to original sources
USGS1998

High-resolution Monte Carlo simulation of flow and conservative transport in heterogeneous porous media: 1. Methodology and flow results

In this, the first of two papers concerned with the use of numerical simulation to examine flow and transport parameters in heterogeneous porous media via Monte Carlo methods, various aspects of the modelling effort are examined. In particular, the need to save on core memory causes one to use only specific realizations that have certain initial characteristics; in effect, these transport simulations are conditioned by these characteristics. Also, the need to independently estimate length scales for the generated fields is discussed. The statistical uniformity of the flow field is investigated by plotting the variance of the seepage velocity for vector components in the x , y , and z directions. Finally, specific features of the velocity field itself are illuminated in this first paper. In particular, these data give one the opportunity to investigate the effective hydraulic conductivity in a flow field which is approximately statistically uniform; comparisons are made with first- and second-order perturbation analyses. The mean cloud velocity is examined to ascertain whether it is identical to the mean seepage velocity of the model. Finally, the variance in the cloud centroid velocity is examined for the effect of source size and differing strengths of local transverse dispersion.

Water Resources Research↗
USGS1998

Simulation of variable-density flow and transport of reactive and nonreactive solutes during a tracer test at Cape Cod, Massachusetts

A multispecies numerical code was developed to simulate flow and mass transport with kinetic adsorption in variable-density flow systems. The two-dimensional code simulated the transport of bromide (Br − ), a nonreactive tracer, and lithium (Li + ), a reactive tracer, in a large-scale tracer test performed in a sand-and-gravel aquifer at Cape Cod, Massachusetts. A two-fraction kinetic adsorption model was implemented to simulate the interaction of Li + with the aquifer solids. Initial estimates for some of the transport parameters were obtained from a nonlinear least squares curve-fitting procedure, where the breakthrough curves from column experiments were matched with one-dimensional theoretical models. The numerical code successfully simulated the basic characteristics of the two plumes in the tracer test. At early times the centers of mass of Br − and Li + sank because the two plumes were closely coupled to the density-driven velocity field. At later times the rate of downward movement in the Br − plume due to gravity slowed significantly because of dilution by dispersion. The downward movement of the Li + plume was negligible because the two plumes moved in locally different velocity regimes, where Li + transport was retarded relative to Br − . The maximum extent of downward transport of the Li + plume was less than that of the Br − plume. This study also found that at early times the downward movement of a plume created by a three-dimensional source could be much more extensive than the case with a two-dimensional source having the same cross-sectional area. The observed shape of the Br − plume at Cape Cod was simulated by adding two layers with different hydraulic conductivities at shallow depth across the region. The large dispersion and asymmetrical shape of the Li + plume were simulated by including kinetic adsorption-desorption reactions.

Massachusetts↗
USGS1998

Nitrogen transport and transformations in a shallow aquifer receiving wastewater discharge: A mass balance approach

Nitrogen transport and transformations were followed over the initial 3 years of development of a plume of wastewater-contaminated groundwater in Cape Cod, Massachusetts. Ammonification and nitrification in the unsaturated zone and ammonium sorption in the saturated zone were predominant, while loss of fixed nitrogen through denitrification was minor. The major effect of transport was the oxidation of discharged organic and inorganic forms to nitrate, which was the dominant nitrogen form in transit to receiving systems. Ammonification and nitrification in the unsaturated zone transformed 16–19% and 50–70%, respectively, of the total nitrogen mass discharged to the land surface during the study but did not attenuate the nitrogen loading. Nitrification in the unsaturated zone also contributed to p H decrease of 2 standard units and to an N 2 O increase (46–660 µg N/L in the plume). Other processes in the unsaturated zone had little net effect: Ammonium sorption removed <1% of the total discharged nitrogen mass; filtering of particulate organic nitrogen was less than 3%; ammonium and nitrate assimilation was less than 6%; and ammonia volatilization was less than 0.25%. In the saturated zone a central zone of anoxic groundwater (DO ≤ 0.05 mg/L) was first detected 17 months after effluent discharge to the aquifer began, which expanded at about the groundwater-flow velocity. Although nitrate was dominant at the water table, the low, carbon-limited rates of denitrification in the anoxic zone (3.0–9.6 (ng N/cm 3 )/d) reduced only about 2% of the recharged nitrogen mass to N 2 . In contrast, ammonium sorption in the saturated zone removed about 16% of the recharged nitrogen mass from the groundwater. Ammonium sorption was primarily limited to anoxic zone, where nitrification was prevented, and was best described by a Langmuir isotherm in which effluent ionic concentrations were simulated. The initial nitrogen load discharged from the groundwater system may depend largely on the growth and stability of the sorbed ammonium pool, which in turn depends on effluent-loading practices, subsurface microbial processes, and saturation of available exchange sites.

Water Resources Research↗
USGS1998

Tritium-helium 3 dating under complex conditions in hydraulically stressed areas of a buried-valley aquifer

The 3 H- 3 He dating method is applied in a buried-valley aquifer near Dayton, Ohio. The study area is large, not all sampling locations lie along well-defined flow paths, and existing wells with variable screen lengths and diameters are used. Reliable use of the method at this site requires addressing several complications: (1) The flow system is disturbed because of high pumping rates and induced infiltration; (2) tritium contamination is present in several areas of the aquifer; and (3) radiogenic helium concentrations are elevated in a significant number of the wells. The 3 H- 3 He ages are examined for self-consistency by comparing the reconstructed tritium evolution to the annual weighted tritium measured in precipitation; deviations result from dispersion, tritium contamination, and mixing. 3 H- 3 He ages are next examined for consistency with chlorofluorocarbon ages; the agreement is poor because of degradation of CFCs. Finally, the 3 H- 3 He ages are examined for consistency with the current understanding of local hydrologic processes; the ages are generally supported by hydrogeologic data and the results of groundwater flow modeling coupled with particle-tracking analyses.

Ohio↗
USGS1998

Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheic-flow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/λ s , of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/λ h = 2.6 hours), and in laboratory batch experiments using streambed sediment (1/λ = 2.7 hours). The modeled depths of subsurface storage zones ( d s = 4–17 cm) and modeled residence times of water in storage zones ( t s = 3–12 min) were both consistent with direct measurements in hyporheic flow paths ( d h = 0–15 cm, t h = 1–25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths ( f s = 8.9%, and f h = 9.3%rpar;. Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The cumulative effect of hyporheic exchange in Pinal Creek basin was to remove approximately 20% of the dissolved manganese flowing out of the drainage basin. Our results illustrate that the cumulative significance of reactive uptake in the hyporheic zone depends on the balance between chemical reaction rates, hyporheic porewater residence time, and turnover of streamflow through hyporheic flow paths. The similarity between the hyporheic reaction timescale (1/λ s ≈ 1.3 hours), and the hyporheic porewater residence timescale ( t s ≈ 8 min) ensured that there was adequate time for the reaction to progress. Furthermore, it was the similarity between the turnover length for stream water flow through hyporheic flow paths ( L s = stream velocity/storage-zone exchange coefficient ≈ 1.3 km) and the length of Pinal Creek ( L ≈ 7 km), which ensured that all stream water passed through hyporheic flow paths several times. As a means to generalize our findings to other sites where similar types of hydrologic and chemical information are available, we suggest a cumulative significance index for hyporheic reactions, R s = λ s t s L / L s (dimensionless); higher values indicate a greater potential for hyporheic reactions to influence geochemical mass balance. Our experience in Pinal Creek basin suggests that values of R s > 0.2 characterize systems where hyporheic reactions are likely to influence geochemical mass balance at the drainage-basin scale.

Water Resources Research↗
USGS1998

Use of 3H/3He Ages to evaluate and improve groundwater flow models in a complex buried-valley aquifer

Combined use of the tritium/helium 3 ( 3 H/ 3 He) dating technique and particle-tracking analysis can improve flow-model calibration. As shown at two sites in the Great Miami buried-valley aquifer in southwestern Ohio, the combined use of 3 H/ 3 He age dating and particle tracking led to a lower mean absolute error between measured heads and simulated heads than in the original calibrated models and/or between simulated travel times and 3 H/ 3 He ages. Apparent groundwater ages were obtained for water samples collected from 44 wells at two locations where previously constructed finite difference models of groundwater flow were available (Mound Plant and Wright-Patterson Air Force Base (WPAFB)). The two-layer Mound Plant model covers 11 km 2 within the buried-valley aquifer. The WPAFB model has three layers and covers 262 km 2 within the buried-valley aquifer and adjacent bedrock uplands. Sampled wells were chosen along flow paths determined from potentiometric maps or particle-tracking analyses. Water samples were collected at various depths within the aquifer. In the Mound Plant area, samples used for comparison of 3 H/ 3 He ages with simulated travel times were from wells completed in the uppermost model layer. Simulated travel times agreed well with 3 H/ 3 He ages. The mean absolute error (MAE) was 3.5 years. Agreement in ages at WPAFB decreased with increasing depth in the system. The MAEs were 1.63, 17.2, and 255 years for model layers 1, 2, and 3, respectively. Discrepancies between the simulated travel times and 3 H/ 3 He ages were assumed to be due to improper conceptualization or incorrect parameterization of the flow models. Selected conceptual and parameter modifications to the models resulted in improved agreement between 3 H/ 3 He ages and simulated travel times and between measured and simulated heads and flows.

Ohio↗
USGS1998

Chemistry of unsaturated zone gases sampled in open boreholes at the crest of Yucca Mountain, Nevada: Data and basic concepts of chemical and physical processes in the mountain

Boreholes open to the unsaturated zone at the crest of Yucca Mountain, Nevada, were variously sampled for CO 2 (including 13 C and 14 C), CH 4 , N 2 , O 2 , Ar, CFC-11, CFC-12, and CFC-113 from 1986 to 1993. Air enters the mountain in outcrops, principally on the eastern slope, is enriched in CO 2 by mixing with soil gas, and is advected to the mountain crest, where it returns to the atmosphere. The CFC data indicate that travel times of the advecting gas in the shallow Tiva Canyon hydrogeologic unit are ≤5 years. The 14 C activities are postbomb to depths of 100 m, indicating little retardation of 14 CO 2 in the shallow flow systems. The 14 C activities from 168 to 404 m in the Topopah Spring hydrogeologic unit are 85–90 pMC at borehole USW-UZ6. The CFC data show that the drilling of USW-UZ6 in 1984 has altered the natural system by providing a conduit through the Paintbrush Nonwelded unit, allowing flow from Topopah Spring outcrops in Solitario Canyon on the west to USW-UZ6, upward in the borehole through the Paintbrush, to the shallow Tiva Canyon flow systems, and out of the mountain.

Nevada↗
USGS1998

Flow modeling and permeability estimation using borehole flow logs in heterogeneous fractured formations

A numerical model of flow in the vicinity of a borehole is used to analyze flowmeter data obtained with high-resolution flowmeters. The model is designed to (1) precisely compute flow in a borehole, (2) approximate the effects of flow in surrounding aquifers on the measured borehole flow, (3) allow for an arbitrary number ( N ) of entry/exit points connected to M < N far-field aquifers, and (4) be consistent with the practical limitations of flowmeter measurements such as limits of resolution, typical measurement error, and finite measurement periods. The model is used in three modes: (1) a quasi-steady pumping mode where there is no ambient flow, (2) a steady flow mode where ambient differences in far-field water levels drive flow between fracture zones in the borehole, and (3) a cross-borehole test mode where pumping in an adjacent borehole drives flow in the observation borehole. The model gives estimates of transmissivity for any number of fractures in steady or quasi-steady flow experiments that agree with straddle-packer test data. Field examples show how these cross-borehole-type curves can be used to estimate the storage coefficient of fractures and bedding planes and to determine whether fractures intersecting a borehole at different locations are hydraulically connected in the surrounding rock mass.

Water Resources Research↗
USGS1998

In situ determination of particle friction angles of fluvial gravels

Particle friction angles Φ represent the physical resistance to initial movement of a sediment particle and are therefore useful for relating initiation of motion to particular flows. We determined over 8000 friction angle values at five natural rivers by applying a new method that uses a digital load cell to directly measure the force F d required to pivot or slide a particle out of its natural resting place. Within each site, median Φ values were very similar to previously reported relations, yet different enough between sites that a location-general predictive empirical relation would produce errors in Φ of ±10 degrees for D i / K s > 1. Furthermore, within a D i / K s class at a given site the range in Φ was as large as 80°, much greater than the range of median values between classes for natural sediment mixtures. Using estimates of τ c * from extensive bed load measurements made by Andrews and Erman [1986] at Sagehen Creek and the in situ Φ measurements made in this study together with a theoretical model developed by Wiberg and Smith [1987], we show that Φ measurements made with this new method can be used to accurately predict τ c * for natural, water-worked sediments. Additionally, these results confirm that a Φ value ≪Φ 50 is more appropriate for predicting τ c * of a given size class.

Water Resources Research↗
USGS1998

Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

Water Resources Research↗
USGS1998

Comparison of hydrochemical tracers to estimate source contributions to peak flow in a small, forested, headwater catchment

Three-component (throughfall, soil water, groundwater) hydrograph separations at peak flow were performed on 10 storms over a 2-year period in a small forested catchment in north-central Maryland using an iterative and an exact solution. Seven pairs of tracers (deuterium and oxygen 18, deuterium and chloride, deuterium and sodium, deuterium and silica, chloride and silica, chloride and sodium, and sodium and silica) were used for three-component hydrograph separation for each storm at peak flow to determine whether or not the assumptions of hydrograph separation routinely can be met, to assess the adequacy of some commonly used tracers, to identify patterns in hydrograph-separation results, and to develop conceptual models for the patterns observed. Results of the three-component separations were not always physically meaningful, suggesting that assumptions of hydrograph separation had been violated. Uncertainties in solutions to equations for hydrograph separations were large, partly as a result of violations of assumptions used in deriving the separation equations and partly as a result of improper identification of chemical compositions of end-members. Results of three-component separations using commonly used tracers were widely variable. Consistent patterns in the amount of subsurface water contributing to peak flow (45-100%) were observed, no matter which separation method or combination of tracers was used. A general conceptual model for the sequence of contributions from the three end-members could be developed for 9 of the 10 storms. Overall results indicated that hydrochemical and hydrometric measurements need to be coupled in order to perform meaningful hydrograph separations.

Maryland↗
USGS1998

Interaction between stream temperature, streamflow, and groundwater exchanges in alpine streams

Four alpine streams were monitored to continuously collect stream temperature and streamflow for periods ranging from a week to a year. In a small stream in the Colorado Rockies, diurnal variations in both stream temperature and streamflow were significantly greater in losing reaches than in gaining reaches, with minimum streamflow losses occurring early in the day and maximum losses occurring early in the evening. Using measured stream temperature changes, diurnal streambed infiltration rates were predicted to increase as much as 35% during the day (based on a heat and water transport groundwater model), while the measured increase in streamflow loss was 40%. For two large streams in the Sierra Nevada Mountains, annual stream temperature variations ranged from 0° to 25°C. In summer months, diurnal stream temperature variations were 30–40% of annual stream temperature variations, owing to reduced streamflows and increased atmospheric heating. Previous reports document that one Sierra stream site generally gains groundwater during low flows, while the second Sierra stream site may lose water during low flows. For August the diurnal streamflow variation was 11% at the gaining stream site and 30% at the losing stream site. On the basis of measured diurnal stream temperature variations, streambed infiltration rates were predicted to vary diurnally as much as 20% at the losing stream site. Analysis of results suggests that evapotranspiration losses determined diurnal streamflow variations in the gaining reaches, while in the losing reaches, evapotranspiration losses were compounded by diurnal variations in streambed infiltration. Diurnal variations in stream temperature were reduced in the gaining reaches as a result of discharging groundwater of relatively constant temperature. For the Sierra sites, comparison of results with those from a small tributary demonstrated that stream temperature patterns were useful in delineating discharges of bank storage following dam releases. Direct coupling may have occurred between streamflow and stream temperature for losing stream reaches, such that reduced streamflows facilitated increased afternoon stream temperatures and increased afternoon stream temperatures induced increased streambed losses, leading to even greater increases in both stream temperature and streamflow losses.

Water Resources Research↗
USGS1998

Detecting influential observations in nonlinear regression modeling of groundwater flow

Nonlinear regression is used to estimate optimal parameter values in models of groundwater flow to ensure that differences between predicted and observed heads and flows do not result from nonoptimal parameter values. Parameter estimates can be affected, however, by observations that disproportionately influence the regression, such as outliers that exert undue leverage on the objective function. Certain statistics developed for linear regression can be used to detect influential observations in nonlinear regression if the models are approximately linear. This paper discusses the application of Cook's D , which measures the effect of omitting a single observation on a set of estimated parameter values, and the statistical parameter DFBETAS, which quantifies the influence of an observation on each parameter. The influence statistics were used to (1) identify the influential observations in the calibration of a three-dimensional, groundwater flow model of a fractured-rock aquifer through nonlinear regression, and (2) quantify the effect of omitting influential observations on the set of estimated parameter values. Comparison of the spatial distribution of Cook's D with plots of model sensitivity shows that influential observations correspond to areas where the model heads are most sensitive to certain parameters, and where predicted groundwater flow rates are largest. Five of the six discharge observations were identified as influential, indicating that reliable measurements of groundwater flow rates are valuable data in model calibration. DFBETAS are computed and examined for an alternative model of the aquifer system to identify a parameterization error in the model design that resulted in overestimation of the effect of anisotropy on horizontal hydraulic conductivity.

Water Resources Research↗
USGS1998

Effect of groundwater springs on NO3− concentrations during summer in Catskill Mountain streams

Groundwater and stream water data collected at three headwater catchments in the Neversink River watershed indicate that base flow is sustained by groundwater from two sources: a shallow flow system within the till and soil and a deep flow system within bedrock fractures and bedding planes that discharges as perennial springs. Data from eight wells finished near the till/bedrock interface indicate that saturated conditions are not maintained in the shallow flow system during most summers. In contrast, the discharge of a perennial spring remained constant during two summer rainstorms, providing evidence that the deep flow system is disconnected from the shallow flow system in summer. Discharge from perennial springs was the principal source of streamflow in a headwater reach during low flow. Mean NO 3 − concentrations were 20–25 μmol L −1 in five perennial springs during the summer but only 5–10 μmol L −1 in shallow groundwater. Thus the deep flow system does not reflect typical NO 3 − concentrations in the soil during summer. A hydrologic budget at a headwater drainage reveals that March and late fall are the principal groundwater recharge periods. Residence time modeling based on analyses of 18 O and 35 S indicates that groundwater in the deep flow system is 6–22 months old. These data indicate that summer base flow largely originates from previous dormant seasons when available soil NO 3 − is greater. In these Catskill watersheds, high base flow concentrations of NO 3 − during summer do not provide sufficient evidence that the atmospheric N deposition rate exceeds the demand of terrestrial vegetation.

Water Resources Research↗
USGS1998

Detection of aquifer system compaction and land subsidence using interferometric synthetic aperture radar, Antelope Valley, Mojave Desert, California

Interferometric synthetic aperture radar (InSAR) has great potential to detect and quantify land subsidence caused by aquifer system compaction. InSAR maps with high spatial detail and resolution of range displacement (±10 mm in change of land surface elevation) were developed for a groundwater basin (∼10 3 km 2 ) in Antelope Valley, California, using radar data collected from the ERS-1 satellite. These data allow comprehensive comparison between recent (1993–1995) subsidence patterns and those detected historically (1926–1992) by more traditional methods. The changed subsidence patterns are generally compatible with recent shifts in land and water use. The InSAR-detected patterns are generally consistent with predictions based on a coupled model of groundwater flow and aquifer system compaction. The minor inconsistencies may reflect our imperfect knowledge of the distribution and properties of compressible sediments. When used in conjunction with coincident measurements of groundwater levels and other geologic information, InSAR data may be useful for constraining parameter estimates in simulations of aquifer system compaction.

California↗
USGS1998

Field study and simulation of diurnal temperature effects on infiltration and variably saturated flow beneath an ephemeral stream

Two experiments were performed to investigate flow beneath an ephemeral stream and to estimate streambed infiltration rates. Discharge and stream-area measurements were used to determine infiltration rates. Stream and subsurface temperatures were used to interpret subsurface flow through variably saturated sediments beneath the stream. Spatial variations in subsurface temperatures suggest that flow beneath the streambed is dependent on the orientation of the stream in the canyon and the layering of the sediments. Streamflow and infiltration rates vary diurnally: Streamflow is lowest in late afternoon when stream temperature is greatest and highest in early morning when stream temperature is least. The lower afternoon Streamflow is attributed to increased infiltration rates; evapotranspiration is insufficient to account for the decreased Streamflow. The increased infiltration rates are attributed to viscosity effects on hydraulic conductivity from increased stream temperatures. The first set of field data was used to calibrate a two-dimensional variably saturated flow model that includes heat transport. The model was calibrated to (1) temperature fluctuations in the subsurface and (2) infiltration rates determined from measured Streamflow losses. The second set of field data was to evaluate the ability to predict infiltration rates on the basis of temperature measurements alone. Results indicate that the variably saturated subsurface flow depends on downcanyon layering of the sediments. They also support the field observations in indicating that diurnal changes in infiltration can be explained by temperature dependence of hydraulic conductivity. Over the range of temperatures and flows monitored, diurnal stream temperature changes can be used to estimate streambed infiltration rates. It is often impractical to maintain equipment for determining infiltration rates by traditional means; however, once a model is calibrated using both infiltration and temperature data, only relatively inexpensive temperature monitoring can later yield infiltration rates that are within the correct order of magnitude.

Water Resources Research↗
USGS1998

The fate of geothermal arsenic in the Madison and Missouri Rivers, Montana and Wyoming

Geothermal As from Yellowstone National Park causes high As concentrations (10–370 μ g/L) in the Madison and Missouri Rivers in Montana and Wyoming. Arsenic transport is largely conservative in the upper basin as demonstrated by the near equivalence of dissolved and total-recoverable As concentrations, the constancy of As loads, and consistent ratios of concentrations of As to conservative geothermal tracers. Diurnal cycling of As between aqueous and solid phases in response to p H-induced changes in sorption equilibria causes small variations of about 10–20% in dissolved As concentrations. HCl-extractable As concentrations in river and lake sediment in the upper basin are variable depending on position relative to the As-rich headwaters and geochemical and physical processes associated with lakes. In the lower Missouri River, large quantities of suspended sediment from tributaries provide sufficient sorption sites for substantial conversion of As from the aqueous phase to the solid phase.

Montana, Wyoming↗
USGS1998

Molybdate transport in a chemically complex aquifer: Field measurements compared with solute-transport model predictions

A natural-gradient tracer test was conducted in an unconfined sand and gravel aquifer on Cape Cod, Massachusetts. Molybdate was included in the injectate to study the effects of variable groundwater chemistry on its aqueous distribution and to evaluate the reliability of laboratory experiments for identifying and quantifying reactions that control the transport of reactive solutes in groundwater. Transport of molybdate in this aquifer was controlled by adsorption. The amount adsorbed varied with aqueous chemistry that changed with depth as freshwater recharge mixed with a plume of sewage-contaminated groundwater. Molybdate adsorption was strongest near the water table where p H (5.7) and the concentration of the competing solutes phosphate (2.3 micromolar) and sulfate (86 micromolar) were low. Adsorption of molybdate decreased with depth as p H increased to 6.5, phosphate increased to 40 micromolar, and sulfate increased to 340 micromolar. A one-site diffuse-layer surface-complexation model and a two-site diffuse-layer surface-complexation model were used to simulate adsorption. Reactions and equilibrium constants for both models were determined in laboratory experiments and used in the reactive-transport model PHAST to simulate the two-dimensional transport of molybdate during the tracer test. No geochemical parameters were adjusted in the simulation to improve the fit between model and field data. Both models simulated the travel distance of the molybdate cloud to within 10% during the 2-year tracer test; however, the two-site diffuse-layer model more accurately simulated the molybdate concentration distribution within the cloud.

Massachusetts↗