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At least 1,225 records · Page 68Linked to original sources
USGS2010

The chemical evolution of a travertine-depositing stream: Geochemical processes and mass transfer reactions

This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO 2 outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO 2 partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO 2 and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO 2 , outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO 2 along the entire 5.2-km flow path. Outgassing of CO 2 drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO 2 by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO 2 outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO 2 . Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

Water Resources Research↗
USGS2010

Stochastic analysis of solute arrival time in heterogeneous porous media

Longitudinal advective solute movement in heterogeneous porous media is investigated by considering the solute arrival time at a plane perpendicular to the mean fluid velocity. The moments of the solute arrival time are defined in terms of the stochastic properties of a statistically anisotropic hydraulic conductivity field. The flux‐averaged concentration is specified by introducing the moments of the arrival time into a probability density function for the arrival time. The quadratic dependence of the arrival time variance on position in the vicinity of an injection point is indicative of a nondiffusive process. For the assumed spatial correlation of the hydraulic conductivity, the variance of the arrival time asymptotically approaches a linear dependence on the position from the injection point similar to a diffusion process. The impact of assuming solute movement to be a diffusive process from the onset of the solute injection causes erroneous estimates of flux‐averaged concentrations at distances from the injection point that are of the order of the correlation length of the hydraulic conductivity. The arrival time analysis and the particle position analysis given in Dagan (1982, 1984) are complementary interpretations of advective solute movement that yield different definitions of the solute concentration; the position analysis intrinsically defines the resident or volume‐averaged concentration, while the flux‐averaged concentration is defined from the arrival time analysis. The temporal variation of the resident and flux‐averaged concentration are similar at a given position for small values of the variance of the hydraulic conductivity, or at distances from the solute injection point that are large relative to correlation length of the hydraulic conductivity.

Water Resources Research↗
USGS2010

Using exogenous variables in testing for monotonic trends in hydrologic time series

One approach that has been used in performing a nonparametric test for monotonic trend in a hydrologic time series consists of a two-stage analysis. First, a regression equation is estimated for the variable being tested as a function of an exogenous variable. A nonparametric trend test such as the Kendall test is then performed on the residuals from the equation. By analogy to stagewise regression and through Monte Carlo experiments, it is demonstrated that this approach will tend to underestimate the magnitude of the trend and to result in some loss in power as a result of ignoring the interaction between the exogenous variable and time. An alternative approach, referred to as the adjusted variable Kendall test, is demonstrated to generally have increased statistical power and to provide more reliable estimates of the trend slope. In addition, the utility of including an exogenous variable in a trend test is examined under selected conditions.

Water Resources Research↗
USGS2010

Estimation of descriptive statistics for multiply censored water quality data

This paper extends the work of Gilliom and Helsel (1986) on procedures for estimating descriptive statistics of water quality data that contain “less than” observations. Previously, procedures were evaluated when only one detection limit was present. Here we investigate the performance of estimators for data that have multiple detection limits. Probability plotting and maximum likelihood methods perform substantially better than simple substitution procedures now commonly in use. Therefore simple substitution procedures (e.g., substitution of the detection limit) should be avoided. Probability plotting methods are more robust than maximum likelihood methods to misspecification of the parent distribution and their use should be encouraged in the typical situation where the parent distribution is unknown. When utilized correctly, less than values frequently contain nearly as much information for estimating population moments and quantiles as would the same observations had the detection limit been below them.

Water Resources Research↗
USGS2010

Nonparametric statistical methods for comparing two sites based on data with multiple nondetect limits

As concern over the effects of trace amounts of pollutants has increased, so has the need for statistical methods that deal appropriately with data that include values reported as “less than” the detection limit. It has become increasingly common for water quality data to include censored values that reflect more than one detection limit for a single analyte. For such multiply censored data sets, standard statistical methods (for example, to compare analyte concentration in two areas) are not valid. In such cases, methods from the biostatistical field of survival analysis are applicable. Several common two‐sample censored data rank tests are explained, and their behaviors are studied via a Monte Carlo simulation in which sample sizes and censoring mechanisms are varied under an assumed lognormal distribution. These tests are applied to shallow groundwater chemistry data from two sites in the San Joaquin Valley, California. The best overall test, in terms of maintained α level, is the normal scores test based on a permutation variance. In cases where the α level is maintained, however, the Peto‐Prentice statistic based on an asymptotic variance performs as well or better.

California↗
USGS2010

Analysis of accuracy of approximate, simultaneous, nonlinear confidence intervals on hydraulic heads in analytical and numerical test cases

Inaccuracies in parameter values, parameterization, stresses, and boundary conditions of analytical solutions and numerical models of groundwater flow produce errors in simulated hydraulic heads. These errors can be quantified in terms of approximate, simultaneous, nonlinear confidence intervals presented in the literature. Approximate confidence intervals can be applied in both error and sensitivity analysis and can be used prior to calibration or when calibration was accomplished by trial and error. In this paper, the method is expanded for use in numerical problems, and the accuracy of the approximate intervals is evaluated using Monte Carlo runs. Four test cases are used to compare results. In two numerical test cases, the approximate, simultaneous confidence intervals are generally accurate and are calculated efficiently enough to indicate that the method is useful for real-world problems. In one of the two analytical test cases considered, the approximate intervals are too wide to be of practical interest. Improving the method used to approximate the uncertainty of the model inputs could make the confidence intervals useful in more problems.

Water Resources Research↗
USGS2010

Convergent radial dispersion: A Laplace transform solution for aquifer tracer testing

A Laplace transform solution was obtained for the injection of a tracer in a well situated in a homogeneous aquifer where steady, horizontal, radially convergent flow has been established due to pumping at a second well. The standard advection-dispersion equation for mass transfer was used as the controlling equation. For boundary conditions, mass balances that account for mixing of the tracer with the fluid residing in the injection and pumped wells were used. The derived solution, which can be adapted for either resident or flux-averaged concentration, is of practical use only for the pumped well. This problem is of interest because it is easily applied to field determination of aquifer dispersivity and effective porosity. Breakthrough curves were obtained by numerical inversion of the Laplace transform solution. It was found that tracer mixing with fluid in the pumped and injection wells, especially in low-porosity aquifers, may have a significant influence on the shape of the tracer breakthrough curves.

Water Resources Research↗
USGS2010

Simulation of calcite dissolution and porosity changes in saltwater mixing zones in coastal aquifers

Thermodynamic models of aqueous solutions have indicated that the mixing of seawater and calcite-saturated fresh groundwater can produce a water that is undersaturated with respect to calcite. Mixing of such waters in coastal carbonate aquifers could lead to significant amounts of limestone dissolution. The potential for such dissolution in coastal saltwater mixing zones is analyzed by coupling the results from a reaction simulation model (PHREEQE) with a variable density groundwater flow and solute transport model. Idealized cross sections of coastal carbonate aquifers are simulated to estimate the potential for calcite dissolution under a variety of hydrologic and geochemical conditions. Results show that limestone dissolution in mixing zones is strongly dependent on groundwater flux and nearly independent of the dissolution kinetics of calcite. The amount of dissolution varies within a mixing zone, depending on the properties, physical dimensions, and boundary conditions of the aquifer system. Nearly all of the dissolution occurs in the fresher side of the mixing zone, with the maximum dissolution occurring in water that is fresher than that predicted solely by geochemical reaction models. The greatest porosity and permeability development occur at the toe and at the top of the mixing zone. If permeability increases as porosity increases, asymmetry in the dissolution causes the mixing zone to migrate landward over time. Dissolution rates indicated by the model show that this mechanism can produce significant increases in porosity and permeability over time spans on the order of tens of thousands of years. Given the comparatively long span of geologic time, this process may be largely responsible for porosity and permeability development observed in those carbonate rocks through which a freshwater-saltwater mixing zone had at one time migrated.

Water Resources Research↗
USGS2010

Accounting for intracell flow in models with emphasis on water table recharge and stream-aquifer interaction: 2. A procedure

Intercepted intracell flow, especially if cell includes water table recharge and a stream ((sink), can result in significant model error if not accounted for. A procedure utilizing net flow per cell ( F n ) that accounts for intercepted intracell flow can be used for both steady state and transient simulations. Germane to the procedure is the determination of the ratio of area of influence of the interior sink to the area of the cell ( A i / A c ). A i is the area in which water table recharge has the potential to be intercepted by the sink. Determining A i / A c requires either a detailed water table map or observation of stream conditions within the cell. A proportioning parameter M , which is equal to 1 or slightly less and is a function of cell geometry, is used to determine how much of the water that has potential for interception is intercepted by the sink within the cell. Also germane to the procedure is the determination of the flow across the streambed ( F s ), which is not directly a function of cell size, due to difference in head between the water level in the stream and the potentiometric surface of the aquifer underlying the streambed. The use of F n for steady state simulations allows simulation of water levels without utilizing head-dependent or constant head boundary conditions which tend to constrain the model-calculated water levels, an undesirable result if a comparison of measured and calculated water levels is being made. Transient simulations of streams usually utilize a head-dependent boundary condition and a leakance value to model a stream. Leakance values for each model cell can be determined from a steady state simulation, which used the net flow per cell procedure. For transient simulation, F n would not include F s . Also, for transient simulation it is necessary to check F n at different time intervals because M and A i / A c are not constant and change with time. The procedure was used successfully in two different models of the aquifer system in the Ozarks. The use of F n was essential to the two model studies because most model cells in both models contained water table recharge and multiple sinks.

Water Resources Research↗
USGS2010

A random spatial network model based on elementary postulates

A model for generating random spatial networks that is based on elementary postulates comparable to those of the random topology model is proposed. In contrast to the random topology model, this model ascribes a unique spatial specification to generated drainage networks, a distinguishing property of some network growth models. The simplicity of the postulates creates an opportunity for potential analytic investigations of the probabilistic structure of the drainage networks, while the spatial specification enables analyses of spatially dependent network properties. In the random topology model all drainage networks, conditioned on magnitude (number of first-order streams), are equally likely, whereas in this model all spanning trees of a grid, conditioned on area and drainage density, are equally likely. As a result, link lengths in the generated networks are not independent, as usually assumed in the random topology model. For a preliminary model evaluation, scale-dependent network characteristics, such as geometric diameter and link length properties, and topologic characteristics, such as bifurcation ratio, are computed for sets of drainage networks generated on square and rectangular grids. Statistics of the bifurcation and length ratios fall within the range of values reported for natural drainage networks, but geometric diameters tend to be relatively longer than those for natural networks.

Water Resources Research↗
USGS2010

The relationship of catchment topography and soil hydraulic characteristics to lake alkalinity in the northeastern United States

We undertook the task of determining whether base flow alkalinity of surface waters in the northeastern United States is related to indices of soil contact time and flow path partitioning that are derived from topographic and soils information. The influence of topography and soils on catchment hydrology has been incorporated previously in the variable source area model TOPMODEL as the relative frequency distribution of ln ( a/Kb tan B ), where ln is the Naperian logarithm, “ a ” is the area drained per unit contour, K is the saturated hydraulic conductivity, b is the soil depth, and tan B is the slope. Using digital elevation and soil survey data, we calculated the ln ( a/Kb tan B ) distribution for 145 catchments. Indices of flow path partitioning and soil contact time were derived from the ln ( a/Kb tan B ) distributions and compared to measurements of alkalinity in lakes to which the catchments drain. We found that alkalinity was, in general, positively correlated with the index of soil contact time, whereas the correlation between alkalinity and the flow path partitioning index was weak at best. A portion of the correlation between the soil contact time index and alkalinity was attributable to covariation with soil base saturation and cation exchange capacity, while another portion was found to be independent of these factors. Although our results indicate that catchments with long soil contact time indices are most likely to produce high alkalinity base flow, a sensitivity analysis of TOPMODEL suggests that surface waters of these same watersheds may be susceptible to alkalinity depressions during storm events, due to the role of flow paths.

Water Resources Research↗
USGS2010

Solute advection in stratified formations

Advection‐dominated solute movement in stratified formations is investigated using a Lagrangian interpretation of particle motion. A probability density function (pdf) for particle position quantifies the expected depth‐integrated resident concentration. A pdf for particle arrival time quantifies the expected depth‐integrated rate of mass arrival, from which the flux‐averaged concentration can be defined. The difference between the flux‐averaged and resident concentrations is shown to be significant for the variability in the hydraulic conductivity that is commonly encountered in field applications. The influence of porosity variations on the advection‐dominated solute movement in stratified porous media is shown to be notable only for large variability in the effective porosity.

Water Resources Research↗
USGS2010

Water content dependence of trapped air in two soils

An improved air pycnometer method was used to examine the water content dependence of trapped-air volumes in two repacked, nonswelling soils. Trapped-air volumes were determined at a series of hydrostatic equilibrium stages which were attained during water pressure-controlled wetting and drying cycles over a range of 0 to −10 kPa for a sand and 0 to −20 kPa for a loam. Small pressure perturbations, between 0.2 and 0.6 kPa, were used in the air pycnometer method. Volumes of trapped air obtained at each hydrostatic equilibrium stage were independent of perturbation level and remained relatively constant over the time required to make repeated determinations. In contrast with most of the results obtained in previous studies, which often showed irregular relations, in this study the volume fraction of trapped air was found to be a regular, monotonically increasing (though possibly hysteretic) function of water content. For the soils studied, the function definitely exceeded zero only at water contents greater than 70% of saturation. However, during the initial drying from complete water saturation, the volume fraction of trapped air was virtually zero. Air trapping influenced the water retention curves significantly only at water contents higher than about 60% of saturation. Except at zero water pressure, however, not all of the differences between the initial and the other drying retention curves were accounted for by observed differences in trapped-air volumes. Air trapping was not required for the onset of hysteresis in the water retention relation for the cases studied, i.e., when drying-to-wetting reversals were imposed at about 27% and 40% of saturation for the sand and loam soils, respectively.

Water Resources Research↗
USGS2010

Air permeability and trapped-air content in two soils

To improve understanding of hysteretic air permeability relations, a need exists for data on the water content dependence of air permeability, matric pressure, and air trapping (especially for wetting-drying cycles). To obtain these data, a special instrument was designed. The instrument is a combination of a gas permeameter (for air permeability determination), a suction plate apparatus (for retentivity curve determination), and an air pycnometer (for trapped-air-volume determination). This design allowed values of air permeability, matric pressure, and air trapping to be codetermined, i.e., determined at the same values of water content using the same sample and the same inflow-outflow boundaries. Such data were obtained for two nonswelling soils. The validity of the air permeability determinations was repeatedly confirmed by rigorous tests of Darcy's law. During initial drying from complete water saturation, supplementary measurements were made to assess the magnitude of gas slip. The extended Darcy equation accurately described the measured flux gradient relations for each condition of absolute gas pressure tested. Air permeability functions exhibited zero-permeability regions at high water contents as well as an abruptly appearing hysteresis at low water contents. Measurements in the zero-permeability regions revealed that the total amount of air in general exceeded the amount of trapped air. This indicates that the medium' s air space is partitioned into three measurable domains: through-flowing air, locally accessible air (i.e., air accessible from only one flow boundary), and trapped air. During repeated wetting and drying, the disappearance and reappearance of air permeability coincided closely with the reappearance and disappearance, respectively, of trapped air. The observed relation between critical features of the air permeability functions and those of the air-trapping functions suggest that water-based blockages play a significant role in the disruption of gas-phase connectivity and in preventing air flow, and must be considered in any effectual model of air permeability relations.

Water Resources Research↗
USGS2010

Multiobjective sampling design for parameter estimation and model discrimination in groundwater solute transport

Sampling design for site characterization studies of solute transport in porous media is formulated as a multiobjective problem. Optimal design of a sampling network is a sequential process in which the next phase of sampling is designed on the basis of all available physical knowledge of the system. Three objectives are considered: model discrimination, parameter estimation, and cost minimization. For the first two objectives, physically based measures of the value of information obtained from a set of observations are specified. In model discrimination, value of information of an observation point is measured in terms of the difference in solute concentration predicted by hypothesized models of transport. Points of greatest difference in predictions can contribute the most information to the discriminatory power of a sampling design. Sensitivity of solute concentration to a change in a parameter contributes information on the relative variance of a parameter estimate. Inclusion of points in a sampling design with high sensitivities to parameters tends to reduce variance in parameter estimates. Cost minimization accounts for both the capital cost of well installation and the operating costs of collection and analysis of field samples. Sensitivities, discrimination information, and well installation and sampling costs are used to form coefficients in the multiobjective problem in which the decision variables are binary (zero/one), each corresponding to the selection of an observation point in time and space. The solution to the multiobjective problem is a noninferior set of designs. To gain insight into effective design strategies, a one-dimensional solute transport problem is hypothesized. Then, an approximation of the noninferior set is found by enumerating 120 designs and evaluating objective functions for each of the designs. Trade-offs between pairs of objectives are demonstrated among the models. The value of an objective function for a given design is shown to correspond to the ability of a design to actually meet an objective.

Water Resources Research↗
USGS2010

Particle velocity interpolation in block-centered finite difference groundwater flow models

A block-centered, finite difference model of two-dimensional groundwater flow yields velocity values at the midpoints of interfaces between adjacent blocks. Method of characteristics, random walk and particle-tracking models of solute transport require velocities at arbitrary particle locations within the finite difference grid. Particle path lines and travel times are sensitive to the spatial interpolation scheme employed, particularly in heterogeneous aquifers. This paper briefly reviews linear and bilinear interpolation of velocity and introduces a new interpolation scheme. Linear interpolation of velocity is consistent with the numerical solution of the flow equation and preserves discontinuities in velocity caused by abrupt (blocky) changes in transmissivity or hydraulic conductivity. However, linear interpolation yields discontinuous and somewhat unrealistic velocities in homogeneous aquifers. Bilinear interpolation of velocity yields continuous and realistic velocities in homogeneous and smoothly heterogeneous aquifers but does not preserve discontinuities in velocity at abrupt transmissivity boundaries. The new scheme uses potentiometric head gradients and offers improved accuracy for nonuniform flow in heterogeneous aquifers with abrupt changes in transmissivity. The new scheme is equivalent to bilinear interpolation in homogeneous media and is equivalent to linear interpolation where gradients are uniform. Selecting the best interpolation scheme depends, in part, on the conceptualization of aquifer heterogeneity, that is, whether changes in transmissivity occur abruptly or smoothly.

Water Resources Research↗
USGS2010

Characterization of transport in an acidic and metal-rich mountain stream based on a lithium tracer injection and simulations of transient storage

Physical parameters characterizing solute transport in the Snake River (an acidic and metal-rich mountain stream near Montezuma, Colorado) were variable along a 5.2-km study reach. Stream cross-sectional area and volumetric inflow each varied by a factor of 3. Because of transient storage, the residence time of injected tracers in the Snake River was longer than would be calculated by consideration of convective travel time alone. Distributed inflows along the stream were a significant source of in-stream chemical variations. These transport characteristics of the Snake River were established on the basis of the assumption of lithium as an ideally conservative tracer and use of simulations of advection, dispersion, and transient storage. Evaluations of the validity of this combined tracer and simulation approach lend confidence to the estimation of the physical transport parameters, but further development is warranted for methods of onsite transport experimentation in hydrologically complex, chemically reactive environments.

Water Resources Research↗
USGS2010

Application of the Stefan-Maxwell Equations to determine limitations of Fick's law when modeling organic vapor transport in sand columns

The organic component of the vapor phase of a porous medium contaminated by an immiscible organic liquid can be significant enough to violate the condition of a dilute species diffusing in a bulk phase assumed by Fick's law. The Stefan-Maxwell equations provide a more comprehensive model for quantifying steady state transport for a vapor phase composed of arbitrary proportions of its constituents. The application of both types of models to the analysis of column experiments demonstrates that use of a Fickian-based transport model can lead to significant overestimates of soil tortuosity constants. Further, the physical displacement of naturally occurring gases (e.g., O 2 ), predicted by the Stefan-Maxwell model but not by application of Fick's Law, can be attributed improperly to a sink term such as microbial degradation in a Fickian-based transport model.

Water Resources Research↗