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At least 271 records · Page 15Linked to original sources

Simultaneous estimation of local-scale and flow path-scale dual-domain mass transfer parameters using geoelectrical monitoring

Anomalous solute transport, modeled as rate-limited mass transfer, has an observable geoelectrical signature that can be exploited to infer the controlling parameters. Previous experiments indicate the combination of time-lapse geoelectrical and fluid conductivity measurements collected during ionic tracer experiments provides valuable insight into the exchange of solute between mobile and immobile porosity. Here, we use geoelectrical measurements to monitor tracer experiments at a former uranium mill tailings site in Naturita, Colorado. We use nonlinear regression to calibrate dual-domain mass transfer solute-transport models to field data. This method differs from previous approaches by calibrating the model simultaneously to observed fluid conductivity and geoelectrical tracer signals using two parameter scales: effective parameters for the flow path upgradient of the monitoring point and the parameters local to the monitoring point. We use regression statistics to rigorously evaluate the information content and sensitivity of fluid conductivity and geophysical data, demonstrating multiple scales of mass transfer parameters can simultaneously be estimated. Our results show, for the first time, field-scale spatial variability of mass transfer parameters (i.e., exchange-rate coefficient, porosity) between local and upgradient effective parameters; hence our approach provides insight into spatial variability and scaling behavior. Additional synthetic modeling is used to evaluate the scope of applicability of our approach, indicating greater range than earlier work using temporal moments and a Lagrangian-based Damköhler number. The introduced Eulerian-based Damköhler is useful for estimating tracer injection duration needed to evaluate mass transfer exchange rates that range over several orders of magnitude.

Water Resources Research↗

Interactions between hyporheic flow produced by stream meanders, bars, and dunes

Stream channel morphology from grain-scale roughness to large meanders drives hyporheic exchange flow. In practice, it is difficult to model hyporheic flow over the wide spectrum of topographic features typically found in rivers. As a result, many studies only characterize isolated exchange processes at a single spatial scale. In this work, we simulated hyporheic flows induced by a range of geomorphic features including meanders, bars and dunes in sand bed streams. Twenty cases were examined with 5 degrees of river meandering. Each meandering river model was run initially without any small topographic features. Models were run again after superimposing only bars and then only dunes, and then run a final time after including all scales of topographic features. This allowed us to investigate the relative importance and interactions between flows induced by different scales of topography. We found that dunes typically contributed more to hyporheic exchange than bars and meanders. Furthermore, our simulations show that the volume of water exchanged and the distributions of hyporheic residence times resulting from various scales of topographic features are close to, but not linearly additive. These findings can potentially be used to develop scaling laws for hyporheic flow that can be widely applied in streams and rivers.

Water Resources Research↗

The influence of stream thermal regimes and preferential flow paths on hyporheic exchange in a glacial meltwater stream

Given projected increases in stream temperatures attributable to global change, improved understanding of relationships between stream temperatures and hyporheic exchange would be useful. We conducted two conservative tracer injection experiments in a glacial meltwater stream, to evaluate the effects of hyporheic thermal gradients on exchange processes, including preferential flow paths (PFPs). The experiments were conducted on the same day, the first (a stream injection) during a cool, morning period and the second (dual stream and hyporheic injections) during a warm, afternoon period. In the morning, the hyporheic zone was thermally uniform at 4°C, whereas by the afternoon the upper 10 cm had warmed to 6–12°C and exhibited greater temperature heterogeneity. Solute transport modeling showed that hyporheic cross-sectional areas (A s ) at two downstream sites were two and seven times lower during the warm experiment. Exchange metrics indicated that the hyporheic zone had less influence on downstream solute transport during the warm, afternoon experiment. Calculated hyporheic depths were less than 5 cm, contrasting with tracer detection at 10 and 25 cm depths. The hyporheic tracer arrival at one downstream site was rapid, comparable to the in-stream tracer arrival, providing evidence for PFPs. We thus propose a conceptual view of the hyporheic zone in this reach as being dominated by discrete PFPs weaving through hydraulically isolated areas. One explanation for the simultaneous increase in temperature heterogeneity and A s decrease in a warmer hyporheic zone may be a flow path preferentiality feedback mechanism resulting from a combination of temperature-related viscosity decreases and streambed heterogeneity.

Water Resources Research↗

Effects of error covariance structure on estimation of model averaging weights and predictive performance

When conducting model averaging for assessing groundwater conceptual model uncertainty, the averaging weights are often evaluated using model selection criteria such as AIC, AICc, BIC, and KIC (Akaike Information Criterion, Corrected Akaike Information Criterion, Bayesian Information Criterion, and Kashyap Information Criterion, respectively). However, this method often leads to an unrealistic situation in which the best model receives overwhelmingly large averaging weight (close to 100%), which cannot be justified by available data and knowledge. It was found in this study that this problem was caused by using the covariance matrix, C E , of measurement errors for estimating the negative log likelihood function common to all the model selection criteria. This problem can be resolved by using the covariance matrix, C ek , of total errors (including model errors and measurement errors) to account for the correlation between the total errors. An iterative two-stage method was developed in the context of maximum likelihood inverse modeling to iteratively infer the unknown C ek from the residuals during model calibration. The inferred C ek was then used in the evaluation of model selection criteria and model averaging weights. While this method was limited to serial data using time series techniques in this study, it can be extended to spatial data using geostatistical techniques. The method was first evaluated in a synthetic study and then applied to an experimental study, in which alternative surface complexation models were developed to simulate column experiments of uranium reactive transport. It was found that the total errors of the alternative models were temporally correlated due to the model errors. The iterative two-stage method using C ek resolved the problem that the best model receives 100% model averaging weight, and the resulting model averaging weights were supported by the calibration results and physical understanding of the alternative models. Using C ek obtained from the iterative two-stage method also improved predictive performance of the individual models and model averaging in both synthetic and experimental studies.

Water Resources Research↗

Statistical mapping of zones of focused groundwater/surface-water exchange using fiber-optic distributed temperature sensing

Fiber-optic distributed temperature sensing (FO-DTS) increasingly is used to map zones of focused groundwater/surface-water exchange (GWSWE). Previous studies of GWSWE using FO-DTS involved identification of zones of focused GWSWE based on arbitrary cutoffs of FO-DTS time-series statistics (e.g., variance, cross-correlation between temperature and stage, or spectral power). New approaches are needed to extract more quantitative information from large, complex FO-DTS data sets while concurrently providing an assessment of uncertainty associated with mapping zones of focused GSWSE. Toward this end, we present a strategy combining discriminant analysis (DA) and spectral analysis (SA). We demonstrate the approach using field experimental data from a reach of the Columbia River adjacent to the Hanford 300 Area site. Results of the combined SA/DA approach are shown to be superior to previous results from qualitative interpretation of FO-DTS spectra alone.

Washington↗

Temporal dynamics of biogeochemical processes at the Norman Landfill site

The temporal variability observed in redox sensitive species in groundwater can be attributed to coupled hydrological, geochemical, and microbial processes. These controlling processes are typically nonstationary, and distributed across various time scales. Therefore, the purpose of this study is to investigate biogeochemical data sets from a municipal landfill site to identify the dominant modes of variation and determine the physical controls that become significant at different time scales. Data on hydraulic head, specific conductance, δ2H, chloride, sulfate, nitrate, and nonvolatile dissolved organic carbon were collected between 1998 and 2000 at three wells at the Norman Landfill site in Norman, OK. Wavelet analysis on this geochemical data set indicates that variations in concentrations of reactive and conservative solutes are strongly coupled to hydrologic variability (water table elevation and precipitation) at 8 month scales, and to individual eco-hydrogeologic framework (such as seasonality of vegetation, surface-groundwater dynamics) at 16 month scales. Apart from hydrologic variations, temporal variability in sulfate concentrations can be associated with different sources (FeS cycling, recharge events) and sinks (uptake by vegetation) depending on the well location and proximity to the leachate plume. Results suggest that nitrate concentrations show multiscale behavior across temporal scales for different well locations, and dominant variability in dissolved organic carbon for a closed municipal landfill can be larger than 2 years due to its decomposition and changing content. A conceptual framework that explains the variability in chemical concentrations at different time scales as a function of hydrologic processes, site-specific interactions, and/or coupled biogeochemical effects is also presented.

Oklahoma↗

Hyporheic zone denitrification: controls on effective reaction depth and contribution to whole-stream mass balance

Stream denitrification is thought to be enhanced by hyporheic transport but there is little direct evidence from the field. To demonstrate at a field site, we injected 15 NO 3 − , Br (conservative tracer), and SF 6 (gas exchange tracer) and compared measured whole-stream denitrification with in situ hyporheic denitrification in shallow and deeper flow paths of contrasting geomorphic units. Hyporheic denitrification accounted for between 1 and 200% of whole-stream denitrification. The reaction rate constant was positively related to hyporheic exchange rate (greater substrate delivery), concentrations of substrates DOC and nitrate, microbial denitrifier abundance (nirS), and measures of granular surface area and presence of anoxic microzones. The dimensionless product of the reaction rate constant and hyporheic residence time, λ hz τ hz define a Damköhler number, Da den-hz that was optimal in the subset of hyporheic flow paths where Da den-hz ≈ 1. Optimal conditions exclude inefficient deep pathways transport where substrates are used up and also exclude inefficient shallow pathways that require repeated hyporheic entries and exits to complete the reaction. The whole-stream reaction significance, R s (dimensionless), was quantified by multiplying Da den-hz by the proportion of stream discharge passing through the hyporheic zone. Together these two dimensionless metrics, one flow-path scale and the other reach-scale, quantify the whole-stream significance of hyporheic denitrification. One consequence is that the effective zone of significant denitrification often differs from the full depth of the hyporheic zone, which is one reason why whole-stream denitrification rates have not previously been explained based on total hyporheic-zone metrics such as hyporheic-zone size or residence time.

Indiana↗

Bridging groundwater models and decision support with a Bayesian network

Resource managers need to make decisions to plan for future environmental conditions, particularly sea level rise, in the face of substantial uncertainty. Many interacting processes factor in to the decisions they face. Advances in process models and the quantification of uncertainty have made models a valuable tool for this purpose. Long-simulation runtimes and, often, numerical instability make linking process models impractical in many cases. A method for emulating the important connections between model input and forecasts, while propagating uncertainty, has the potential to provide a bridge between complicated numerical process models and the efficiency and stability needed for decision making. We explore this using a Bayesian network (BN) to emulate a groundwater flow model. We expand on previous approaches to validating a BN by calculating forecasting skill using cross validation of a groundwater model of Assateague Island in Virginia and Maryland, USA. This BN emulation was shown to capture the important groundwater-flow characteristics and uncertainty of the groundwater system because of its connection to island morphology and sea level. Forecast power metrics associated with the validation of multiple alternative BN designs guided the selection of an optimal level of BN complexity. Assateague island is an ideal test case for exploring a forecasting tool based on current conditions because the unique hydrogeomorphological variability of the island includes a range of settings indicative of past, current, and future conditions. The resulting BN is a valuable tool for exploring the response of groundwater conditions to sea level rise in decision support.

Water Resources Research↗

Effect of correlated observation error on parameters, predictions, and uncertainty

Correlations among observation errors are typically omitted when calculating observation weights for model calibration by inverse methods. We explore the effects of omitting these correlations on estimates of parameters, predictions, and uncertainties. First, we develop a new analytical expression for the difference in parameter variance estimated with and without error correlations for a simple one-parameter two-observation inverse model. Results indicate that omitting error correlations from both the weight matrix and the variance calculation can either increase or decrease the parameter variance, depending on the values of error correlation (ρ) and the ratio of dimensionless scaled sensitivities (r dss ). For small ρ, the difference in variance is always small, but for large ρ, the difference varies widely depending on the sign and magnitude of r dss . Next, we consider a groundwater reactive transport model of denitrification with four parameters and correlated geochemical observation errors that are computed by an error-propagation approach that is new for hydrogeologic studies. We compare parameter estimates, predictions, and uncertainties obtained with and without the error correlations. Omitting the correlations modestly to substantially changes parameter estimates, and causes both increases and decreases of parameter variances, consistent with the analytical expression. Differences in predictions for the models calibrated with and without error correlations can be greater than parameter differences when both are considered relative to their respective confidence intervals. These results indicate that including observation error correlations in weighting for nonlinear regression can have important effects on parameter estimates, predictions, and their respective uncertainties.

Water Resources Research↗

Evaluating the use of “goodness‐of‐fit” measures in hydrologic and hydroclimatic model validation

Correlation and correlation‐based measures (e.g., the coefficient of determination) have been widely used to evaluate the “goodness‐of‐fit” of hydrologic and hydroclimatic models. These measures are oversensitive to extreme values (outliers) and are insensitive to additive and proportional differences between model predictions and observations. Because of these limitations, correlation‐based measures can indicate that a model is a good predictor, even when it is not. In this paper, useful alternative goodness‐of‐fit or relative error measures (including the coefficient of efficiency and the index of agreement) that overcome many of the limitations of correlation‐based measures are discussed. Modifications to these statistics to aid in interpretation are presented. It is concluded that correlation and correlation‐based measures should not be used to assess the goodness‐of‐fit of a hydrologic or hydroclimatic model and that additional evaluation measures (such as summary statistics and absolute error measures) should supplement model evaluation tools.

Water Resources Research↗

Evaluation of the atmosphere as a source of volatile organic compounds in shallow groundwater

The atmosphere as a source of volatile organic compounds (VOCs) in shallow groundwater was evaluated over an area in southern New Jersey. Chloroform, methyl tertbutyl ether (MTBE), 1,1,1‐trichloroethane, tetrachloroethylene (PCE), and carbon disulfide (not a VOC) were detected frequently at low‐level concentrations in a network of 78 shallow wells in the surficial Kirkwood‐Cohansey aquifer system. The atmosphere was sampled for these compounds and only MTBE concentrations were high enough to potentially explain frequent detection in shallow groundwater. A mathematical model of reactive transport through the unsaturated zone is presented to explain how variations in unsaturated properties across the study area could explain differences in MTBE concentrations in shallow groundwater given the atmosphere as the source. Even when concentrations of VOCs in groundwater are low compared to regulatory concentration limits, it is critical to know the source. If the VOCs originate from a point source((), concentrations in groundwater could potentially increase over time to levels of concern as groundwater plumes evolve, whereas if the atmosphere is the source, then groundwater concentrations would be expected to remain at low‐level concentrations not exceeding those in equilibrium with atmospheric concentrations. This is the first analysis of VOC occurrence in shallow groundwater involving colocated atmosphere data.

Water Resources Research↗

Correlative velocity fluctuations over a gravel river bed

Velocity fluctuations in a steep, coarse‐bedded river were measured in flow depths ranging from 0.8 to 2.2 m, with mean velocities at middepth from 1.1 to 3.1 m s −1 . Analyses of synchronous velocity records for two and three points in the vertical showed a broad range of high coherence for wave periods from 10 to 100 s, centering around 10–30 s. Streamwise correlations over distances of 9 and 14 m showed convection velocities near mean velocity for the same wave periods. The range of coherent wave periods was a small multiple of predicted “boil” periods. Correlative fluctuations in synchronous velocity records in the vertical direction suggested the blending of short pulses into longer wave periods. The highest spectral densities were measured beyond the range of coherent wave periods and were probably induced by migration of low‐relief bed forms.

Water Resources Research↗

Quantification of precipitation measurement discontinuity induced by wind shields on national gauges

Various combinations of wind shields and national precipitation gauges commonly used in countries of the northern hemisphere have been studied in this paper, using the combined intercomparison data collected at 14 sites during the World Meteorological Organization's (WMO) Solid Precipitation Measurement Intercomparison Project. The results show that wind shields improve gauge catch of precipitation, particularly for snow. Shielded gauges, on average, measure 20–70% more snow than unshielded gauges. Without a doubt, the use of wind shields on precipitation gauges has introduced a significant discontinuity into precipitation records, particularly in cold and windy regions. This discontinuity is not constant and it varies with wind speed, temperature, and precipitation type. Adjustment for this discontinuity is necessary to obtain homogenous precipitation data for climate change and hydrological studies. The relation of the relative catch ratio (RCR, ratio of measurements of shielded gauge to unshielded gauge) versus wind speed and temperature has been developed for Alter and Tretyakov wind shields. Strong linear relations between measurements of shielded gauge and unshielded gauge have also been found for different precipitation types. The linear relation does not fully take into account the varying effect of wind and temperature on gauge catch. Overadjustment by the linear relation may occur at those sites with lower wind speeds, and underadjustment may occur at those stations with higher wind speeds. The RCR technique is anticipated to be more applicable in a wide range of climate conditions. The RCR technique and the linear relation have been tested at selected WMO intercomparison stations, and reasonable agreement between the adjusted amounts and the shielded gauge measurements was obtained at most of the sites. Test application of the developed methodologies to a regional or national network is therefore recommended to further evaluate their applicability in different climate conditions. Significant increase of precipitation is expected due to the adjustment particularly in high latitudes and other cold regions. This will have a meaningful impact on climate variation and change analyses.

Water Resources Research↗

Long‐term trends in stream water and precipitation chemistry at five headwater basins in the northeastern United States

Stream water data from five headwater basins in the northeastern United States covering water years 1968–1996 and precipitation data from eight nearby precipitation monitoring sites covering water years 1984‐1996 were analyzed for temporal trends in chemistry using the nonparametric seasonal Kendall test. Concentrations of SO 4 declined at three of five streams during 1968–1996 ( p < 0.1), and all of the streams exhibited downward trends in SO 4 over the second half of the period (1984–1996). Concentrations of SO 4 in precipitation declined at seven of eight sites from 1984 to 1996, and the magnitudes of the declines (−0.7 to −2.0 µeq L −1 yr −1 ) generally were similar to those of stream water SO 4 . These results indicate that changes in precipitation SO 4 were of sufficient magnitude to account for changes in stream water SO 4 . Concentrations of Ca + Mg declined at three of five streams and five of eight precipitation sites from 1984 to 1996. Precipitation acidity decreased at five of eight sites during the same period, but alkalinity increased in only one stream. In most cases the decreases in stream water SO 4 were similar in magnitude to declines in stream water Ca + Mg, which is consistent with the theory of leaching by mobile acid anions in soils. In precipitation the magnitudes of SO 4 declines were similar to those of hydrogen, and declines in Ca +Mg were much smaller. This indicates that recent decreases in SO 4 deposition are now being reflected in reduced precipitation acidity. The lack of widespread increases in stream water alkalinity, despite the prevalence of downward trends in stream water SO 4 , suggests that at most sites, increases in stream water p H and acid‐neutralizing capacity may be delayed until higher soil base‐saturation levels are achieved.

Water Resources Research↗

Improved method for the determination of nonpurgeable suspended organic carbon in natural water by silver filter filtration, wet chemical oxidation, and infrared spectrometry

Precision and accuracy are reported for the first time for the analysis of nonpurgeable suspended organic carbon by silver membrane filtration followed by wet chemical oxidation. A water sample is pressure filtered through a 0.45‐μm‐pore‐size, 47‐mm‐diameter silver membrane filter. The silver membrane filter then is cut into ribbons and placed in a flame‐sealable glass ampule. The organic material trapped on the membrane filter strips is acidified, purged with oxygen to remove inorganic carbonates and volatile organic compounds, and oxidized to carbon dioxide (CO 2 ) using phosphoric acid and potassium persulfate in the sealed glass ampule. The resulting CO 2 is measured by a nondispersive infrared CO 2 detector. The amount of CO 2 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the environmental water sample. The quantitation and method detection limit for routine analysis is 0.2 mg/L. The average percent recovery in five representative matrices was 97 ± 11%. The errors associated with sampling and sample preparation of nonpurgeable suspended organic carbon are also described.

Water Resources Research↗

Comment on “Field study of spatial variability in unsaturated flow beneath and adjacent to playas” by Bridget R. Scanlon and Richard S. Goldsmith

The Scanlon and Goldsmith [1997] paper contains a wealth of data that provides a useful contribution to the understand ing of the spatial variability of matrix recharge in and around playa basins on the Southern High Plains. However, a signifi cant clarification is necessary in the analysis of their "water flux" because in this system "water flux" must be placed in the context of both matrix and macropore flux.

Water Resources Research↗

Quantification of aerobic biodegradation and volatilization rates of gasoline hydrocarbons near the water table under natural attenuation conditions

Aerobic biodegradation and volatilization near the water table constitute a coupled pathway that contributes significantly to the natural attenuation of hydrocarbons at gasoline spill sites. Rates of hydrocarbon biodegradation and volatilization were quantified by analyzing vapor transport in the unsaturated zone at a gasoline spill site in Beaufort, South Carolina. Aerobic biodgradation rates decreased with distance above the water table, ranging from 0.20 to 1.5 g m −3 d −1 for toluene, from 0.24 to 0.38 g m −3 d −1 for xylene, from 0.09 to 0.24 g m −3 d −1 for cyclohexene, from 0.05 to 0.22 g m −3 d −1 for ethylbenzene, and from 0.02 to 0.08 g m −3 d −1 for benzene. Rates were highest in the capillary zone, where 68% of the total hydrocarbon mass that volatilized from the water table was estimated to have been biodegraded. Hydrocarbons were nearly completely degraded within 1m above the water table. This large loss underscores the importance of aerobic biodradation in limiting the transport of hydrocarbon vapors in the unsaturated zone and implies that vapor‐plume migration to basements and other points of contact may only be significant if a source of free product is present. Furthermore, because transport of the hydrocarbon in the unsaturated zone can be limited relative to that of oxygen and carbon dioxide, soil‐gas surveys conducted at hydrocarbon‐spill sites would benefit by the inclusion of oxygen‐ and carbon‐dioxide‐gas concentration measurements. Aerobic degradation kinetics in the unsaturated zone were approximately first‐order. First‐order rate constants near the water table were highest for cyclohexene (0.21–0.65 d −1 ) and nearly equivalent for ethylbenzene (0.11–0.31 d −1 ), xylenes (0.10–0.31 d −1 ), toluene (0.09–0.30 d −1 ), and benzene (0.07–0.31 d −1 ). Hydrocarbon mass loss rates at the water table resulting from the coupled aerobic biodgradation and volatilization process were determined by extrapolating gas transport rates through the capillary zone. Mass loss rates from groundwater were highest for toluene (0.20–0.84 g m −2 d −1 ), followed by xylenes (0.12–0.69 g m −2 d −1 ), cyclohexene (0.05–0.15 g m −2 d −1 ), ethylbenzene (0.02–0.12 g m −2 d −1 ), and benzene (0.01–0.04 g m −2 d −1 ). These rates exceed predicted rates of solubilization to groundwater, demonstrating the effectiveness of aerobic biodgradation and volatilization as a combined natural attenuation pathway.

Water Resources Research↗

Simulations of snow distribution and hydrology in a mountain basin

We applied a version of the Regional Hydro-Ecologic Simulation System (RHESSys) that implements snow redistribution, elevation partitioning, and wind-driven sublimation to Loch Vale Watershed (LVWS), an alpine-subalpine Rocky Mountain catchment where snow accumulation and ablation dominate the hydrologic cycle. We compared simulated discharge to measured discharge and the simulated snow distribution to photogrammetrically rectified aerial (remotely sensed) images. Snow redistribution was governed by a topographic similarity index. We subdivided each hillslope into elevation bands that had homogeneous climate extrapolated from observed climate. We created a distributed wind speed field that was used in conjunction with daily measured wind speeds to estimate sublimation. Modeling snow redistribution was critical to estimating the timing and magnitude of discharge. Incorporating elevation partitioning improved estimated timing of discharge but did not improve patterns of snow cover since wind was the dominant controller of areal snow patterns. Simulating wind-driven sublimation was necessary to predict moisture losses.

Water Resources Research↗