Time scales of DNAPL migration in sandy aquifers examined via numerical simulation

The time required for dense nonaqueous phase liquid (DNAPL) to cease migrating following release to the subsurface is a valuable component of a site conceptual model. This study uses numerical simulation to investigate the migration of six different DNAPLs in sandy aquifers. The most influential parameters governing migration cessation time are the density and viscosity of the DNAPL and the mean hydraulic conductivity of the aquifer. Releases of between 1 and 40 drums of chlorinated solvent DNAPLs, characterized by relatively high density and low viscosity, require on the order of months to a few years to cease migrating in a heterogeneous medium sand aquifer having an average hydraulic conductivity of 7.4 x 10(-3) cm/s. In contrast to this, the release of 20 drums of coal tar (rho(D)= 1061 kg/m(3), micro(D)= 0.161 Pa.s) requires more than 100 years to cease migrating in the same aquifer. Altering the mean hydraulic conductivity of the aquifer results in a proportional change in cessation times. Parameters that exhibit relatively little influence on migration time scales are the DNAPL-water interfacial tension, release volume, source capillary pressure, mean aquifer porosity, and ambient ground water hydraulic gradient. This study also demonstrates that low-density DNAPLs (e.g., coal tar) give rise to greater amounts of lateral spreading and greater amounts of pooling on capillary barriers than high-density DNAPLs such as trichloroethylene or tetrachloroethylene.     

Evaluation of an upscaled model for DNAPL dissolution kinetics in heterogeneous aquifers

Estimates of contaminant fluxes from DNAPL sources as a function of time and DNAPL mass reduction are important to assess the long-term sustainability and costs of monitored natural attenuation and to determine the benefits of partial source removal. We investigate the accuracy of the upscaled mass transfer function (MTF) proposed by Parker and Park [Parker JC, Park E. Modeling field-scale dense nonaqueous phase liquid dissolution kinetics in heterogeneous aquifers. WRR 2004;40:W05109] to describe field-scale dissolved phase fluxes from DNAPL sources for a range of scenarios generated using high-resolution 3-D numerical simulations of DNAPL infiltration and long-term dissolved phase transport. The results indicate the upscaled MTF is capable of accurately describing field-scale DNAPL dissolution rates as a function of time. For finger-dominated source regions, an empirical mass depletion exponent in the MTF takes on values greater than one which results in predicted mass flux rates that decrease continuously with diminishing DNAPL mass over time. Lens-dominated regions exhibit depletion exponents less than one, which results in more step-function like mass flux versus time behavior. Mass fluxes from DNAPL sources exhibiting both lens- and finger-dominated subregions were less accurately described by the simple MTF, but were well described by a dual-continuum model of the same form for each subregion. The practicality of calibrating a dual-continuum model will likely depend on the feasibility of obtaining spatially resolved field measurements of contaminant fluxes or concentrations associated with the subregions using multilevel sampling or some other means.     

Tidal influence on BTEX biodegradation in sandy coastal aquifers

A numerical study was conducted to investigate the influence of tides on the fate of terrestrially derived BTEX discharging through an unconfined aquifer to coastal waters. Previous studies have revealed that tide-induced seawater circulations create an active salt–freshwater mixing zone in the near-shore aquifer and alter the specific subsurface pathway for contaminants discharging to the coastal environment. Here the coupled density-dependent flow and multi-species reactive transport code PHWAT was used to examine the impact of these tidal effects on the aerobic biodegradation of BTEX released in a coastal aquifer and its subsequent loading to coastal waters. Simulations indicated that tides significantly enhance BTEX attenuation in the near-shore aquifer. They also reduce the rate of chemical transfer from the aquifer to the ocean and exit concentrations at the beach face. For the base case consisting of toluene transport and biodegradation, 79% of toluene initially released in the aquifer was attenuated prior to discharge with tides present, compared to only 1.8% for the non-tidal case. The magnitude of tidal forcing relative to the fresh groundwater flow rate was shown to influence significantly the extent of biodegradation as it controls the intensity of salt–freshwater mixing, period of exposure of the contaminant to the mixing zone and rate of oxygen delivery to the aquifer. The oxygen available for biodegradation also depends on the rate at which oxygen is consumed by natural processes such as organic matter decomposition. While simulations conducted with heterogeneous conductivity fields highlighted the uncertainties associated with predicting contaminant loadings, the study revealed overall that BTEX may undergo significant attenuation in tidally influenced aquifers prior to discharge.     

Carbon flux and landscape evolution in epigenic karst aquifers modeled from geochemical mass balance

This paper considers the contributions of epigenic karst processes as a major element of the carbon cycle and a significant agent of landscape evolution. Geochemical models developed from monitoring data and water samples are used to estimate the variation and magnitude of dissolved inorganic carbon (DIC) flux in karst landscapes at several scales, from local to global. At the local scale, the Cumberland River watershed of southeast Kentucky, these geochemical models are also used to evaluate the potential role of sulfur in the production of DIC and to compute an estimated rate of landscape erosion. Geochemical modeling using ionic species and modeled discharge reveal a variable rate of DIC flux driven by large fluctuations in calcite saturation and discharge. Ratios of reaction products and principal component analyses (PCA) suggest that some bedrock dissolution may be driven by the oxidation of reduced sulfur derived from brines entrained into the karst aquifers. Over the 3730 km² of carbonate exposure in the Cumberland River, 25.8–62.4 Gg/yr of carbon dioxide (CO₂) is conveyed from the atmosphere through the dissolution of carbonate. At the global scale, this translates to 123–296 Tg/yr of CO₂ delivered by karst processes into the aqueous system. The bedrock portion of DIC equates to a flux of 32.6 ± 2.6 m³ – 35.2 ± 2.8 m³ of bedrock during the period of study of which 29% was dolomite. This translates to a landscape erosion rate of 13.1–17.9 mm/ka in the 3.45–4.32 km² of carbonate exposure in the studied watershed. Based upon 16+ km of cave survey data spanning a vertical range of 72 to 75 m above base level, this suggests that cave development in the watershed spans the Plio‐Pleistocene. Using the modeled erosion rates, the ages of cave levels, 4.03–5.71, 3.08–4.56, 1.57–2.43, 1.01–1.67, 0.45–0.91, and < 0.45 Ma, are in good agreement with regional studies of Plio‐Pleistocene landscape evolution in the Appalachian Lowland Plateaus. Copyright © 2015 John Wiley & Sons, Ltd.     

Transition probability/Markov chain analyses of DNAPL source zones and plumes

At sites where a dense nonaqueous phase liquid (DNAPL) was spilled or released into the subsurface, estimates of the mass of DNAPL contained in the subsurface from core or monitoring well data, either in the nonaqueous or aqueous phase, can be highly uncertain because of the erratic distribution of the DNAPL due to geologic heterogeneity. In this paper, a multiphase compositional model is applied to simulate, in detail, the DNAPL saturations and aqueous-phase plume migration in a highly characterized, heterogeneous glaciofluvial aquifer, the permeability and porosity data of which were collected by researchers at the University of Tübingen, Germany. The DNAPL saturation distribution and the aqueous-phase contaminant mole fractions are then reconstructed by sampling the data from the forward simulation results using two alternate approaches, each with different degrees of sampling conditioning. To reconstruct the DNAPL source zone architecture, the aqueous-phase plume configuration, and the contaminant mass in each phase, one method employs the novel transition probability/Markov chain approach (TP/MC), while the other involves a traditional variogram analysis of the sampled data followed by ordinary kriging. The TP/MC method is typically used for facies and/or hydraulic conductivity reconstruction, but here we explore the applicability of the TP/MC method for the reconstruction of DNAPL source zones and aqueous-phase plumes. The reconstructed geometry of the DNAPL source zone, the dissolved contaminant plume, and the estimated mass in each phase are compared using the two different geostatistical modeling approaches and for various degrees of data sampling from the results of the forward simulation. It is demonstrated that the TP/MC modeling technique is robust and accurate and is a preferable alternative compared to ordinary kriging for the reconstruction of DNAPL saturation patterns and dissolved-phase contaminant plumes.     

Remediation of DNAPL source zones with granular iron: laboratory and field tests

Degradation of dissolved chlorinated solvents using granular iron is an established in situ technology. This paper reports on investigations into mixing iron and bentonite with contaminated soil for in situ containment and degradation of dense nonaqueous phase liquid source zones. In the laboratory, hypovials containing soil, water, bentonite, iron, and free-phase trichloroethene (TCE) were assembled. Periodic measurement of TCE, chloride, and degradation products showed progressive degradation of TCE to nondetectable levels. Subsequently, a demonstration was conducted at Canadian Forces Base Borden near Alliston, Ontario, Canada, where, in 1991, a portion of the surficial aquifer was isolated and free-phase tetrachloroethene (PCE) was introduced. Using a drill rig equipped with large-diameter mixing blades, three mixed zones were prepared containing 0%, 5%, and 10% granular iron by volume. The bentonite was added to serve as a lubricant to facilitate injection of the iron and to isolate the contaminated zone. Analysis of core samples showed reasonably uniform distributions of iron through the mixed zones. Monitoring over a 13-month period following installation showed, relative to the control, a decline in PCE concentrations to virtually nondetectable values. Reaction rates in the laboratory tests were similar to those reported in the literature, while the rate in the field test was substantially lower. The lower rate may be a consequence of mass transfer limitations under the static conditions of the field test. Results indicate that mixing iron and bentonite into source zones may be an effective means of source-zone remediation, with the particular advantage of being relatively immune to effects of geologic heterogeneity.     

Hydrogeological interactions between fault zones and alluvial aquifers in regional flow systems

The hydrological influence of fault zones in tectonic areas is usually difficult to depict from field data. Numerical simulation allows representation of such flow systems and an estimation of flow lines and rates. This paper reports on simulations of the groundwater flow in a range‐and‐basin area affected by a regional fault zone, which may drain or recharge an overlaying alluvial aquifer. Different hydraulic conductivity values for the range rocks, the fault‐zone, and the sedimentary infill of the basin are considered, as well as different fault‐zone widths and boundary conditions. Results show that upward and downward fluxes develop in the upper part of the fault zone, controlled by the action of the alluvial aquifer, influencing the recharge of the sedimentary basin. This paper shows the hydrological efficiency of fault zones as preferential flow; it also analyses the constraints that determine groundwater recharge to the surrounding basins. These results contribute to the understanding of hydrogeological dynamics in tectonic areas. Copyright © 2008 John Wiley & Sons, Ltd.     

Exceedance probability distributions of steady conduit flow in karst aquifers

Discharge exceedance probabilities are calculated for a simple model karst aquifer composed of a few multilevel conduits with recharge from a single sinking stream with an exponential flow exceedance distribution. It is assumed that outflow instantaneously matches inflow, so that the conduit volume is constant but discharge is governed by the head in a volumeless shaft at the top end of the system. It is shown that small single conduit aquifers will frequently overflow at the surface during floods and the exceedance probability of flow through the aquifer and over the surface can be defined as a function of the inflow distribution and the form of the aquifer. Systems with multiple conduits will overflow less frequently, but each conduit will exhibit a flow distribution characteristic of its form and position in the vertical hierarchy. Comparison of these findings with actual flow data from a conduit aquifer shows that the approach is valid, although imprecise. The model is unlikely to be applied directly, as it requires unusually detailed data. However, it provides for the first time an indication of typical flow durations for surface overflows and individual conduits in a karst aquifer. Contrasts in flow duration will have a profound influence on solutional and sedimentary processes in the karst system.     

Quantification of bedform dynamics and bedload sediment flux in sandy braided rivers from airborne and satellite imagery

Images from specially-commissioned aeroplane sorties (manned aerial vehicle, MAV), repeat unmanned aerial vehicle (UAV) surveys, and Planet CubeSat satellites are used to quantify dune and bar dynamics in the sandy braided South Saskatchewan River, Canada. Structure-from-Motion (SfM) techniques and application of a depth-brightness model are used to produce a series of Digital Surface Models (DSMs) at low and near-bankfull flows. A number of technical and image processing challenges are described that arise from the application of SfM in dry and submerged environments. A model for best practice is presented and analysis suggests a depth-brightness model approach can represent the different scales of bedforms present in sandy braided rivers with low-turbidity and shallow (< 2 m deep) water. The aerial imagery is used to quantify the spatial distribution of unit bar and dune migration rate in an 18 km reach and three ~1 km long reaches respectively. Dune and unit bar migration rates are highly variable in response to local variations in planform morphology. Sediment transport rates for dunes and unit bars, obtained by integrating migration rates (from UAV) with the volume of sediment moved (from DSMs using MAV imagery) show near-equivalence in sediment flux. Hence, reach-based sediment transport rate estimates can be derived from unit bar data alone. Moreover, it is shown that reasonable estimates of sediment transport rate can be made using just unit bar migration rates as measured from 2D imagery, including from satellite images, so long as informed assumptions are made regarding average bar shape and height. With recent availability of frequent, repeat satellite imagery, and the ease of undertaking repeat MAV and UAV surveys, for the first time, it may be possible to provide global estimates of bedload sediment flux for large or inaccessible low-turbidity rivers that currently have sparse information on bedload sediment transport rates. © 2018 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.     

DNAPL accumulation in wells and DNAPL recovery from wells: Model development and application to a laboratory study

Dense nonaqueous phase liquid (DNAPL) accumulation and recovery from wells cannot be accurately modeled through typical pressure or flux boundary conditions due to gravity segregation of water and DNAPL in the wellbore, the effects of wellbore storage, and variations of wellbore inflow and outflow rates with depth, particularly in heterogeneous formations. A discrete wellbore formulation is presented for numerical modeling of DNAPL accumulation in observation wells and DNAPL removal from recovery wells. The formulation includes fluid segregation, changing water and DNAPL levels in the well and the corresponding changes in fluid storage in the wellbore. The method was added to a three-dimensional finite difference model (CompSim) for three phase (water, gas, DNAPL) flow. The model predictions are compared to three-dimensional pilot scale experiments of DNAPL (benzyl alcohol) infiltration, redistribution, recovery, and water flushing. Model predictions match experimental results well, indicating the appropriateness of the model formulation. Characterization of mixing in the extraction well is important for predicting removal of highly soluble organic compounds like benzyl alcohol. A sensitivity analysis shows that the incorporation of hysteresis is critical for accurate prediction. Among the multiphase flow and transport parameters required for modeling, results are most sensitive to soil intrinsic permeability.     

The influence of dimensionality on simulations of mass recovery from nonuniform dense non-aqueous phase liquid (DNAPL) source zones

The influence of model dimensionality on predictions of mass recovery from dense non-aqueous phase liquid (DNAPL) source zones in nonuniform permeability fields was investigated using a modified version of the modular three-dimensional transport simulator (MT3DMS). Thirty-two initial two- (2D) and three-dimensional (3D) tetrachloroethene–DNAPL source zone architectures, taken from a recent modeling study, were used as initial conditions for this analysis. Commonly employed source zone metrics were analyzed to determine differences between 2D and 3D predictions: (i) down-gradient flux-averaged contaminant concentration, (ii) reductions in contaminant mass flux through a down-gradient boundary, (iii) source zone ganglia-to-pool (GTP) ratio, and (iv) time required to achieve a remediation objective. 3D flux-averaged contaminant concentrations were approximately 3.5 times lower than concentrations simulated in 2D. This difference was attributed to dilution of the contaminant concentrations down gradient of the source zone. Contaminant flux reduction predictions for a given mass recovery were generally 5% higher in 3D simulations than in 2D simulations. The GTP ratio declined over time as mass was recovered in both 2D and 3D simulations. Although the source longevity (i.e., time required to achieve 99.99% mass recovery) differed between individual 2D and 3D realizations, the mean source longevity for the 2D and 3D simulation ensembles was within 2%. 2D simulations tended to over-predict the time required to achieve lower mass recovery levels (e.g. 50% mass recovery) due to a smaller contaminated area exposed to uncontaminated water. These findings suggest that ensemble averages of 2D numerical simulations of DNAPL migration, entrapment, dissolution, and mass recovery in statistically homogenous, nonuniform media may provide reasonable approximations to average behavior obtained using simulations conducted in fully three-dimensional domains.     

Mapping of thin sandy aquifers by using high resolution reflection seismics and 2-D electrical tomography

Electrical tomography, which gives good results even in fairly complex geological environments, has given a new lease of life to electrical methods in hydrogeological surveys. Nevertheless, a rapid decline in resolution with increasing depth remains the main problem of the electrical methods. In the Pannonian basin in Croatia, at a test area, combining both electrical tomography and seismic reflection methods provides data that better constrain the lithological and hydrogeological model of the subsurface.Electrical tomography revealed a rather thick packet of sediments with increased resistivity at depths of 40–100 m. Using the electrical forward modelling, the existence of two different hydrogeological models was shown. The first model presupposes a reasonably homogeneous packet of sandy clays or clayey sands, and the other model presupposes the alternation between layers of clays and sands. From the hydrogeological point of view, the second model is perspective, but unfortunately, the use of electrical tomography alone does not allow the ambiguity to be resolved. The separation of these two models became possible using seismic reflection. Three seismic environments were isolated from the seismic profile treated, and the strongest reflections were discovered in the first seismic environment, which covers the depths from 40 to 100 m. It was determined that the second model is more acceptable, because these reflections are caused by lithological changes, that is, the alternations of sands and clays. The interpretation is consistent with exploratory borehole data. The conclusion is that electrical tomography gives data concerning the sediment lithology up to depths of 40 m, but at greater depths combined interpretation of electrical and seismic data constrains the subsurface model better.     

Air and water flows induced by pumping tests in unconfined aquifers with low‐permeability zones

Air flows from the atmosphere into an unconfined aquifer when the water table falls during pumping tests. Pumping test results in unconfined aquifers may be significantly affected by low‐permeability zones (LPZs) near the initial water table position, because they restrict the downward movement of air. A transient, three‐dimensional air–water two‐phase flow model is employed to investigate numerically the effects of local heterogeneity on pumping test results in unconfined aquifers. Two cases of local heterogeneities are considered herein: a LPZ around the pumping well and on one side of the pumping well. Results show that the drawdown with the LPZ is significantly greater than that of the homogeneous aquifer. The differences in drawdown are the most significant at intermediate times and gradually diminish at later times. The LPZ significantly reduces air flow from the atmosphere to the aquifer. The pore air velocity in the LPZ is very low. The air pressure at the observation point under the LPZ when air begins to enter is significantly lower than the air pressure of the homogeneous aquifer at the same point. After that, the air pressure increases quickly and then increases slowly. The time for the air pressure to reach the atmospheric pressure is significantly longer. Copyright © 2013 John Wiley & Sons, Ltd.     

Delineation of spatial redox zones using discriminant analysis and geochemical modelling in arsenic‐affected alluvial aquifers

This study characterized the redox conditions in arsenic‐affected groundwater aquifers of the Lanyang plain, Taiwan. Discriminant analysis was adopted to delineate three redox zones (oxidative, transitional and reductive zones) in different aquifers and yielded 92·3% correctness on groundwater quality data. Arsenic is mainly distributed in the reductive zone, and arsenic distribution in the shallow aquifer is mainly affected by surface activities. According to PHREEQC modelling results, possible mechanisms for arsenic release to groundwater in Lanyang plain are explored. Arsenic released to groundwater in the oxidative zone (zone 1) is primarily caused by the oxidations of arsenic‐bearing pyrite minerals, and arsenate is the predominant species. While the reductive dissolution of Fe‐oxides are responsible for the high arsenic concentration found in the transitional and reductive zones (zones 2 and 3), arsenite is the predominant species. The reduction potential of groundwater rises as the depths and zones increase. Some sulphates may be reduced to form sulphide ions, which then react with arsenic to form arseno‐sulphide deposits (such as realgar, orpiment) and then slightly lower groundwater arsenic concentrations. A conceptual diagram which summarized the possible release processes of arsenic in different redox zones along groundwater flow in Lanyang plain is postulated. Arsenic‐bearing pyrite and arsenopyrite (FeAsS) are oxidized as they are exposed to the infiltrated oxygenated rainwater, releasing soluble arsenate Fe(II) and SO₄^2? into zone 1. The dissolution of arsenic‐rich Fe‐oxides due to the onset of reducing conditions in zones 2 and 3 is responsible for the mobility of arsenic and likely to be the primary mechanism of arsenic release to groundwater in the Lanyang plain Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of meteorological and hydrogeological factors on gross recharge percentage at unconfined sandy aquifers with an equatorial climate

A thorough understanding of rainfall recharge processes and their controlling factors is essential for management of groundwater systems. This study investigates the effects of various meteorological and hydrogeological factors on the gross recharge percentages, the rainfall–recharge relationships and the recharge threshold values for unconfined sandy aquifers under an equatorial climate. Among the meteorological factors investigated, rainfall intensity was found to have the most significant impact on the gross recharge rate. The effects of potential evaporation rate, relative humidity and air temperature on the gross recharge percentage were significant when the vadose zone thickness is larger than 2·5 m. The recharge threshold values were found to depend strongly on the vadose zone thickness. The rainfall–recharge relationships could generally be well defined by a normal–log relationship. The rainfall–recharge relationships derived here are applicable to yield estimates of gross recharge percentages for unconfined sandy aquifers under an equatorial climate, using rainfall intensity and vadose zone thickness as input variables. In this study, a theory was developed and validated to provide physical explanations for the observations, based on the residence time of the percolated rainwater within the vadose zone. Among the soil hydraulic parameters tested, porosity and saturated hydraulic conductivity were found to have the most pronounced effects on the gross recharge percentage. Utilizing the sensitivity results and the theory derived, an approach was developed for extending the application of the derived rainfall–recharge relationships to other sand textures. The approach was found to be capable of producing rough and fast estimations of gross recharge percentage for other sand textures. Copyright © 2007 John Wiley & Sons, Ltd.     

Spatial and temporal intensification of lateral hyporheic flux in narrowing intra‐meander zones

Meander bends in alluvial rivers morphologically evolve towards meander cut‐off with narrowing intra‐meander necks, and this should steepen hydraulic gradients and intensify intra‐meander hyporheic flux. This research used dye tracking and head loss measurements in a 1 : 500 planimetrically scaled laboratory river table to quantify the spatial and temporal intensification of intra‐meander flux rates at two evolution ages. The younger meander bend, M1, had a sinuosity of 2.3, a river neck width of 0.39 cm, and 0.6% river slope, and the older meander bend, M3, had a sinuosity of 5.2, a river neck width of 0.12 cm, and 0.5% river slope. Flux into and out of the meander bend was estimated along the normalized curvilinear distance s*, with the meander neck at s* = 0.1 and s* = 0.9, the meander centroid at s* = 0.37 and s* = 0.63, and the apex at s* = 0.5. Between the meander centroid and neck, we documented a 60% spatial intensification for M1 and a 90% spatial intensification for M3. Between M1 and M3, we documented a 135% temporal intensification at the neck and a 100% intensification at the centroid. Our empirical spatial and temporal intensification rates involving the M1 and the M3 scenario were one to three times lower than theoretical rates derived from a river evolution model with equivalent M1 and M3 planimetry. Overestimation by the theoretical model was attributed to exaggerated head loss caused by the model neglecting groundwater contributions to river stage. Hyporheic exchange provides critical ecosystem services, and its spatial and temporal variation with meander evolution should be considered in river management. Copyright © 2012 John Wiley & Sons, Ltd.     

Preliminary reconstruction of the desert and sandy land distributions in China since the last interglacial period

The desert and sandy land are the products of arid climate. The spatial distribution of modern deserts and sandy land in China and their relation to climate show following characteristics: arid and hyper-arid desert zones, at isohyet of less than 200 mm, are dominated by mobile dunes; semi-arid steppe and arid desert steppe with the precipitation between 200–400 mm, are dominated by semi-fixed and fixed sand dunes; the precipitation of sub-humid forest grassland and humid forest zones with scattered fixed sand land is higher than 400 mm. With this as reference, in combination with considerable amount of paleoclimatic data in desert regions and adjacent regions, the distributions of desert and sandy land in China during the last interglacial period, the last glacial maximum (LGM), and the Holocene megathermal, were preliminarily reconstructed. The results compared with that of today show that the distribution of desert and sandy land in China was greatly dwindled during last interglacial period, and the mobile dune area was about two-thirds of that of today’s, but greatly expanded during LGM. However, the dwindling area of desert and sandy land in the Holocene megathermal was smaller than that in the last interglacial period. The forcing mechanism was mainly related to the changes of East Asian winter and summer monsoon, south-northward swing of the westerlies and the variations of the Qinghai-Tibet Plateau monsoon intensity caused by global climate changes during the cold and warm intervals since the last interglacial period.