Implementation of Solute Transport in the Vadose Zone into the “HYDRUS Package for MODFLOW”

The “HYDRUS package for MODFLOW” is an existing MODFLOW package that allows MODFLOW to simultaneously evaluate transient water flow in both unsaturated and saturated zones. The package is based on incorporating parts of the HYDRUS-1D model (to simulate unsaturated water flow in the vadose zone) into MODFLOW (to simulate saturated groundwater flow). The coupled model is effective in addressing spatially variable saturated-unsaturated hydrological processes at the regional scale. However, one of the major limitations of this coupled model is that it does not have the capability to simulate solute transport along with water flow and therefore, the model cannot be employed for evaluating groundwater contamination. In this work, a modified unsaturated flow and transport package (modified HYDRUS package for MODFLOW and MT3DMS) has been developed and linked to the three-dimensional (3D) groundwater flow model MODFLOW and the 3D groundwater solute transport model MT3DMS. The new package can simulate, in addition to water flow in the vadose zone, also solute transport involving many biogeochemical processes and reactions, including first-order degradation, volatilization, linear or nonlinear sorption, one-site kinetic sorption, two-site sorption, and two-kinetic sites sorption. Due to complex interactions at the groundwater table, certain modifications of the pressure head (compared to the original coupling) and solute concentration profiles were incorporated into the modified HYDRUS package. The performance of the newly developed model is evaluated using HYDRUS (2D/3D), and the results indicate that the new model is effective in simulating the movement of water and contaminants in the saturated-unsaturated flow domains.     

Batch and Column Experiments to Support Heavy Metals (Cu,Zn, and Mn) Transport Modeling in Alluvial Sediments Between the Mogan Lake and the Eymir Lake,Gölbaşı, Ankara

This article describes laboratory batch sorption and column transport experiments that were conducted using heterogeneous alluvial sediments with a wide physical characteristic from wells, located between Lake Mogan and Lake Eymir, Gölbaşı, Ankara. The batch sorption experiment was conducted in two separate systems, that is, single and multicomponents. Single batch experiment was performed to determine equilibrium condition between the heavy metal ions and the soil adsorption sites. The sorption isotherms data from multibatch experiments were used to calculate the sorption parameters. Single batch experiment indicated that equilibrium was attained within 9 days from the start of the sorption test. As a result of multicomponents batch experiments, for Zn and Mn, the sorption process was well described by the Freundlich or Langmuir isotherm model, whereas sorption of Cu was better described by the linear isotherm model. The K_d of Cu were found to be highest in soil 1 (32550.350 L kg⁻¹) and lowest in soil 5 (18170.76 L kg⁻¹). The maximum and minimum sorption capacity values for Zn were found to be in soil 1 (10985.148 mg kg⁻¹) and in soil 2 (8597.14 mg kg⁻¹) units, respectively. [Correction added after online publication 15 July, 2010: In the preceding sentence, the words “minimum” and “maximum” were initially switched.] Similarly, soil 1 (7587.391 mg kg⁻¹) and soil 5 (4908.695 mg kg⁻¹) units provided the maximum and minimum values for Mn. In the column experiments, flow and tracer transport was studied under saturated conditions using conservative tracer to determine the transport parameters. Transport parameter values were obtained by curve-fitting using the nonlinear least-squares optimization code CXTFIT. Results of the column experiments indicated that the dispersivity values obtained for soil samples were in the range of 0.024 to 1.13 cm.     

Modeling plume behavior for nonlinearly sorbing solutes in saturated homogeneous porous media

Transport of a sorbing solute in a two-dimensional steady and uniform flow field is modeled using a particle tracking random walk method. The solute is initially introduced from an instantaneous point source. Cases of linear and nonlinear sorption isotherms are considered. Local pore velocity and mechanical dispersion are used to describe the solute transport mechanisms at the local scale. The numerical simulation of solute particle transport yields the large scale behavior of the solute plume. Behavior of the plume is quantified in terms of the center-of-mass displacement distance, relative velocity of the center-of-mass, mass breakthrough curves, spread variance, and longitudinal skewness. The nonlinear sorption isotherm affects the plume behavior in the following way relative to the linear isotherm: (1) the plume velocity decreases exponentially with time; (2) the longitudinal variance increases nonlinearly with time; (3) the solute front is steepened and tailing is enhanced     

Simulating Stable Isotope Ratios in Plumes of Groundwater Pollutants with BIOSCREEN‐AT‐ISO

BIOSCREEN is a well‐known simple tool for evaluating the transport of dissolved contaminants in groundwater, ideal for rapid screening and teaching. This work extends the BIOSCREEN model for the calculation of stable isotope ratios in contaminants. A three‐dimensional exact solution of the reactive transport from a patch source, accounting for fractionation by first‐order decay and/or sorption, is used. The results match those from a previously published isotope model but are much simpler to obtain. Two different isotopes may be computed, and dual isotope plots can be viewed. The dual isotope assessment is a rapidly emerging new approach for identifying process mechanisms in aquifers. Furthermore, deviations of isotope ratios at specific reactive positions with respect to “bulk” ratios in the whole compound can be simulated. This model is named BIOSCREEN‐AT‐ISO and will be downloadable from the journal homepage.     

Equilibrium-type and link-type lattice Boltzmann models for generic advection and anisotropic-dispersion equation

We extend lattice Boltzmann (LB) methods to advection and anisotropic-dispersion equations (AADE). LB methods are advocated for the exactness of their conservation laws, the handling of different length and time scales for flow/transport problems, their locality and extreme simplicity. Their extension to anisotropic collision operators (L-model) and anisotropic equilibrium distributions (E-model) allows to apply them to generic diffusion forms. The AADE in a conventional form can be solved by the L-model. Based on a link-type collision operator, the L-model specifies the coefficients of the symmetric diffusion tensor as linear combination of its eigenvalue functions. For any type of collision operator, the E-model constructs the coefficients of the transformed diffusion tensors from linear combinations of the relevant equilibrium projections. The model is able to eliminate the second order tensor of its numerical diffusion. Both models rely on mass conserving equilibrium functions and may enhance the accuracy and stability of the isotropic convection–diffusion LB models.The link basis is introduced as an alternative to a polynomial collision basis. They coincide for one particular eigenvalue configuration, the two-relaxation-time (TRT) collision operator, suitable for both mass and momentum conservation laws. TRT operator is equivalent to the BGK collision in simplicity but the additional collision freedom relates it to multiple-relaxation-times (MRT) models. “Optimal convection” and “optimal diffusion” eigenvalue solutions for the TRT E-model allow to remove next order corrections to AADE. Numerical results confirm the Chapman–Enskog and dispersion analysis.     

Adsorption Behaviour of Low-Biodegradable Organics on Activated Carbon Surfaces

Adsorption isotherms of various low-biodegradable aromatic compounds on two different activated carbons were determined experimentally and described by FREUNDLICH-type isotherm equations. The equilibrium solid loadings derived from the measurements correlate reasonably well with the adsorbent surface areas and show decreasing values in the order 3-nitro-aniline ～ 4-chloroaniline > 3.5-dinitrobenzoic acid < phenylurea. Kinetic experiments in a differential column batch reactor were conducted in order to evaluate liquid-phase mass transfer and intraparticle diffusion parameters. The homogeneous surface diffusion model could be successfully applied for calculating surface diffusivities and predicting experimental concentration/time profiles.     

Modeling Arsenic Sorption in the Subsurface with a Dual‐Site Model

Arsenic is a well‐known groundwater contaminant that causes toxicological and carcinogenic effects in humans. Predicting the transport of arsenic in the subsurface is often problematic because of its complex sorption characteristics. Numerous researchers have reported that arsenic sorption on soil material is initially fast and then subsequently slow. A dual‐site numerical sorption model was previously developed to describe arsenic desorption from arsenic‐contaminated soils in batch experiments in terms of two different release mechanisms. Experiments involving synthetic acid rain leaching of four arsenic‐contaminated soil columns were performed to verify the dual‐site numerical sorption model in the context of one‐dimensional vertical transport. The fitted models successfully simulated the signature long tailings and the two‐stage arsenic leaching patterns for all four soil columns. The dual‐site sorption model was incorporated within the general solute transport simulation code Modular Three‐Dimensional Multispecies (MT3DMS), version 5.10. The resulting version was named MT3DDS and is available for public access. This experimental study has shown that MT3DDS is capable of simulating phase redistribution during transport, and thus provides a new numerical tool for simulating arsenic transport in the subsurface.     

Computerprogramm „ADSORB”︁ — ein optimiertes mathematisches Verfahren zur Charakterisierung organischer Vielstoffgemische in Wässern mittels Adsorptionsanalyse

The computing program ?ADSORB”? allows a very fast mathematical evaluation of adsorption isotherms for the preparation of adsorption analyses. With the program ?ADSORB”? it is possible to calculate any number of pseudocomponents of organic multicomponent mixtures of different adsorbability. Only few minutes are required for the mathematical evaluation of an sorption analysis by means of ?ADSORB”?. adsorption analysis, adsorption isotherm, mathematical modelling     

Assessing titanium dioxide nanoparticles transport models by Bayesian uncertainty analysis

With the rapid growth of nanotechnology industry, nanomaterials as an emerging pollutant are gradually released into subsurface environments and become great concerns. Simulating the transport of nanomaterials in groundwater is an important approach to investigate and predict the impact of nanomaterials on subsurface environments. Currently, a number of transport models are used to simulate this process, and the outputs of these models could be inconsistent with each other due to conceptual model uncertainty. However, the performances of different models on simulating nanoparticles transport in groundwater are rarely assessed in Bayesian framework in previous researches, and these will be the primary objective of this study. A porous media column experiment is conducted to observe the transport of Titanium Dioxide Nanoparticles (nano-TiO₂). Ten typical transport models which consider different chemical reaction processes are used to simulate the transport of nano-TiO₂, and the observed nano-TiO₂ breakthrough curves data are used to calibrate these models. For each transport model, the parameter uncertainty is evaluated using Markov Chain Monte Carlo, and the DREAM_(ZS) algorithm is used to sample parameter probability space. Moreover, the Bayesian model averaging (BMA) method is used to incorporate the conceptual model uncertainty arising from different chemical reaction based transport models. The results indicate that both two-sites and nonequilibrium sorption models can well reproduce the retention of nano-TiO₂ transport in porous media. The linear equilibrium sorption isotherm, first-order degradation, and mobile-immobile models fail to describe the nano-TiO₂ retention and transport. The BMA method could instead provide more reliable estimations of the predictive uncertainty compared to that using a single model.     

Adsorption Kinetics,Isotherms, and Desorption of Monocrotophos and Dichlorvos on Various Indian Soils

Pesticide sorption on to the soil has a significant role in deciding the fate and behavior of pesticides in soil and aquatic environment. The present study investigates the adsorption of monocrotophos (MCP) and dichlorvos (DDVP) on the three soils of Malwa region of Punjab, India under different conditions. Batch adsorption experiments were preformed in replicates using 2 g of air‐dried soil and varying concentrations of pesticides and 20 mL of 0.01 M CaCl₂ as background electrolyte. The results revealed high adsorption of MCP and DDVP in soil B with k_f‐values 0.1261 and 0.0498 and n‐values 2.7345 and 1.831, respectively. The adsorption isotherms obtained were analyzed and the data was subjected to classical Langmuir, Freundlich, and Temkin models. The experimental data best fitted to the logarithm form of Freundlich and Temkin model. Kinetics analyses were performed using pseudo‐first order, pseudo‐second order, and intraparticle diffusion models. The regression results showed that the experimental data fitted very well with the pseudo‐second order kinetic model as correlation coefficient value is very closer to 1 and also followed the intraparticle diffusion model, whereas, diffusion is not only the rate controlling step. The percentages desorption with tap and distilled water is 32–64% for MCP and 25–48% for DDVP.     

Vertical Discretization Impact in Numerical Modeling of Matrix Diffusion in Contaminated Groundwater

Understanding the effects of contaminants that can diffuse into low-permeability (“low-k”) zones is crucial for effective groundwater remedial decision-making. Because low-k zones can serve as low-level sources of contamination to more transmissive zones over time, an accurate evaluation of the impacts of matrix diffusion at contaminated sites is vital. This study compared numerical groundwater flow and transport simulations using MODFLOW/RT3D at a hypothetical site using three cases, each with increasing discretization of the vertical 10-m thick domain: (1) a coarse multilayer heterogeneous grid based on one layer for each of four different hydrogeological units, (2) a “low-resolution” discretization approach where the low-k units were divided into several sublayers giving the model 10 layers, and (3) a “high-resolution” numerical model with 199 layers that are a few centimeters thick. When comparing the results of each case, significant differences were observed between the discretizations used, even though all other model input data were identical. The conventional grid models (Cases 1 and 2) appeared to underestimate groundwater plume concentrations by a factor ranging from 1.1 to 36 when compared to the high-resolution grid model (Case 3), and underestimated predicted cleanup times by more than a factor of 10 for some of the hypothetical sampling points in the modeling domain. These results validate the implication of Chapman et al. (2012), that conventional vertical discretization of numerical groundwater flow and transport models at contaminated sites (with layers that are greater than 1 m thick) can lead to significant errors when compared to more accurate high-resolution vertical discretization schemes (layers that are centimeters thick).     

Sorptive Potential of Beach Sand to Remove Ni(II) Ions: An Equilibrium Isotherm Study

The potential to remove Ni(II) ions from aqueous solutions using sea beach sand, a carbonate‐quartz mineral, was thoroughly investigated. The effects of relevant parameters such as solution pH, adsorbent dose, metal ions concentration, and temperature on Ni(II) sorption onto beach sand were examined. The sorption data followed the Langmuir, Freundlich and Dubinin‐Radushkevich (D‐R) isotherms. The adsorption was endothermic in nature at ambient temperature and the computation of the parameters, ΔH, ΔS and ΔG indicated the interactions between sorbate and sorbent to be thermodynamically favorable. Equilibrium was achieved very quickly within 30 min of shaking. A pseudo‐first order Lagergren equation was used to test the adsorption kinetics. Other kinetic models, e. g., the Morris‐Weber and Reichenberg equations, were used to calculate the rate constant of intraparticle diffusion and the fate of the diffusion process, respectively. The influence of some of the common cations and anions were also a subject of this study.     

The New Potential for Understanding Groundwater Contaminant Transport

The groundwater remediation field has been changing constantly since it first emerged in the 1970s. The remediation field has evolved from a dissolved‐phase centric conceptual model to a DNAPL‐dominated one, which is now being questioned due to a renewed appreciation of matrix diffusion effects on remediation. Detailed observations about contaminant transport have emerged from the remediation field, and challenge the validity of one of the mainstays of the groundwater solute transport modeling world: the concept of mechanical dispersion (Payne et al. 2008). We review and discuss how a new conceptual model of contaminant transport based on diffusion (the usurper) may topple the well‐established position of mechanical dispersion (the status quo) that is commonly used in almost every groundwater contaminant transport model, and evaluate the status of existing models and modeling studies that were conducted using advection‐dispersion models.     

First-principles derivation of reactive transport modeling parameters for particle tracking and PDE approaches

Both Eulerian and Lagrangian reactive transport simulations in natural media require selection of a parameter that controls the “promiscuity” of the reacting particles. In Eulerian models, measurement of this parameter may be difficult because its value will generally differ between natural (diffusion-limited) systems and batch experiments, even though both are modeled by reaction terms of the same form. And in Lagrangian models, there previously has been no a priori way to compute this parameter. In both cases, then, selection is typically done by calibration, or ad hoc. This paper addresses the parameter selection problem for Fickian transport by deriving, from first principles and D (the diffusion constant) the reaction-rate-controlling parameters for particle tracking (PT) codes and for the diffusion–reaction equation (DRE). Using continuous time random walk analysis, exact reaction probabilities are derived for pairs of potentially reactive particles based on D and their probability of reaction provided that they collocate. Simultaneously, a second PT scheme directly employing collocation probabilities is derived. One-to-one correspondence between each of D, the reaction radius specified for a PT scheme, and the DRE decay constant are then developed. These results serve to ground reactive transport simulations in their underlying thermodynamics, and are confirmed by simulations.     

Effect of Temporal Changes in Air Injection Rate on Air Sparging Performance Groundwater Remediation

Air sparging (AS) is a commonly applied method for treating groundwater contaminated with volatile organic compounds (VOCs). When using a constant injection of air (continuous mode), a decline in remediation efficiency is often observed, resulting from insufficient mixing of contaminants at the pore scale. It is well known that turning the injection on and off (pulsed mode) may lead to a better remediation performance. In this article, we investigate groundwater mixing and contaminant removal efficiency in different injection modes (i.e., continuous and pulsed), and compare them to those achieved in a third mode, which we denote as “rate changing.” In this mode, injection is always on, and its rate is varying with time by abrupt changes. For the purpose of this investigation, we conducted two separate sets of experiments in a laboratory tank. In the first set of experiments, we used dye plume tracing to characterize the mixing induced by AS. In the second set of experiments, we contaminated the tank with a VOC and compared the remediation efficiency between the different injection modes. As expected, we observed that time‐variable injection modes led to enhanced mixing and contaminant removal. The decrease in contaminant concentrations during the experiment was found to be double for the “rate changing” and “pulsed” modes compared to the continuous mode, with a slightly preferable performance for the “rate changing” mode. These results highlight the critical role that mixing plays in AS, and support the need for further investigation of the proposed “rate changing” injection mode.     

Laborative Untersuchungen zur Beschreibung des Migrationsverhaltens sprengstofftypischer Verbindungen in Porengrundwasserleitern

Laboratory Experiments for Describing the Migration of Explosives in Sandy Aquifers Leaching the munition residues from the former explosive production site Elsnig in the Upper Elbe Valley (Saxony, Germany) resulted in an undefined plume of groundwater contaminated by nitroaromatics and nitroamines approaching important drinking water resources. Laboratory experiments were carried out to investigate transport and fate phenomena of such substances in aquifer materials. Specific solute storage and migration parameters for modelling the subsurface migration processes were obtained from steady state experiments in soil cores used as 0-dimensional reactors and from dynamic breakthrough curves in soil columns. Using the 0-dimensional reactor tests we focused on isotherm estimation. Sorption was found to be reflected best by Freundlich isotherms for concentrations of nitroaromatics less than 10 mg L^?1 and low organic carbon content in the tested subsurface material. TNT-adsorption was slow and strongly correlated with soil permeability. Preliminary kinetic measurements revealed sorption equilibrium after two days. RDX-adsorption was low. All sorption experiments were conducted under non-sterile and aerobic conditions. Microbial activity was controlled by measuring the enzyme activity and the biomass in water and soil samples. After steady state experiments in the 0-dimensional reactors, products initiated by biodegradation of explosives such as aminonitrotoluenes were found. Based on literature, degradation was estimated and correlated with soil texture. For five components, different retardation was observed depending on soil texture by using native groundwater samples in the columns. Specially designed reactor facilities and soil column installations with temperature and flux control as well as on-line measurements of pH, pE, and conductivity were applied. Concentrations of contaminants were analysed both by high performance liquid chromatography and thin layer chromatography. Photolytic reactions have been prevented. Based on all these laboratory experiments, sorption, degradation, and retardation parameters of trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), dinitrobenzene (DNB), dinitrotoluene (DNT), and mononitrotoluene (MNT) in Elsnig sandy aquifers were estimated.     

Optimal and sustainable extraction of groundwater in coastal aquifers

Four examples are investigated for the optimal and sustainable extraction of groundwater from a coastal aquifer under the threat of seawater intrusion. The objectives and constraints of these management scenarios include maximizing the total volume of water pumped, maximizing the profit of selling water, minimizing the operational and water treatment costs, minimizing the salt concentration of the pumped water, and controlling the drawdown limits. The physical model is based on the density-dependent advective-dispersive solute transport model. Genetic algorithm is used as the optimization tool. The models are tested on a hypothetical confined aquifer with four pumping wells located at various depths. These solutions establish the feasibility of simulating various management scenarios under complex three-dimensional flow and transport processes in coastal aquifers for the optimal and sustainable use of groundwater.     

Effects of geosorbent and solution properties on sorption and desorption of PAHs

Characteristics of phenanthrene and pyrene's sorption and desorption on two local soils in solutions of simulated groundwater,simulated lung fluid,and simulated saliva were studied with batch equilibrium experiments to understand the fate of PAHs in the karst region of southwestern China and to assess the environmental exposure and the health risk of PAHs.The results showed that the sorption and desorption isotherms of phenanthrene and pyrene on two target soils in the three solution systems could be adequately described by the Freundlich model,while the fitted isotherm parameters for the simulated groundwater solution distinguished notably from those for the simulated body fluid solutions.For the sorption experiments,in the simulated groundwater,the n values were 0.722 and 0.672 for phenanthrene and were 0.724 and0.663 for pyrene,respectively,on the yellow soil and the limestone soil;The log KF values were 3.118 and 3.323 for phenanthrene and were 3.648 and 3.846 for pyrene,respectively,on the yellow soil and the limestone soil.In the simulated body fluids,the n values for phenanthrene and pyrene ranged from 0.622 to 0.836 and from 0.590 to0.865,respectively,and the log KF values of phenanthrene and pyrene ranged from 2.845 to 3.327 and from 3.344 to3.779,respectively.For the desorption experiments,in the simulated groundwater,the n values were 0.662 and 0.744 for phenanthrene and were 0.702 and 0.647 for pyrene,respectively,on the yellow soil and the limestone soil.The log K_F values were 3.666 and 3.686 for phenanthrene and were 4.128 and 4.225 for pyrene,respectively,on the yellow soil and the limestone soil.In the simulated body fluids,the n values for phenanthrene and pyrene ranged from 0.612 to 0.668 and from 0.631 to 0.819,respectively,and the log KF values of phenanthrene and pyrene ranged from 3.134 to 3.407 and from 3.533 to 3.839,respectively.The limestone soil had relatively higher log KF values but lower K_(OC) values compared to those of the yellow soil,indicated that the nature of sorbent soils played the dominant role in sorption and desorption behaviors of PAHs.The experimental results showed a remarkable differences in sorption and desorption behaviors of PAHs in simulated body fluids and groundwater.The nonlinearities of measured isotherms and the measured sorption capacities of soils in simulated body fluids were significantly lower than corresponding those in the simulated groundwater,and HI values for simulated body fluids systems were significantly smaller than corresponding those for the simulated groundwater systems.The results underscore cautions in assessing environmental exposure and health risks of PAHs based on their sorption-desorption data in simulated groundwater as this is traditionally done.     

Homogenization of the transport behavior of nonlinearly adsorbing pollutants in physically and chemically heterogeneous aquifers

This paper addresses the question of how spatial variability in the hydraulic and chemical properties of groundwater systems affects the transport and sorption behavior of pollutants at the field scale. In this paper, we limit our investigations on pollutants that adsorb according to an equilibrium controlled nonlinear Freundlich sorption isotherm. The new contribution of this paper is take into account not only spatially variable Freundlich distribution coefficients _KS$K_S$ but spatially variable Freundlich nonlinearity parameters p as well. Using a homogenization theory approach, we shortly review the impact of spatially variable hydraulic properties on the transport and extend the theory to spatially variable chemical properties. We show that spatially variable Freundlich exponents cause a very different field scale transport and sorption behavior than spatial variations in the distribution coefficients only since in the first case field scale Freundlich parameters and field scale dispersion coefficients become concentration dependent. In particular, field scale retardation is much larger than small-scale retardation.