Determination of specific LNAPL volumes in soils having a multimodal pore-size distribution.

In this paper we present modifications to previously published models for determining the specific volume of non-aqueous phase liquids (LNAPLs) in the subsurface at and near the groundwater table following a spill or leak from the soil surface. The modifications account for porous media having multimodal pore-size distributions as is often the case with tropical soils. Data from the literature are used to show that the use of multimodal pore-size distributions can lead to significantly different subsurface LNAPL specific volume predictions and possible LNAPL recovery rates, compared to when only unimodal pore-size distributions are considered. Differences of up to 200% are possible when the dual-porosity nature of the pore system is ignored, which can yield erroneous estimates of the time needed to remediate LNAPLs from contaminated areas when conventional systems are employed.

Evaluation of a horizontal permeable reactive barrier for preventing upward diffusion of volatile organic compounds through the unsaturated zone.

Permeable reactive barriers are commonly used to treat contaminant plumes in the saturated zone. However, no known applications of horizontal permeable reactive barriers (HPRBs) exist for oxidizing volatile organic compounds (VOCs) in the unsaturated zone. In this study, laboratory column experiments were carried out to investigate the ability of a HPRB containing solid potassium permanganate, to oxidize the vapors of trichloroethylene (TCE), toluene, and ethanol migrating upward from a contaminated saturated zone. Results revealed that an increase in initial water saturation and HPRB thickness strongly affected the removal efficiency of the HPRB. Installing the HPRB relatively close to the water table was more effective due to the high background water content and enhanced diffusion of protons and/or hydroxides away from the HPRB. Inserting the HPRB far above the water table caused rapid changes in pH within the HPRB, leading to lower oxidation rates. The pH effects were included in a reactive transport model, which successfully simulated the TCE and toluene experimental observations. Simulations for ethanol were not affected by pH due to condensation of water during ethanol oxidation, which caused some dilution in the HRPB.

Quasi-Saturated Layer: Implications for Estimating Recharge and Groundwater Modeling.

This study presents an extension of the concept of "quasi-saturation" to a quasi-saturated layer, defined as the uppermost dynamic portion of the saturated zone subject to water table fluctuations. Entrapped air here may cause substantial reductions in the hydraulic conductivity (K) and fillable pore water. Air entrapment is caused by a rising water table, usually as a result of groundwater recharge. The most significant effects of entrapped air are recharge overestimation based on methods that use specific yield (Sy ), such as the water table fluctuation method (WTF), and reductions in K values. These effects impact estimation of fluid flow velocities and contaminant migration rates in groundwater. In order to quantify actual groundwater recharge rates and the effects of entrapped air, numerical simulations with the FEFLOW (Version 7.0) groundwater flow model were carried out using a quasi-saturated layer for a pilot area in Rio Claro, Brazil. The calculated recharge rate represented 16% of the average precipitation over an 8-year period, approximately half of estimates using the WTF method. Air entrapment amounted to a fillable porosity of 0.07, significant lower that the value of 0.17 obtained experimentally for Sy . Numerical results showed that the entrapped air volume in the quasi-saturated layer can be very significant (0.58 of the air fraction) and hence can significantly affect estimates of groundwater recharge and groundwater flow rates near the water table.

Colloid transport in unsaturated porous media: the role of water content and ionic strength on particle straining.

Packed column and mathematical modeling studies were conducted to explore the influence of water saturation, pore-water ionic strength, and grain size on the transport of latex microspheres (1.1 microm) in porous media. Experiments were carried out under chemically unfavorable conditions for colloid attachment to both solid-water interfaces (SWI) and air-water interfaces (AWI) using negatively charged and hydrophilic colloids and modifying the solution chemistry with a bicarbonate buffer to pH 10. Interaction energy calculations and complementary batch experiments were conducted and demonstrated that partitioning of colloids to the SWI and AWI was insignificant across the range of the ionic strengths considered. The breakthrough curve and final deposition profile were measured in each experiment indicating colloid retention was highly dependent on the suspension ionic strength, water content, and sand grain size. In contrast to conventional filtration theory, most colloids were found deposited close to the column inlet, and hyper-exponential deposition profiles were observed. A mathematical model, accounting for time- and depth-dependent straining, produced a reasonably good fit for both the breakthrough curves and final deposition profiles. Experimental and modeling results suggest that straining--the retention of colloids in low velocity regions of porous media such as grain junctions--was the primary mechanism of colloid retention under both saturated and unsaturated conditions. The extent of stagnant regions of flow within the pore structure is enhanced with decreasing water content, leading to a greater amount of retention. Ionic strength also contributes to straining, because the number of colloids that are held in the secondary energy minimum increases with ionic strength. These weakly associated colloids are prone to be translated to stagnation regions formed at grain-grain junctions, the solid-water-air triple point, and dead-end pores and then becoming trapped.

Dissolution kinetics of volatile organic compound vapors in water: An integrated experimental and computational study.

In this study we performed batch experiments to investigate the dissolution kinetics of trichloroethylene (TCE) and toluene vapors in water at room temperature and atmospheric pressure. The batch systems consisted of a water reservoir and a connected headspace, the latter containing a small glass cylinder filled with pure volatile organic compound (VOC). Results showed that air phase concentrations of both TCE and toluene increased relatively quickly to their maximum values and then became constant. We considered subsequent dissolution into both stirred and unstirred water reservoirs. Results of the stirred experiments showed a quick increase in the VOC concentrations with time up to their solubility limit in water. VOC vapor dissolution was found to be independent of pH. In contrast, salinity had a significant effect on the solubility of TCE and toluene vapors. VOC evaporation and vapor dissolution in the stirred water reservoirs followed first-order rate processes. Observed data could be described well using both simplified analytical solutions, which decoupled the VOC dynamics in the air and water phases, as well as using more complete coupled solutions. However, the estimated evaporation (ke) and dissolution (kd) rate constants differed by up to 70% between the coupled and uncoupled formulations. We also numerically investigated the effects of fluid withdrawal from the small water reservoir due to sampling. While decoupling the VOC air and water phase mass transfer processes produced unreliable estimates of kd, the effects of fluid withdrawal on the estimated rate constants were found to be less important. The unstirred experiments showed a much slower increase in the dissolved VOC concentrations versus time. Molecular diffusion of the VOCs within the aqueous phase became then the limiting factor for mass transfer from air to water. Fluid withdrawal during sampling likely caused some minor convection within the reservoir, which was simulated by increasing the apparent liquid diffusion coefficient.

A Mathematical View of Water Table Fluctuations in a Shallow Aquifer in Brazil.

Detailed monitoring of the groundwater table can provide important data about both short- and long-term aquifer processes, including information useful for estimating recharge and facilitating groundwater modeling and remediation efforts. In this paper, we presents results of 4 years (2002 to 2005) of monitoring groundwater water levels in the Rio Claro Aquifer using observation wells drilled at the Rio Claro campus of São Paulo State University in Brazil. The data were used to follow natural periodic fluctuations in the water table, specifically those resulting from earth tides and seasonal recharge cycles. Statistical analyses included methods of time-series analysis using Fourier analysis, cross-correlation, and R/S analysis. Relationships could be established between rainfall and well recovery, as well as the persistence and degree of autocorrelation of the water table variations. We further used numerical solutions of the Richards equation to obtain estimates of the recharge rate and seasonable groundwater fluctuations. Seasonable soil moisture transit times through the vadose zone obtained with the numerical solution were very close to those obtained with the cross-correlation analysis. We also employed a little-used deep drainage boundary condition to obtain estimates of seasonable water table fluctuations, which were found to be consistent with observed transient groundwater levels during the period of study.

2,4-Dichlorophenoxyacetic acid (2,4-D) sorption and degradation dynamics in three agricultural soils.

The fate and transport of 2,4-dichlorophenoxyacetic acid (2,4-D) in the subsurface is affected by a complex, time-dependent interplay between sorption and mineralization processes. 2,4-D is biodegradable in soils, while adsorption/desorption is influenced by both soil organic matter content and soil pH. In order to assess the dynamic interactions between sorption and mineralization, 2,4-D mineralization experiments were carried using three different soils (clay, loam and sand) assuming different contact times. Mineralization appeared to be the main process limiting 2,4-D availability, with each soil containing its own 2,4-D decomposers. For the clay and the loamy soils, 45 and 48% of the applied dose were mineralized after 10 days. By comparison, mineralization in the sandy soil proceeded initially much slower because of longer lag times. While 2,4-D residues immediately after application were readily available (>93% was extractable), the herbicide was present in a mostly unavailable state (<2% extractable) in all three soils after incubation for 60 days. We found that the total amount of bound residue decreased between 30 and 60 incubation days. Bioaccumulation may have led to reversible immobilization, with some residues later becoming more readily available again to extraction and/or mineralization.

Bacteriophage PRD1 batch experiments to study attachment, detachment and inactivation processes.

Knowledge of virus removal in subsurface environments is pivotal for assessing the risk of viral contamination of water resources and developing appropriate protection measures. Columns packed with sand are frequently used to quantify attachment, detachment and inactivation rates of viruses. Since column transport experiments are very laborious, a common alternative is to perform batch experiments where usually one or two measurements are done assuming equilibrium is reached. It is also possible to perform kinetic batch experiments. In that case, however, it is necessary to monitor changes in the concentration with time. This means that kinetic batch experiments will be almost as laborious as column experiments. Moreover, attachment and detachment rate coefficients derived from batch experiments may differ from those determined using column experiments. The aim of this study was to determine the utility of kinetic batch experiments and investigate the effects of different designs of the batch experiments on estimated attachment, detachment and inactivation rate coefficients. The experiments involved various combinations of container size, sand-water ratio, and mixing method (i.e., rolling or tumbling by pivoting the tubes around their horizontal or vertical axes, respectively). Batch experiments were conducted with clean quartz sand, water at pH 7 and ionic strength of 20 mM, and using the bacteriophage PRD1 as a model virus. Values of attachment, detachment and inactivation rate coefficients were found by fitting an analytical solution of the kinetic model equations to the data. Attachment rate coefficients were found to be systematically higher under tumbling than under rolling conditions because of better mixing and more efficient contact of phages with the surfaces of the sand grains. In both mixing methods, more sand in the container yielded higher attachment rate coefficients. A linear increase in the detachment rate coefficient was observed with increased solid-water ratio using tumbling method. Given the differences in the attachment rate coefficients, and assuming the same sticking efficiencies since chemical conditions of the batch and column experiments were the same, our results show that collision efficiencies of batch experiments are not the same as those of column experiments. Upscaling of the attachment rate from batch to column experiments hence requires proper understanding of the mixing conditions. Because batch experiments, in which the kinetics are monitored, are as laborious as column experiments, there seems to be no major advantage in performing batch instead of column experiments.

Groundwater recharge at five representative sites in the Hebei Plain, China.

Accurate estimates of groundwater recharge are essential for effective management of groundwater, especially when supplies are limited such as in many arid and semiarid areas. In the Hebei Plain, China, water shortage is increasingly restricting socioeconomic development, especially for agriculture, which heavily relies on groundwater. Human activities have greatly changed groundwater recharge there during the past several decades. To obtain better estimates of recharge in the plain, five representative sites were selected to investigate the effects of irrigation and water table depth on groundwater recharge. At each site, a one-dimensional unsaturated flow model (Hydrus-1D) was calibrated using field data of climate, soil moisture, and groundwater levels. A sensitivity analysis of evapotranspirative fluxes and various soil hydraulic parameters confirmed that fine-textured surface soils generally generate less recharge. Model calculations showed that recharge on average is about 175 mm/year in the piedmont plain to the west, and 133 mm/year in both the central alluvial and lacustrine plains and the coastal plain to the east. Temporal and spatial variations in the recharge processes were significant in response to rainfall and irrigation. Peak time-lags between infiltration (rainfall plus irrigation) and recharge were 18 to 35 days in the piedmont plain and 3 to 5 days in the central alluvial and lacustrine plains, but only 1 or 2 days in the coastal plain. This implies that different time-lags corresponding to different water table depths must be considered when estimating or modeling groundwater recharge.

Organic acids enhance the uptake of lead by wheat roots.

The uptake and bioavailability of lead (Pb) in soil-plant systems remain poorly understood. This study indicates that acetic and malic acids enhance the uptake of Pb by wheat (Triticum aestivum L.) roots under hydroponic conditions. The net concentration-dependent uptake influx of Pb in the presence and absence of organic acids was characterized by Michaelis-Menten type nonsaturating kinetic curves that could be resolved into linear and saturable components. Fitted maximum uptake rates (V (max)) of the Michaelis-Menton saturable component in the presence of acetic and malic acids were, respectively, 2.45 and 1.63 times those of the control, while the Michaelis-Menten K (m) values of 5.5, 3.7 and 2.2 microM, respectively, remained unchanged. Enhanced Pb uptake by organic acids was partially mediated by Ca(2+) and K(+) channels, and also depended upon the physiological function of the plasma membrane P-type ATPase. Uptake may have been further enhanced by an effectively thinner unstirred layer of Pb adjacent to the roots, leading to more rapid diffusion towards roots. X-ray absorption spectroscopic studies provided evidence that the coordination environment of Pb in wheat roots was similar to that of Pb(CH(3)COO)(2)x3H(2)O in that one Pb atom was coordinated to four oxygen atoms via the carboxylate group.

Modeling colloid attachment, straining, and exclusion in saturated porous media.

A conceptual model for colloid transport is developed that accounts for colloid attachment straining, and exclusion. Colloid attachment and detachment is modeled using first-order rate expressions, whereas straining is described using an irreversible first-order straining term that is depth dependent. Exclusion is modeled by adjusting transport parameters for colloid-accessible pore space. Fitting attachment and detachment model parameters to colloid transport data provided a reasonable description of effluent concentration curves, but the spatial distribution of retained colloids at the column inlet was severely underestimated for systems that exhibited significant colloid mass removal. A more physically realistic description of the colloid transport data was obtained by simulating both colloid attachment and straining. Fitted straining coefficients were found to systematically increase with increasing colloid size and decreasing median grain size. A correlation was developed to predict the straining coefficient from colloid and porous medium information. Numerical experiments indicated that increasing the colloid excluded volume of the pore space resulted in earlier breakthrough and higher peak effluent concentrations as a result of higher pore water velocities and lower residence times, respectively. Velocity enhancement due to colloid exclusion was predicted to increase with increasing exclusion volume and increasing soil gradation.