Minimizing Virus Transport in Porous Media by Optimizing Solid Phase Inactivation.

The influence of virus type (PRD1 and ΦX174), temperature (flow at 4 and 20°C), a no-flow storage duration (0, 36, 46, and 70 d), and temperature cycling (flow at 20°C and storage at 4°C) on virus transport and fate were investigated in saturated sand-packed columns. The vast majority (84-99.5%) of viruses were irreversibly retained on the sand, even in the presence of deionized water and beef extract at pH = 11. The reversibly retained virus fraction () was small (1.6 × 10 to 0.047) but poses a risk of long-term virus contamination. The value of and associated transport risk was lower at a higher temperature and for increases in the no-flow storage period due to the temperature dependency of the solid phase inactivation. A model that considered advective-dispersive transport, attachment (), detachment (), solid phase inactivation (µ), and liquid phase inactivation (µ) coefficients, and a Langmuirian blocking function provided a good description of the early portion of the breakthrough curve. The removal parameters were found to be in the order of > µ >> µ. Furthermore, µ was an order of magnitude higher than µ for PRD1, whereas µ was two and three orders of magnitude higher than µ for ΦX174 at 4 and 20°C, respectively. Transport modeling with two retention, release, and inactivation sites demonstrated that a small fraction of viruses exhibited a much slower release and solid phase inactivation rate, presumably because variations in the sand and virus surface roughness caused differences in the strength of adhesion. These findings demonstrate the importance of solid phase inactivation, temperature, and storage periods in eliminating virus transport in porous media. This research has potential implications for managed aquifer recharge applications and guidelines to enhance the virus removal by controlling the temperature and aquifer residence time.

Evaluating the Transport of Bacillus subtilis Spores as a Potential Surrogate for Cryptosporidium parvum Oocysts.

The U.S. Environmental Protection Agency has recommended the use of aerobic spores as an indicator for Cryptosporidium oocysts when determining groundwater under the direct influence of surface water. Surface properties, interaction energies, transport, retention, and release behavior of B. subtilis spores were measured over a range of physicochemical conditions, and compared with reported information for C. parvum oocysts. Interaction energy calculations predicted a much larger energy barrier and a shallower secondary minimum for spores than oocysts when the solution ionic strength (IS) equaled 0.1, 1, and 10 mM, and no energy barrier when the IS = 100 mM. Spores and oocysts exhibited similar trends of increasing retention with IS and decreasing Darcy water velocity (qw), and the predicted setback distance to achieve a six log removal was always larger for spores than oocysts. However, low levels of observed spore and oocyst release significantly influenced the predicted setback distance, especially when the fraction of reversibly retained microbes (Frev) was high. An estimate for Frev was obtained from large release pulses of spore and oocyst when the IS was reduced to deionized water. The value of Frev always increased with qw, whereas an opposition trend for Frev with IS was observed for spores (decreasing) and oocysts (increasing).

Determining Parameters and Mechanisms of Colloid Retention and Release in Porous Media.

A modeling framework is presented to determine fundamental parameters and controlling mechanisms of colloid (microbes, clays, and nanoparticles) retention and release on surfaces of porous media that exhibit wide distributions of nanoscale chemical heterogeneity, nano- to microscale roughness, and pore water velocity. Primary and/or secondary minimum interactions in the zone of electrostatic influence were determined over the heterogeneous solid surface. The Maxwellian kinetic energy model was subsequently employed to determine the probability of immobilization and diffusive release of colloids from each of these minima. In addition, a balance of applied hydrodynamic and resisting adhesive torques was conducted to determine locations of immobilization and hydrodynamic release in the presence of spatially variable water flow and microscopic roughness. Locations for retention had to satisfy both energy and torque balance conditions for immobilization, whereas release could occur either due to diffusion or hydrodynamics. Summation of energy and torque balance results over the elementary surface area of the porous medium provided estimates for colloid retention and release parameters that are critical to predicting environmental fate, including the sticking and release efficiencies and the maximum concentration of retained colloids on the solid phase. Nanoscale roughness and chemical heterogeneity produced localized primary minimum interactions that controlled long-term retention, even when mean chemical conditions were unfavorable. Microscopic roughness played a dominant role in colloid retention under low ionic strength and high hydrodynamic conditions, especially for larger colloids.

Modeling microorganism transport and survival in the subsurface.

An understanding of microbial transport and survival in the subsurface is needed for public health, environmental applications, and industrial processes. Much research has therefore been directed to quantify mechanisms influencing microbial fate, and the results demonstrate a complex coupling among many physical, chemical, and biological factors. Mathematical models can be used to help understand and predict the complexities of microbial transport and survival in the subsurface under given assumptions and conditions. This review highlights existing model formulations that can be used for this purpose. In particular, we discuss models based on the advection-dispersion equation, with terms for kinetic retention to solid-water and/or air-water interfaces; blocking and ripening; release that is dependent on the resident time, diffusion, and transients in solution chemistry, water velocity, and water saturation; and microbial decay (first-order and Weibull) and growth (logistic and Monod) that is dependent on temperature, nutrient concentration, and/or microbial concentration. We highlight a two-region model to account for microbe migration in the vicinity of a solid phase and use it to simulate the coupled transport and survival of species under a variety of environmentally relevant scenarios. This review identifies challenges and limitations of models to describe and predict microbial transport and survival. In particular, many model parameters have to be optimized to simulate a diversity of observed transport, retention, and survival behavior at the laboratory scale. Improved theory and models are needed to predict the fate of microorganisms in natural subsurface systems that are highly dynamic and heterogeneous.

Colloid interaction energies for physically and chemically heterogeneous porous media.

The mean and variance of the colloid interaction energy (Φ*) as a function of separation distance (h) were calculated on physically and/or chemically heterogeneous solid surfaces at the representative elementary area (REA) scale. Nanoscale roughness was demonstrated to have a significant influence on the colloid interaction energy for different ionic strengths. Increasing the roughness height reduced the magnitude of the energy barrier (Φmax*) and the secondary minimum (Φ2min*). Conversely, increasing the fraction of the solid surface with roughness increased the magnitude of Φmax* and Φ2min*. Our results suggest that primary minimum interactions tend to occur in cases where only a portion of the solid surface was covered with roughness (i.e., isolated roughness pillars), but their depths were shallow as a result of Born repulsion. The secondary minimum was strongest on smooth surfaces. The variance in the interaction energy was also a strong function of roughness parameters and h. In particular, the variance tended to increase with the colloid size, the magnitude of Φ*, the height of the roughness, and especially the size (cross-sectional area) of the heterogeneity. Nonzero values of the variance for Φ2min* implied the presence of a tangential component of the adhesive force and a resisting torque that controls immobilization and release for colloids at this location. Heterogeneity reduced the magnitude of Φ* in comparison to the corresponding homogeneous situation. Physical heterogeneity had a greater influence on mean properties of Φ* than similar amounts of chemical heterogeneity, but the largest reduction occurred on surfaces with both physical and chemical heterogeneity. The variance in Φ* tended to be higher for a chemically heterogeneous solid.

A theoretical analysis of colloid attachment and straining in chemically heterogeneous porous media.

A balance of applied hydrodynamic (T(H)) and resisting adhesive (T(A)) torques was conducted over a chemically heterogeneous porous medium that contained random roughness of height h(r) to determine the fraction of the solid surface area that contributes to colloid immobilization (S(f)*) under unfavorable attachment conditions. This model considers resistance due to deformation and the horizontal component of the adhesive force (F(AT)), spatial variations in the pore scale velocity distribution, and the influence of hr on lever arms for T(H) and T(A). Values of S(f)* were calculated for a wide range of physicochemical properties to gain insight into mechanisms and factors influencing colloid immobilization. Colloid attachment processes were demonstrated to depend on solution ionic strength (IS), the colloid radius (r(c)), the Young's modulus (K), the amount of chemical heterogeneity (P+), and the Darcy velocity (q). Colloid immobilization was also demonstrated to occur on a rough surface in the absence of attachment. In this case, S(f)* depended on IS, r(c), the roughness fraction (f0), h(r), and q. Roughness tended to enhance T(A) and diminish T(H). Consequently, the effect of IS on S(f)* was enhanced by h(r) relative to attachment. In contrast, the effects of r(c) and q on S(f)* were diminished by hr in comparison to attachment. Colloid immobilization adjacent to macroscopic roughness locations shares many similarities to grain-grain contact points and may be viewed as a type of straining process. In general, attachment was more important for higher IS and variance in the secondary minimum, and for smaller r(c), q, and K, but diffusion decreased these values. Conversely, straining was dominant for the opposite conditions. Discrepancies in the literature on mechanisms of colloid retention are likely due to a lack of consideration of all of these factors.

Release of quantum dot nanoparticles in porous media: role of cation exchange and aging time.

Understanding the fate and transport of engineered nanoparticles (ENPs) in subsurface environments is required for developing the best strategy for waste management and disposal of these materials. In this study, the deposition and release of quantum dot (QD) nanoparticles were studied in saturated sand columns. The QDs were first deposited in columns using 100 mM NaCl or 2 mM CaC12 solutions. Deposited QDs were then contacted with deionized (DI) water and/or varying Na(+) concentrations to induce release. QDs deposited in 100 mM Na(+) were easily reversible when the column was rinsed with DI water. Conversely, QDs deposited in the presence of Ca(2+) exhibited resistance to release with DI water. However, significant release occurred when the columns were flushed with NaCl solutions. This release behavior was explained by cation exchange (Ca(2+) in exchange sites were replaced by Na(+)) which resulted in the breakdown of calcium bridging. We also studied the effect of aging time on the QD release. As the aging time increased, smaller amounts of QDs were released following cation exchange. However, deposited QDs were subsequently released when the column was flushed with DI water. The release behavior was modeled using a single first-order kinetic release process and changes in the maximum solid phase concentration of deposited QDs with transition in solution chemistry. The results of this study demonstrate that the presence of carboxyl groups on ENPs and divalent ions in the solution plays a key role in controlling ENP mobility in the subsurface environment.

Colloid adhesive parameters for chemically heterogeneous porous media.

A simple modeling approach was developed to calculate colloid adhesive parameters for chemically heterogeneous porous media. The area of the zone of electrostatic influence between a colloid and solid-water interface (A(z)) was discretized into a number of equally sized grid cells to capture chemical heterogeneity within this region. These cells were divided into fractions having specific zeta potentials (e.g., negative or positive values). Mean colloid adhesive parameters such as the zeta potential, the minimum and maximum in the interaction energy, the colloid sticking efficiency (α), and the fraction of the solid surface area that contributes to colloid immobilization (S(f)) were calculated for possible charge realizations within A(z). The probability of a given charge realization in A(z) was calculated using a binomial mass distribution. Probability density functions (PDFs) for the colloid adhesive parameters on the heterogeneous surface were subsequently calculated at the representative elementary area (REA) scale for a porous medium. This approach was applied separately to the solid-water interface (SWI) and the colloid, or jointly to both the SWI and colloid. To validate the developed model, the mean and standard deviation of the interaction energy distribution on a chemically heterogeneous SWI were calculated and demonstrated to be consistent with published Monte Carlo simulation output using the computationally intensive grid surface integration technique. Our model results show that the PDFs of colloid adhesive parameters at the REA scale were sensitive to the size of the colloid and the heterogeneity, the charge and number of grid cells, and the ionic strength.

Cell preparation methods influence Escherichia coli D21g surface chemistry and transport in saturated sand.

The effect of cell preparation methods on the surface chemistry and retention of Escherichia coli D21 g was investigated over a range of ionic strength conditions. The cell preparation methods that were considered included filtration and centrifugation (at various speeds and for different durations). For a given ionic strength condition, it was found that cells prepared by filtration were more negatively charged and hydrophobic than cells prepared by centrifugation. Increasing the centrifugation speed (force imposed) or duration produced cells with a higher zeta potential (less negative) and a lower hydrophobicity. Column transport experiments for E. coli D21 g were also conducted with ultra pure quartz sand and the same solution chemistries. The first-order retention rate coefficient for E. coli D21 g increased with increasing speed and duration of centrifugation, and was lowest in the case of filtered cells. Moreover, the influence of cell preparation method was more pronounced in lower ionic strength solutions.

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.

Unraveling the complexities of the velocity dependency of E. coli retention and release parameters in saturated porous media.

Escherichia coli transport and release experiments were conducted to investigate the pore-water velocity (v) dependency of the sticking efficiency (α), the fraction of the solid surface area that contributed to retention (Sf), the percentage of injected cells that were irreversibly retained (Mirr), and cell release under different (10-300mM) ionic strength (IS) conditions. Values of α, Sf, and Mirr increased with increasing IS and decreasing v, but the dependency on v was greatest at intermediate IS (30 and 50mM). Following the retention phase, successive increases in v up to 100 or 150mday-1 and flow interruption of 24h produced negligible amounts of cell release. However, excavation of the sand from the columns in excess electrolyte solution resulted in the release of >80% of the retained bacteria. These observations were explained by: (i) extended interaction energy calculations on a heterogeneous sand collector; (ii) an increase in adhesive strength with the residence time; and (iii) torque balance consideration on rough surfaces. In particular, α, Sf, and Mirr increased with IS due to lower energy barriers and stronger primary minima. The values of α, Sf, and Mirr also increased with decreasing v because the adhesive strength increased with the residence time (e.g., an increased probability to diffuse over the energy barrier) and lower hydrodynamic forces diminished cell removal. The controlling influence of lever arms at microscopic roughness locations and grain-grain contacts were used to explain negligible cell removal with large increases in v and large amounts of cell recovery following sand excavation. Results reveal the underlying causes (interaction energy, torque balance, and residence time) of the velocity dependency of E. coli retention and release parameters (ksw, α, and Sf) that are not accounted for in colloid filtration theory.

Temperature dependency of virus and nanoparticle transport and retention in saturated porous media.

The influence of temperature on virus (PRD1 and ΦX174) and carboxyl-modified latex nanoparticle (50 and 100nm) attachment was examined in sand-packed columns under various physiochemical conditions. When the solution ionic strength (IS) equaled 10 and 30mM, the attachment rate coefficient (katt) increased up to 109% (p<0.0002) and the percentage of the sand surface area that contributed to attachment (Sf) increased up to 160% (p<0.002) when the temperature was increased from 4 to 20°C. Temperature effects at IS=10 and 30mM were also dependent on the system hydrodynamics; i.e., enhanced retention at a lower pore water velocity (0.1m/day). Conversely, this same temperature increase had a negligible influence on katt and Sf values when IS was 1mM or >50mM. An explanation for these observations was obtained from extended interaction energy calculations that considered nanoscale roughness and chemical heterogeneity on the sand surface. Interaction energy calculations demonstrated that the energy barrier to attachment in the primary minimum (∆Φa) decreased with increasing IS, chemical heterogeneity, and temperature, especially in the presence of small amounts of nanoscale roughness (e.g., roughness fraction of 0.05 and height of 20nm in the zone of influence). Temperature had a negligible effect on katt and Sf when the IS=1mM because of the large energy barrier, and at IS=50mM because of the absence of an energy barrier. Conversely, temperature had a large influence on katt and Sf when the IS was 10 and 30mM because of the presence of a small ∆Φa on sand with nanoscale roughness and a chemical (positive zeta potential) heterogeneity. This has large implications for setting parameters for the accurate modeling and transport prediction of virus and nanoparticle contaminants in ground water systems.

Critical role of surface roughness on colloid retention and release in porous media.

This paper examines the critical role of surface roughness (both nano- and micro-scale) on the processes of colloid retention and release in porous media under steady-state and transient chemical conditions. Nanoscale surface roughness (NSR) in the order of a few nanometers, which is common on natural solid surfaces, was incorporated into extended-DLVO calculations to quantify the magnitudes of interaction energy parameters (e.g. the energy barrier to attachment, ΔΦa , and detachment, ΔΦd , from a primary minimum). This information was subsequently used to explain the behavior of colloid retention and release in column and batch experiments under different ionic strength (IS) and pH conditions. Results demonstrated that the density and height of NSR significantly influenced the interaction energy parameters and consequently the extent and kinetics of colloid retention and release. In particular, values of ΔΦa and ΔΦd significantly decreased in the presence of NSR. Therefore, consistent with findings of column experiments, colloid retention in the primary minimum was predicted to occur at some specific locations on the sand surface, even at low IS conditions. However, NSR yielded a much weaker primary minimum interaction compared with that of smooth surfaces. Colloid release from primary minima upon decreasing IS and increasing pH was attributed to the impact of NSR on the values of ΔΦd . Pronounced differences in the amount of colloid retention in batch and column experiments indicated that primary minimum interactions were weak even at high IS conditions. Negligible colloid retention in batch experiments was attributed to hydrodynamic torques overcoming adhesive torques, whereas significant colloid retention in column experiments was attributed to nano- and micro-scale roughness which would dramatically alter the lever arms associated with hydrodynamic and adhesive torques.

Transport and retention of bacteria and viruses in biochar-amended sand.

The transport and retention of Escherichia coli and bacteriophages (PRD1, MS2 and ФX174), as surrogates for human pathogenic bacteria and viruses, respectively, were studied in the sand that was amended with several types of biochar produced from various feedstocks. Batch and column studies were conducted to distinguish between the role of attachment and straining in microbe retention during transport. Batch experiments conducted at various solution chemistries showed negligible attachment of viruses and bacteria to biochar before or after chemical activation. At any given solution ionic strength, the attachment of viruses to sand was significantly higher than that of biochar, whereas bacteria showed no attachment to either sand or biochar. Consistent with batch results, biochar addition (10% w/w) to sand reduced virus retention in the column experiments, suggesting a potential negative impact of biochar application to soil on virus removal. In contrast, the retention of bacteria was enhanced in biochar-amended sand columns. However, elimination of the fine fraction (<60µm) of biochar particles in biochar-amended sand columns significantly reduced bacteria retention. Results from batch and column experiments suggest that land application of biochar may only play a role in microbe retention via straining, by alteration of pore size distribution, and not via attachment. Consequently, the particle size distribution of biochar and sediments is a more important factor than type of biochar in determining whether land application of biochar enhances or diminishes microbial retention.

Equilibrium and kinetic models for colloid release under transient solution chemistry conditions.

We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and kinetic, and two-site kinetic models were developed to describe various rates of colloid release. These models were subsequently applied to experimental colloid release datasets to investigate the influence of variations in ionic strength (IS), pH, cation exchange, colloid size, and water velocity on release. Various combinations of equilibrium and/or kinetic release models were needed to describe the experimental data depending on the transient conditions and colloid type. Release of Escherichia coli D21g was promoted by a decrease in solution IS and an increase in pH, similar to expected trends for a reduction in the secondary minimum and nanoscale chemical heterogeneity. The retention and release of 20nm carboxyl modified latex nanoparticles (NPs) were demonstrated to be more sensitive to the presence of Ca(2+) than D21g. Specifically, retention of NPs was greater than D21g in the presence of 2mM CaCl2 solution, and release of NPs only occurred after exchange of Ca(2+) by Na(+) and then a reduction in the solution IS. These findings highlight the limitations of conventional interaction energy calculations to describe colloid retention and release, and point to the need to consider other interactions (e.g., Born, steric, and/or hydration forces) and/or nanoscale heterogeneity. Temporal changes in the water velocity did not have a large influence on the release of D21g for the examined conditions. This insensitivity was likely due to factors that reduce the applied hydrodynamic torque and/or increase the resisting adhesive torque; e.g., macroscopic roughness and grain-grain contacts. Our analysis and models improve our understanding and ability to describe the amounts and rates of colloid release and indicate that episodic colloid transport is expected under transient physicochemical conditions.

Colloid release and clogging in porous media: Effects of solution ionic strength and flow velocity.

The release and retention of in-situ colloids in aquifers play an important role in the sustainable operation of managed aquifer recharge (MAR) schemes. The processes of colloid release, retention, and associated permeability changes in consolidated aquifer sediments were studied by displacing native groundwater with reverse osmosis-treated (RO) water at various flow velocities. Significant amounts of colloid release occurred when: (i) the native groundwater was displaced by RO-water with a low ionic strength (IS), and (ii) the flow velocity was increased in a stepwise manner. The amount of colloid release and associated permeability reduction upon RO-water injection depended on the initial clay content of the core. The concentration of released colloids was relatively low and the permeability reduction was negligible for the core sample with a low clay content of about 1.3%. In contrast, core samples with about 6 and 7.5% clay content exhibited: (i) close to two orders of magnitude increase in effluent colloid concentration and (ii) more than 65% permeability reduction. Incremental improvement in the core permeability was achieved when the flow velocity increased, whereas a short flow interruption provided a considerable increase in the core permeability. This dependence of colloid release and permeability changes on flow velocity and colloid concentration was consistent with colloid retention and release at pore constrictions due to the mechanism of hydrodynamic bridging. A mathematical model was formulated to describe the processes of colloid release, transport, retention at pore constrictions, and subsequent permeability changes. Our experimental and modeling results indicated that only a small fraction of the in-situ colloids was released for any given change in the IS or flow velocity. Comparison of the fitted and experimentally measured effluent colloid concentrations and associated changes in the core permeability showed good agreement, indicating that the essential physics were accurately captured by the model.

An explanation for differences in the process of colloid adsorption in batch and column studies.

It is essential to understand the mechanisms that control virus and bacteria removal in the subsurface environment to assess the risk of groundwater contamination with fecal microorganisms. This study was conducted to explicitly provide a critical and systematic comparison between batch and column experiments. The aim was to investigate the underlying factors causing the commonly observed discrepancies in colloid adsorption process in column and batch systems. We examined the colloid adsorption behavior of four different sizes of carboxylate-modified latex (CML) microspheres, as surrogates for viruses and bacteria, on quartz sand in batch and column experiments over a wide range of solution ionic strengths (IS). Our results show that adsorption of colloids in batch systems should be considered as an irreversible attachment because the attachment/detachment model was found to be inadequate in describing the batch results. An irreversible attachment-blocking model was found to accurately describe the results of both batch and column experiments. The rate of attachment was found to depend highly on colloid size, solution IS and the fraction of the sand surface area favorable for attachment (Sf). The rate of attachment and Sf values were different in batch and column experiments due to differences in the hydrodynamic of the system, and the role of surface roughness and pore structure on colloid attachment. Results from column and batch experiments were generally not comparable, especially for larger colloids (≥0.5µm). Predictions based on classical DLVO theory were found to inadequately describe interaction energies between colloids and sand surfaces.

Impacts of bridging complexation on the transport of surface-modified nanoparticles in saturated sand.

The transport of polyacrylic acid capped cadmium telluride (CdTe) quantum dots (QDs), carboxylate-modified latex (CML), and bare silica nanoparticles (NPs) was studied in packed columns at various electrolyte concentrations and cation types. The breakthrough curves (BTCs) of QDs and CML particles in acid-treated Accusand showed significant amounts of increasing deposition with 0.5, 1, and 2 mM Ca(2+), but only minute deposition at 50 and 100 mM Na(+). Negligible QD and CML deposition occurred at 2mM Ca(2+) in columns packed with ultrapure quartz sand that was similar in size to the Accusand. These observations are not consistent with interpretations based on Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations of interaction energies. Scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis demonstrated that there were regions on the acid-treated Accusand covered with small amounts of clay that were absent on the ultrapure quartz sand. A salt cleaning method was therefore used to remove the clay from the acid-treated Accusand. The BTCs of QDs and CML in this acid+salt treated Accusand exhibited much less deposition at any given Ca(2+) concentration compared to those obtained from the acid-treated sand. SEM images showed that most of the QD deposited in acid-treated Accusand occurred on clay surfaces. Unlike our results with QDs and CML, negligible deposition of bare silica NPs occurred at 5 and 10 mM Ca(2+) in acid-treated Accusand. The high deposition of QDs and CML particles was therefore attributed to bridging complexation in which Ca(2+) serves as a bridge between the cation exchange locations on the clay and carboxyl functional groups on the QD and CML particles, which were absent on the bare silica NPs. Our results suggest that the transport of carboxylic ligand-modified NPs may be limited in subsurface environments because of the ubiquitous presence of clay and divalent cations.

Transport and deposition of functionalized CdTe nanoparticles in saturated porous media.

Comprehensive understanding of the transport and deposition of engineered nanoparticles (NPs) in subsurface is required to assess their potential negative impact on the environment. We studied the deposition behavior of functionalized quantum dot (QD) NPs (CdTe) in different types of sands (Accusand, ultrapure quartz, and iron-coated sand) at various solution ionic strengths (IS). The observed transport behavior in ultrapure quartz and iron-coated sand was consistent with conventional colloid deposition theories. However, our results from the Accusand column showed that deposition was minimal at the lowest IS (1mM) and increased significantly as the IS increased. The effluent breakthrough occurred with a delay, followed by a rapid rise to the maximum normalized concentration of unity. Negligible deposition in the column packed with ultrapure quartz sand (100mM) and Accusand (1mM) rules out the effect of straining and suggests the importance of surface charge heterogeneity in QD deposition in Accusand at higher IS. Data analyses further show that only a small fraction of sand surface area contributed in QD deposition even at the highest IS (100mM) tested. The observed delay in breakthrough curves of QDs was attributed to the fast diffusive mass transfer rate of QDs from bulk solution to the sand surface and QD mass transfer on the solid phase. Scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis were used to examine the morphology and elemental composition of sand grains. It was observed that there were regions on the sand covered with layers of clay particles. EDX spectra collected from these regions revealed that Si and Al were the major elements suggesting that the clay particles were kaolinite. Additional batch experiments using gold NPs and SEM analysis were performed and it was observed that the gold NPs were only deposited on clay particles originally on the Accusand surface. After removing the clays from the sand surface, we observed negligible QD deposition even at 100mM IS. We proposed that nanoscale charge heterogeneities on clay particles on Accusand surface played a key role in QD deposition. It was shown that the value of solution IS determined the extent to which the local heterogeneities participated in particle deposition.

Hysteresis of colloid retention and release in saturated porous media during transients in solution chemistry.

Saturated packed column and micromodel transport studies were conducted to gain insight on mechanisms of colloid retention and release under unfavorable attachment conditions. The initial deposition of colloids in porous media was found to be a strongly coupled process that depended on solution chemistry and pore space geometry. During steady state chemical conditions, colloid deposition was not a readily reversible process, and micromodel photos indicated that colloids were immobilized in the presence of fluid drag. Upon stepwise reduction in eluting solution ionic strength (IS), a sharp release of colloids occurred in each step which indicates that colloid retention depends on a balance of applied (hydrodynamic) and resisting (adhesive) torques which varied with pore space geometry, surface roughness, and interaction energy. When the eluting fluid IS was reduced to deionized water, the final retention locations occurred near grain-grain contacts, and colloid aggregation was sometimes observed in micromodel experiments. Significant amounts of colloid retention hysteresis with IS were observed in the column experiments, and it depended on the porous medium (glass beads compared with sand), the colloid size (1.1 and 0.5 mum), and on the initial deposition IS. These observations were attributed to weak adhesive interactions that depended on the double layer thickness (e.g., the depth of the secondary minimum and/or nanoscale heterogeneity), colloid mass transfer on the solid phase to regions where the torque and force balances were favorable for retention, the number and extent of grain-grain contacts, and surface roughness.