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Derjaguin-Landau-Verwey-Overbeek (DLVO) theory is typically used to quantify surface interactions between engineered nanoparticles (ENPs), soil nanoparticles (SNPs), and/or porous media, which are used to assess environmental risk and fate of ENPs. This study investigates the co-transport behavior of functionalized multiwalled carbon nanotubes (MWCNTs) with positively (goethite nanoparticles, GNPs) and negatively (bentonite nanoparticles, BNPs) charged SNPs in quartz sand (QS). The presence of BNPs increased the transport of MWCNTs, but GNPs inhibited the transport of MWCNTs. In addition, we, for the first time, observed that the transport of negatively (BNPs) and positively (GNPs) charged SNPs was facilitated by the presence of MWCNTs. Traditional mechanisms associated with competitive blocking, heteroaggregation, and classic DLVO calculations cannot explain such phenomena. Direct examination using batch experiments and Fourier transform infrared (FTIR) spectroscopy, asymmetric flow field flow fractionation (AF4) coupled to UV and inductively coupled plasma mass spectrometry (AF4-UV-ICP-MS), and molecular dynamics (MD) simulations demonstrated that MWCNTs-BNPs or MWCNT-GNPs complexes or aggregates can be formed during co-transport. Non-DLVO interactions (e.g., H-bonding and Lewis acid-base interaction) helped to explain observed MWCNT deposition, associations between MWCNTs and both SNPs (positively or negatively), and co-transport. This research sheds novel insight into the transport of MWCNTs and SNPs in porous media and suggests that (i) mutual effects between colloids (e.g., heteroaggregation, co-transport, and competitive blocking) need to be considered in natural soil; and (ii) non-DLVO interactions should be comprehensively considered when evaluating the environmental risk and fate of ENPs.

Hypothesis Analytical expressions for calculating Hamaker constant (HC) and van der Waals (VDW) energy/force for interaction of a particle with a solid water interface has been reported for over eighty years. This work further developed novel analytical expressions and numerical approaches for determining HC and VDW interaction energy/force for the particle approaching and penetrating air-water interface (AWI), respectively. Methods The expressions of HC and VDW interaction energy/force before penetrating were developed through analysis of the variation in free energy of the interaction system with bringing the particle from infinity to the vicinity of the AWI. The surface element integration (SEI) technique was modified to calculate VDW energy/force after penetrating. Findings We explain why repulsive VDW energy exists inhibiting the particle from approaching the AWI. We found very significant VDW repulsion for a particle at a concave AWI after penetration, which can even exceed the capillary force and cause strong retention in water films on a solid surface and at air-water-solid interface line. The methods and findings of this work are critical to quantification and understanding of a variety of engineered processes such as particle manipulation (e.g., bubble flotation, Pickering emulsion, and particle laden interfaces).

Colloidal particles can attach to surfaces during transport, but the attachment depends on particle size, hydrodynamics, solid and water chemistry, and particulate matter. The attachment is quantified in filtration theory by measuring attachment or sticking efficiency (Alpha). A comprehensive Alpha database (2538 records) was built from experiments in the literature and used to develop a machine learning (ML) model to predict Alpha. The training (r-squared: 0.86) was performed using two random forests capable of handling missing data. A holdout dataset was used to validate the training (r-squared: 0.98), and the variable importance was explored for training and validation. Finally, an additional validation dataset was built from quartz crystal microbalance experiments using surface-modified polystyrene, poly (methyl methacrylate), and polyethylene. The experiments were performed in the absence or presence of humic acid. Full database regression (r-squared: 0.90) predicted Alpha for the additional validation with an r-squared of 0.23. Nevertheless, when the original database and the additional validation dataset were combined into a new database, both the training (r-squared: 0.95) and validation (r-squared: 0.70) increased. The developed ML model provides a data-driven prediction of Alpha over a big database and evaluates the significance of 22 input variables.

Colloid aggregation and retention in the presence of macromolecular coatings (e.g., adsorbed polymers, surfactants, proteins, biological exudates, and humic materials) have previously been correlated with electric double layer interactions or repulsive steric interactions, but the underlying causes are not fully resolved. An interaction energy model that accounts for double layer, van der Waals, Born, and steric interactions as well as nanoscale roughness and charge heterogeneity on both surfaces was extended, and theoretical calculations were conducted to address this gap in knowledge. Macromolecular coatings may produce steric interactions in the model, but non-uniform or incomplete surface coverage may also create compressible nanoscale roughness with a charge that is different from the underlying surface. Model results reveal that compressible nanoscale roughness reduces the energy barrier height and the magnitude of the primary minimum at separation distances exterior to the adsorbed organic layer. The depth of the primary minimum initially alters (e.g., increases or decreases) at separation distances smaller than the adsorbed organic coating because of a decrease in the compressible roughness height and an increase in the roughness fraction. However, further decreases in the separation distance create strong steric repulsion that dominates the interaction energy profile and limits the colloid approach distance. Consequently, adsorbed organic coatings on colloids can create shallow primary minimum interactions adjacent to organic coatings that can explain enhanced stability and limited amounts of aggregation and retention that have commonly been observed. The approach outlined in this manuscript provides an improved tool that can be used to design adsorbed organic coatings for specific colloid applications or interpret experimental observations.

The presence and/or coating of natural colloids (e.g., clays and metal oxides or hydroxides) on collector surfaces has frequently been demonstrated to enhance the retention of engineered colloids that are negatively charged due to favorable electrostatic interactions. However, this work demonstrates that the presence of natural clay coating can lead to reduced or nonmonotonic retention of micro- and nanoplastics (MNPs). Column experiments were carried out to systematically investigate the transport of MNPs with different sizes in relatively smooth and rough sands that had various clay coating fractions. These coating fractions on the collector were found to significantly influence MNP retention in a complex manner that changed with the colloid size and the roughness properties of the sand. This observation was attributed to the impact of clay coatings on the roughness and morphology properties of collector surfaces that were dominant over surface charge. Scanning electron microscopy and interaction energy calculations on surfaces with pillars or valleys indicate that mechanisms that contributed to MNP retention changed with the colloid size. In particular, retention of nanosized plastics was mainly controlled by interactions on convex/concave locations that changed with the solution chemistry, whereas microsized plastics were also strongly influenced by the applied hydrodynamic torque and straining processes. Additionally, the significant sensitivity of MNP retention under a low-level ionic strength also reflects the importance of roughness and charge heterogeneities. These observations are important for investigating the mechanisms of colloid transport in natural systems that ubiquitously exhibit clay coating on their surfaces.

Since its first publication in 1970, the Critical Reviews in Environmental Science and Technology (CREST) journal has served as an international forum for the publication of comprehensive, critical...

Drywells (DWs) and infiltration basins (IBs) are widely used as managed aquifer recharge (MAR) devices to capture stormwater runoff and recharge groundwater. However, no published research has compared the performance of these two engineered systems under shared conditions. Numerical experiments were conducted on an idealized 2D‐axisymmetric domain using the HYDRUS (2D/3D) software to systematically study the performance of a circular IB design (diameter and area) and partially penetrating DW (38 m length with water table > 60 m). The effects of subsurface heterogeneity on infiltration, recharge, and storage from the DW and IB under constant head conditions were investigated. The mean cumulative infiltration (μI) and recharge (μR) volumes increased, and the arrival time of recharge decreased with the IB area. Values of μI were higher for a 70 m diameter IB than an DW, whereas the value of μR was higher for a DW after 1-year of a constant head simulation under selected subsurface heterogeneity conditions. A comparison between mean μI, μR, and mean vadose zone storage (μS) values for all DW and IB stochastic simulations (70 for each MAR scenario) under steady-state conditions demonstrated that five DWs can replace a 70 m diameter IB to achieve significantly higher infiltration and recharge over 20 years of operation. Additional numerical experiments were conducted to study the influence of a shallow clay layer by considering an IB, DW, and a DW integrated into an IB. The presence of such a low permeable layer delayed groundwater recharge from an IB. In contrast, a DW can penetrate tight clay layers and release water below them and facilitate rapid infiltration and recharge. The potential benefits of a DW compared to an IB include a smaller footprint, the potential for pre-treatments to remove contaminants, less evaporation, less mobilization of in-situ contaminants, and potentially lower maintenance costs. Besides, this study demonstrates that combining both IB and DW helps to get the best out of both MAR techniques.

An understanding of nanobubble (NB) migration in porous media is needed for potential environmental applications. The solution chemistry is well known to be a critical factor in determining interactions of other colloids and nanoparticles with surfaces. However, little quantitative research has examined the influence of solution chemistry on NB transport. One-dimensional column experiments were therefore conducted to investigate the transport, retention, and release of NBs in glass beads under different solution chemistry conditions. NB concentrations in the effluent were reduced with an increase in ionic strength (IS) or a decrease in pH due to a reduction in the repulsive force between the glass surface and NBs, especially when the solution contained Ca2+ as compared to Na+ and for larger NBs. This result was somewhat surprising because electrostatic and van der Waals interactions for NBs were both repulsive on a homogeneous glass bead surface. NB retention on the surface was explained by ubiquitous nan...

Application of biochar in the field has received considerable attention in recent years, but there is still little known about the fate and transport of biochar colloids (BCs) in the subsurface. Natural organic matter (NOM), which mainly consists of humic substance (HS) and proteins, is ubiquitous in the natural environment and its dissolved fraction is active and mobile. In this study, the transport of BCs in saturated porous media has been examined in the presence of two HS (humic and fulvic acids) and two proteins. Bull serum albumin (BSA) and Cytochrome c (Cyt) were selected to present the negatively and positively charged protein, respectively. At low and high salt concentration and different pH conditions, the transport of BCs was strongly promoted by HS. HS significantly increased the mobility of BCs in porous media under both low and high salt conditions due to the enhanced electrostatic repulsion and modification of surface roughness and charge heterogeneity. While BC mobility in porous media was suppressed by both BSA and Cyt in the low salt solution, the presence of BSA largely promoted and Cyt slightly enhanced the transport of BCs in high salt solutions. BSA and Cyt adsorption onto BC surface decreased the negative charge of BC and resulted in a less repulsive interaction in low salt solutions. In high salt solutions, the adsorbed BSA layers disaggregated BCs and reduced the strength of the interaction between BC and the sand. Adsorbed Cyt on BCs caused more attractive patches between BC and sand surface, and greater retention than BSA.

Colloid suspensions commonly exhibit a distribution of sizes, but most transport models only consider a single colloid size. A mathematical model was therefore developed to describe the advective and dispersive transport and first-order retention and release of a stable or aggregating polydispersed colloid suspension in porous media. The colloid size distribution was described using a unimodal or a bimodal lognormal probability density function (PDF), and Brownian aggregation was considered by making lognormal PDF parameters a function of time. Filtration theory was used to predict the retention rate coefficients for the various colloid sizes. The amount of retention for a stable polydispersed suspension was highly dependent on the colloid size distribution parameters, especially for a bimodal lognormal PDF. Increasing the distribution variance produced hyper-exponential retention profiles and an increase or a decrease in colloid retention depending on whether the medium colloid size was close to the optimum size for transport. Aggregation produced a similar decrease in the breakthrough concentrations with injection time as ripening, especially when the sticking efficiency was low. Aggregation effects were much more pronounced at higher input concentration levels, which also produced retention profiles that were increasingly hyper-exponential. Simulation results indicate that the colloid size distribution of stable and aggregating polydispersed suspensions always becomes more uniform and approaches the optimum transport size with increasing distance, suggesting that consideration of polydispersed suspensions is of primary importance near the injection surface.

Nano zero‐valent iron (nZVI) has been used for in situ groundwater remediation due to its strong adsorption and reaction characteristics. However, oxyanion contaminants in groundwater can ready adsorbed onto the surface of nZVI. This can potentially alter the mobility of nZVI and create a secondary pollution source, but these issues have not yet been systematically investigated. In this study, polyaniline‐supported nZVI (PnZVI) and phosphate‐sorbed PnZVI (PS‐PnZVI) were synthesized in the laboratory. The sedimentation and transport behavior of these two nZVI particles were investigated, compared, and mathematically modeled to better understand the impact of phosphate adsorption on these processes. Results showed that phosphate adsorption can enhance the stability and mobility of PnZVI. Interaction energy calculations that considered van der Waals and magnetic attraction, electrostatic double layer and Born repulsion, and the influence of nanoscale roughness and binary charge heterogeneity were conducted to better infer mechanisms causing nZVI particle sedimentation and retention. Nanoscale roughness and binary charge heterogeneity were found to significantly decrease the energy barrier, but not to low enough levels to explain the observed behavior. The rapid settling of PnZVI was attributed to strong magnetic attraction between particles, which produced rapid aggregation and retention due to straining and/or hydrodynamic bridging. Phosphate adsorption enhanced the mobility of PS‐PnZVI in comparison with PnZVI due to a decrease in particle size and aggregation, and an increase in the energy barrier with the porous media. A potential risk of nZVI particles to facilitate oxyanion contaminant transport was demonstrated for phosphate.

As in many other soil science disciplines, in soil physics and hydrology, we have arrived at a point where substantial gains in knowledge depend to a large extent on reaching out to related disciplines. The purpose of this special section on “Transdisciplinary Contributions and Opportunities in Soil Physical Hydrology” is to honor Professor Emeritus Jan W. Hopmans, University of California Davis, CA, as one of the pioneers in transdisciplinary research. In this introduction, the 12 articles collected for this special section are summarized, and their relationship to Hopmans’ work during his productive career is emphasized. The contributions reflect the depth and width of soil physics and hydrology and are aimed to stimulate transdisciplinary science to meet the existing challenges in agriculture and the environment.

Many viruses, such as severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and human immunodeficiency virus (HIV), have a structure consisting of spikes protruding from an underlying spherical surface. Research in biological and colloidal sciences has revealed secrets of why spikes exist on virus surfaces. Specifically, the spikes favor virus attachment on surfaces via receptor-specific interactions (RSIs), mediate the membrane fusion, and determine or change viral tropism. The spikes also facilitate viruses to approach surfaces before attachment and subsequently escape back to the environment if RSIs do not occur (i.e., easy come and easy go). Therefore, virus spikes create the paradox of having a large capacity for binding with cells (high infectivity) and meanwhile great mobility in the environment. Such structure-function relationships have important implications for the fabrication of virus-like particles and analogous colloids (e.g., hedgehog- and raspberry-like particles) for applications such as the development of antiviral vaccines and drug delivery.

Many studies have examined the role that conjugation plays in disseminating antibiotic resistance genes in bacteria. However, relatively little research has quantitively examined and modeled the dynamics of conjugation under growing and nongrowing conditions beyond a couple of hours. We therefore examined growing and nongrowing cultures of Escherichia coli over a 24-h period to understand the dynamics of bacterial conjugation in the presence and absence of antibiotics with pUUH239.2, an IncFII plasmid containing multiantibiotic- and metal-resistant genes. Our data indicate that conjugation occurs after E. coli cells divide and before they have transitioned to a nongrowing phase. The result is that there is only a small window of opportunity for E. coli to conjugate with pUUH239.2 under both growing and nongrowing conditions. Only a very small percentage of the donor cells likely are capable of even undergoing conjugation, and not all transconjugants can become donor cells due to molecular regulatory controls and not being in the correct growth phase. Once a growing culture enters stationary phase, the number of capable donor cells decreases rapidly and conjugation slows to produce a plateau. Published models did not provide accurate descriptions of conjugation under nongrowing conditions. We present here a modified modeling approach that accurately describes observed conjugation behavior under growing and nongrowing conditions. IMPORTANCE There has been growing interest in horizontal gene transfer of antibiotic resistance plasmids as the antibiotic resistance crisis has worsened over the years. Most studies examining conjugation of bacterial plasmids focus on growing cultures of bacteria for short periods, but in the environment, most bacteria grow episodically and at much lower rates than in the laboratory. We examined conjugation of an IncFII antibiotic resistance plasmid in E. coli under growing and nongrowing conditions to understand the dynamics of conjugation under which the plasmid is transferred. We found that conjugation occurs in a narrow time frame when E. coli is transitioning from a growing to nongrowing phase and that the conjugation plateau develops because of a lack of capable donor cells in growing cultures. From an environmental aspect, our results suggest that episodic growth in nutrient-depleted environments could result in more conjugation than sustained growth in a nutrient rich environment.

Drywells are widely used as managed aquifer recharge devices to capture stormwater runoff and recharge groundwater, but little research has examined the role of subsurface heterogeneity in hydraulic properties on drywell recharge efficiency. Numerical experiments were therefore conducted on a 2D‐axisymmetric domain using the HYDRUS (2D/3D) software to systematically study the influence of various homogenous soil types and subsurface heterogeneity on recharge from drywells under constant head conditions. The mean cumulative infiltration (μI) and recharge (μR) volumes increased with an increase in the saturated hydraulic conductivity ( K s ) for various homogeneous soils. Subsurface heterogeneity was described by generating ten stochastic realizations of soil hydraulic properties with selected standard deviation (σ), and horizontal (X) and vertical (Z) correlation lengths. After 365 days, values of μI, μR, and the radius of the recharge area increased with σ and X but decreased with Z. The value of μR was always smaller for a homogeneous than a heterogeneous domain. This indicates that recharge for a heterogeneous profile cannot be estimated with an equivalent homogeneous profile. The value of μR was always smaller than μI and correlations were highly non-linear due to vadose zone storage. Knowledge of only infiltration volume can, therefore, lead to misinterpretation of recharge efficiency, especially at earlier times. The arrival time of the wetting front at the bottom boundary (60 m) ranged from 21 to 317 days, with earlier times occurring for increasing σ and Z. The corresponding first arrival location can be 0.1–44 m away from the bottom releasing point of a drywell in the horizontal direction, with greater distances occurring for increasing σ and X. This knowledge is important to accurately assess drywell recharged performance, water quantity, and water quality.

Although nanoscale surface roughness has been theoretically demonstrated to be a crucial factor in the interaction of colloids and surfaces, little experimental research has investigated the influence of roughness on colloid or silver nanoparticle (AgNP) retention and release in porous media. This study experimentally examined AgNP retention and release using two sands with very different surface roughness properties over a range of solution pH and/or ionic strength (IS). AgNP transport was greatly enhanced on the relatively smooth sand in comparison to the rougher sand, at higher pH, and lower IS and fitted model parameters showed systematic changes with these physicochemical factors. Complete release of the retained AgNPs was observed from the relatively smooth sand when the solution IS was decreased from 40mM NaCl to deionized (DI) water and then the solution pH was increased from 6.5 to 10. Conversely, less than 40% of the retained AgNPs was released in similar processes from the rougher sand. These observations were explained by differences in the surface roughness of the two sands which altered the energy barrier height and the depth of the primary minimum with solution chemistry. Limited numbers of AgNPs apparently interacted in reversible, shallow primary minima on the smoother sand, which is consistent with the predicted influence of a small roughness fraction (e.g., pillar) on interaction energies. Conversely, larger numbers of AgNPs interacted in deeper primary minima on the rougher sand, which is consistent with the predicted influence at concave locations. These findings highlight the importance of surface roughness and indicate that variations in sand surface roughness can greatly change the sensitivity of nanoparticle transport to physicochemical factors such as IS and pH due to the alteration of interaction energy and thus can strongly influence nanoparticle mobility in the environment.

A thorough knowledge of the interaction energy between a hollow particle (HP) and a surface or between two HPs is critical to the optimization of HP-based products and assessing the environmental risks of HPs and HP-associated pollutants. The van der Waals (vdW) energy between a HP and a surface is often calculated by subtracting the vdW energies of the inner and outer HP geometries. In this study, we show that this subtraction method is only valid when the interior and exterior fluids are the same, for example, for water-filled HPs (WHPs) dispersed in an aqueous solution. Expressions were developed to calculate the vdW energies for HPs whose interiors were filled with air (AHPs). The vdW energies were then calculated between a planar surface and a spherical or cylindrical WHP and AHP, and between WHPs or AHPs. The vdW attraction between a surface and a WHP was decreased at large separation distances compared to solid particles, and this reduced the depth of the secondary minimum. In contrast, the vdW attraction for AHPs and a surface was significantly reduced at all separation distances, and even became repulsive for thin shells, and this inhibited both primary and secondary minimum interactions. The vdW attraction between WHPs decreased with increasing shell thicknesses, and this reduced aggregation in both primary and secondary minima. In contrast, aggregation of AHPs was increased in both minima with decreasing shell thicknesses because of an increase in vdW attraction. Our theoretical calculations show the evolution of vdW and total interaction energies for HPs with different interior fluids and shell thicknesses. These results help explain various experimental observations such as inhibited attachment and favorable aggregation for AHPs (e.g., carbon nanotubes) and favorable bubble coalescence.

The stability of carbon black nanoparticles (CB-NPs) was investigated in five different ecotoxicity test media for fish, daphnia, and algae (i.e., ISO Test water, Elendt M4 medium, OECD TG 201 medium, AAP medium, and Bold’s Basal Medium) in the presence and absence of Suwannee River Humic Acid (SRHA) as a function of time. Hydrodynamic size, particle sedimentation rate, and visual images of suspensions were analyzed for 96 h, and the SRHA concentration was varied from 0 to 10 mg/L. Zeta potential and water contact angle of CB-NP, and SRHA sorption to CB-NPs were also examined to complement stability analyses. CB-NPs always exhibited negative zeta potential regardless of media type and SRHA concentration, and became more negative in the presence of SRHA due to SRHA sorption. Moreover, CB-NPs were found to be hydrophobic in the absence of SRHA, whereas they became hydrophilic when SRHA was adsorbed. Stability test results showed that regardless of test media, the hydrodynamic size increased fast and the sedimentation rate was high in the absence of SRHA, indicating poor stability of the CB-NPs. Conversely, the presence of SRHA substantially increased the stability of CB-NPs over 96 h, regardless of the SRHA concentration and test media type. Stability trends in the presence and absence of SRHA were not consistent with predictions from classical Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. However, extended and modified DLVO theories, that also accounted for hydrophobic-attractive forces due to the inherent nature of CB-NPs and steric repulsive forces associated with the brush-like conformation of SRHA adsorbed to CB-NPs, better described CB-NPs’ stability in the absence and presence of SRHA, respectively.

The transport and retention behavior of polymer- (PVP-AgNP) and surfactant-stabilized (AgPURE) silver nanoparticles in carbonate-dominated saturated and unconsolidated porous media was studied at the laboratory scale. Initial column experiments were conducted to investigate the influence of chemical heterogeneity (CH) and nano-scale surface roughness (NR) arising from mixtures of clean, positively charged calcium carbonate sand (CCS), and negatively charged quartz sands. Additional column experiments were performed to elucidate the impact of CH and NR arising from the presence and absence of soil organic matter (SOM) on a natural carbonate-dominated aquifer material. The role of the nanoparticle capping agent was examined under all conditions tested in the column experiments. Nanoparticle transport was well described using a numerical model that facilitated blocking on one or two retention sites. Results demonstrate that an increase in CCS content in the artificially mixed porous medium leads to delayed breakthrough of the AgNPs, although AgPURE was much less affected by the CCS content than PVP-AgNPs. Interestingly, only a small portion of the solid surface area contributed to AgNP retention, even on positively charged CCS, due to the presence of NR which weakened the adhesive interaction. The presence of SOM enhanced the retention of AgPURE on the natural carbonate-dominated aquifer material, which can be a result of hydrophobic or hydrophilic interactions or due to cation bridging. Surprisingly, SOM had no significant impact on PVP-AgNP retention, which suggests that a reduction in electrostatic repulsion due to the presence of SOM outweighs the relative importance of other binding mechanisms. Our findings are important for future studies related to AgNP transport in shallow unconsolidated calcareous and siliceous sands.

Colloid transport and retention in porous media is a common phenomenon in nature. However, retention mechanisms are not fully revealed based on macroscale experimental observations. The pore-network model (PNM) is an effective method to account for the pore structure of a porous medium and provides a direct connection between pore-scale retention mechanisms and macroscale phenomenon. In this study, PNMs with cylindrical pore throats and spherical pore bodies are used to upscale water flow and colloid transport from pore- to macro-scales, taking into consideration surface deposition, hydrodynamic bridging, and straining. Numerical experiments were conducted to investigate the effect of colloid size, initial concentration, and flow velocity of pore water on colloid transport and retention behavior. Results show that hydrodynamic bridging and straining produce hyper-exponential retention profiles, whereas surface deposition due to nanoscale roughness and charge heterogeneity yields exponential or uniform retention profiles. Hydrodynamic bridging will not happen when the colloid size, initial concentration and flow velocity are lower than some threshold value (rp ≤ 500 nm, C0 ≤ 7.1 × 1014 Nc/m3, U0 ≤ 0.1 m/d under the conditions of this study). The relative importance of hydrodynamic bridging in comparison to surface deposition increases with an increase in the colloid size, initial concentration, and flow velocity. The PNM is a useful tool to discriminate different retention mechanisms and to predict colloid transport and retention behavior in 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.

Many arid and semi-arid regions of the world face challenges in maintaining the water quantity and quality needs of growing populations. A drywell is an engineered vadose zone infiltration device widely used for stormwater capture and managed aquifer recharge. To our knowledge, no prior studies have quantitatively examined virus transport from a drywell, especially in the presence of subsurface heterogeneity. Axisymmetric numerical experiments were conducted to systematically study virus fate from a drywell for various virus removal and subsurface heterogeneity scenarios under steady-state flow conditions from a constant head reservoir. Subsurface domains were homogeneous or had stochastic heterogeneity with selected standard deviation (σ) of lognormal distribution in saturated hydraulic conductivity and horizontal ([Formula: see text]) and vertical (Z) correlation lengths. Low levels of virus concentration tailing can occur even at a separation distance of 22 m from the bottom of the drywell, and 6-log(10) virus removal was not achieved when a small detachment rate [Formula: see text] is present in a homogeneous domain. Improved virus removal was achieved at a depth of 22 m in the presence of horizontal lenses (e.g., [Formula: see text] =10 m, [Formula: see text] =0.1 m, [Formula: see text] =1) that enhanced the lateral movement and distribution of the virus. In contrast, faster downward movement of the virus with an early arrival time at a depth of 22 m occurred when considering a vertical correlation in permeability ([Formula: see text] =1 m, [Formula: see text] =2 m, [Formula: see text] =1). Therefore, the general assumption of a 1.5–12 m separation distance to protect water quality may not be adequate in some instances, and site-specific microbial risk assessment is essential to minimize risk. Microbial water quality can potentially be improved by using an in situ soil treatment with iron oxides to increase irreversible attachment and solid-phase inactivation.

The surface element integration technique was used to systematically study Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energies/forces between hollow spherical particles (HPs) and a planar surface or two intercepting half planes under different ionic strength conditions. The inner and outer spheres of HPs were concentric (CHP) or in point contact (PHP). In comparison to a solid particle, the attractive van der Waals interaction was reduced with increasing inner radius of the CHP, but the reduction effect was less significant for the CHP at smaller separation distance. Increasing the inner radius for CHP therefore reduced the depths of the secondary minima, but had minor influence on the energy barrier heights and depths of the primary minima. Consequently, increasing inner radius reduced the potential for CHP retention in secondary minima, whereas did not influence the retention in primary minima. For PHP these interaction energy parameters and colloid retention depended on the orientation of the inner sphere relative to interacting surface. In particular, the van der Waals attraction was significantly reduced at all separation distances when the inner sphere was closest to the interacting surface, and this diminished retention in both secondary and primary minima. The PHP retention was similar to that of CHP when the inner sphere was farthest from the interaction surface. These orientation dependent interaction energies/forces resulted in directional bonds between PHPs and the formation of aggregates with contact points of the primary PHPs facing outward. The findings in this study have important implications for the design and utilization of HPs in soil remediation and colloid assembly.

All natural surfaces exhibit nanoscale roughness (NR) and chemical heterogeneity (CH) to some extent. Expressions were developed to determine the mean interaction energy between a colloid and a solid-water interface, as well as for colloid-colloid interactions, when both surfaces contain binary NR and CH. The influence of heterogeneity type, roughness parameters, solution ionic strength (IS), mean zeta potential, and colloid size on predicted interaction energy profiles was then investigated. The role of CH was enhanced on smooth surfaces with larger amounts of CH, especially for smaller colloids and higher IS. However, predicted interaction energy profiles were mainly dominated by NR, which tended to lower the energy barrier height and the magnitudes of both the secondary and primary minima, especially when the roughness fraction was small. This dramatically increased the relative importance of primary to secondary minima interactions on net electrostatically unfavorable surfaces, especially when roughness occurred on both surfaces and for conditions that produced small energy barriers (e.g., higher IS, lower pH, lower magnitudes in the zeta potential, and for smaller colloid sizes) on smooth surfaces. The combined influence of roughness and Born repulsion frequently produced a shallow primary minimum that was susceptible to diffusive removal by random variations in kinetic energy, even under electrostatically favorable conditions. Calculations using measured zeta potentials and hypothetical roughness properties demonstrated that roughness provided a viable alternative explanation for many experimental deviations that have previously been attributed to electrosteric repulsion (e.g., a decrease in colloid retention with an increase in solution IS; reversible colloid retention under favorable conditions; and diminished colloid retention and enhanced colloid stability due to adsorbed surfactants, polymers, and/or humic materials).

Saturated soil column experiments were conducted to investigate the transport, retention, and release behavior of a low concentration (1mgL-1) of functionalized 14C-labeled multi-walled carbon nanotubes (MWCNTs) in a natural soil under various solution chemistries. Breakthrough curves (BTCs) for MWCNTS exhibited greater amounts of retardation and retention with increasing solution ionic strength (IS) or in the presence of Ca2+ in comparison to K+, and retention profiles (RPs) for MWCNTs were hyper-exponential in shape. These BTCs and RPs were well described using the advection-dispersion equation with a term for time- and depth-dependent retention. Fitted values of the retention rate coefficient and the maximum retained concentration of MWCNTs were higher with increasing IS and in the presence of Ca2+ in comparison to K+. Significant amounts of MWCNT and soil colloid release was observed with a reduction of IS due to expansion of the electrical double layer, especially following cation exchange (when K+ displaced Ca2+) that reduced the zeta potential of MWCNTs and the soil. Analysis of MWCNT concentrations in different soil size fractions revealed that >23.6% of the retained MWCNT mass was associated with water-dispersible colloids (WDCs), even though this fraction was only a minor portion of the total soil mass (2.38%). More MWCNTs were retained on the WDC fraction in the presence of Ca2+ than K+. These findings indicated that some of the released MWCNTs by IS reduction and cation exchange were associated with the released clay fraction, and suggests the potential for facilitated transport of MWCNT by WDCs.

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 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.

Contamination of groundwater by enteric pathogens has commonly been associated with disease outbreaks. Proper management and treatment of pathogen sources are important prerequisites for preventing groundwater contamination. However, non-point sources of pathogen contamination are frequently difficult to identify, and existing approaches for pathogen detection are costly and only provide semi-quantitative information. Microbial indicators that are readily quantified often do not correlate with the presence of pathogens. Pathogens of emerging concern and increasing detections of antibiotic resistance among bacterial pathogens in groundwater are topics of growing concern. Adequate removal of pathogens during soil passage is therefore critical for safe groundwater extraction. Processes that enhance pathogen transport (e.g., high velocity zones and preferential flow) and diminish pathogen removal (e.g., reversible retention and enhanced survival) are of special concern because they increase the risk of groundwater contamination, but are still incompletely understood. Improved theory and modeling tools are needed to analyze experimental data, test hypotheses, understand coupled processes and controlling mechanisms, predict spatial and/or temporal variability in model parameters and uncertainty in pathogen concentrations, assess risk, and develop mitigation and best management approaches to protect groundwater.

Our understanding of colloidal biochar (CB) transport and release is largely unknown in environments with transient chemical conditions, e.g., ionic strength (IS), pH, and especially humic acid (HA). In this study, column experiments were conducted to investigate CB transport and retention in the presence and absence of HA, and CB release under transient IS and pH conditions in saturated sand. Step reductions in solution IS from 25 to 0.01 mM produced significant release peaks of CB due to a reduction in the depth of the primary minima on rough surfaces with small energy barriers. In contrast, step increases of solution pH from 4 to 10 only slightly increased CB release presumably due to the strong buffering capacity of CB. The CB retention was diminished by HA during the deposition phase. However, the release of CB with transients in IS and pH was not influenced much when deposition occurred in the presence of HA. These observations indicate that HA increased the energy barrier during deposition but did not have a large influence on the depth of the interacting minimum during transient release. Potential explanations for these effects of HA on CB retention and transient release include enhanced repulsive electrostatic interactions and/or altering of surface roughness properties. Our findings indicated that the release of retained CB is sensitive to transient IS conditions, but less dependent on pH increases and CB deposition in the presence of HA. This information is needed to quantify potential benefits and/or adverse risks of mobile CB in natural environments.

Drywells are increasingly used to capture stormwater runoff for surface infiltration and aquifer recharge, but little research has examined the role of ubiquitous subsurface heterogeneity in hydraulic properties on drywell performance. Numerical experiments were therefore conducted using the HYDRUS (2D/3D) software to systematically study the influence of subsurface heterogeneity on drywell infiltration. Subsurface heterogeneity was described deterministically by defining soil layers or lenses, or by generating stochastic realizations of soil hydraulic properties with selected variance (σ) and horizontal (X) and vertical (Z) correlation lengths. The infiltration rate increased when a high permeability layer/lens was located at the bottom of the drywell, and had larger vertical and especially horizontal dimensions. Furthermore, the average cumulative infiltration (I) for 100 stochastic realizations of a given subsurface heterogeneity increased with σ and X, but decreased with Z. This indicates that the presence of many highly permeable, laterally extending lenses provides a larger surface area for enhanced infiltration than the presence of isolated, highly permeable lenses. The ability to inversely determine soil hydraulic properties from numerical drywell infiltration results was also investigated. The hydraulic properties and the lateral extension of a highly permeable lens could be accurately determined for certain idealized situations (e.g., simple layered profiles) using constant head tests. However, variability in soil hydraulic properties could not be accurately determined for systems that exhibited more realistic stochastic heterogeneity. In this case, the heterogeneous profile could be replaced with an equivalent homogeneous profile and values of an effective isotropic saturated conductivity (Ks) and the shape parameter in the soil water retention function (α) could be inversely determined. The average value of Ks for 100 stochastic realizations showed a similar dependency to I on σ, X, and Z. Whereas, the average value of α had large confidence interval for soil heterogeneity parameters and played a secondary role in drywell infiltration. This research provides valuable insight on the selection of site, design, installation, and long-term performance of a drywell.

Natural soils have frequently been considered to decrease the mobility of engineered nanoparticles (NPs) in comparison to quartz sand due to the presence of colloids that provide additional retention sites. In contrast, this study demonstrates that the transport and release of silver nanoparticles (AgNPs) in sandy clay loam and loamy sand soils were enhanced in the presence of soil colloids that altered soil grain surface roughness. In particular, we found that the retention of AgNPs in purified soils (colloid-free and acid-treated) was more pronounced than in raw (untreated) soils or soils treated to remove organic matter (H2O2 or 600 °C treated). Chemical analysis and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy demonstrated that the grain surfaces of raw and organic matter-removed soils were abundant with metal oxides and colloids compared to purified soil. Column transport and release experimental results, SEM images, and interaction energy calculations revealed that a significant amount of concave locations on purified soils hindered AgNP release by diffusion or ionic strength (IS) reduction due to deep primary energy minima. Conversely, AgNPs that were retained in soils in the presence of soil colloids were more susceptible to release under IS reduction because the primary minimum was shallow on the tops of convex locations created by attached soil colloids. Additionally, a considerable fraction of retained AgNPs in raw soil was released after cation exchange followed by IS reduction, while no release occurred for purified soil under the same conditions. The AgNP release was highly associated with soil colloids and co-transport of AgNPs and soil colloids was observed. Our work is the first to show that the presence of soil colloids can inhibit deposition and facilitate the release and co-transport of NPs in soil by alteration of the soil grain surface morphology and shallow primary minimum interactions.

The concentration of nonionic surfactants like Triton X-100 (TX100) can influence the transport and fate of emerging contaminants (e.g., carbon nanotubes) in porous media, but limited research has previously addressed this issue. This study investigates the co-transport of functionalized multi-walled carbon nanotubes (MWCNTs) and various concentrations of TX100 in saturated quartz sand (QS). Batch experiments and molecular dynamics simulations were conducted to investigate the interactions between TX100 and MWCNTs. Results indicated that the concentration ratio of MWCNTs and TX100 strongly influences the dispersion of MWCNTs and interaction forces between MWCNTs and QS during the transport. Breakthrough curves of MWCNTs and TX100 and retention profiles of MWCNTs were determined and simulated in column studies. MWCNTs strongly enhanced the retention of TX100 in QS due to the high affinity of TX100 for MWCNTs. Conversely, the concentration of TX100 had a non-monotonic impact on MWCNT retention. The maximum transport of MWCNTs in the QS occurred at an input concentration of TX100 that was lower than the critical micelle concentration. This suggests that the relative importance of factors influencing MWCNTs changed with TX100 sorption. Results from interaction energy calculations and modeling of competitive blocking indicate that the predictive ability of interaction energy calculations and colloid filtration theory may be lost because TX100 mainly altered intermolecular forces between the MWCNT and porous media. This study provides new insights into the co-transport of surfactants and MWCNTs in porous media, which can be useful for environmental applications and risk management.

Transport and retention behavior of multi-walled carbon nanotubes (MWCNTs) was studied in mixtures of negatively charged quartz sand (QS) and positively charged goethite-coated sand (GQS) to assess the role of chemical heterogeneity. The linear equilibrium sorption model provided a good description of batch results, and the distribution coefficients (KD) drastically increased with the GQS fraction that was electrostatically favorable for retention. Similarly, retention of MWCNTs increased with the GQS fraction in packed column experiments. However, calculated values of KD on GQS were around 2 orders of magnitude smaller in batch than packed column experiments due to differences in lever arms associated with hydrodynamic and adhesive torques at microscopic roughness locations. Furthermore, the fraction of the sand surface area that was favorable for retention (Sf) was much smaller than the GQS fraction because nanoscale roughness produced shallow interactions that were susceptible to removal. These observations indicate that only a minor fraction of the GQS was favorable for MWCNT retention. These same observations held for several different sand sizes. Column breakthrough curves were always well described using an advective-dispersive transport model that included retention and blocking. However, depth-dependent retention also needed to be included to accurately describe the retention profile when the GQS fraction was small. Results from this research indicate that roughness primarily controlled the retention of MWCNTs, although goethite surfaces played an important secondary role.