Significance of Non-DLVO Interactions on the Co-Transport of Functionalized Multiwalled Carbon Nanotubes and Soil Nanoparticles in Porous Media.

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.

Colloid Interaction Energies for Surfaces with Steric Effects and Incompressible and/or Compressible Roughness.

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.

Comparison of recharge from drywells and infiltration basins: A modeling study.

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.

The Conjugation Window in an Escherichia coli K-12 Strain with an IncFII Plasmid.

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.

Groundwater Recharge from Drywells Under Constant Head Conditions.

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 (Ks ) 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 21-317 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.

Nanobubble Retention in Saturated Porous Media under Repulsive van der Waals and Electrostatic Conditions.

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 nanoscale roughness on the glass beads that significantly lowered the energy barrier and localized attractive charge heterogeneity and/or hydrophobic interactions. In contrast to Na+, adsorbed Ca2+ ions produced charge heterogeneity that enhanced NB retention and inhibited release with IS reduction.

Drywell infiltration and hydraulic properties in heterogeneous soil profiles.

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.

DLVO Interaction Energies for Hollow Particles: The Filling Matters.

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.

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 drywells for stormwater management and enhanced aquifer recharge.

Drywells are increasingly used for stormwater management and enhanced aquifer recharge, but only limited research has quantitatively determined the performance of drywells. Numerical and field scale experiments were, therefore, conducted to improve our understanding and ability to characterize the drywell behavior. In particular, HYDRUS (2D/3D) was modified to simulate transient head boundary conditions for the complex geometry of the Maxwell Type IV drywell; i.e., a sediment chamber, an overflow pipe, and the variable geometry and storage of the drywell system with depth. Falling-head infiltration experiments were conducted on drywells located at the National Training Center in Fort Irwin, California (CA) and a commercial complex in Torrance, CA to determine in situ soil hydraulic properties (the saturated hydraulic conductivity, Ks , and the retention curve shape parameter, α) for an equivalent uniform soil profile by inverse parameter optimization. A good agreement between the observed and simulated water heights in wells was obtained for both sites as indicated by the coefficient of determination 0.95-0.99-%, unique parameter fits, and small standard errors. Fort Irwin and Torrance drywells had very distinctive soil hydraulic characteristics. The fitted value of Ks =1.01 × 10-3 m min-1 at the Torrance drywell was consistent with the sandy soil texture at this site and the default value for sand in the HYDRUS soil catalog. The drywell with this Ks = 1.01 × 10-3 m min-1 could easily infiltrate predicted surface runoff from a design rain event (∼51.3 m3) within 5760 min (4 d). In contrast, the fitted value of Ks=2.25 × 10-6 m min-1 at Fort Irwin was very low compared to the Torrance drywell and more than an order of magnitude smaller than the default value reported in the HYDRUS soil catalog for sandy clay loam at this site, likely due to clogging. These experiments and simulations provide useful information to characterize effective soil hydraulic properties in situ, and to improve the design of drywells for enhanced recharge.

Contributions of Nanoscale Roughness to Anomalous Colloid Retention and Stability Behavior.

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).

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).

Do Goethite Surfaces Really Control the Transport and Retention of Multi-Walled Carbon Nanotubes in Chemically Heterogeneous Porous Media?

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.

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.

Microbial Transport and Fate in the Subsurface Environment: Introduction to the Special Section.

Microorganisms constitute an almost exclusive form of life in the earth's subsurface environment (not including caves), particularly at depths exceeding the soil horizon. While of broad interest to ecology and geology, scientific interest in the fate and transport of microorganisms, particularly those introduced through the anthropogenic environment, has focused on understanding the subsurface environment as a pathway for human pathogens and on optimizing the use of microbial organisms for remediation of potable groundwater. This special section, inspired by the 2014 Ninth International Symposium for Subsurface Microbiology, brings together recent efforts to better understand the spatiotemporal occurrence of anthropogenic microbial groundwater contamination and the fate and transport of microbes in the subsurface environment: in soils, deep unsaturated zones, and within aquifer systems. Work includes field reconnaissance, controlled laboratory studies to improve our understanding of specific fate and transport processes, and the development and application of improved mechanistic understanding of microbial fate and transport processes in the subsurface environment. The findings confirm and also challenge the limitations of our current understanding of highly complex microbial fate and transport processes across spatiotemporal scales in the subsurface environment; they also add to the increasing knowledge base to improve our ability to protect drinking water resources and perform in situ environmental remediation.

Langmuirian Blocking of Irreversible Colloid Retention: Analytical Solution, Moments, and Setback Distance.

Soil and aquifer materials have a finite capacity for colloid retention. Blocking of the limited number of available retention sites further decreases the rate of retention with time and enhances risks (e.g., pathogens or colloid-associated contaminants) or benefits (e.g., remediation by microorganisms or nanoparticles) of colloid migration. Our objective was to use a straightforward procedure, based on variable transformation and Laplace transform, to solve the problem of advective colloid transport with irreversible retention and Langmuirian blocking for a pulse-type condition. Formulas for the mean breakthrough time and retardation factor were obtained using zero- and first-order time moments of the breakthrough curves. Equations for the time and position (setback distance) for a particular colloid concentration were obtained from this information. D21 g breakthrough curves and retention profiles in fine sand at four ionic strengths were well described by the model when parameters were optimized. Illustrative simulations demonstrated that blocking becomes more important for smaller retention capacity () and for larger retention rate coefficient (), input concentration (), and pulse duration. Blocking tended to delay colloid arrival time at a particular location relative to a conservative tracer, and produced larger setback distances for smaller and /.

Release of E. coli D21g with transients in water content.

Transients in water content are well-known to mobilize microorganisms that are retained in the vadose zone. However, there is no consensus on the relative importance of drainage and imbibition events on microorganism release. To overcome this limitation, we have systematically studied the release of Escherichia coli D21g during cycles of drainage and imbibition under various solution chemistry and initial conditions. Results from these column studies revealed the influence of imbibition and drainage on D21g release. In particular, imbibition efficiently released cells from the air-water interface (AWI) that were initially retained under steady-state unsaturated conditions by expansion of water films and destruction of the AWI. Conversely, significant release and transport of cells during drainage only occurred below a critical water saturation (water film thickness). In this case, a fraction of the cells that were initially retained on the solid-water interface (SWI) partitioned into the mobile aqueous phase and the AWI as the receding water film thickness decreased during drainage. The efficiency of cell release from the SWI during drainage was much less than for the AWI during imbibition. Cycles of drainage and imbibition removed cells from the SWI and the AWI, respectively. However, the peak concentration and amount of cells that were released increased with the number of retained cells and the amount of drainage and imbibition, and decreased with the number of drainage and imbibition cycles. Release of cells during drainage and imbibition was found to be more pronounced in the presence of a weak secondary minimum when the ionic strength (IS) was 5 mM NaCl. Increases in the solution IS decreased the influence of water transients on release, especially during drainage. Complete recovery of the retained cells could be achieved using both IS reduction and cycles of drainage and imbibition, even when the cells were retained under favorable attachment conditions. In general, cell release was more pronounced with transients in water content than transients in IS when the IS ≥ 5 mM.

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.

Dual roles of goethite coating on the transport of plastic nanoparticles in heterogeneous porous media: The significance of collector surface roughness.

This study systematically examines the roles of positive goethite on the retention and release of negative plastic nanoparticles (PSNPs) with different surface functional groups (Blank, -COOH, and -NH2). It provides the first evidence for the dual roles of goethite coatings on colloid transport; e.g., increased transport caused by surface morphology modification or decreased transport due to increased surface roughness and charge heterogeneity. Although previous work has shown that goethite-coated sand increases the retention of negative colloids, this work demonstrates that collector surface roughness can also reduce the retention of PSNPs due to increased interaction energy profiles. Nonmonotonic retention of all the different functionalized PSNPs was observed in goethite-coated rough sand, and the magnitude of variations was contingent on the PSNP functionalization, the solution ionic strength (IS), and the goethite coating. The release of PSNPs with IS decrease (phase I) and pH increase (phase II) varied significantly due to differences in energy barriers to detachment, e.g., release in phase I was inhibited in both goethite-coated sands, whereas release in phase II was enhanced in coated smooth sand but completely inhibited in rough sand. The findings of this study provide innovative insight into transport mechanisms for colloidal and colloid-associated contaminants.

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.