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.

On the Use of Mechanistic Soil-Plant Uptake Models: A Comprehensive Experimental and Numerical Analysis on the Translocation of Carbamazepine in Green Pea Plants.

Food contamination is a major worldwide risk for human health. Dynamic plant uptake of pollutants from contaminated environments is the preferred pathway into the human and animal food chain. Mechanistic models represent a fundamental tool for risk assessment and the development of mitigation strategies. However, difficulty in obtaining comprehensive observations in the soil-plant continuum hinders their calibration, undermining their generalizability and raising doubts about their widespread applicability. To address these issues, a Bayesian probabilistic framework is used, for the first time, to calibrate and assess the predictive uncertainty of a mechanistic soil-plant model against comprehensive observations from an experiment on the translocation of carbamazepine in green pea plants. Results demonstrate that the model can reproduce the dynamics of water flow and solute reactive transport in the soil-plant domain accurately and with limited uncertainty. The role of different physicochemical processes in bioaccumulation of carbamazepine in fruits is investigated through Global Sensitivity Analysis, which shows how soil hydraulic properties and soil solute sorption regulate transpiration streams and bioavailability of carbamazepine. Overall, the analysis demonstrates the usefulness of mechanistic models and proposes a comprehensive numerical framework for their assessment and use.

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.

Chitinase Chit62J4 Essential for Chitin Processing by Human Microbiome Bacterium Clostridium paraputrificum J4.

Commensal bacterium Clostridium paraputrificum J4 produces several extracellular chitinolytic enzymes including a 62 kDa chitinase Chit62J4 active toward 4-nitrophenyl N,N'-diacetyl-ß-d-chitobioside (pNGG). We characterized the crude enzyme from bacterial culture fluid, recombinant enzyme rChit62J4, and its catalytic domain rChit62J4cat. This major chitinase, securing nutrition of the bacterium in the human intestinal tract when supplied with chitin, has a pH optimum of 5.5 and processes pNGG with Km = 0.24 mM and kcat = 30.0 s-1. Sequence comparison of the amino acid sequence of Chit62J4, determined during bacterial genome sequencing, characterizes the enzyme as a family 18 glycosyl hydrolase with a four-domain structure. The catalytic domain has the typical TIM barrel structure and the accessory domains-2x Fn3/Big3 and a carbohydrate binding module-that likely supports enzyme activity on chitin fibers. The catalytic domain is highly homologous to a single-domain chitinase of Bacillus cereus NCTU2. However, the catalytic profiles significantly differ between the two enzymes despite almost identical catalytic sites. The shift of pI and pH optimum of the commensal enzyme toward acidic values compared to the soil bacterium is the likely environmental adaptation that provides C. paraputrificum J4 a competitive advantage over other commensal bacteria.

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.

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.

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.

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.

Retention and remobilization of stabilized silver nanoparticles in an undisturbed loamy sand soil.

Column experiments were conducted with undisturbed loamy sand soil under unsaturated conditions (around 90% saturation degree) to investigate the retention of surfactant stabilized silver nanoparticles (AgNPs) with various input concentration (Co), flow velocity, and ionic strength (IS), and the remobilization of AgNPs by changing the cation type and IS. The mobility of AgNPs in soil was enhanced with decreasing solution IS, increasing flow rate and input concentration. Significant retardation of AgNP breakthrough and hyperexponential retention profiles (RPs) were observed in almost all the transport experiments. The retention of AgNPs was successfully analyzed using a numerical model that accounted for time- and depth-dependent retention. The simulated retention rate coefficient (k1) and maximum retained concentration on the solid phase (Smax) increased with increasing IS and decreasing Co. The high k1 resulted in retarded breakthrough curves (BTCs) until Smax was filled and then high effluent concentrations were obtained. Hyperexponential RPs were likely caused by the hydrodynamics at the column inlet which produced a concentrated AgNP flux to the solid surface. Higher IS and lower Co produced more hyperexponential RPs because of larger values of Smax. Retention of AgNPs was much more pronounced in the presence of Ca(2+) than K(+) at the same IS, and the amount of AgNP released with a reduction in IS was larger for K(+) than Ca(2+) systems. These stronger AgNP interactions in the presence of Ca(2+) were attributed to cation bridging. Further release of AgNPs and clay from the soil was induced by cation exchange (K(+) for Ca(2+)) that reduced the bridging interaction and IS reduction that expanded the electrical double layer. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, and correlations between released soil colloids and AgNPs indicated that some of the released AgNPs were associated with the released clay fraction.

Estimating the impact of vadose zone heterogeneity on agricultural managed aquifer recharge: A combined experimental and modeling study.

Agricultural managed aquifer recharge (Ag-MAR) is a promising approach to replenish groundwater resources using flood water and cropland as spreading grounds. However, site selection, particularly the layering of sediment deposits in the subsurface, can greatly influence Ag-MAR efficacy as it controls water flow and solute transport in the vadose zone. In this study, we use the HYDRUS-1D software to simulate water flow and solute transport from the land surface to the groundwater table in three vadose zone profiles (LS, MS, HS) characterized by differing fractions of sand (44 %, 47 %, and 64 %). For each profile, the single- and dual-porosity models (i.e., considering or not nonequilibrium water flow and solute transport) were calibrated using observed surface ponding, soil water content, and KBr breakthrough data. Water flow and bromide transport in the profile with the lowest sand fraction (LS) were best captured using the model that considered both preferential flow and nonequilibrium bromide transport. Water flow and bromide transport in the profile with the highest sand fraction (HS) was best simulated with the model that considered preferential flow and equilibrium bromide transport. Uniform water flow and nonequilibrium bromide transport provided the best fit for the third profile (MS). The degree of preferential flow was highest in the profile with the largest sand fraction (HS), which also showed the largest flow velocities compared to the profiles with lower sand amounts (LS and MS). Preferential flow did not significantly impact the overall water balance (within 3 %), but caused a significant decrease in vadose zone travel times (bromide) by up to 38 %, relative to a single-porosity model fit. Recharge efficiency varied between 88 % and 90 %, while the average travel times from the soil surface to groundwater varied up to 119 % (from 3.6 to 7.9 days) between the three sites. This study demonstrates that similar recharge efficiency can be achieved at sites with differing soil texture profiles, but subsurface heterogeneity can substantially affect contaminant transport processes and their travel times.

Comparison of methods to estimate air-water interfacial areas for evaluating PFAS transport in the vadose zone.

When performing calculations or numerical simulations for the fate and transport of PFAS and other surface-active solutes in the vadose zone, accurately representing the relationship between the area of the air-water interfaces (Aaw) as a function of water saturation (Sw), and changes in that relationship resulting from changes in soil texture, are equally important as accurately characterizing interfacial adsorption coefficients and the concentration dependence for PFAS solutes. This is true because the magnitude of the Aaw directly governs the degree of air-water interfacial adsorption, which contributes to the transport retardation of these solutes within unsaturated porous media. Herein, a well-known thermodynamic-based model for predicting the Aaw-Sw relationship is evaluated through comparisons to literature data collected using various measurement techniques for model sands and a limited number of soils using data collected from the current published literature. This predictive model, herein termed the Leverett thermodynamic model (LTM), relies on the characterization of the soil-water retention curve (SWRC) for a given soil, using the van Genuchten (VG) equation for the pressure head-vs-Sw relationship. Therefore, methods to estimate the VG equation parameters are also compared as to the Aaw-Sw relationships predicted. Comparisons suggest that the LTM provides the best estimate of the actual Aaw-Sw relationships for water containing non-surface-active solutes. Because PFAS solutes are also surface-active, Aaw measurement methods utilizing surface-active tracers are considered to provide the most accurate representation of the Aaw-Sw relationship for these solutes. Differences between Aaw-Sw relationships derived from tracer methods and the LTM are described in relation to media surface roughness effects. Based on the available literature data, a practical empirical model is proposed to adjust the LTM prediction to account for the effects of surface roughness on the magnitude of the Aaw for surface-active solutes. Finally, example retention calculations are performed to demonstrate the sensitivity of the predicted Aaw-Sw relationship on the vadose zone transport of of a representative PFAS, perfluorooctane sulfonate.

A novel multiscale biophysical model to predict the fate of ionizable compounds in the soil-plant continuum.

Soil pollution from emerging contaminants poses a significant threat to water resources management and food production. The development of numerical models to describe the reactive transport of chemicals in both soil and plant is of paramount importance to elaborate mitigation strategies. To this aim, in the present study, a multiscale biophysical model is developed to predict the fate of ionizable compound in the soil-plant continuum. The modeling framework connects a multi-organelles model to describe processes at the cell level with a semi-mechanistic soil-plant model, which includes the widely used Richards-based solver, HYDRUS. A Bayesian probabilistic framework is used to calibrate and assess the capability of the model in reproducing the observations from an experiment on the translocation of five pharmaceuticals in green pea plants. Results show satisfactory fitting performance and limited predictive uncertainty. The subsequent validation with the cell model indicates that the estimated soil-plant parameters preserve a physically realistic meaning, and their calibrated values are comparable with the existing literature values, thus confirming the overall reliability of the analysis. Model results further suggest that pH conditions in both soil and xylem play a crucial role in the uptake and translocation of ionizable compounds.

Simulated leaching of PFAS from land-applied municipal biosolids at agricultural sites.

Biosolids are an important resource for agricultural practice but have recently received increased focus as a potential source of per- and polyfluoroalkyl substances (PFAS) in the environment. Few studies have investigated the transport of PFAS through the unsaturated zone under conditions relevant to biosolids application sites. Herein, the unsaturated flow and transport model HYDRUS is used to evaluate the leaching of per- and polyfluoroalkyl substances (PFAS) from land-applied biosolids used in agricultural practice to determine the impacts of PFAS leaching on underlying groundwater resources. This numerical case study was based on conditions and operations at two test sites in central Illinois where biosolids were applied at agronomic rates and where PFAS contents and desorption characteristics were previously characterized. Each site possessed different vadose zone soil textural heterogeneity. Simulations were performed under actual present-day meteorological conditions and extended 150 years beyond the initial biosolids application. These long-term simulations demonstrate how soil equilibrium sorption/desorption processes within the biosolids-amended surface soils effectively control the transport rate of individual PFAS to groundwater. Air-water interfacial (AWI) adsorption, which is sometimes considered to be a significant source of PFAS retention in vadose zone soils, was observed to have minimal impacts on PFAS leaching rates within the biosolids-amended surface soils at these sites. Additionally, the impact of AWI adsorption was found to be most significant for PFAS transport within the underlying vadose zone soils when these soils were more texturally homogeneous and considerably less significant within the texturally heterogeneous soils represented herein. The results of multiple long-term simulations were used to develop an empirical equation that relates predicted maximum PFAS pore-water concentrations reaching the saturated zone with changes in PFAS concentrations in the biosolids-amended soil for various biosolids re-application events. This approach is shown to be very useful in developing site-specific PFAS soil screening levels and/or maximum leachate levels for PFAS in support of establishing best management practices (BMPs) for land application of biosolids.

Virus transport from drywells under constant head conditions: A modeling study.

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 (X) 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-log10 virus removal was not achieved when a small detachment rate (kd1=1 × 10⁻5 min⁻¹) 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., X=10 m, Z=0.1 m, σ=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 (X=1 m, Z=2 m, σ=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.

Evaluating soil nitrate dynamics in an intercropping dripped ecosystem using HYDRUS-2D.

The competition mechanisms between crop species for water and nutrients, especially nitrate (NO3-N), in intercropping ecosystems are still poorly understood. Therefore, an experiment involving high (300 kg ha-1 for corn and 250 kg ha-1 for tomato), medium (210 kg ha-1 for corn and 175 kg ha-1 for tomato), and low (150 kg ha-1 for corn and 125 kg ha-1 for tomato) N-fertilizer applications (HF, MF, LF, respectively) was conducted in the corn and tomato intercropping ecosystem during 2014 (a calibration period for modeling) and 2015 (a validation period for modeling). The modified HYDRUS-2D code was used to analyze soil NO3-N concentrations (SNC) in the middle between corn rows (Pc), between corn and tomato rows (Pb), and between tomato rows (Pt), NO3-N exchange in the horizontal direction between different regions, NO3-N leaching from the corn, the bare, and the tomato region, and N uptake by crops. Simulated SNCs were in good agreement with measurements, with RMSE, NSE, and MRE of 0.01-0.06 mg cm-3, 0.75-0.98, and 8.7-19.1%, respectively, during the validation period (2015). Average SNCs in the 0-40 cm soil layer were different between Pc, Pt, and Pb. Intensive NO3-N exchange in the horizontal direction occurred during the second stage (Day After Sowing [DAS] 37-113 in 2014; DAS 29-120 in 2015). NO3-N exchange between the corn and bare regions was lower than between the tomato and bare regions due to smaller concentration gradients. However, in the vertical direction, NO3-N leaching from the corn region in both years was 4.1 and 8.8 times larger, respectively, than from the tomato region under HF since NO3-N mainly moved from the tomato region to the corn region. Our results reveal the competition between corn and tomato for N and provide a rationale for formulating and optimizing different fertilizer regimes for different crops in the intercropping ecosystem.

Evidence for the critical role of nanoscale surface roughness on the retention and release of silver nanoparticles in porous media.

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 40 mM 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.