Tanapon Phenrat

Estimating Attachment of Nano- and Submicrometer-particles Coated with Organic Macromolecules in Porous Media: Development of an Empirical Model

Assessing the environmental transport and fate of manufactured nanoparticles (NPs) and potential exposure risks requires models for predicting attachment of NPs coated with organic macromolecules in porous media. The objective of this study was to determine the properties of coated nanoparticles that control their attachment behavior. Deposition data for a variety of nanoparticles with different types of anionic organic coatings, including natural organic matter (NOM)-coated latex and hematite nanoparticles, and poly(styrenesulfonate)-, carboxymethylcellulose-, and polyaspartate-coated hematite and titanium dioxide nanoparticles (80 data points), were used to develop an empirical correlation between measurable NP properties and their sticking coefficient (alpha) under a variety of electrolyte conditions and flow velocities. Available semiempirical correlations used to predict the attachment efficiency of electrostatically stabilized (uncoated) NPs overestimate the attachment efficiency of nanoparticles coated with NOM or synthetic polyelectrolytes because the correlations neglect electrosteric repulsions and the decreased friction afforded by such coatings that can inhibit attachment to surfaces. Adding a dimensionless parameter (N(LEK)) representing steric repulsions and the decreased friction force afforded by adsorbed NOM or anionic polyelectrolytes in the correlation significantly improves the correlation. This establishes the importance of including the adsorbed NOM- or polyelectrolyte layer properties for estimating the attachment efficiency of NPs in the environment. The form of N(LEK) suggests that limiting unintended transport and exposure to NPs could be achieved by using coatings with the smallest adsorbed mass and polymer density, shortest extended layer thickness, and largest molecular weight that would still afford the desired functionality of the coating.

Effect of kaolinite, silica fines and pH on transport of polymer-modified zero valent iron nano-particles in heterogeneous porous media.

Polymer coatings on nano-sized remediation agents and subsurface heterogeneity will affect their transport, likely in a pH-dependent manner. The effect of pH on the aggregation of polymer-coated nanoscale zerovalent iron (nZVI) and its deposition onto sand and clay (kaolinite) surfaces was studied. nZVI coatings included a high molecular weight (90 kg/mol) strong polyanion, poly(methacrylic acid)-b-(methy methacrylate)-b-(styrenesulfonate) (PMAA-PMMA-PSS) and a low molecular weight (2.5 kg/mol) weak polyanion, polyaspartate. Aggregation and deposition increased with decreasing pH for both polyelectrolytes. The extent was greater for the low MW polyaspartate coated nZVI. Enhanced deposition at lower pH was indicated because the elutability of polyaspartate-modified hematite (which did not aggregate) also decreased at lower pH. The greater deposition onto clay minerals compared to similar sized silica fines is attributed to charge heterogeneity on clay mineral surfaces, which is sensitive to pH. Heteroaggregation between kaolinite particles and nZVI over the pH range 6-8 confirmed this assertion. Excess unadsorbed polyelectrolyte in solution (100mg/L) enhanced the transport of modified nZVI by minimizing aggregation and deposition onto sand and clay. These results indicate that site physical and chemical heterogeneity must be considered when designing an nZVI emplacement strategy.

Hydrophobic interactions increase attachment of gum Arabic- and PVP-coated Ag nanoparticles to hydrophobic surfaces.

A fundamental understanding of attachment of surface-coated nanoparticles (NPs) is essential to predict the distribution and potential risks of NPs in the environment. Column deposition studies were used to examine the effect of surface-coating hydrophobicity on NP attachment to collector surfaces in mixtures with varying ratios of octadecylichlorosilane (OTS)-coated (hydrophobic) glass beads and clean silica (hydrophilic) glass beads. Silver nanoparticles (AgNPs) coated with organic coatings of varying hydrophobicity, including citrate, polyvinylpyrrolidone (PVP), and gum arabic (GA), were used. The attachment efficiencies of GA and PVP AgNPs increased by 2- and 4-fold, respectively, for OTS-coated glass beads compared to clean glass beads. Citrate AgNPs showed no substantial change in attachment efficiency for hydrophobic compared to hydrophilic surfaces. The attachment efficiency of PVP-, GA-, and citrate-coated AgNPs to hydrophobic collector surfaces correlated with the relative hydrophobicity of the coatings. The differences in the observed attachment efficiencies among AgNPs could not be explained by classical DLVO, suggesting that hydrophobic interactions between AgNPs and OTS-coated glass beads were responsible for the increase in attachment of surface-coated AgNPs with greater hydrophobicity. This study indicates that the overall attachment efficiency of AgNPs will be influenced by the hydrophobicity of the NP coating and the fraction of hydrophobic surfaces in the environment.

Transport and deposition of polymer-modified Fe0 nanoparticles in 2-D heterogeneous porous media: effects of particle concentration, Fe0 content, and coatings.

Concentrated suspensions of polymer-modified Fe(0) nanoparticles (NZVI) are injected into heterogeneous porous media for groundwater remediation. This study evaluated the effect of porous media heterogeneity and the dispersion properties including particle concentration, Fe(0) content, and adsorbed polymer mass and layer thickness which are expected to affect the delivery and emplacement of NZVI in heterogeneous porous media in a two-dimensional (2-D) cell. Heterogeneity in hydraulic conductivity had a significant impact on the deposition of NZVI. Polymer modified NZVI followed preferential flow paths and deposited in the regions where fluid shear is insufficient to prevent NZVI agglomeration and deposition. NZVI transported in heterogeneous porous media better at low particle concentration (0.3 g/L) than at high particle concentrations (3 and 6 g/L) due to greater particle agglomeration at high concentration. High Fe(0) content decreased transport during injection due to agglomeration promoted by magnetic attraction. NZVI with a flat adsorbed polymeric layer (thickness ∼30 nm) could not be transported effectively due to pore clogging and deposition near the inlet, while NZVI with a more extended adsorbed layer thickness (i.e., ∼70 nm) were mobile in porous media. This study indicates the importance of characterizing porous media heterogeneity and NZVI dispersion properties as part of the design of a robust delivery strategy for NZVI in the subsurface.

Empirical correlations to estimate agglomerate size and deposition during injection of a polyelectrolyte-modified Fe0 nanoparticle at high particle concentration in saturated sand

Controlled emplacement of polyelectrolyte-modified nanoscale zerovalent iron (NZVI) particles at high particle concentration (1-10 g/L) is needed for effective in situ subsurface remediation using NZVI. Deep bed filtration theory cannot be used to estimate the transport and deposition of concentrated polyelectrolyte-modified NZVI dispersions (>0.03 g/L) because particles agglomerate during transport which violates a fundamental assumption of the theory. Here we develop two empirical correlations for estimating the deposition and transport of concentrated polyelectrolyte-modified NZVI dispersions in saturated porous media when NZVI agglomeration in porous media is assumed to reach steady state quickly. The first correlation determines the apparent stable agglomerate size formed during NZVI transport in porous media for a fixed hydrogeochemical condition. The second correlation estimates the attachment efficiency (sticking coefficient) of the stable agglomerates. Both correlations are described using dimensionless numbers derived from parameters affecting deposition and agglomeration in porous media. The exponents for the dimensionless numbers are determined from statistical analysis of breakthrough data for polyelectrolyte-modified NZVI dispersions collected in laboratory scale column experiments for a range of ionic strength (1, 10, and 50mM Na(+) and 0.25, 1, and 1.25 mM Ca(2+)), approach velocity (0.8 to 55 × 10(-4)m/s), average collector sizes (d(50)=99 μm, 300 μm, and 880 μm), and polyelectrolyte surface modifier properties. Attachment efficiency depended on approach velocity and was inversely related to collector size, which is contrary to that predicted from classic filtration models. High ionic strength, the presence of divalent cations, lower extended adsorbed polyelectrolyte layer thickness, decreased approach velocity, and a larger collector size promoted NZVI agglomeration and deposition and thus limited its mobility in porous media. These effects are captured quantitatively in the two correlations developed. The application and limitations of using the correlations for preliminary design of in situ NZVI emplacement strategies is discussed.

Polymer-modified Fe0 nanoparticles target entrapped NAPL in two dimensional porous media: effect of particle concentration, NAPL saturation, and injection strategy.

Polymer-modified nanoscale zerovalent iron (NZVI) particles are delivered into porous media for in situ remediation of nonaqueous phase liquid (NAPL) source zones. A systematic and quantitative evaluation of NAPL targeting by polymer-modified NZVI in two-dimensional (2-D) porous media under field-relevant conditions has not been reported. This work evaluated the importance of NZVI particle concentration, NAPL saturation, and injection strategy on the ability of polymer-modified NZVI (MRNIP2) to target the NAPL/water interface in situ in a 2-D porous media model. Dodecane was used as a NAPL model compound for this first demonstration of source zone targeting in 2-D. A driving force for NAPL targeting, the surface activity of MRNIP2 at the NAPL/water interface was verified ex situ by its ability to emulsify NAPL in water. MRNIP2 at low particle concentration (0.5 g/L) did not accumulate in or near entrapped NAPL, however, MRNIP2 at moderate and high particle concentrations (3 and 15 g/L) did accumulate preferentially at entrapped NAPL, i.e., it was capable of in situ targeting. The amount of MRNIP2 that targets a NAPL source depends on NAPL saturation (S(n)), presumably because the saturation controls the available NAPL/water interfacial area and the flow field through the NAPL source. At effective S(n) close or equal to 100%, MRNIP2 bypassed NAPL and accumulated only at the periphery of the entrapped NAPL region. At lower S(n), flow also carries MRNIP2 to NAPL/water interfaces internal to the entrapped NAPL region. However, the mass of accumulated MRNIP2 per unit available NAPL/water interfacial area is relatively constant (∼0.8 g/m(2) for MRNIP2 = 3 g/L) from S(n) = 13 to ∼100%, suggesting that NAPL targeting is mostly controlled by MRNIP2 sorption onto the NAPL/water interface.

Parameter Identifiability in Application of Soft Particle Electrokinetic Theory To Determine Polymer and Polyelectrolyte Coating Thicknesses on Colloids

Soft particle electrokinetic models have been used to determine adsorbed nonionic polymer and polyelectrolyte layer properties on nanoparticles or colloids by fitting electrophoretic mobility data. Ohshima first established the formalism for these models and provided analytical approximations ( Ohshima, H. Adv. Colloid Interface Sci.1995, 62, 189 ). More recently, exact numerical solutions have been developed, which account for polarization and relaxation effects and require fewer assumptions on the particle and soft layer properties. This paper characterizes statistical uncertainty in the polyelectrolyte layer charge density, layer thickness, and permeability (Brinkman screening length) obtained from fitting data to either the analytical or numerical electrokinetic models. Various combinations of particle core and polymer layer properties are investigated to determine the range of systems for which this analysis can provide a solution with reasonably small uncertainty bounds, particularly for layer thickness. Identifiability of layer thickness in the analytical model ranges from poor confidence for cases with thick, highly charged coatings, to good confidence for cases with thin, low-charged coatings. Identifiability is similar for the numerical model, except that sensitivity is improved at very high charge and permeability, where polarization and relaxation effects are significant. For some poorly identifiable cases, parameter reduction can reduce collinearity to improve identifiability. Analysis of experimental data yielded results consistent with expectations from the simulated theoretical cases. Identifiability of layer charge density and permeability is also evaluated. Guidelines are suggested for evaluation of statistical confidence in polymer and polyelectrolyte layer parameters determined by application of the soft particle electrokinetic theory.

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone.

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.

Chapter 18 – Physicochemistry of Polyelectrolyte Coatings that Increase Stability, Mobility, and Contaminant Specificity of Reactive Nanoparticles Used for Groundwater Remediation

Publisher Summary This chapter reveals that the novel reactive nanomaterials offer the potential for efficient targeted delivery of remedial agents to subsurface contaminants such as chlorinated solvents and heavy metals. The primary challenge to their application is to overcome rapid aggregation and deposition of these nanomaterials in water-saturated porous media, and to improve the efficiency by increasing the specificity of the nanoparticles for specific subsurface contaminants. The amphiphilic nature of some coatings provides the particles specificity for the dense nonaqueous phase liquid (DNAPL)/water interface; whereas other coatings use ligands to specifically sequester heavy metals or hydrophobic nanoparticles to selectively adsorb very hydrophobic organic contaminants. This chapter describes the state-of-the art in polymeric surface modification for reactive nanoparticles used for in situ groundwater remediation, explains the fundamental physieochemical processes by which polyelectrolyte surface modification and functionalization inhibit aggregation and deposition, and increases mobility in the subsurface. It also describes the methods used for targeting specific subsurface contaminants.