The early stage aggregation kinetics of bare and alginate-coated hematite nanoparticles are acquired through time-resolved dynamic light scattering (DLS). Varying concentrations of monovalent (NaCl) and divalent (MgCl2 and CaCl2) electrolytes are employed to induce aggregation. In the presence of NaCl and MgCl2, the alginate-coated hematite nanoparticles undergo aggregation through electrostatic destabilization as described by the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. This is ascertained through examination of the favorable and unfavorable regimes of the stability curves depicting the attachment efficiency as a function of salt concentration. Additional evidence may be found in the aggregation kinetics of alginate-coated particles, which, under favorable aggregation conditions, are reasonably close to that of bare hematite nanoparticles. However, in the presence of CaCl2, the aggregate growth rate of alginate-coated hematite nanoparticles is much higher than that which conventional diffusive aggregation predicts. Dispersed hematite primary particles and lower-order aggregates enmeshed within extended alginate gel networks were observed under transmission electron microscope (TEM). The proposed mechanism for enhanced aggregation suggests an apparent increase in the collision radii of alginate-coated hematite nanoparticles through alginate gel network formation from the particle surface. Additionally, cross-linking between unadsorbed (suspended) alginate macromolecules may form bridges between hematite-alginate gel clusters. It is further established that the presence of background electrolyte NaCl in solution is detrimental to the calcium-induced enhanced aggregation.

The stability and aggregation behavior of iron oxide colloids in natural waters play an important role in controlling the fate, transport, and bioavailability of trace metals. Time-resolved dynamic light scattering experiments were carried out in a study of the aggregation kinetics and aggregate structure of natural organic matter (NOM) coated hematite colloids and bare hematite colloids. The aggregation behavior was examined over a range of solution chemistries, by adjusting the concentration of the supporting electrolyte-NaCl, CaCl2, or simulated seawater. With the solution pH adjusted so that NOM-coated and bare hematite colloids were at the same zeta potential, we observed a significant difference in colloid stability which results from the stability imparted to the colloids by the adsorbed NOM macromolecules. This enhanced stability of NOM-coated hematite colloids was not observed with CaCl2. Aggregate form expressed as fractal dimension was determined for both NOM-coated and bare hematite aggregates in both NaCl and CaCl2. The fractal dimensions of aggregates formed in the diffusion-limited regime indicate slightly more loosely packed aggregates for bare hematite than theory predicts. For NOM-coated hematite, a small decrease in fractal dimension was observed when the solution composition changed from NaCl to CaCl2. For systems in the reaction-limited regime, the measured fractal dimensions agreed with those in the literature. Colloid aggregation was also studied in synthetic seawater, a mixed cation system to simulate estuarine mixing. Those results describe the important phenomena of iron oxide aggregation and sedimentation in estuaries. When compared to field data from the Mullica Estuary, U.S.A., it is shown that collision efficiency is a good predictor of the iron removal in this natural system.

Early-stage aggregation kinetics studies of alginate-coated hematite nanoparticles in solutions containing alkaline-earth metal cations revealed enhanced aggregation rates in the presence of Ca2+, Sr2+, and Ba2+, but not with Mg2+. Transmission electron microscopy (TEM) imaging of the aggregates provided evidence that alginate gel formation was essential for enhanced aggregation to occur. Dynamic light scattering (DLS) aggregation results clearly indicated that a much lower concentration of Ba2+ compared to Ca2+ and Sr2+ was required to achieve a similar degree of enhanced aggregation in each system. To elucidate the relationship between the alginate's affinities for divalent cations and the enhanced aggregation of the alginate-coated hematite nanoparticles, atomic force microscopy (AFM) was employed to probe the interaction forces between alginate-coated hematite surfaces under the solution chemistries used for the aggregation study. Maximum adhesion forces, maximum pull-off distances, and the work of adhesion were used as indicators to gauge the alginate's affinity for the divalent cations and the resulting attractive interactions between alginate-coated hematite nanoparticles. The results showed that alginate had higher affinity for Ba2+ than either Sr2+ or Ca2+. This same trend was consistent with the cation concentrations required for comparable enhanced aggregation kinetics, suggesting that the rate of alginate gel formation controls the enhanced aggregation kinetics. An aggregation mechanism incorporating the gelation of alginate is proposed to explain the accelerated aggregate growth in the presence of Ca2+, Sr2+, and Ba2+.

This work extends investigations into the development and use of a kinetic model to simulate and improve the iron-catalyzed oxidation of organic compounds using Fenton's reagent. While a number of recent studies have successfully modeled the kinetics and species behavior in simple Fenton systems, none have extended and applied the model to examine the effect of operating parameters such as pH on treatment performance. The purpose of this work is to investigate the effect of pH in Fenton-based oxidation systems and to use kinetic modeling to gain insight into the reaction mechanism and speciation of the iron catalyst. Laboratory experiments were conducted across a range of starting concentrations of Fe(II) and H2O2 at pHs of 2.5, 3.0, and 4.0, both in the presence and absence of a target organic, formic acid (HCOOH). With minor modifications, the model presented is capable of accurately describing changes in Fe(II) concentrations over a wide range of reaction conditions and, provided account is taken of additional hydroxyl radical scavenging pathways, also accounts for the oxidation of formic acid over extended reaction times at all pHs considered. The use of composite values for rate constants of reactions involving weakly acidic species is shown to be appropriate, and analysis of the model reveals the catalytic role iron plays in the oxidation process. Experimental and simulated data at the different pHs highlights the effect the catalytic redox cycling of iron has on the performance and oxidation capacity of the Fenton system.

Aggregation kinetics of rotavirus in aqueous solutions and its deposition kinetics on silica surface in the presence of divalent (Ca(2+), Mg(2+)) cations were studied using complementary techniques of time-resolved dynamic light scattering (TR-DLS) and quartz crystal microbalance (QCM). Within a reasonable temporal window of 4 h, aggregation could be observed at levels as low as 10 mM of Ca(2+) and 20 mM of Mg(2+). Attachment efficiencies were always greater in Ca(2+) solutions of the same concentration, and the critical coagulation concentration (CCC) for rotavirus in Ca(2+) solutions was slightly smaller than that in Mg(2+) solutions. No aggregation was detected in Na(+) solution within the temporal window of 4 h. Deposition experiments showed higher attachment coefficients in solutions containing Ca(2+) compared to those obtained in Mg(2+) solution. The classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory failed to predict both the aggregation behavior of rotavirus and its deposition on silica surface. Besides electrostatic interactions, steric repulsions and specific interactions with divalent cations were important mechanisms in controlling rotavirus deposition and aggregation. Experimental results presented here suggest that rotavirus is not expected to aggregate in groundwater with typical hardness (up to 6 mM Ca(2+)) and rotavirus deposition on silica soil would be more favorable in the presence of Ca(2+) than Mg(2+).

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The stability of functionalized nanoparticles generally results from both steric and electrostatic interactions. Viruses like bacteriophage MS2 have adopted similar strategies for stability against aggregation, including a net negative charge under natural water conditions and using polypeptides that form loops extending from the surface of the protein capsid for stabilization. In natural systems, dissolved organic matter can adsorb to and effectively functionalize nanoparticle surfaces, affecting the fate and transport of these nanoparticles. We used time-resolved dynamic light scattering to measure the aggregation kinetics of a model virus, bacteriophage MS2, across a range of solution chemistries to determine what factors might destabilize viruses in aquatic systems. In monovalent electrolytes (LiCl, NaCl, and KCl), aggregation of MS2 could not be induced within a reasonable kinetic time frame, and MS2 was stable even at salt concentrations greater than 1.0 M. Aggregation of MS2 could be induced in divalent electrolytes when we employed Ca(2+). This trend was also observed in solutions containing 10 mg/L Suwannee River organic matter (SROM) reference material. Even at Ca(2+) concentrations as high 200 mM, diffusion-controlled aggregation was never achieved, demonstrating an additional barrier to aggregation. These results were confirmed by small-angle X-ray scattering experiments, which indicate a transition from repulsive to attractive interactions between MS2 virus particles as monovalent salts are replaced by divalent salts.

[1] The movement of particulate matter within wetland surface waters affects nutrient cycling, contaminant mobility, and the evolution of the wetland landscape. Despite the importance of particle transport in influencing wetland form and function, there are few data sets that illuminate, in a quantitative way, the transport behavior of particulate matter within surface waters containing emergent vegetation. We report observations from experiments on the transport of 1 mm latex microspheres at a wetland field site located in Water Conservation Area 3A of the Florida Everglades. The experiments involved line source injections of particles inside two 4.8-m-long surface water flumes constructed within a transition zone between an Eleocharis slough and Cladium jamaicense ridge and within a Cladium jamaicense ridge. We compared the measurements of particle transport to calculations of two-dimensional advection-dispersion model that accounted for a linear increase in water velocities with elevation above the ground surface. The results of this analysis revealed that particle spreading by longitudinal and vertical dispersion was substantially greater in the ridge than within the transition zone and that particle capture by aquatic vegetation lowered surface water particle concentrations and, at least for the timescale of our experiments, could be represented as an irreversible, first-order kinetics process. We found generally good agreement between our field-based estimates of particle dispersion and water velocity and estimates determined from published theory, suggesting that the advective-dispersive transport of particulate matter within complex wetland environments can be approximated on the basis of measurable properties of the flow and aquatic vegetation.