Modeling the Role in pH on Contaminant Sequestration by Zerovalent Metals: Chromate Reduction by Zerovalent Magnesium.

The role of pH in sequestration of Cr(VI) by zerovalent magnesium (ZVMg) was characterized by global fitting of a kinetic model to time-series data from unbuffered batch experiments with varying initial pH values. At initial pH values ranging from 2.0 to 6.8, ZVMg (0.5 g/L) completely reduced Cr(VI) (18.1 µM) within 24 h, during which time pH rapidly increased to a plateau value of ∼10. Time-series correlation analysis of the pH and aqueous Cr(VI), Cr(III), and Mg(II) concentration data suggested that these conditions are controlled by combinations of reactions (involving Mg0 oxidative dissolution and Cr(VI) sequestration) that evolve over the time course of each experiment. Since this is also likely to occur during any engineering applications of ZVMg for remediation, we developed a kinetic model for dynamic pH changes coupled with ZVMg corrosion processes. Using this model, the synchronous changes in Cr(VI) and Mg(II) concentrations were fully predicted based on the Langmuir-Hinshelwood kinetics and transition-state theory, respectively. The reactivity of ZVMg was different in two pH regimes that were pH-dependent at pH < 4 and pH-independent at the higher pH. This contrasting pH effect could be ascribed to the shift of the primary oxidant of ZVMg from H+ to H2O at the lower and higher pH regimes, respectively.

Ferrous ion mitigates the negative effects of humic acid on removal of 4-nitrophenol by zerovalent iron.

In this study, Fe2+ addition was employed to overcome the negative effects of humic acid (HA) on contaminant removal by zerovalent iron (ZVI), and its feasibility to improve electron efficiency of ZVI was also tested. HA at high concentrations suppressed the removal of 4-nitrophenol (4-NP) by ZVI, while the addition of 0.25-1.0 mM Fe2+ could greatly mitigate this inhibitory effect and enhance 4-NP reduction. Specifically, with a mixed-order model, global fitting results showed that the addition of Fe2+ increased the rate constant from 0.124 × 10-2-0.219 × 10-2 mM/min to 0.227 × 10-2-0.417 × 10-2 mM/min and shortened lag period from 19.7-47.9 min to 8.0-15.2 min for 4-NP removal. The mechanistic investigation revealed this trend could be explained by the following aspects: i) Fe2+ can facilitate the generation of Fe(II)-containing oxides, which can act as an electron mediator or direct electron donor for 4-NP reduction; ii) the presence of Fe2+ could lead to aggregation of HA particles and accordingly reduced its coverage on ZVI surface. But the results of respike experiments indicate that Fe2+ addition did not show remarkable effect on the electron efficiency of 4-NP by ZVI, which should be associated with that Fe2+ was not able to favor the enrichment of 4-NP on ZVI surface.

Modeling the Kinetics of Hydrogen Formation by Zerovalent Iron: Effects of Sulfidation on Micro- and Nano-Scale Particles.

The hydrogen evolution reaction (HER) that generates H2 from the reduction of H2O by Fe0 is among the most fundamental of the processes that control reactivity in environmental systems containing zerovalent iron (ZVI). To develop a comprehensive kinetic model for this process, a large and high-resolution data set for HER was measured using five types of ZVI pretreated by acid-washing and/or sulfidation (in pH 7 HEPES buffer). The data were fit to four alternative kinetic models using nonlinear regression analysis applied to the whole data set simultaneously, which allowed some model parameters to be treated globally across multiple experiments. The preferred model uses two independent reactive phases to match the two-stage character of most HER data, with rate constants ( k's) for each phase fitted globally by iron type and phase quantities ( S's) fitted as fully local (independent) parameters. The first, faster stage was attributed to a reactive mineral intermediate (RMI) phase like Fe(OH)2, which may form in all experiments during preequilibration, but is rapidly consumed, leaving the second, slower stage of HER, which is due to reaction of Fe0. In addition to providing a deterministic model to explain the kinetics of HER by ZVI over a wide range of conditions, the results provide an improved quantitative basis for comparing the effects of sulfidation on ZVI.

Effects of Sulfidation, Magnetization, and Oxygenation on Azo Dye Reduction by Zerovalent Iron.

Applications of zerovalent iron (ZVI) for water treatment under aerobic conditions include sequestration of metals (e.g., in acid mine drainage) and decolorization of dyes (in wastewaters from textile manufacturing). The processes responsible for contaminant removal can be a complex mixture of reduction, oxidation, sorption, and coprecipitation processes, which are further complicated by the dynamics of oxygen intrusion, mixing, and oxide precipitation. To better understand such systems, the removal of an azo dye (Orange I) by micron-sized granular ZVI at neutral pH was studied in open (aerobic) stirred batch reactors, by measuring the kinetics of Orange I decolorization and changes in "geochemical" properties (DO, Fe(II), and Eh), with and without two treatments that might improve the long-term performance of this system: sulfidation by pretreatment with sulfide and magnetization by application of a weak magnetic field (WMF). The results show that the changes in solution chemistry are coupled to the dynamics of oxygen intrusion, which was modeled as analogous to dissolved oxygen sag curves. Both sulfidation and magnetization increased Orange I removal rates 2.4-71.8-fold, but there was little synergistic benefit to applying both enhancements together. Respike experiments showed that the enhancement from magnetization carries over from magnetization to sulfidation, but not the reverse.

Understanding the mechanisms of solid-water reactions through analysis of surface topography.

The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic information about the surface. Our results also indicate that root-mean-square roughness cannot be used to reliably characterize the surface topography of fractal surfaces because it is an inherently noisy parameter for such surfaces with the scale of the noise being independent of length scale.

Reduction of 2,4,6-trinitrotoluene by iron metal: kinetic controls on product distributions in batch experiments.

The reaction kinetics and product distributions for the reduction of 2,4,6-trinitrotoluene (TNT) by granular iron metal (Fe0) were studied in batch experiments under a variety of initial concentrations of TNT and Fe0. Although the kinetics of TNT disappearance were found to behave in accord with the standard theory for surface-mediated reactions, a complex relationship was found between the initial concentrations of TNT and Fe0 and the appearance of the expected nitro reduction product, 2,4,6-triaminotoluene (TAT). TNT was completely converted to TAT only when the initial concentration of TNT was low and/or the initial concentration of Fe0 was high. Mathematical analysis of a range of generic reaction schemes that produce stable end products in addition to TAT showed that (i) surface complexation of TAT is insufficient to describe all of our data and (ii) polymerization reactions involving TAT and/or various reaction intermediates are the likely source of the incomplete conversion of TNT to TAT at high initial TNT concentration and low Fe0 concentration. The relationship between TAT production and reaction conditions is shown to imply that passivation due to reaction products is more likely when the ratio of initial TNT concentration to Fe0 concentration is high and, therefore, that passivation rates observed at the laboratory scale are likely to be faster than those which would be observed at the field scale.

Diversity of contaminant reduction reactions by zerovalent iron: role of the reductate.

The reactions of eight model contaminants with nine types of granular Fe(0) were studied in batch experiments using consistent experimental conditions. The model contaminants (herein referred to as "reductates" because they were reduced by the iron metal) included cations (Cu2+), anions (CrO4(2-), NO3(-), and 5,5',7,7'-indigotetrasulfonate), and neutral species (2-chloroacetophenone, 2,4,6-trinitrotoluene, carbon tetrachloride, and trichloroethene). The diversity of this range of reductates offers a uniquely broad perspective on the reactivity of Fe(0). Rate constants for disappearance of the reductates vary over as much as four orders of magnitude for particular reductates (due to differences in the nine types of iron) but differences among the reductates were even larger, ranging over almost seven orders of magnitude. Various ways of summarizing the data all suggest that relative reactivities with Fe(0) vary in the order Cu2+, 5,5',7,7'-indigotetrasulfonate > 2-chloroacetophenone, 2,4,6-trinitrotoluene > carbon tetrachloride, CrO4(2-) > trichloroethene > NO3(-). Although the reductate has the largest effect on disappearance kinetics, more subtle differences in reactivity due to the type of Fe(0) suggests that removal of CrO2(2-) and NO3(-) (the inorganic anions) involves adsorption to oxides on the Fe(0), whereas the disappearance kinetics of all other types of reductants is favored by reduction on comparatively oxide-free metal. Correlation analysis of the disappearance rate constants using descriptors of the reductates calculated by molecular modeling (energies of the lowest unoccupied molecular orbitals, LUMO, highest occupied molecular orbitals, HOMO, and HOMO-LUMO gaps) showed that reactivities generally decrease with increasing E(LUMO) and increasing E(GAP) (and, therefore, increasing chemical hardness eta).

Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron.

The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.