Michelle M. Scherer

Chemistry and microbiology of permeable reactive barriers for in situ groundwater clean up

Permeable reactive barriers (PRBs) are receiving a great deal of attention as an innovative, cost-effective technology for in situ clean up of groundwater contamination. A wide variety of materials are being proposed for use in PRBs, including zero-valent metals (e.g., iron metal), humic materials, oxides, surfactant-modified zeolites (SMZs), and oxygen- and nitrate-releasing compounds. PRB materials remove dissolved groundwater contaminants by immobilization within the barrier or transformation to less harmful products. The primary removal processes include: (1) sorption and precipitation, (2) chemical reaction, and (3) biologically mediated reactions. This article presents an overview of the mechanisms and factors controlling these individual processes and discusses the implications for the feasibility and long-term effectiveness of PRB technologies.

Adsorption of Organic Acids on TiO2 Nanoparticles: Effects of pH, Nanoparticle Size, and Nanoparticle Aggregation

In this study, the adsorption of two organic acids, oxalic acid and adipic acid, on TiO2 nanoparticles was investigated at room temperature, 298 K. Solution-phase measurements were used to quantify the extent and reversibility of oxalic acid and adipic acid adsorption on anatase nanoparticles with primary particle sizes of 5 and 32 nm. At all pH values considered, there were minimal differences in measured Langmuir adsorption constants, K ads, or surface-area-normalized maximum adsorbate-surface coverages, Gamma max, between 5 and 32 nm particles. Although macroscopic differences in the reactivity of these organic acids as a function of nanoparticle size were not observed, ATR-FTIR spectroscopy showed some distinct differences in the absorption bands present for oxalic acid adsorbed on 5 nm particles compared to 32 nm particles, suggesting different adsorption sites or a different distribution of adsorption sites for oxalic acid on the 5 nm particles. These results illustrate that molecular-level differences in nanoparticle reactivity can still exist even when macroscopic differences are not observed from solution phase measurements. Our results also allowed the impact of nanoparticle aggregation on acid uptake to be assessed. It is clear that particle aggregation occurs at all pH values and that organic acids can destabilize nanoparticle suspensions. Furthermore, 5 nm particles can form larger aggregates compared to 32 nm particles under the same conditions of pH and solid concentrations. The relative reactivity of 5 and 32 nm particles as determined from Langmuir adsorption parameters did not appear to vary greatly despite differences that occur in nanoparticle aggregation for these two different size nanoparticles. Although this potentially suggests that aggregation does not impact organic acid uptake on anatase particles, these data clearly show that challenges remain in assessing the available surface area for adsorption in nanoparticle aqueous suspensions because of aggregation.

Effects of natural organic matter, anthropogenic surfactants, and model quinones on the reduction of contaminants by zero-valent iron.

Recent studies of contaminant reduction by zero-valent iron metal (Fe0) have highlighted the role of iron oxides at the metal-water interface and the effect that sorption has at the oxide-water interface on contaminant reduction kinetics. The results suggest that a variety of organic surface-active substances might enhance or inhibit contaminant degradation, depending on the degree to which they promote solubilization, sorption. and/or reaction. Of particular interest is the effect of natural organic matter (NOM), because of its ubiquitous presence in natural waters and amphiphilic properties; anthropogenic surfactants, because of their use in groundwater remediation; and certain quinones, which represent the redox-active functional groups associated with NOM. In this study, no well-defined effects of these substances were found on the reduction of nitro benzene by Fe0, but the reduction of carbon tetrachloride and trichloroethylene (TCE) was inhibited by NOM. Results with carbon tetrachloride showed that the inhibitory effect of humic acids was greater than fulvic acids, but that several quinonoid NOM model compounds (juglone, lawsone. and anthraquinone disulfonate) increased the rate of reduction by Fe0. Isotherms for adsorption of TCE and NOM onto Fe0 showed evidence of competition for surface sites.

Chemistry and Microbiology of Permeable Reactive Barriers for In Situ Groundwater Clean up

Permeable reactive barriers (PRBs) are receiving a great deal of attention as an innovative, cost-effective technology for in situ clean up of groundwater contamination. A wide variety of materials are being proposed for use in PRBs, including zero-valent metals (e.g., iron metal), humic materials, oxides, surfactant-modified zeolites (SMZs), and oxygen- and nitrate-releasing compounds. PRB materials remove dissolved groundwater contaminants by immobilization within the barrier or transformation to less harmful products. The primary removal processes include: (1) sorption and precipitation, (2) chemical reaction, and (3) biologically mediated reactions. This article presents an overview of the mechanisms and factors controlling these individual processes and discusses the implications for the feasibility and long-term effectiveness of PRB technologies.

Redox Behavior of Magnetite: Implications for Contaminant Reduction

The factors controlling rates of contaminant reduction by magnetite (Fe3O4) are poorly understood. Here, we measured the reduction rates of three ArNO2 compounds by magnetite particles ranging from highly oxidized (x = Fe2+/Fe3+ = 0.31) to fully stoichiometric (x = 0.50). Rates of ArNO2 reduction became almost 5 orders of magnitude faster as the particle stoichiometry increased from x = 0.31 to 0.50. To evaluate what was controlling the rate of ArNO2 reduction, we measured apparent 15N kinetic isotope effects ((15)N-AKIE) values for nitrobenzene and magnetite open-circuit potentials (E(OCP)). 15N-AKIE values were greater than unity for all magnetite stoichiometries investigated, indicating that mass transfer processes are not controlling the rate of ArNO2 reduction by magnetite. E(OCP) measurements showed that the E(OCP) for magnetite was linearly related to the stoichiometry, with more stoichiometric magnetite having a lower potential. Based on these results, we propose that conceptual models that incorporate both redox and Fe2+ diffusion processes, rather than those that rely solely on diffusion of Fe2+, are more appropriate for understanding contaminant reduction by magnetite. Our work indicates that particle stoichiometry should be considered when evaluating rates of contaminant reduction by magnetite.

Determination of nanoparticulate magnetite stoichiometry by Mössbauer spectroscopy, acidic dissolution, and powder X-ray diffraction: A critical review

Abstract A solid solution can exist of magnetite (Fe3O4) and maghemite (γ-Fe2O3), which is commonly referred to as nonstoichiometric or partially oxidized magnetite. The degree of stoichiometry in magnetite is quantitatively measured by determining the ratio of Fe2+ to Fe3+. Magnetite stoichiometry (x = Fe2+/Fe3+) strongly influences several physical properties, including the coercitivity, sorption capacity, reduction potential, and crystalline structure. Magnetite stoichiometry has been extensively studied, although very little work exists examining the stoichiometry of nanoparticulate samples (<<100 nm); when the stoichiometry was measured for nanoparticulate samples, it was not validated with a secondary technique. Here, we review the three most common techniques to determine magnetite stoichiometry: (1) acidic dissolution; (2) Mössbauer spectroscopy; and (3) powder X-ray diffraction (pXRD), specifically with nanoparticulate samples in mind. Eight samples of nonstoichiometric magnetite were synthesized with x ranging from 0 to 0.50 and with the particle size kept as similar as possible (BET specific surface area = 63 ± 7 m2/g; particle size ≈ 20 nm). Our measurements indicate excellent agreement between stoichiometries determined from Mössbauer spectra and by acidic dissolution, suggesting that Mössbauer spectroscopy may be a useful means for estimating magnetite stoichiometry in nanoparticulate, multi-phases samples, such as those found in the environment. A significant linear correlation was also observed between the unit-cell length (a) of magnetite measured by pXRD and magnetite stoichiometry, indicating that pXRD may also be useful for determining particle stoichiometry, especially for mixed phased samples

Spectroscopic Evidence for Interfacial Fe(II)−Fe(III) Electron Transfer in a Clay Mineral

Interfacial electron transfer has been shown to occur between sorbed Fe(II) and structural Fe(III) in Fe oxides, but it is unknown whether a similar reaction occurs between sorbed Fe(II) and Fe(III)-bearing clay minerals. Here, we used the isotopic specificity of (57)Fe Mössbauer spectroscopy to demonstrate electron transfer between sorbed Fe(II) and structural Fe(III) in an Fe-bearing smectite clay mineral (NAu-2, nontronite). Mössbauer spectra of NAu-2 reacted with aqueous (56)Fe(II) (which is invisible to (57)Fe Mössbauer spectroscopy) showed direct evidence for reduction of NAu-2 by sorbed Fe(II). Mössbauer spectra using aqueous (57)Fe(II) showed that sorbed Fe(II) is oxidized upon sorption to the clay and pXRD patterns indicate that the oxidation product is lepidocrocite. Spectra collected at different temperatures indicate that reduction of structural Fe(III) by sorbed Fe(II) induces electron delocalization in the clay structure. Our results also imply that interpretation of room temperature and 77 K Mössbauer spectra may significantly underestimate the amount of Fe(II) in Fe-bearing clays. These findings provide compelling evidence for abiotic reduction of Fe-bearing clay minerals by sorbed Fe(II), and require us to reframe our conceptual model for interpreting biological reduction of clay minerals, as well as contaminant reduction by reduced clays.

Influence of Magnetite Stoichiometry on U VI Reduction

Hexavalent uranium (U(VI)) can be reduced enzymatically by various microbes and abiotically by Fe(2+)-bearing minerals, including magnetite, of interest because of its formation from Fe(3+) (oxy)hydroxides via dissimilatory iron reduction. Magnetite is also a corrosion product of iron metal in suboxic and anoxic conditions and is likely to form during corrosion of steel waste containers holding uranium-containing spent nuclear fuel. Previous work indicated discrepancies in the extent of U(VI) reduction by magnetite. Here, we demonstrate that the stoichiometry (the bulk Fe(2+)/Fe(3+) ratio, x) of magnetite can, in part, explain the observed discrepancies. In our studies, magnetite stoichiometry significantly influenced the extent of U(VI) reduction by magnetite. Stoichiometric and partially oxidized magnetites with x ≥ 0.38 reduced U(VI) to U(IV) in UO(2) (uraninite) nanoparticles, whereas with more oxidized magnetites (x < 0.38) and maghemite (x = 0), sorbed U(VI) was the dominant phase observed. Furthermore, as with our chemically synthesized magnetites (x ≥ 0.38), nanoparticulate UO(2) was formed from reduction of U(VI) in a heat-killed suspension of biogenic magnetite (x = 0.43). X-ray absorption and Mössbauer spectroscopy results indicate that reduction of U(VI) to U(IV) is coupled to oxidation of Fe(2+) in magnetite. The addition of aqueous Fe(2+) to suspensions of oxidized magnetite resulted in reduction of U(VI) to UO(2), consistent with our previous finding that Fe(2+) taken up from solution increased the magnetite stoichiometry. Our results suggest that magnetite stoichiometry and the ability of aqueous Fe(2+) to recharge magnetite are important factors in reduction of U(VI) in the subsurface.

Simulated atmospheric processing of iron oxyhydroxide minerals at low pH: Roles of particle size and acid anion in iron dissolution

A number of recent studies have shown that iron dissolution in Fe-containing dust aerosol can be linked to source material (mineral or anthropogenic), mineralogy, and iron speciation. All of these factors need to be incorporated into atmospheric chemistry models if these models are to accurately predict the impact of Fe-containing dusts into open ocean waters. In this report, we combine dissolution measurements along with spectroscopy and microscopy to focus on nanoscale size effects in the dissolution of Fe-containing minerals in low-pH environments and the importance of acid type, including HNO3, H2SO4, and HCl, on dissolution. All of these acids are present in the atmosphere, and dust particles have been shown to be associated with nitrate, sulfate, and/or chloride. These measurements are done under light and dark conditions so as to simulate and distinguish between daytime and nighttime atmospheric chemical processing. Both size (nano- versus micron-sized particles) and anion (nitrate, sulfate, and chloride) are found to play significant roles in the dissolution of α-FeOOH under both light and dark conditions. The current study highlights these important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

Coal Fly Ash as a Source of Iron in Atmospheric Dust

Anthropogenic coal fly ash (FA) aerosol may represent a significant source of bioavailable iron in the open ocean. Few measurements have been made that compare the solubility of atmospheric iron from anthropogenic aerosols and other sources. We report here an investigation of iron dissolution for three FA samples in acidic aqueous solutions and compare the solubilities with that of Arizona test dust (AZTD), a reference material for mineral dust. The effects of pH, simulated cloud processing, and solar radiation on iron solubility have been explored. Similar to previously reported results on mineral dust, iron in aluminosilicate phases provides the predominant component of dissolved iron. Iron solubility of FA is substantially higher than of the crystalline minerals comprising AZTD. Simulated atmospheric processing elevates iron solubility due to significant changes in the morphology of aluminosilicate glass, a dominant material in FA particles. Iron is continuously released into the aqueous solution as FA particles break up into smaller fragments. These results suggest that the assessment of dissolved atmospheric iron deposition fluxes and their effect on the biogeochemistry at the ocean surface should be constrained by the source, environmental pH, iron speciation, and solar radiation.