Disentangling the size-dependent redox reactivity of iron oxides using thermodynamic relationships.

Nanoparticles often exhibit size-dependent redox reactivities, with smaller particles being more reactive in some cases, while less reactive in others. Predicting trends between redox reaction rates and particle sizes is often complicated because a particle's dimensions can simultaneously influence its aggregation state, reactive surface area, and thermodynamic properties. Here, we tested the hypothesis that interfacial redox reaction rates for nanoparticles with different sizes can be described with a single linear free-energy relationship (LFER) if size-dependent reactive surface areas and thermodynamic properties are properly considered. We tested this hypothesis using a well-known interfacial redox reaction: the reduction of nitrobenzene to aniline by iron-oxide-bound Fe2+. We measured the reduction potential (EH) values of nano-particulate hematite suspensions containing aqueous Fe2+ using mediated potentiometry and characterized the size and aggregation states of hematite samples at circumneutral pH values. We used the measured EH values to calculate surface energies and reactive surface areas using thermodynamic relationships. Nitrobenzene reduction rates were lower for smaller particles, despite their larger surface areas, due to their higher surface energies. When differences in surface areas and thermodynamic properties were considered, nitrobenzene reduction kinetics for all particle sizes was described with a LFER. Our results demonstrate that when Fe2+ serves as a reductant, an antagonistic effect exists, with smaller particles having larger reactive surface areas but also more positive reduction potentials. When Fe3+ serves as an oxidant, however, these two effects work in concert, which likely explains past discrepancies regarding how iron oxide particle sizes influence redox reaction rates.

Thin-Film Composite Membranes for Hydrogen Evolution with a Saline Catholyte Water Feed.

Hydrogen gas evolution using an impure or saline water feed is a promising strategy to reduce overall energy consumption and investment costs for on-site, large-scale production using renewable energy sources. The chlorine evolution reaction is one of the biggest concerns in hydrogen evolution with impure water feeds. The "alkaline design criterion" in impure water electrolysis was examined here because water oxidation catalysts can exhibit a larger kinetic overpotential without interfering chlorine chemistry under alkaline conditions. Here, we demonstrated that relatively inexpensive thin-film composite (TFC) membranes, currently used for high-pressure reverse osmosis (RO) desalination applications, can have much higher rejection of Cl- (total crossover of 2.9 ± 0.9 mmol) than an anion-exchange membrane (AEM) (51.8 ± 2.3 mmol) with electrolytes of 0.5 M KOH for the anolyte and 0.5 M NaCl for the catholyte with a constant current (100 mA/cm2 for 20 h). The membrane resistances, which were similar for the TFC membrane and the AEM based on electrochemical impedance spectroscopy (EIS) and Ohm's law methods, could be further reduced by increasing the electrolyte concentration or removal of the structural polyester supporting layer (TFC-no PET). TFC membranes could enable pressurized gas production, as this membrane was demonstrated to be mechanically stable with no change in permeate flux at 35 bar. These results show that TFC membranes provide a novel pathway for producing green hydrogen with a saline water feed at elevated pressures compared to systems using AEMs or porous diaphragms.

Thermodynamic and Kinetic Analyses of Ion Intercalation/Deintercalation Using Different Temperatures on NiHCF Electrodes for Battery Electrode Deionization.

Prussian blue analogues are used in electrochemical deionization due to their cation sorption capabilities and ion selectivity properties. Elucidating the fundamental mechanisms underlying intercalation/deintercalation is important for the development of ion-selective electrodes. We examined the thermodynamic and kinetic properties of nickel hexacyanoferrate electrodes by studying different temperatures effects on intercalation/deintercalation with monovalent ions (Li+, Na+, K+, and NH4+) relevant to battery electrode deionization applications. Higher temperatures reduced the interfacial charge transfer resistance and increased the diffusion coefficient of cations in the solid material. Ion transport in the solid material, rather than interfacial charge transfer, was found to be the rate-controlling step, as shown by higher activation energies for ion transport (e.g., 31 ± 3 kJ/mol for K+) than for interfacial charge transfer (5 ± 1 kJ/mol for K+). The largest increase in cation adsorption capacity with temperature was observed for NH4+ (28.1% from 15 to 75 °C) due to its smallest activation energy. These results indicate that ion hydration energy determines the intercalation potential and activation energies of ion transport in solid material control intercalation/deintercalation rate. Together with the endothermic behavior of deintercalation and exothermic behavior of intercalation, the higher operating temperature results in improvement of ion adsorption capacity depending on specific cations.

Metal-Ion Depletion Impacts the Stability and Performance of Battery Electrode Deionization over Multiple Cycles.

Prussian blue hexacyanoferrate (HCF) materials, such as copper hexacyanoferrate (CuHCF) and nickel hexacyanoferrate (NiHCF), can produce higher salt removal capacities than purely capacitive materials when used as electrode materials during electrochemical water deionization due to cation intercalation into the HCF structure. One factor limiting the application of HCF materials is their decay in deionization performance over multiple cycles. By examining the performance of CuHCF and NiHCF electrodes at three different pH values (2.5, 6.3, and 10.2) in multiple-cycle deionization tests, losses in capacity (up to 73% for CuHCF and 39% for NiHCF) were shown to be tied to different redox-active centers through analysis of dissolution of electrode metals. Both copper and iron functioned as active centers for Na+ removal in CuHCF, while iron was mainly the active center in NiHCF. This interaction of Na+ and active centers was demonstrated by correlating the decrease in performance to the concentration of these metal ions in the effluent solutions collected over multiple cycles at different pHs (up to 0.86 ± 0.14 mg/L for iron and 0.42 ± 0.17 mg/L for copper in CuHCF and 0.38 ± 0.05 mg/L for iron in NiHCF). Both materials were more stable (<11% decay for CuHCF and no decay for NiHCF) when the appropriate metal salt (copper or nickel) was added to the feed solutions to inhibit electrode dissolution. At a pH of 2.5, there was an increased competition between protons and Na+ ions, which decreased the Na+ removal amount and lowered the thermodynamic energy efficiency for deionization for both electrode materials. Therefore, while an acidic pH provided the most stable performance, a circumneutral pH would be useful to produce a better balance between performance and longevity.

Electrochemical Desalination Using Intercalating Electrode Materials: A Comparison of Energy Demands.

One approach for desalinating brackish water is to use electrode materials that electrochemically remove salt ions from water. Recent studies found that sodium-intercalating electrode materials (i.e., materials that reversibly insert Na+ ions into their structures) have higher specific salt storage capacities (mgsalt/gmaterial) than carbon-based electrode materials over smaller or similar voltage windows. These observations have led to the hypothesis that energy demands of electrochemical desalination systems can be decreased by replacing carbon-based electrodes with intercalating electrodes. To test this hypothesis and directly compare intercalation materials, we examined nine electrode materials thought to be capable of sodium intercalation in an electrochemical flow cell with respect to volumetric energy demands (W·h·L-1) and thermodynamic efficiencies as a function of productivity (i.e., the rate of water desalination, L·m-2·h-1). We also examined how the materials' charge-storage capacities changed over 50 cycles. Intercalation materials desalinated brackish water more efficiently than carbon-based electrodes when we assumed that no energy recovery occurred (i.e., no energy was recovered when the cell produced electrical power during cycling) and exhibited similar efficiencies when we assumed complete energy recovery. Nickel hexacyanoferrate exhibited the lowest energy demand among all of the materials and exhibited the highest stability over 50 cycles.

Role of Carbonate in Thermodynamic Relationships Describing Pollutant Reduction Kinetics by Iron Oxide-Bound Fe2.

The reduction of environmental pollutants by Fe2+ bound to iron oxides is an important process that determines pollutant toxicities and mobilities. Recently, we showed that pollutant reduction rates depend on the thermodynamic driving force of the reaction in a linear free energy relationship that was a function of the solution pH value and the reduction potential, EH, of the interfacial Fe3+/Fe2+ redox couple. In this work, we studied how carbonate affected the free energy relationship by examining the effect that carbonate has on nitrobenzene reduction rates by Fe2+ bound to goethite (α-FeOOH). Carbonate slowed nitrobenzene reduction rates by inducing goethite particle aggregation, as evidenced by surface charge and particle size measurements. We observed no evidence for carbonate affecting Fe3+/Fe2+ reduction potentials or the mechanism of nitrobenzene reduction. The linear free energy relationship accurately described the data collected in the presence of carbonate when we accounted for the effect it had on the reactive surface area of goethite. The findings from this work provide a framework for determining why common groundwater constituents affect the EH-dependence of reaction rates involving oxide-bound Fe2+ as a reductant.

Improving the Thermodynamic Energy Efficiency of Battery Electrode Deionization Using Flow-Through Electrodes.

Ion intercalation electrodes are being investigated for use in mixed capacitive deionization (CDI) and battery electrode deionization (BDI) systems because they can achieve selective ion removal and low energy deionization. To improve the thermodynamic energy efficiency (TEE) of these systems, flow-through electrodes were developed by coating porous carbon felt electrodes with a copper hexacyanoferrate composite mixture. The TEE for ion separation using flow-through electrodes was compared to a system using flow-by electrodes with the same materials. The flow-through BDI system increased the recoverable energy nearly 3-fold (0.009 kWh m-3, compared to a 0.003 kWh m-3), which increased the TEE from ∼6% to 8% (NaCl concentration reduction from 50 to 42 mM; 10 A m-2, 50% water recovery, and 0.5 mL min-1). The TEE was further increased to 12% by decreasing the flow rate from 0.50 to 0.25 mL min-1. These findings suggest that, under similar operational conditions and materials, flow-through battery electrodes could achieve better energy recovery and TEE for desalination than flow-by electrodes.

Surveying Manganese Oxides as Electrode Materials for Harnessing Salinity Gradient Energy.

The potential energy contained in the controlled mixing of waters with different salt concentrations (i.e., salinity gradient energy) can theoretically provide a substantial fraction of the global electrical demand. One method for generating electricity from salinity gradients is to use electrode-based reactions in electrochemical cells. Here, we examined the relationship between the electrical power densities generated from synthetic NaCl solutions and the crystal structures and morphologies of manganese oxides, which undergo redox reactions coupled to sodium ion uptake and release. Our aim was to make progress toward developing rational frameworks for selecting electrode materials used to harvest salinity gradient energy. We synthesized 12 manganese oxides having different crystal structures and particle sizes and measured the power densities they produced in a concentration flow cell fed with 0.02 and 0.5 M NaCl solutions. Power production varied considerably among the oxides, ranging from no power produced (ß-MnO2) to 1.18 ± 0.01 W/m2 (sodium manganese oxide). Power production correlated with the materials' specific capacities, suggesting that cyclic voltammetry may be a simple method to screen possible materials. The highest power densities were achieved with manganese oxides capable of intercalating sodium ions when their potentials were prepoised prior to power production.

Electro-Forward Osmosis.

The impact of ion migration induced by an electrical field on water flux in a forward osmosis (FO) process was examined using a thin-film composite (TFC) membrane, held between two cation exchange membranes. An applied fixed current of 100 mA (1.7 mA cm-2) was sustained by the proton flux through the TFC-BW membrane using a feed of 34 mM NaCl, and a 257 mM NaCl draw solution. Protons generated at the anode were transported through the cation exchange membrane and into the draw solution, lowering the pH of the draw solution. Additional proton transport through the TFC-BW membrane also lowered the pH of the feed solution. The localized accumulation of the protons on the draw side of the TFC-BW membrane resulted in high concentration polarization modulus of 1.41 × 105, which enhanced the water flux into the draw solution (5.56 LMH at 100 mA), compared to the control (1.10 LMH with no current). These results using this electro-forward osmosis (EFO) process demonstrated that enhanced water flux into the draw solution could be achieved using ion accumulation induced by an electrical field. The EFO system could be used for FO applications where a limited use of draw solute is necessary.

Linking Thermodynamics to Pollutant Reduction Kinetics by Fe2+ Bound to Iron Oxides.

Numerous studies have reported that pollutant reduction rates by ferrous iron (Fe2+) are substantially enhanced in the presence of an iron (oxyhydr)oxide mineral. Developing a thermodynamic framework to explain this phenomenon has been historically difficult due to challenges in quantifying reduction potential ( EH) values for oxide-bound Fe2+ species. Recently, our group demonstrated that EH values for hematite- and goethite-bound Fe2+ can be accurately calculated using Gibbs free energy of formation values. Here, we tested if calculated EH values for oxide-bound Fe2+ could be used to develop a free energy relationship capable of describing variations in reduction rate constants of substituted nitrobenzenes, a class of model pollutants that contain reducible aromatic nitro groups, using data collected here and compiled from the literature. All the data could be described by a single linear relationship between the logarithms of the surface-area-normalized rate constant ( kSA) values and EH and pH values [log( kSA) = - EH/0.059 V - pH + 3.42]. This framework provides mechanistic insights into how the thermodynamic favorability of electron transfer from oxide-bound Fe2+ relates to redox reaction kinetics.

Mediated Electrochemical Reduction of Iron (Oxyhydr-)Oxides under Defined Thermodynamic Boundary Conditions.

Iron (oxyhydr-)oxide reduction has been extensively studied because of its importance in pollutant redox dynamics and biogeochemical processes. Yet, experimental studies linking oxide reduction kinetics to thermodynamics remain scarce. Here, we used mediated electrochemical reduction (MER) to directly quantify the extents and rates of ferrihydrite, goethite, and hematite reduction over a range of negative reaction free energies, ΔrG, that were obtained by systematically varying pH (5.0 to 8.0), applied reduction potentials (-0.53 to -0.17 V vs SHE), and Fe2+ concentrations (up to 40 µM). Ferrihydrite reduction was complete and fast at all tested ΔrG values, consistent with its comparatively low thermodynamic stability. Reduction of the thermodynamically more stable goethite and hematite changed from complete and fast to incomplete and slow as ΔrG values became less negative. Reductions at intermediate ΔrG values showed negative linear correlations between the natural logarithm of the reduction rate constants and ΔrG. These correlations imply that thermodynamics controlled goethite and hematite reduction rates. Beyond allowing to study iron oxide reduction under defined thermodynamic conditions, MER can also be used to capture changes in iron oxide reducibility during phase transformations, as shown for Fe2+-facilitated transformation of ferrihydrite to goethite.

Chemical Degradation of Polyacrylamide during Hydraulic Fracturing.

Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including decisions on strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by 2 orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluids. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-µM hydroxyl radical concentrations. The shale sample adsorbed some PAM (∼30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe2+ at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

Susceptibility of Goethite to Fe2+-Catalyzed Recrystallization over Time.

Recent work has shown that iron oxides, such as goethite and hematite, may recrystallize in the presence of aqueous Fe2+ under anoxic conditions. This process, referred to as Fe2+-catalyzed recrystallization, can influence water quality by causing the incorporation/release of environmental contaminants and biological nutrients. Accounting for the effects of Fe2+-catalyzed recrystallization on water quality requires knowing the time scale over which recrystallization occurs. Here, we tested the hypothesis that nanoparticulate goethite becomes less susceptible to Fe2+-catalyzed recrystallization over time. We set up two batches of reactors in which 55Fe2+ tracer was added at two different time points and tracked the 55Fe partitioning in the aqueous and goethite phases over 60 days. Less 55Fe uptake occurred between 30 and 60 days than between 0 and 30 days, suggesting goethite recrystallization slowed with time. Fitting the data with a box model indicated that 17% of the goethite recrystallized after 30 days of reaction, and an additional 2% recrystallized between 30 and 60 days. The decreasing susceptibility of goethite to recrystallize as it reacted with aqueous Fe2+ suggested that recrystallization is likely only an important process over short time scales.

Self-Generated Electrokinetic Fluid Flows during Pseudomorphic Mineral Replacement Reactions.

Pseudomorphic mineral replacement reactions involve one mineral phase replacing another, while preserving the original mineral's size and texture. Macroscopically, these transformations are driven by system-wide equilibration through dissolution and precipitation reactions. It is unclear, however, how replacement occurs on the molecular scale and what role dissolved ion transport plays. Here, we develop a new quantitative framework to explain the pseudomorphic replacement of KBr crystal in a saturated KCl solution through a combination of microscopic, spectroscopic, and modeling techniques. Our observations reveal that pseudomorphic mineral replacement (pMRR) is transport-controlled for this system and that convective fluid flows, caused by diffusioosmosis, play a key role in the ion transport process across the reaction-induced pores in the product phase. Our findings have important implications for understanding mineral transformations in natural environments and suggest that replacement could be exploited in commercial and laboratory applications.

Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization.

When goethite is exposed to aqueous Fe(2+), rapid and extensive Fe atom exchange can occur between solid-phase Fe(3+) and aqueous Fe(2+) in a process referred to as Fe(2+)-catalyzed recrystallization. This process can lead to the structural incorporation or release of trace elements, which has important implications for contaminant remediation and nutrient biogeochemical cycling. Prior work found that the process did not cause major changes to the goethite structure or morphology. Here, we further investigated if and how goethite morphology and aggregation behavior changed temporally during Fe(2+)-catalyzed recrystallization. On the basis of existing literature, we hypothesized that Fe(2+)-catalyzed recrystallization of goethite would not result in changes to individual particle morphology or interparticle interactions. To test this, we reacted nanoparticulate goethite with aqueous Fe(2+) at pH 7.5 over 30 days and used transmission electron microscopy (TEM), cryogenic TEM, and (55)Fe as an isotope tracer to observe changes in particle dimensions, aggregation, and isotopic composition over time. Over the course of 30 days, the goethite particles substantially recrystallized, and the particle dimensions changed anisotropically, resulting in a preferential increase in the mean particle width. The temporal changes in goethite morphology could not be completely explained by a single mineral-transformation mechanism but rather indicated that multiple transformation mechanisms occurred concurrently. Collectively, these results demonstrate that the morphology of goethite nanoparticles does change during recrystallization, which is an important step toward identifying the driving force(s) of recrystallization.

Harvesting Energy from Salinity Differences Using Battery Electrodes in a Concentration Flow Cell.

Salinity-gradient energy (SGE) technologies produce carbon-neutral and renewable electricity from salinity differences between seawater and freshwater. Capacitive mixing (CapMix) is a promising class of SGE technologies that captures energy using capacitive or battery electrodes, but CapMix devices have produced relatively low power densities and often require expensive materials. Here, we combined existing CapMix approaches to develop a concentration flow cell that can overcome these limitations. In this system, two identical battery (i.e., faradaic) electrodes composed of copper hexacyanoferrate (CuHCF) were simultaneously exposed to either high (0.513 M) or low (0.017 M) concentration NaCl solutions in channels separated by a filtration membrane. The average power density produced was 411 ± 14 mW m(-2) (normalized to membrane area), which was twice as high as previously reported values for CapMix devices. Power production was continuous (i.e., it did not require a charging period and did not vary during each step of a cycle) and was stable for 20 cycles of switching the solutions in each channel. The concentration flow cell only used inexpensive materials and did not require ion-selective membranes or precious metals. The results demonstrate that the concentration flow cell is a promising approach for efficiently harvesting energy from salinity differences.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides­hematite and goethite­and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+­goethite redox couple and 769 ± 2 mV for the aqueous Fe2+­hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Electrochemical analyses of redox-active iron minerals: a review of nonmediated and mediated approaches.

Redox-active minerals are ubiquitous in the environment and are involved in numerous electron transfer reactions that significantly affect biogeochemical processes and cycles as well as pollutant dynamics. As a consequence, research in different scientific disciplines is devoted to elucidating the redox properties and reactivities of minerals. This review focuses on the characterization of mineral redox properties using electrochemical approaches from an applied (bio)geochemical and environmental analytical chemistry perspective. Establishing redox equilibria between the minerals and working electrodes is a major challenge in electrochemical measurements, which we discuss in an overview of traditional electrochemical techniques. These issues can be overcome with mediated electrochemical analyses in which dissolved redox mediators are used to increase the rate of electron transfer and to facilitate redox equilibration between working electrodes and minerals in both amperometric and potentiometric measurements. Using experimental data on an iron-bearing clay mineral, we illustrate how mediated electrochemical analyses can be employed to derive important thermodynamic and kinetic data on electron transfer to and from structural iron. We summarize anticipated methodological advancements that will further contribute to advance an improved understanding of electron transfer to and from minerals in environmentally relevant redox processes.

Linear free energy relationships for the biotic and abiotic reduction of nitroaromatic compounds.

Nitroaromatic compounds (NACs) are ubiquitous environmental contaminants that are susceptible to biological and abiotic reduction. Prior works have found that for the abiotic reduction of NACs, the logarithm of the NACs' rate constants correlate with one-electron reduction potential values of the NACs (EH,NAC1) according to linear free energy relationships (LFERs). Here, we extend the application of LFERs to the bioreduction of NACs and to the abiotic reduction of NACs by bioreduced (and pasteurized) iron-bearing clay minerals. A linear correlation (R2=0.96) was found between the NACs' bioreduction rate constants (kobs) and EH,NAC1 values. The LFER slope of log kobs versus EH,NAC1/(2.303RT/F) was close to one (0.97), which implied that the first electron transfer to the NAC was the rate-limiting step of bioreduction. LFERs were also established between NAC abiotic reduction rate constants by bioreduced iron-bearing clay minerals (montmorillonite SWy-2 and nontronite NAu-2). The second-order NAC reduction rate constants (k) by bioreduced SWy-2 and NAu-2 were well correlated to EH,NAC1 (R2=0.97 for both minerals), consistent with bioreduction results. However, the LFER slopes of log k versus EH,NAC1/(2.303RT/F) were significantly less than one (0.48­0.50) for both minerals, indicating that the first electron transfer to the NAC was not the rate-limiting step of abiotic reduction. Finally, we demonstrate that the rate of 4-acetylnitrobenzene reduction by bioreduced SWy-2 and NAu-2 correlated to the reduction potential of the clay (EH,clay, R2=0.95 for both minerals), indicating that the clay reduction potential also influences its reactivity.

Iron(III)-bearing clay minerals enhance bioreduction of nitrobenzene by Shewanella putrefaciens CN32.

Iron-bearing clay minerals are ubiquitous in the environment, and the clay-Fe(II)/Fe(III) redox couple plays important roles in abiotic reduction of several classes of environmental contaminants. We investigated the role of Fe-bearing clay minerals on the bioreduction of nitrobenzene. In experiments with Shewanella putrefaciens CN32 and excess electron donor, we found that the Fe-bearing clay minerals montmorillonite SWy-2 and nontronite NAu-2 enhanced nitrobenzene bioreduction. On short time scales (<50 h), nitrobenzene reduction was primarily biologically driven, but at later time points, nitrobenzene reduction by biologically formed structural Fe(II) in the clay minerals became increasingly important. We found that chemically reduced (dithionite) iron-bearing clay minerals reduced nitrobenzene more rapidly than biologically reduced iron-bearing clay minerals despite the minerals having similar structural Fe(II) concentrations. We also found that chemically reduced NAu-2 reduced nitrobenzene faster as compared to chemically reduced SWy-2. The different reactivity of SWy-2 versus NAu-2 toward nitrobenzene was caused by different forms of structural clay-Fe(II) in the clay minerals and different reduction potentials (Eh) of the clay minerals. Because most contaminated aquifers become reduced via biological activity, the reactivity of biogenic clay-Fe(II) toward reducible contaminants is particularly important.