Nanoscale Metallic Iron for Environmental Remediation: Prospects and Limitations

The amendment of the subsurface with nanoscale metallic iron particles (nano-Fe0) has been discussed in the literature as an efficient in situ technology for groundwater remediation. However, the introduction of this technology was controversial and its efficiency has never been univocally established. This unsatisfying situation has motivated this communication whose objective was a comprehensive discussion of the intrinsic reactivity of nano-Fe0 based on the contemporary knowledge on the mechanism of contaminant removal by Fe0 and a mathematical model. It is showed that due to limitations of the mass transfer of nano-Fe0 to contaminants, available concepts cannot explain the success of nano-Fe0 injection for in situ groundwater remediation. It is recommended to test the possibility of introducing nano-Fe0 to initiate the formation of roll-fronts which propagation would induce the reductive transformation of both dissolved and adsorbed contaminants. Within a roll-front, FeII from nano-Fe0 is the reducing agent for contaminants. FeII is recycled by biotic or abiotic FeIII reduction. While the roll-front concept could explain the success of already implemented reaction zones, more research is needed for a science-based recommendation of nano- Fe0 for subsurface treatment by roll-front

Rapid dechlorination of polychlorinated dibenzo-p-dioxins by bimetallic and nanosized zerovalent iron

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), especially the 2,3,7,8-substituted congeners, are extremely toxic, persistent, and recalcitrant to remediation. Dechlorination of PCDD/Fs by zerovalent iron (ZVI) is thermodynamically feasible, but useful rates of reaction have not been previously reported. Here we show that ZVI (both micro- and nanosized ZVI, without palladization) dechlorinates PCDD congeners with four or more chlorines in aqueous systems, but the reaction is too slow to achieve complete dechlorination within a practical period of time. In contrast, palladized nanosized ZVI (Pd/nFe) rapidly dechlorinates PCDDs, including the mono- to tetra-chlorinated congeners. The rate of 1,2,3,4-tetrachloro dibenzo-p-dioxin (1,2 3,4-TeCDD) degradation using Pd/nFe was about 3 orders of magnitude faster than 1,2,3,4-TeCDD degradation using unpalladized ZVI. The distribution of products obtained from dechlorination of 1,2,3,4-TeCDD suggests that palladization shifts the pathways of contaminant degradation toward a greater role of H atom transfer rather than electron transfer.X119994sciescopu

Modeling the Reductive Dechlorination of Polychlorinated Dibenzo-p-Dioxins: Kinetics, Pathway, and Equivalent Toxicity

Reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs) involves 256 reactions linking 76 congeners with highly variable toxicities, so it is challenging to assess the overall effect of this process on the environmental impact of PCDD contamination. This study describes a quantitative solution to this problem that allows calculation of the toxic equivalent quantity FEW of the mixture of PCDD congeners predicted by a linear free-energy relationship (LFER) that relates rate constants of dechlorination to calculated reduction potentials. The reduction potentials were derived from Gibbs free energies, calculated using density functional theory (DFT) and vapor pressures and solubilities for individual congeners. The LFER was calibrated with rate constants that we recently reported for PCDD dechlorination by nano-zerovalent iron (nZVI). Simulation done with this model predicts that more than 100 years would be required for complete dechlorination of octachlorinated dibenzo-p-dioxin (OCDD) to dibenzo-p-dioxin (OD) under conditions representative of treatment with nZVI and that the TEQ of the mixture of intermediates during this process increases 10-fold, peaking at around 3-6 years, mainly because of the higher toxicity of 2,3,7,8-substituted congeners.X111313sciescopu

Remediation of trichloroethylene by fes-coated iron nanoparticles in simulated and real groundwater: Effects of water chemistry

The reactivity of FeS-coated iron nanoparticles (nFe/FeS) toward trichloroethylene (TCE) reduction was examined in both synthetic and real groundwater matrices to evaluate the potential performance of nFe/FeS in field treatment. The rate of TCE reduction increased with increasing pH, which is consistent with the pH effect reported previously for iron sulfide systems, but opposite that has been observed for (nonsulfidic) Fe-0 systems. The rates of TCE reduction were unaffected by ionic strength over the range of 0.1-10 mM NaCl, increased with Ca2+ or Mg2+ concentrations, and inhibited by the presence of humic acid. The inhibitory effect of humic acid on the reactivity of nFe/FeS was largely alleviated when humic acid was combined with Ca2+/Mg2+, Presumably due to decreased adsorption of humic acid onto nFe/FeS surface by the formation of humic acid-Ca2+/Mg2+ complexes.X115345sciescopu

Effects of Metal Ions on the Reactivity and Corrosion Electrochemistry of Fe/FeS Nanoparticles

Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd2+, Cu2+, Ni2+, Co2+, and Mn2+) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn2+ and Cu2+ decreased TCE reduction rates, while Pd2+, Co2+, and Ni2+ increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (k(obs)) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, k(obs) was best described by the exchange current density for activation of hydrogen, whereas k(obs) for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.X112619sciescopu

Reactivity of Fe/FeS Nanoparticles: Electrolyte Composition Effects on Corrosion Electrochemistry

Zerovalent iron nanoparticles (Fe-0 NPs or nZVI) synthesized by reductive precipitation in aqueous solution (Fe/FeO) differ in composition and reactivity from the NPs obtained by reductive precipitation in the presence of a S-source such as dithionite (Fe/FeS). To compare the redox properties of these types of NPs under a range of environmentally relevant solution conditions, stationary powder disk electrodes (PDEs) made from Fe/FeO and Fe/FeS were characterized using a series of complementary electrochemical techniques: open-circuit chronopotentiometry (CP), linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). The passive films on these materials equilibrate within minutes of first immersion and do not show further breakdown until >1 day of exposure. During this period, the potentials and currents measured by LPR and LSV suggest that Fe/FeS undergoes more rapid corrosion and is more strongly influence by solution chemical conditions than Fe/FeO. Chloride containing media were strongly activating and natural organic mildly passivating for both materials. These effects were also seen in the impedance data obtained by EIS, and equivalent circuit modeling of the electrodes composed of these powders suggested that the higher reactivity of Fe/FeS is due to greater abundance of defects in its passive film.X112421sciescopu

Technetium Stabilization in Low-Solubility Sulfide Phases: A Review

Technetium contamination remains a major environmental problem at nuclear reprocessing sites, e.g., the Hanford Site, Washington, USA. At these sites, Tc is present in liquid waste destined for immobilization in a waste form or has been released into the subsurface environment. The high environmental risk associated with Tc is due to its long half-life (214 000 years) and the mobility of the oxidized anionic species Tc(VII)O4-. Under reducing conditions, TcO4- is readily reduced to Tc(IV), which commonly exists as a relatively insoluble and therefore immobile, hydrous Tc-oxide (TcO2·nH2O). The stability of Tc(IV) sequestered as solid phases depends on the solubility of the solid and susceptibility to reoxidation to TcO4-, which in turn depend on the (biogeo)chemical conditions of the environment and/or nuclear waste streams. Unfortunately, the solubility of crystalline TcO2 or amorphous TcO2·H2O is still above the maximum contaminant level (MCL) established by the U.S. EPA (900 pCi/L), and the kinetics of TcO2 oxidative dissolution can be on the order of days to years. In addition to oxygen, sulfur can form complexes that significantly affect the adsorption, solubility, and reoxidation potential of Tc, especially Tc(IV). The principal technetium sulfides are TcS2 and Tc2S7, but much less is known about the mechanisms of formation, stabilization, and reoxidation of Tc-sulfides. A common assumption is that sulfides are less soluble than their oxyhydrous counterparts. Determination of the molecular structure of Tc2S7 in particular has been hampered by the propensity of this phase to precipitate as an amorphous substance. Recent work indicates that the oxidation state of Tc in Tc2S7 is Tc(IV), in apparent contradiction to its nominal stoichiometry. Technetium is relatively immobile in reduced sediments and soils, but in many cases the exact sink for Tc has not been identified. Experiments and modeling have demonstrated that both abiotic and biologic mechanisms can exert strong controls on Tc mobility and that Tc binding or uptake into sulfide phases can occur. These and similar investigations also show that extended exposure to oxidizing conditions results in transformation of sulfide-stabilized Tc(IV) to a Tc(IV)O2-like phase without formation of measurable dissolved TcO4-, suggesting a solid-state transformation in which Tc(IV)-associated sulfide is preferentially oxidized before the Tc(IV) cation. This transformation of Tc(IV)-sulfides to Tc(IV)-oxides may be the main process that limits remobilization of Tc as Tc(VII)O4-. The efficacy of the final waste form to retain Tc also strongly depends on the ability of oxidizing species to enter the waste and convert Tc(IV) to Tc(VII). Many waste form designs are reducing (e.g., cementitious waste forms such as salt stone) and, therefore, attempt to restrict access of oxidizing species such that diffusion is the rate-limiting step in remobilization of Tc