Transformation of halogenated organic compounds (HOCs) by zero-valent iron represents one of the latest innovative technologies for environmental remediation. For example, iron can be used to construct a reactive wall in the path of a contaminated groundwater plume to degrade HOCs. In this paper, an efficient method of synthesizing nanoscale (1−100 nm) iron and palladized iron particles is presented. Nanoscale particles are characterized by high surface area to volume ratios and high reactivities. BET specific surface area of the synthesized metal particles is 33.5 m2/g. In comparison, a commercially available Fe powder (<10 μm) has a specific surface area of just 0.9 m2/g. Batch studies demonstrated that these nanoscale particles can quickly and completely dechlorinate several chlorinated aliphatic compounds and a mixture of PCBs at relatively low metal to solution ratio (2−5 g/100 mL). Surface-area-normalized rate constants (KSA) are calculated to be 10−100 times higher than those of commercially availa...

Synthesizing Nanoscale Iron Particles for Rapid and Complete Dechlorination of TCE and PCBs

Remediation technologies for heavy metal contaminated groundwater.

https://www.eng.uwo.ca/grc/pdfs/groundwater_remediation/Nanoscale.pdf

Nanoscale zero valent iron and bimetallic particles for contaminated site remediation

The kinetics of nitrate, nitrite, and Cr(VI) reduction by three types of iron metal (Fe0) were studied in batch reactors for a range of Fe0 surface area concentrations and solution pH values (5.5−9.0). At pH 7.0, there was only a modest difference (2−4×) in first-order rate coefficients (kobs) for each contaminant among the three Fe0 types investigated (Fisher, Peerless, and Connelly). The kobs values at pH 7.0 for both nitrite and Cr(VI) reduction were first-order with respect to Fe0 surface area concentration, and average surface area normalized rate coefficients (kSA) of 9.0 × 10-3 and 2.2 × 10-1 L m-2 h-1 were determined for nitrite and Cr(VI), respectively. Unlike nitrite and Cr(VI), Fe0 surface area concentration had little effect on rates of nitrate reduction (with the exception of Connelly Fe0, which reduced nitrate at slower rates at higher Fe0 surface areas). The rates of nitrate, nitrite, and Cr(VI) reduction by Fisher Fe0 decreased with increasing pH with apparent reaction orders of 0.49 ± 0.0...

Kinetics of nitrate, nitrite, and Cr(VI) reduction by iron metal.

https://stormwater.ucf.edu/fileRepository/docs/chemicaltreatment/documents/Blowes%20et%20al.,%202000.pdf

Treatment of inorganic contaminants using permeable reactive barriers

Zero-valent iron for the in situ remediation of selected metals in groundwater

Adsorption–desorption reactions are important processes that affect the transport of contaminants in the environment. Various empirical approaches, such as the distribution coefficient and Freundlich and Langmuir isotherm equations, have been used to represent adsorption. The empirical approaches are not capable of accounting for the effects of variable chemical conditions, such as pH, on adsorption reactions. This can be done using chemical models such as surface complexation models. These models define specific surface species, chemical reactions, equilibrium constants, mass balances, and charge balances, and their molecular features can be given thermodynamic significance. Ion adsorption mechanisms and surface configurations for the surface complexation models can be established from independent experimental observations. These include both indirect measurements, such as point of zero charge shifts, ionic strength effects, and calorimetry, and direct spectroscopic techniques, including vibrational spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and X-ray absorption spectroscopy. Surface complexation models were developed for single mineral phases but have now been applied to natural mineral assemblages using both component additivity (CA) and generalized composite (GC) approaches. Surface complexation models have been incorporated into subsurface transport models at several field sites, although simplifying assumptions are needed to deal with heterogeneous materials. Surface complexation models for contaminant adsorption have the potential to increase the confidence and scientific credibility of transport modeling by reducing the uncertainty in quantifying retardation and providing a means of quantifying that uncertainty.

Adsorption–Desorption Processes in Subsurface Reactive Transport Modeling

Gas leakage from deep storage reservoirs is a major risk factor associated with geologic carbon sequestration (GCS). A systematic understanding of how such leakage would impact the geochemistry of potable aquifers and the vadose zone is crucial to the maintenance of environmental quality and the widespread acceptance of GCS. This paper reviews the current literature and discusses current knowledge gaps on how elevated CO2 levels could influence geochemical processes (e.g., adsorption/desorption and dissolution/precipitation) in potable aquifers and the vadose zone. The review revealed that despite an increase in research and evidence for both beneficial and deleterious consequences of CO2 migration into potable aquifers and the vadose zone, significant knowledge gaps still exist. Primary among these knowledge gaps is the role/influence of pertinent geochemical factors such as redox condition, CO2 influx rate, gas stream composition, microbial activity, and mineralogy in CO2-induced reactions. Although the...

Geochemical Implications of Gas Leakage Associated with Geologic CO2 Storage - A Qualitative Review

This report compiles in a single source the Kd values measured with Hanford sediment for radionuclides and toxic compounds that have the greatest potential for driving risk to human health and safety in the vadose zone and groundwater at the Hanford Site.

/pdf/hanford-contaminant-distribution-coefficient-database-and-4uawd9n5ll.pdf

Hanford Contaminant Distribution Coefficient Database and Users Guide

Previous studies have demonstrated that gas-phase H2S can immobilize certain redox-sensitive contaminants (e.g., Cr, U, Tc) in vadose zone environments. A key issue for effective and efficient delivery of H2S in these environments is the reactivity of the gas with indigenous iron oxides. To elucidate the factors that control the transport of H2S in the vadose zone, laboratory column experiments were conducted to identify reaction mechanisms and measure rates of H2S oxidation by iron oxide-coated sands using several carrier gas compositions (N2, air, and O2) and flow rates. Most experiments were conducted using ferrihydrite-coated sand. Additional studies were conducted with goethite- and hematite-coated sand and a natural sediment. Selective extractions were conducted at the end of each column experiment to determine the mass balance of the reaction products. XPS was used to confirm the presence of the reaction products. For column experiments in which ferrihydrite-coated sand was the substrate and N2 was the carrier gas, the major H2S oxidation products were FeS and elemental sulfur (mostly S8(0), represented as S(0) for simplicity) at ratios that were consistent with the stoichiometry of the postulated reactions. When air or O2 were used as the carrier gas, S(0) became the dominant reaction product along with FeS2 and smaller amounts of FeS, sulfate, and thiosulfate. A mathematical model of reactive transport was used to test the hypothesis that S(0) forming on the iron oxide surfaces reduces access of H2S to the reactive surface. Several conceptual models were assessed in the context of the postulated reactions with the final model based on a linear surface poisoning model and fitted reaction rates. These results indicate that carrier gas selection is a critical consideration with significant tradeoffs for remediation objectives.

Kirk J. Cantrell

Papers

Zero-valent iron for the in situ remediation of selected metals in groundwater

Adsorption–Desorption Processes in Subsurface Reactive Transport Modeling

Geochemical Implications of Gas Leakage Associated with Geologic CO2 Storage - A Qualitative Review

Hanford Contaminant Distribution Coefficient Database and Users Guide

Oxidation of H2S by Iron Oxides in Unsaturated Conditions