Timothy L. Johnson

Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe0) is mediated by the thin film of iron (hydr)oxides found on Fe0 under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl4) degradation by Fe0 was studied under the influence of various anions, ligands, and initial CCl4 concentrations ([P]o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl4 disappearance (kCCl4), and zero order for the appearance of dissolved Fe2+ (kFe2+). The rate of dechlorination exhibits saturation kinetics with respect to [P]o, suggesting that CCl4 is transformed at a limited number of reactive surface sites. Because oxidation of Fe0 by CCl4 is the major corrosion reaction in these systems, kFe2+ also approaches a limiting value at high CCl4 concentrations. The adsorption of borate strongly inhibited reduction of CCl4, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased kCCl4 (and kFe2+). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.

Pilot Test of a Surfactant-modified Zeolite Permeable Barrier for Groundwater Remediation

Two pilot-scale tests of surfactant-modified zeolite (SMZ) permeable barriers were conducted at the Large Experimental Aquifer Facility of the Oregon Graduate Institute. The tests were performed in an 8.5-m-wide, 8.5-m-long, 3-m-deep concrete tank. The SMZ was installed in a 1-m-wide, 6-m-long, 2-m-deep barrier frame in the center of the tank. The rest of the tank was filled with sand to form a simulated aquifer. A three-dimensional sampling array consisting of 405 sampling points was installed in the tank. Controlled water flow across the tank was maintained using ten upgradient injection wells and ten downgradient withdrawal wells. A specific discharge of 0.17 m day−1 was imposed, resulting in an average linear groundwater velocity of approximately 0.5 m day−1 in the sand. The upgradient wells allowed injection of a three-dimensional contaminant plume composed of 10 mg L−1 (0.19 mmolL−1) Cr, in the form of chromate, and 1.8 mg L−1 (0.011 mmol L−1) perchloroethylene (PCE).

Diagnosis of in situ air sparging performance using transient groundwater pressure changes during startup and shutdown

Groundwater pressure measurements during startup and shutdown of in situ air sparging (IAS) systems are used to diagnose air flow behavior below the water table. The magnitude of the pressure response provides insight into the permeability of the zone into which the air is flowing. The duration of elevated pressures during startup and reduced pressures during shutdown indicate the extent to which air is being trapped below the water table by lower-permeability layers. The pressure measurements can be easily and quickly repeated and as a result are useful for both pilot tests and for optimizing operating conditions of existing IAS systems. Whether used alone or in conjunction with other diagnostic tools, pressure measurements are an important tool for assessing IAS performance.

SURFACE-ALTERED ZEOLITES AS PERMEABLE BARRIERS FOR IN SITU TREATMENT OF CONTAMINATED GROUNDWATER

The overall objective of this effort is to develop and test a zeolite-based permeable barrier system for containing and remediating contaminated groundwater. The projected product is an engineered and tested permeable barrier system that can be adopted by the commercial sector.

Diagnostic Tools for Integrated In Situ Air Sparging Pilot Tests

In situ air sparging (IAS) pilot test procedures have been developed that provide rapid, on-site information about IAS performance. The standard pilot test consists of six activities conducted to look for indicators of infeasibility and to characterize the air distribution to the extent necessary to make design decisions about IAS well placement. In addition, safety hazards that need to be addressed prior to full-scale design are identified. Two additional pilot test activities are described in those cases where air distribution must be more precisely defined. The test activities include both chemical tests (tracking contaminant concentrations, dissolved oxygen and tracers) and physical tests (air flow rate and injection pressure, groundwater pressure response). Pilot test data from Eielson Air Force Base, Alaska illustrates implementation of the pilot test and interpretation of the data.

Helium Tracer Tests for Assessing Contaminant Vapor Recovery and Air Distribution During In Situ Air Sparging

Helium tracer tests are used as an alternative to soil-gas pressure measurements to assess the effectiveness of soil vapor extraction (SVE) systems for capturing contaminant vapors liberated by in situ air sparging (IAS). The tracer approach is simple to conduct and provides more direct and reliable measures than the soil-gas pressure approach. The tracer test described here can be used to both determine SVE system capture efficiency and to evaluate air distribution during IAS pilot tests. The tests can also be conducted on operating, full-scale systems to confirm system performance. In addition, the tests can be easily repeated, which allows system parameters to be modified and the impact of those modifications to be quickly assessed. Whether used alone or in conjunction with other diagnostic tools, helium tracer tests provide an important measure of IAS system performance.