Figure 4-34: Typical Chemical Oxidation System

The Chemical oxidants most commonly employed to date include peroxide, ozone, and permanganate. These oxidants have been able to cause the rapid and complete chemical destruction of many toxic organic chemicals; other organics are amenable to partial degradation as an aid to subsequent bioremediation. In general the oxidants have been capable of achieving high treatment efficiencies (e.g., > 90 percent) for unsaturated aliphatic (e.g., trichloroethylene [TCE]) and aromatic compounds (e.g., benzene), with very fast reaction rates (90 percent destruction in minutes). Field applications have clearly affirmed that matching the oxidant and in situ delivery system to the contaminants of concern (COCs) and the site conditions is the key to successful implementation and achieving performance goals.

Peroxide

Oxidation using liquid hydrogen peroxide (H₂O₂) in the presence of native or supplemental ferrous iron (Fe⁺²) produces Fenton’s Reagent which yields free hydroxyl radicals (OH^-). These strong, nonspecific oxidants can rapidly degrade a variety of organic compounds. Fenton’s Reagent oxidation is most effective under very acidic pH (e.g., pH 2 to 4) and becomes ineffective under moderate to strongly alkaline conditions. The reactions are extremely rapid and follow second-order kinetics. 

Ozone addition

Ozone gas can oxidize contaminants directly or through the formation of hydroxyl radicals. Like peroxide, ozone reactions are most effective in systems with acidic pH. The oxidation reaction proceeds with extremely fast, pseudo first order kinetics. Due to ozone’s high reactivity and instability, O₃ is produced onsite, and it requires closely spaced delivery points (e.g., air sparging wells). In situ decomposition of the ozone can lead to beneficial oxygenation and biostimulation.

Permanganate

The reaction stoichiometry of permanganate (typically provided as liquid or solid KMnO₄, but also available in Na, Ca, or Mg salts) in natural systems is complex. Due to its multiple valence states and mineral forms, Mn can participate in numerous reactions. The reactions proceed at a somewhat slower rate than the previous two reactions, according to second order kinetics. Depending on pH, the reaction can include destruction by direct electron transfer or free radical advanced oxidation—permanganate reactions are effective over a pH range of 3.5 to 12. 

Synonyms:

DSERTS Code: N13 (Chemical Reduction/Oxidation).

Applicability:

The rate and extent of degradation of a target COC are dictated by the properties of the chemical itself and its susceptibility to oxidative degradation as well as the matrix conditions, most notably, pH, temperature, the concentration of oxidant, and the concentration of other oxidant-consuming substances such as natural organic matter and reduced minerals as well as carbonate and other free radical scavengers. Given the relatively indiscriminate and rapid rate of reaction of the oxidants with reduced substances, the method of delivery and distribution throughout a subsurface region is of paramount importance. Oxidant delivery systems often employ vertical or horizontal injection wells and sparge points with forced advection to rapidly move the oxidant into the subsurface. 

Permanganate is relatively more stable and relatively more persistent in the subsurface; as a result, it can migrate by diffusive processes. Consideration also must be given to the effects of oxidation on the system. All three oxidation reactions can decrease the pH if the system is not buffered effectively. Other potential oxidation-induced effects include: colloid genesis leading to reduced permeability; mobilization of redox-sensitive and exchangeable sorbed metals; possible formation of toxic byproducts; evolution of heat and gas; and biological perturbation

Limitations:

The following factors may limit the applicability and effectiveness of chemcial oxidation include:

•  Requirement for handling large quantities of hazardous oxidizing chemicals due to the oxidant demand of the target organic chemicals and the unproductive oxidant consumption of the formation.

• Some COCs are resistant to oxidation.

• There is a potential for process-induced detrimental effects. Further research and development is ongoing to advance the science and engineering of in situ chemical oxidation and to increase its overall cost effectivenes.

Data Needs:

Engineering of in situ chemical oxidation must be done with due attention paid to reaction chemistry and transport processes. It is also critical that close attention be paid to worker training and safe handling of process chemicals as well as proper management of remediation wastes. The design and implementation process should rely on an integrated effort involving screening level characterization tests and reaction transport modeling, combined with treatability studies at the lab and field scale.

Performance Data:

In situ chemical oxidation is a viable remediation technology for mass reduction in source areas as well as for plume treatment. The potential benefits of in situ oxidation include the rapid and extensive reactions with various COCs applicable to many bio-recalcitrant organics and subsurface environments. Also, in situ chemical oxidation can be tailored to a site and implemented with relatively simple, readily available equipment. Some potential limitations exist including the requirement for handling large quantities of hazardous oxidizing chemicals due to the oxidant demand of the target organic chemicals and the unproductive oxidant consumption of the formation; some COCs are resistant to oxidation; and there is a potential for process-induced detrimental effects. Further research and development is ongoing to advance the science and engineering of in situ chemical oxidation and to increase its overall cost effectiveness

Cost:

The key cost driver information and cost analysis was developed in 2006 using the Remedial Action Cost Engineering and Requirements (RACER) software.

Key Cost Drivers 

·        Economy of Scale

o       Quantity of material treated has a large impact

·        Moisture content in waste

o       Slight increase in costs between soil and sludge

·        Contaminant concentrations

o       High influent and low effluent concentrations will drive up costs

Cost Analysis

The following table represents estimated costs (by common unit of measure) to apply chemical oxidation technology at sites of varying size and complexity.   A more detailed cost estimate table which includes specific site characteristics and significant cost elements that contributed to the final costs can be viewed by clicking on the link below.

 Detailed Cost Estimate

References:

Innovative Remediation Technologies:  Field Scale Demonstration Project in North America, 2nd Edition

Abstracts of Remediation Case Studies, Volume 4,  June, 2000, EPA 542-R-00-006

Guide to Documenting and Managing Cost and Performance Information for Remediation Projects - Revised Version, October, 1998, EPA 542-B-98-007

EPA, 2000.Ground Water Currents, December 2000, Issue No. 41: Current Issue: Interagency Demonstrations on DNAPL Conducted at Cape Canaveral 

EPA, 2000.Ground Water Currents, September 2000, Issue No. 37: Current Issue: In Situ Chemical Oxidation for Remediation of Contaminated Soil and Ground Water

EPA, 1988, Guidance for Conducting Remedial Investigations and Feasibility Studies under CERCLA, OSWER- 9355.3-01, Washington, DC

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