Remediation of Contaminated Sites

In Situ Chemical Oxidation

Reading n. 12
 In Situ Chemical Oxidation (ISCO)

• Used in municipal and industrial wastewater treatment since

decades, recently applied to contaminated soils and
groundwater

• Delivery of chemical oxidants to contaminated media in

order to reduce mass, mobility and/or toxicity of
contamination

• Target contaminants: • PCE

• TCE
• Benzene
• PAHs
• Pesticides
 Oxidants used

Common oxidants:  Hydrogen peroxide (H2O2)

 Fenton’s reagent (H2O2 + Fe2+)
 Ozone (O3)
 Permanganate (MnO4-)
 Persulphate (S2O82-)

Readily available Few months of process

Economically feasible
 Hydrogen peroxide

H2O2 + H2O H+ + HO2- Dissociation greater than in water

Hydroperoxide ion : HO2-

Oxygen Oxygen
H
 Fenton’s Reagent

• Mixture of hydrogen peroxide with ferrous sulphate

• Injected in the contaminated soil under acidic conditions

(optimal pH = 2 ÷ 4)

• pH adjuster: acetic or sulphuric acid

• Rapid exothermic reaction

 Fenton’s Reagent

H2O2 + Fe+2 Fe+3 + OH - + OH 

H2O2 + Fe+3 Fe2+ + H+ + HO2

OH  Hydroxyl radical HO2 Hydroperoxide radical

Oxygen Oxygen Oxygen

H
H
 Limitations of the Fenton’s reagent

Groundwater Soil

• pH between 3 and 5 • Adequate hydraulic

conductivity (≥10-5 cm/sec)
• Moderate calcium carbonate,
hardness and organic matter • Low clay content to allow
content (<400 ppm) reagent penetration
 Ozone
• Oxidation of contaminants through formation of hydroxyl
radicals (OH°)

• Reaction with TCE:

O3 + H2O + C2HCl3 2CO2 + 3 HCl

• Strongly influenced by pH, ozone concentration and

free radical scavengers (e.g. CO32-)

• H2O2 often added to ozone/water system

• Produced onsite by electrical generators

 Permanganate
• KMnO4, NaMnO4- used

• Frequently used for TCE contamination:

2KMnO4 + C2HCl3 2MnO2(s) + 2CO2 + 2K+ + 3Cl- + H+

KMnO4 Easy to monitor

Relatively slow reaction,

compound available for longer
times in the contaminated area
Scheme of the ISCO process
 Design criteria

• Volume and chemical composition of the treatment based

on the contaminants and on the site characteristics

Geophysical, hydrogeological and chemical investigations

• Methods of delivery: • Groundwater wells

• Horizontal/vertical recirculation
wells
• Permeation by vertical lances
• Deep soil mixing equipment
• Hydraulic fracturing
 Design criteria

Injection of air, oxygen, ozone,

hydrogen peroxide, or a
combination of them

Ozone pressure: 1.4÷1.8 bar

1 hour of injection

1 hour without injection

Duration of the process:

weeks ÷ months

Figure 1. Injection point design from Pavlick et al., 2005.

 Natural and Total Oxidant Demand

• NOD: measure of how much oxidant can be consumed by

non target species at a treatment site

• Non-target reactants: • Humic acids

• Oxidizable metals and minerals
• Radical scavengers

• Key issue for dimensioning ISCO applications

• TOD = NOD + anthropogenic compounds oxidant demand

 Process efficiency

High treatment efficiencies can be reached (>90%) for

TCE, PCE and aromatic compounds

Cases of low performance of the process are due to:

• Poor uniformity of oxidant delivery
• Excessive oxidant consumption by natural materials
• Presence of DNAPLs
• Incomplete degradation
 Potential benefits and limitations

Benefits Limitations

Fast treatment Handling of strong oxidants

Large quantities of
Few waste material generated
chemicals can be required
Formation of gas, heat,
Temporary facilities in situ
toxic by-products
Applicable to a wide range of
Metals mobilization
contaminants
Potential enhancement of
Permeability reduction
microbial activity
 Example of ISCO application

Figure 2. ISCO operation using FR (NAS Pensacola).

 Example of ISCO application

Figure 3. Direct injection of H2O2 via vertical filters (City Chlor, 2013).
 Example of ISCO application

Figure 3. Soil mixing using ISCO at a former dry cleaning facility (Regenesis
Remediation ServicesTM) .