ENVI24: Environmental Technology and Management 2

Shella Ira Talampas 2nd Semester SY 2018 - 2019

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OUTLINE
1. INTRODUCTION
1.1. OVERVIEW: CHEMICALS
1.2. ENVIRONMENTAL FATE: ORGANIC COMPOUNDS IN THE ENVIRONMENT
1.3. CONTAMINATED LAND
1.4. WASTE MANAGEMENT AND DISPOSAL
1.5. LEGISLATION – CONTAMINATED LAND AND WASTE MANAGEMENT
2. TYPES OF CHEMICAL POLLUTANT REMEDIATION
2.1. BIOREMEDIATION
2.2. PHYTOREMEDIATION
2.3. SOIL WASHING
2.4. STABILIZATION/ SOLIDIFICATION
2.5. CHEMICAL OXIDATION

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 2. TYPES OF CHEMICAL POLLUTANT REMEDIATION

2.5. CHEMICAL OXIDATION

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CHEMICAL OXIDATION METHOD
What is it?
• Oxidation chemically converts hazardous contaminants to non-hazardous or
less toxic compounds that are more stable, less mobile, and/or inert
• In situ chemical oxidation (ISCO)
• A technique whereby an oxidant is introduced into the subsurface to
chemically oxidize organic contaminants changing them to harmless
substances
• Ex situ chemical oxidation (ESCO)
• A technique whereby involves mixing an oxidizing compound with
contaminated groundwater in a vessel
CHEMICAL OXIDATION METHOD
SOURCE VS. PLUME

• ISCO reduces contaminant

mass through the oxidation
process
• Mass reduction = reduction in
risk
• Source versus plume
• Usually combined with
something else (e.g.,
monitored natural
attenuation)
SUITABLE FOR
• MTBE
• Chlorinated solvents (PCE, TCE, DCA)
• Polychlorinated Biphenols (PCBs)
• Pentachlorophenol (PCPs)
• Solvent stabilizers
• Free product or hot spots
• Fuel hydrocarbons and BTEX
• Pesticides (DDT, DDE, etc.)
OXIDIZING AGENTS
• The oxidizing agents most commonly used are:
• Ozone (O3)
• Hydrogen peroxide (H2O2) as Fenton’s Reagent
• Hypochlorites (ClO−)
• Chlorine (Cl)
• Chlorine dioxide (ClO2)
• Permanganate (KMnO4)

• The oxidants have been capable of achieving high treatment efficiencies (>
90%) for unsaturated aliphatic (e.g., trichloroethylene [TCE]) and aromatic
compounds (e.g., benzene), with very fast reaction rates (90% destruction in
minutes)
TRADITIONALLY USED OXIDANTS
• Permanganate
• Potassium permanganate (KMnO4)
• Crystalline solid
• Sodium permanganate (NaMnO4)
• Concentrated liquid
• Ozone
• O3 (gas)
• Peroxide (Fenton’s Reagent)
• H2O2 and ferrous iron react to produce radicals
• More accurately catalyzed peroxide propagation
EMERGING/CURRENTLY PREFERRED OXIDANTS
• Persulfate
• Sodium persulfate - most commonly used
• Potassium persulfate - very low solubility
• Persulfate anions (S2O82 –) dissociate in water
• Oxidative strength greatly increased with addition of heat or a ferrous
salt (Iron II)
• Attributed to production of sulfate free radical (SO4 – •)

• Other oxidants – solid peroxides

• Magnesium peroxide (MgO2)
• Calcium peroxide (CaO2)
• Sodium percarbonate (Na2CO3•3H2O2)
TYPES OF TREATMENT METHOD
Hydrogen Peroxide/Fenton’s Reagent
• 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), ferric iron (Fe3+), and hydroxyl ions (OH-)
• 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
TYPES OF TREATMENT METHOD
Ozone Addition
• Ozone gas can oxidize contaminants directly or through the formation of
hydroxyl radicals
• Ozone reactions are most effective in systems with acidic pH and 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
TYPES OF TREATMENT METHOD
Permanganate
• 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
TYPICAL CHEMICAL OXIDATION SYSTEM

https://frtr.gov/
OXIDANT SPECIFIC MONITORING PARAMETERS
•Permanganate
• Monitor well - color, oxidation/reduction potential (ORP), conductivity,
chloride, manganese dioxide
•Persulfate
• pH, dissolved oxygen (DO), ORP, conductivity, and/or persulfate in
monitor wells
•Ozone
• Continuous monitoring of ozone gas, carbon dioxide (CO2), volatile
organic compounds (VOCs), and oxygen (O2)
•Peroxide (Fenton’s)
• Injection well - pH, temperature, pressure
• Monitor well - pH, temperature, color, ORP, DO, conductivity, VOCs
OXIDANT SPECIFIC MONITORING PARAMETERS
• As the remedial effort progresses, you should see a trend towards:
• High O2
• Low CO2 and PID readings
….meaning the remediation treatment reaction is almost complete

• The Chemox treatment process is completed:

• When the desired amount of treatment chemistry has been
applied
• When the reagents are spent; the chemistry will continue to
react in the subsurface
• either by self-destruction (e.g., Fenton’s)
• or by contacting contaminants or other organic matter
MONITORING LOCATIONS
CONSIDERATIONS FOR ISCO
CHEMICAL OXIDATION TECHNOLOGIES COMPARATIVE MATRIX

Advantages H₂O₂ Permanga Ozone

nate
Potential to complete remediation in shortest time X
Capacity to oxidize MTBE and benzene X X
No significant VOC off-gas produced by heat of reaction X¹ X
Oxidizes over extended period, increasing possibility of
X
contact with contaminants
Increases dissolved oxygen levels for potentially enhanced
X X
aerobic bioremediation
Reduced health and safety concerns during application X²
Can be applied using automated system X
1 If solid peroxide is injected below 10% strength, the heat of dilution is mitigated and VOC generation typically avoided
2 Note that sodium permanganate is often applied as a liquid at 40% strength, which poses a significant handling and explosion risk

USEPA 2004
CHEMICAL OXIDATION TECHNOLOGIES COMPARATIVE MATRIX

Disadvantages H₂O₂ Permanganate Ozone

Inability to effectively oxidize benzene or MTBE X X
Increased risk of fugitive vapors entering building structures,
utility conduits, particularly in absence of adequate vapor X X
recovery technology (e.g., soil vapor extraction)
Increased risk of plume reconfiguration X X
Low permeability soil horizons less likely to be penetrated by
X X X
oxidant over short injection period
On-site reactive chemical handling and storage required X X X
On-site gas production and delivery equipment (e.g., ozone
X
generator) required
Few petroleum remediation projects completed using this
X
technology due to limited effectiveness
Possible production of unwanted compounds or by-products in
X X X
the subsurface
Potential to precipitate solids and clog aquifer pores X X

USEPA 2004
IN SITU APPLICATION: Batch vs. Recirculation
DESIGN CONSIDERATIONS

• Combination technologies
• Site characterization/model development
• Oxidant demand
• Bench/pilot tests
• Modeling
• Dosage
• Costs
DIRECT PUSH INJECTION
EXAMPLE INJECTION SITE
SPECIALIZED INJECTION TRAILER
SPECIALIZED INJECTION TRAILER
TRAILER FLOW DIAGRAM & DETAILS
IN SITU OZONATED WATER INJECTION
IN SITU OZONE SPARGING
PRIMARY ADVANTAGES AND DISADVANTAGES
ADVANTAGES
•Contaminant mass can be destroyed in-situ
•Rapid destruction/degradation of contaminants (measurable reductions in
weeks or months)
•Produces no significant wastes (VOC off-gas is minimal), except Fenton’s
•Some oxidants (not Fenton’s) are capable of completely oxidizing MTBE (but
production of degradation products may be problematic)
•Reduced operation and monitoring costs
•Compatible with post treatment monitored natural attenuation and can even
enhance aerobic and anaerobic biodegradation of residual hydrocarbons
•Some oxidation technologies cause only minimal disturbance to site operations
PRIMARY ADVANTAGES AND DISADVANTAGES
DISADVANTAGES

•Potentially higher initial and overall costs relative to other source area solutions
•Contamination in low permeability soils may not be readily contacted and
destroyed by chemical oxidants
•Fenton’s Reagent can produce significant quantity of explosive off-gas. Special
precautions (i.e., SVE system) are required for appropriate implementation of
remedial action involving Fenton’s Reagent/hydrogen peroxide
•Dissolved contaminant concentrations may rebound weeks or months following
chemical oxidation treatment
PRIMARY ADVANTAGES AND DISADVANTAGES
DISADVANTAGES

•Dissolved contaminant plume configuration may be altered by chemical oxidation

application
•Significant health and safety concerns are associated with applying oxidants
•May not be technically or economically able to reduce contaminants to background
or very low concentrations
•Significant losses of chemical oxidants may occur as they react with soil/bedrock
material rather than contaminants
•May significantly alter aquifer geochemistry; can cause clogging of aquifer through
precipitation of minerals in pore spaces
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
▪ Quantity of material treated has a large impact
 Moisture content in waste
▪ Slight increase in costs between soil and sludge
 Contaminant concentrations
▪ 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.

Scenario A Scenario B Scenario C Scenario D

Small Site Large Site
Easy Difficult Easy Difficult
Galloons Processed 21,024,000 21,024,000 262,800,000 262,800,000
Cost per gallon $0.02 $0.02 $0.003 $0.004
Cost per 10,000 gallons $156 $175 $31 $39

https://frtr.gov/
EX SITU CHEMICAL OXIDATION
• Ex-situ treatment examples for soil and groundwater
• Backhoe / Soil Tilling / Heads: mixing soil with oxidants
• Frac tanks: mixing groundwater with oxidants
ADVANTAGES AND LIMITATIONS
ADVANTAGES
•The main advantage of ex-situ chemical oxidation as opposed to in-situ chemical
oxidation is that it allows sufficient time for oxidation to occur in a controlled
environment.
LIMITATIONS AND CONCERNS
•Incomplete oxidation or formation of intermediate contaminants may occur
depending upon the contaminants and oxidizing agents used.
•The process is not cost-effective for high contaminant concentrations because of
the large amounts of oxidizing agent required.
•When chlorine is used for oxidation, undesirable substitution products such as
chloromethanes can form.
•Chemicals other than contaminants may consume oxidizing agents, increasing
treatment cost and creating the potential for forming undesirable byproducts.
REFERENCES
T. Aspray. (2014). EMMCChIR. [PDF Slides].
United States Environmental Protection Agency (USEPA). (2004). How to Evaluate Alternative Cleanup Technologies for
Underground Storage Tank Sites.
Federal Remediation Technologies Roundtable (FRTR). (2016). Remediation Technologies Screening Matrix and Reference
Guide.
Hamby, D.M. Site Remediation Techniques Supporting Environmental Restoration Activities: A Review.
Kevin Taylor. (2012). A Final Report: The Chemical Oxidation of Polycyclic Aromatic Hydrocarbons at a Former Manufactured
Gas Plant in Bay Shore , New York.
ITRC. (2005). Technical and Regulatory Guidance for In Situ Chemical Oxidation of Contaminated Soil and Groundwater.
Ci. Schreier, L. Kinsman. Chemical Oxidation Technologies: Lessons Learned & Best Practices from Expert Perspectives. [PDF
Slides].
http://www.cpeo.org.
https://frtr.gov.
https://www.epa.gov.

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OUTLINE
1. INTRODUCTION
1.1. OVERVIEW: CHEMICALS
1.2. ENVIRONMENTAL FATE: ORGANIC COMPOUNDS IN THE ENVIRONMENT
1.3. CONTAMINATED LAND
1.4. WASTE MANAGEMENT AND DISPOSAL
1.5. LEGISLATION – CONTAMINATED LAND AND WASTE MANAGEMENT
2. TYPES OF CHEMICAL POLLUTANT REMEDIATION
2.1. BIOREMEDIATION
2.2. PHYTOREMEDIATION
2.3. SOIL WASHING
2.4. STABILIZATION/ SOLIDIFICATION
2.5. CHEMICAL OXIDATION

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