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SEMINRIO INTERNACIONAL Tecnologias de Remdiao In Situ Aplicaes e Resultados

ISCO or ISCR
How do you decide?
Dr. Dick Brown, ERM 3 June 2011, So Paulo, Brazil

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Outline
Problem Statement The name of the game Electron transfer Overview of ISCO Overview of ISCR Selection criteria for ISCO or ISCR Summary

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Problem Statement:

ISCO and ISCR are both efficient electron transfer reactions. They can both be used for treating a number of contaminants, especially chlorinated solvents. However, for a given site, they may not be equally effective. How does one determine which technology to apply? Neither technology is universally applicable.

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Electron Transfer in Remediation


Dechlorinated Contaminant

ISCO
Oxidant Electrons Contaminant

ISCR
Electrons Reductant

CO2, H2O, X-

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ISCO Overview

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What is ISCO
In Situ Chemical Oxidation Transfer of electrons from substrate (contaminant)
to oxidant Substrate must have transferable electrons
- Aromatics - Double bonds - Few chlorines

- Too many Cl - CCl4 + 2H2O CO2 + 4H+ + 4Cl- No e-

Oxidant must be able to accept electrons


- Capacity = Equivalent weight (MW/No. e-)

Ultimate end point is mineralization


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Release of Electrons - ISCO

The more electrons available, the easier they are released


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Ionization Potential vs Electrons Available


Vinyl Chloride
CH2=CHCl + 4H2O 2CO2 + Cl- + 10H+ + 9eIP = 9.99

Acetic Acid
CH3COOH + 2H2O 2CO2 + 8H+ + 8e

IP = 10.66

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Styrene
C6H5CH=CH2 +16H2O 8CO2 + 40H+ + 40eIP = 8.4

Benzene
C6H6 + 12H2O 6CO2 + 30H+ + 30eIP = 9.24

Structure determines oxidizability


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ISCO Tools

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Available Oxidants
Hydrogen Peroxide (requires activation)
Carrier compounds (hydrolize to peroxide)
- RegenOx 2Na2CO33H2O2 - Calcium/magnesium peroxide CaO2

Sodium/potassium permanganate Sodium Persulfate (requires activation)


Diperoxysulfate S2O8-2 -O3S-OO-SO3 Monopersulfate SO5-2 (oxone) -OO-SO3-

Ozone
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Physical and Chemical Properties


Oxidant Formula O3 State Soubility E0 2.07 eV 2.76 HO 1.77 eV 2.76 HO Electrons Mol Wt Equiv Wt Max Equiv/m3 10% Gas '2.7to 5.4 Water 1.25 to 2.5 10% Conc. 2900 to 5800 No Decomp 1214 max 500 Pract. 20% 4230 25% 1050 to 2100 Gas mixture 3-5% Air 60.0 mg/L 5-10% O2 @ 10% Gen. on site Liquid 30% Strength Purple Crystaline Solid Purple Liquid Liquid 30% Strength Miscible

Ozone

1-2

48

24-48

Hydrogen Peroxide Potassium Permanganate Sodium Permanganate Sodium Persulfate

H2O2

1-2

34

17 - 34

KMnO4 NaMnO4 Na2S2O8

64 g/L Max 20-30 g/L 1.695 eV Practical 400 g/L 560 g/L 1.695 eV 2.01 eV 2.5 SO4

3 3 1-2

158.04 141.9 238

52.7 47.3 119-238

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Free Radical Formation Enhanced Reactivity

Ozone

O3 + 2H+ + 2e- O2 + H2O Eo 2.07v O3 + H2O O2 + 2OH 2O3 + 3H2O2 4O2 + 2OH + 2H2O

Persulfate

2OH + 2H+ + 2e- 2H2O Eo 2.76v S2O8= + 2e- 2SO4= Eo 2.01v S2O8= 2(SO4-) (SO4-) + e- SO4= Eo 2.5v H2O2 + 2H+ + 2e- 2H2O Eo 1.77v H2O2 2OH ; 2OH + 2H+ + 2e- 2H2O Eo 2.76v

Hydrogen Peroxide

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How Oxidants React

Chemical Energy

Activation Energy

Catalysts Temperature

Oxidized State Electrode Potential Reduced State

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Reactivity of Oxidants
Oxygen Activation Energy Persulfate Hydrogen Peroxide

Permanganate

Ozone Persulfate Hydroxyl Radical Radical

Electrode Potential
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Oxidant
Peroxide, Old Fenton's Peroxide, New Fenton's Potassium Permanganate Sodium Permanganate Sodium Persulfate, Fe

Amenable VOC's
PCE, TCE, DCE, VC, CB, BTEX, PAHs, MTBE, TBA PCE, TCE, DCE, VC, CB, BTEX, PAHs, MTBE, TBA PCE, TCE, DCE, VC, TEX, PAH PCE, TCE, DCE, VC, TEX, PAH PCE, TCE, DCE, VC, CB, BTEX, PAHs, MTBE, TBA

Reluctant VOCs
DCA, CH2Cl2 DCA, CH2Cl2,TCA, CT, CHCl3 MTBE, TBA

Recalcitrant VOCs
TCA, CT, CHCl3

TCA, CT, B, CHCl3, DCA, CB, CH2Cl2 TCA, CT, B, CHCl3, DCA, CB, CH2Cl2 TCA, CT

MTBE, TBA DCA, CH2Cl2, CHCl3

Sodium All VOCs Persulfate, Base Sodium All VOCs Persulfate, Heat Ozone PCE, TCE, DCE, VC, CB, BTEX, PAHs, MTBE, TBA DCA, CH2Cl2, CHCl3, TCA, CT

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Oxidant Usage
[Oxidant]Required = [Stoichiometric Demand]Contaminant +
[Soil Matrix Demand] + [Metals]Red [Organic Carbon]Oxidizable [Decomposition]Oxidant

Non-Beneficial Consumption

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Equivalent Weights
Theoretical 300 250 Equiv Wt, g 200 150 100 50 0 H2O2 O3 OH. MnO4 S2O8 Practical (w NBC)

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Non-Beneficial Consumption

Decomposition SOD - Metals SOD - Organics Advection

Peroxide XXXXX XXXX --X

Persulfate XX XXXX ---X

Permanganate -XXXX XXXXX X

Ozone XX XX --XX

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When do you use each oxidant?


Contaminants Best Suited for Ethenes, Aromatics (not B or Permanganate, Na & K MCB), TNT, PAHs, Phenols, Pesticides w aromatic groups Ethenes, Ethanes, Methanes (3, 4 Cl) Aromatics , Explosives, PAHs, Persulfate (Base & Heat Phenols, Pesticides w aromatic Activation) groups, PCBs, Dioxane, MTBE/TBA Ethenes, Aromatics (not B or Hydrogen Peroxide (CHP) MCB), TNT, PAHs, Phenols, Pesticides w aromatic groups SVOCs - PAHs, Pesticides, Ozone Phenols, PCBs, PAHs, TPH Oxidant Geochemistry Best Suited for Low NOD (< 5g/Kg). Low levels FeS

Low Mn. Low levels FeS. Tolerant of NOD

Low Fe, Mn. Low FeS, Tolerant of NOD Permeable Lithology, Tolerant of NOD

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The Key to Success


Treatment Success is having Delivery & enough agent in contact Distribution with the contaminant for a long enough period of time Contaminant to react effectively Destruction

Dosage Kinetics Persistence

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ISCO Summary
Multiple Oxidants Available
Different reaction pathways (by oxidant)

Limited Oxidant Lifetime


Non-Beneficial Consumption

Non-selective reactions
End products are CO2, Water

Oxidants are applied, there are no persistent


naturally occuring oxidants
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Overview of ISCR

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What is ISCR
In Situ Chemical Reduction Transfer of electrons from reductant to substrate
(contaminant) Reductant must have transferable electrons
- Reduced Metals (Mainly Iron)

Substrate must be able to accept electrons


- Oxidized substrates (Chloro and nitro organics)

Endpoint is CHO organic


No Cl-, NO3W.O./Init./Date, 23

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Reducibility & Electrons

Reducible

Non-Reducible

Electron rich compounds dont reduce


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Reducibility versus Number of Chlorines

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The Four Pillars of ISCR


1. Abiotic processes are based on reduced metals a. ZVI (added) b. DVI (added or natural) Abiotic pathways are different than biological pathways Abiotic process are mostly surface catalyzed a. Reactive Solids b. But also Metal Complexes Abiotic processes can be enhanced by chemical reductants or biological reduction

2. 3.

4.

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1980 Sweeney, 1980 Cu0/Fe0 1990 Gillham, 1990 ZVI (Fe0)

1st Generation

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The Development of ISCR


Tratnyek, 1994 ZVI/Fe Oxides Kriegman-King, 1994 Pyrite

2000 2008

2nd Generation

Zhang 1997, Nano-Fe Batchelor 1998, ZVI/Clay Daramend 2001 Fruchter, 2003 ISRM EZVI 2003 BiRD 2006 EHC-L 2011

Ferrey & Wilson 2002, Abiotic MNA

DVI (Iron II) uses many of the same Reaction Pathways as ZVI

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Reduced Iron Minerals (DVI) Active in Dechlorination



Makinawite FeS, Pyrite FeS2 Green Rust [Fe2+6Fe3+2(OH)184(H2O)] Magnetite Fe3+2Fe2+O4 Glauconite K0.6Na0.05Fe3+1.3Mg0.4Fe2+0.2Al0.3Si3.8O10(OH)2 Biotite KMg2.5Fe2+0.5AlSi3O10(OH)1.75F0.25

Siderite FeCO3 Artificially Created


Steel Slag amended with Fe+2 Cement amended with Fe+2 Minerals treated with Fe+2(aq) Minerals treated with reductants (ISRM)

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Comparison of Fe+2 and ZVI


Figure 3: Effect of Iron Valence on Reactivity
Ferrous 100 80 60 40 20 0
PCE TCE cis-DCE

ZVI

% Loss from Control @ 4 Weeks

-20

1,1,1TCA

1,1-DCE 1,1-DCA

CT

CF

DCM

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ISCR Tools Iron Products

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Iron Products used in ISCR


ZVI products
Macro to Nano Iron
- Mass density vs Reactivity - Reactivity = f(Surface Area)

DVI Products
Natural Minerals (MNA) Biogenic minerals
- FeS BiRD

Bioaugmented ZVI
- EHC products (Eh!) - EZVI

Chelated Iron
- EHCTM-L

Bimetallics
- Ni, Pt

ISRM Reductant Injection

ZVI-Clay

ZVZ under development


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Reaction Pathways

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Reductive Electron Transfer Processes


Vogel, Criddle, & McCarty 1987

Hydrogenolysis
H Cl Cl H H

C=C + H+ + 2eCl Cl

C=C
Cl

+ Cl-

Biotic Pathway

-elimination:
H Cl

C=C

+ 2eCl

H-C
H H H

C-Cl + 2Cl- Abiotic Pathway


Cl

Coupling
2
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Cl

H H H

C C

Cl H+ Cl

2e-

C C C C
Cl

H H H

+ 2Cl-

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Other Abiotic (Non-Reductive) Pathways

Dehydrohalogenation
Cl Cl Cl H

C
H

Cl

C=C
Cl H

+ HCl

Hydrolysis
Cl Cl Cl H HO H + 3H2O H O

H H H

+ 3HCl

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Potential Chloroethene Abiotic Degradation Pathways


Cl

Biotic

Cl

C=C

Cl + H+ + 2e H Cl
- Cl - HCl + H+ + 2e - Cl

Cl

C=C

Cl + H+ + 2e H Cl
- Cl - HCl + H+ + 2e - Cl

Cl

C=C

H + H+ + 2e H Cl
- Cl - HCl

C=C

H Cl

+ 2e - 2Cl

+ 2e - 2Cl

+ 2e - 2Cl

Cl CC Cl
+H2O

H CC Cl
+H2O

H CC H
+ 2H+ + 2e

+ H+ + 2e

- Cl

H H

Cl H

C=C

OH Cl

H H

C=C

OH Cl

C=C

H H

+ 2H+ + 2e

+H2O

+H2O

Cl Cl H C C OH H OH
- HCl

Cl Cl H C C OH H OH
- HCl

H H H C C H H H
Dihalo-elimination Hydrogenolysis Hydrolysis Dehydrohalogenation

OH Cl H C C H O

OH H H C C H O

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Potential Chloroethane Abiotic Degradation Pathways


Cl H H C C H Cl H
+ H+ + 2e + H + 2e - Cl
+

Biotic

Cl H Cl C C H Cl H
+H2O - HCL

- HCl

Cl Cl

- HCl +H2O

C=C

H H

+ H+ + 2e Cl - Cl

C=C
- HCl

H H

H H H C C H Cl H

- Cl

- HCl

Cl H HO C C H Cl H Cl H HO C C H HO H
- HCl + 2H+ + 2e +H2O - HCL - HCl

H CC Cl H H
+H2O +H2O

+ H+ + 2e

- Cl + 2H+ + 2e

H CC H H H H H

C=C

OH Cl

C=C

+ 2H+ + 2e

Hydrogenolysis Hydrolysis Dehydrohalogenation

OH H H C C H O

H Cl H C C OH H OH
- HCl

H H H C C H H H

OH H H C C H O
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ISCR Tools
Reactivity

Abiotic

Particle size Micro (5-100 m) Nano (1-10 nm) Bimetallics

Naturally Occurring Reduced Minerals


Abiotic MNA

Delivery
Injectable Micro/nano iron ZVI - Clay

ISRM (In Situ Redox Manipulation) Complexes of Fe+2

Biotic

EHCTM EZVI (emulsified ZVI)

BiRD (Biogeocemical Reductive dechlorination)

ZVI
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DVI

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ISCO versus ISCR How to Make a Choice

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Oxidation & Reduction

ISCO
Oxidation removes electrons

CO2 +e-eContaminant R-Xn +eOxidant Reduced

Note: Chlorine and Oxygen are oxidants. Highly Chlorinated = Oxidized

-eOxidized Reductant

Reduction adds electrons

R-H
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ISCR

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Factors to Consider in Making a Choice

Contaminants Redox environment


Geochemistry

Contaminant mass and distribution Performance

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Applicability of ISCO/ISCR for COCs


ISCR
Chlorinated compounds
Ethenes Ethanes Methanes PCBs Pesticides Clx

ISCO
Chlorinated Compounds
Ethenes XXXXX Ethanes XXX Methanes X PCBs Pesticides C=C

Non-Chlorinated Inorganics
As Cr Perchlorate Zn, Cu, Ni (S-2)

BTEX PAHs, Phenols Other Organics Metals - As


- MTBE, Dioxane - Explosives

- Nitrated (Explosives)

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Factors to Consider in Making a Choice

Contaminants Redox environment


Geochemistry

Contaminant mass and distribution Performance

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What Controls Redox


Contact with atmosphere Mineralogy
Redox active metals
- Reduced iron FeSx, Green Rust, Magnetite, Glauconite, Siderite - Oxidized iron - Goethite, hematite - manganese minerals - White and tan versus Red, black , brown and green

Color

Decomposition Catalysts

Labile Carbon
Natural Peat Anthropogenic Contaminants
- Degradability

Biology
Anaerobic
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- Driven by carbon

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Redox Environment

En vir on me nts

in Co n Ae tact r Gr ou obic with nd At Tra wa mo ns sp itio ter Re he nE du re nv ce iro dE nm nv en iro t nm en t

ISC O ISC R
A Gr erob ou nd ic wa ter

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Redox Factors for ISCO and ISCR


ISCO
Favorable Shallow Groundwater Low Carbon Oxidized Mineralogy No soil color High DO Unfavorable High Carbon Reduced metals FeS Black, Green soils Very Low DO Favorable High Carbon Reduced metals Black, Grey, Green soil Anaerobic Biology Deep Groundwater Low DO
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ISCR
Unfavorable Shallow Groundwater Red or Brown soil High DO

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Factors to Consider in Making a Choice

Contaminants Redox environment


Geochemistry

Contaminant mass and distribution Performance

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Impact of Contaminant Distribution


ISCO
LNAPL DNAPL - CVOC DNAPL - PAHs Applicable; Direct injection and soil mixing. Applicable; Direct injection and soil mixing. Applicable; Direct injection and soil mixing, Ozone injection

ISCR

Applicable - ZVI-Clay Not Applicable

Source

Adsorbed

Applicable Direct injection Applicable; Direct injection and soil mixing. and soil mixing; ZVI-Clay Applicable Direct injection Generally not applicable except for ozone sparge barrier Not Applicable Not Applicable - limited life time of oxidants; Repeted injections can work Applicable Direct injection and soil mixing; ZVI-Clay Appicable PRB Applicable Abiotic MNA, PRBs Applicable - Ijection of Iron, PRBs, Abiotic MNA

Small GW Plume Large GW Plume with moderate to high Conc. Large dilute GW Plume Matrix Diffusion

GW

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ISCR

ISCO

Not Applicable to Hydrocarbons LNAPL

Factors to Consider in Making a Choice

Contaminants Redox environment


Geochemistry

Contaminant mass and distribution Performance

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Performance Factors to Consider


Speed
ISCO > ISCR
Time to achieve effect Lag Time?

Longevity of Effect ISCR > ISCO


Agent lifetime Rebound

Ease of Application
Injectability Handling
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ISCO > ISCR ISCR > ISCO

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Summary and Conclusion

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ISCO
Multiple Oxidants
Different reaction pathways
- Non-Contaminant Specific - Oxidant Specific - Geochemical effects

ISCR
ZVI and DVI (added, created or
natural) Reaction pathways elimination primary reaction Combination of electron transfer and non-transfer reactions
- Metal catalyzed?

None naturally occuring Limited Oxidant Lifetime Non-Beneficial Consumption Non-selective reactions End products are CO2, Water

Long Lifetime
Minimal Non-Beneficial Consumption
- DO and Nitrate

End products are

dechlorinated organics Few Daughters

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Applicability of ISCO/ISCR

S2O8= MnO4-

LNAPL

Adsorbed

O3 H2 O2
Dissolved
DNAPL

Fe

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ISCR
Preferred Geological/Geochemical Conditions Available iron mineralogy

ISCO
Low FOC (Permanganate), Low Mn/Fe (Peroxide), Low Mn (Persulfate) Very good for all

BRD
Available natural organics, LowModerate Fe/Mn (competitive metabolism) Good for PCE/TCE, sometimes stalls @ DCE or VC Accumulation possible Generally reactive but accumulates chloroethane Generally reactive but accumulates DCM

Applicability to Chloroethenes PCE, TCE, cis-DCE Vinyl chloride production/reactivity Applicability to Chlorethanes TCA; 1,1-DCA; 1,2-DCA

Very good for PCE/TCE, slow for cis-DCE Little accumulation Treats TCA, 1,1DCA, 1,2-DCA

Applicability to Chloromethanes CT, CF, DCM

Treats CT, CF. Little accumulation of DCM

Relative rate of treatment

Slow to moderate

Does not form VC. Reactive to VC Limited applicability, Requires very aggressive systems for Chloroethanes Limited applicability, Requires aggressive systems for Chloromethanes, such as heated persulfate Fast

Slow to moderate

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ISCR
Key factors limiting success Available iron, reduced iron Very good

ISCO
Stability/consumption of oxidant No effect on down gradient MNA. Limits MNA in treatment area

BRD
Requisite bacteria, available carbon source Very good if right bacteria present and properly maintained with multiple additions of agents (substrate) Works best in anoxic to anaerobic conditions. Not compatible with highly aerobic conditions Carbon source, inoculum, nutrients

Compatibility with MNA

Effect of Redox conditions

Agents needed

Works best in anoxic to anaerobic conditions. Not compatible with highly aerobic conditions Reducing agent, available iron

Works best in oxic to aerobic conditions. Not compatible with highly reducing conditions

Residual effect after agent spent

Reduced iron continues activity. No reapplication may be needed

Oxidant and in some cases a reaction catalyst (persulfate, peroxide) No reaction without oxidant. Reapplication may be required to meet goals

No degradation without carbon. Reapplication required to meet goals

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Factors to Consider in Making a Choice

Contaminants
What do I want to treat?

Redox environment
What are my biogeochemical conditions?

Contaminant mass and distribution


How much is there and where is it?

Performance
What are my performance goals?
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