Iscr Vs Isco Dick Brown

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
Delivering sustainable solutions in a more competitive world
Outline
Problem Statement The name of the game Electron transfer Overview of ISCO Overview of ISCR Selection criteria for ISCO or ISCR Summary
W.O./Init./Date, 2
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.
W.O./Init./Date, 3
Electron Transfer in Remediation

Dechlorinated Contaminant
ISCO
Oxidant Electrons Contaminant
ISCR
Electrons Reductant
CO2, H2O, X-
W.O./Init./Date, 4
ISCO Overview
W.O./Init./Date, 5
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

W.O./Init./Date, 6
Release of Electrons - ISCO
The more electrons available, the easier they are released

W.O./Init./Date, 7
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
_____________________________________________________________________________________________________________________
Styrene
C6H5CH=CH2 +16H2O 8CO2 + 40H+ + 40eIP = 8.4
Benzene
C6H6 + 12H2O 6CO2 + 30H+ + 30eIP = 9.24
Structure determines oxidizability

W.O./Init./Date, 8
ISCO Tools
W.O./Init./Date, 9
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
W.O./Init./Date, 10
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
W.O./Init./Date, 11
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
W.O./Init./Date, 12
How Oxidants React
Chemical Energy
Activation Energy
Catalysts Temperature
Oxidized State Electrode Potential Reduced State
W.O./Init./Date, 13
Reactivity of Oxidants
Oxygen Activation Energy Persulfate Hydrogen Peroxide
Permanganate
Ozone Persulfate Hydroxyl Radical Radical
Electrode Potential
W.O./Init./Date, 14
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
W.O./Init./Date, 15
Oxidant Usage
[Oxidant]Required = [Stoichiometric Demand]Contaminant +
[Soil Matrix Demand] + [Metals]Red [Organic Carbon]Oxidizable [Decomposition]Oxidant
Non-Beneficial Consumption
W.O./Init./Date, 16
Equivalent Weights
Theoretical 300 250 Equiv Wt, g 200 150 100 50 0 H2O2 O3 OH. MnO4 S2O8 Practical (w NBC)
W.O./Init./Date, 17
Decomposition SOD - Metals SOD - Organics Advection
Peroxide XXXXX XXXX --X
Persulfate XX XXXX ---X
Permanganate -XXXX XXXXX X
Ozone XX XX --XX
W.O./Init./Date, 18
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
W.O./Init./Date, 19
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
W.O./Init./Date, 20
ISCO Summary
Multiple Oxidants Available
Different reaction pathways (by oxidant)
Limited Oxidant Lifetime

Non-selective reactions
End products are CO2, Water
Oxidants are applied, there are no persistent

naturally occuring oxidants
W.O./Init./Date, 21
Overview of ISCR
W.O./Init./Date, 22
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
Reducibility & Electrons
Reducible
Non-Reducible
Electron rich compounds dont reduce

W.O./Init./Date, 24
Reducibility versus Number of Chlorines
W.O./Init./Date, 25
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.
W.O./Init./Date, 26
W.O./Init./Date, 27
1980 Sweeney, 1980 Cu0/Fe0 1990 Gillham, 1990 ZVI (Fe0)
1st Generation
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
W.O./Init./Date, 28
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)
W.O./Init./Date, 29
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
W.O./Init./Date, 30
ISCR Tools Iron Products
W.O./Init./Date, 31
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

W.O./Init./Date, 32
Reaction Pathways
W.O./Init./Date, 33
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
W.O./Init./Date, 34
Cl
H H H
C C
Cl H+ Cl
2e-
C C C C
Cl
H H H
+ 2Cl-
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
W.O./Init./Date, 35
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
W.O./Init./Date, 36
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
W.O./Init./Date, 37
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
W.O./Init./Date, 38
DVI
ISCO versus ISCR How to Make a Choice
W.O./Init./Date, 39
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
W.O./Init./Date, 40
ISCR
Factors to Consider in Making a Choice
Contaminants Redox environment

Geochemistry
Contaminant mass and distribution Performance
W.O./Init./Date, 41
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)
W.O./Init./Date, 42

Geochemistry
W.O./Init./Date, 43
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
W.O./Init./Date, 44
- Driven by carbon
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
W.O./Init./Date, 45
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
W.O./Init./Date, 46
ISCR
Unfavorable Shallow Groundwater Red or Brown soil High DO

Geochemistry
W.O./Init./Date, 47
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
W.O./Init./Date, 48
ISCR
ISCO
Not Applicable to Hydrocarbons LNAPL

Geochemistry
W.O./Init./Date, 49
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
W.O./Init./Date, 50
ISCO > ISCR ISCR > ISCO
Summary and Conclusion
W.O./Init./Date, 51
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
W.O./Init./Date, 52
Applicability of ISCO/ISCR
S2O8= MnO4-
LNAPL
Adsorbed
O3 H2 O2
Dissolved
DNAPL
Fe
W.O./Init./Date, 53
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
W.O./Init./Date, 54
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
W.O./Init./Date, 55
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?
W.O./Init./Date, 56

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SEMINRIO INTERNACIONAL Tecnologias de Remdiao In Situ Aplicaes e Resultados

Delivering sustainable solutions in a more competitive world

Delivering sustainable solutions in a more competitive world

Delivering sustainable solutions in a more competitive world

Electron Transfer in Remediation

Delivering sustainable solutions in a more competitive world

Delivering sustainable solutions in a more competitive world

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

Oxidant must be able to accept electrons

Ultimate end point is mineralization

Delivering sustainable solutions in a more competitive world

Release of Electrons - ISCO

The more electrons available, the easier they are released

Delivering sustainable solutions in a more competitive world

Ionization Potential vs Electrons Available

Structure determines oxidizability

Delivering sustainable solutions in a more competitive world

Delivering sustainable solutions in a more competitive world

Sodium/potassium permanganate Sodium Persulfate (requires activation)

Delivering sustainable solutions in a more competitive world

Physical and Chemical Properties

Hydrogen Peroxide Potassium Permanganate Sodium Permanganate Sodium Persulfate

KMnO4 NaMnO4 Na2S2O8

158.04 141.9 238

52.7 47.3 119-238

Delivering sustainable solutions in a more competitive world

Free Radical Formation Enhanced Reactivity

Delivering sustainable solutions in a more competitive world

How Oxidants React

Oxidized State Electrode Potential Reduced State

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Ozone Persulfate Hydroxyl Radical Radical

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MTBE, TBA DCA, CH2Cl2, CHCl3

Delivering sustainable solutions in a more competitive world

Delivering sustainable solutions in a more competitive world

Delivering sustainable solutions in a more competitive world

Decomposition SOD - Metals SOD - Organics Advection

Peroxide XXXXX XXXX --X

Persulfate XX XXXX ---X

Permanganate -XXXX XXXXX X

Delivering sustainable solutions in a more competitive world

When do you use each oxidant?

Low Mn. Low levels FeS. Tolerant of NOD

Delivering sustainable solutions in a more competitive world

The Key to Success

Dosage Kinetics Persistence

Delivering sustainable solutions in a more competitive world

Limited Oxidant Lifetime

Oxidants are applied, there are no persistent

Delivering sustainable solutions in a more competitive world

Delivering sustainable solutions in a more competitive world

Substrate must be able to accept electrons

Endpoint is CHO organic

Delivering sustainable solutions in a more competitive world

Reducibility & Electrons

Electron rich compounds dont reduce

Delivering sustainable solutions in a more competitive world

Reducibility versus Number of Chlorines

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The Four Pillars of ISCR

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