Optimization of ZVI Technology for In-Situ

Remediation of Chlorinated Contaminants

Dr. John Freim

OnMaterials, LLC
Escondido, CA
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Keys To Success Its a Contact Sport

To implement a successful in-situ remediation program you must:

Modify / control groundwater chemistry

By

Delivering / distributing amendments

where needed

Photos: OnMaterials
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Abiotic Reactions: Zero Valent Iron and TCE

4Fe0 + C2HCl3 + 5 H+ 4 Fe+2 + C2H6 + 3 Cl-

Reaction pathway can bypass toxic daughter products

 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Abiotic Reactions Reduced Iron Sulfides

Precipitated Iron Sulfide

ZVI

Fe+2 + Native Sulfate Ferrous Sulfides FexSy

Fe+3 + H2

4 FexSy + C2HCl3 + H+ 4Fe+3 + C2H2 +4 S-2 + 3 Cl-

 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Biotic Degradation - Metal-Assisted Bioremediation

PCE TCE c-1,2-DCE VC Ethene

Cl Cl Cl H H H H H H H
C C C C C C C C C C
Cl Cl Cl Cl Cl Cl Cl H H H

Hydrogenolysis: 2 e- Photos: OnMaterials

Co-application of:

ZVI Water EVO (EDS - ER)

Dechlorinating Microbes pH Modifiers

 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Metal-Assisted Bioremediation
Benefits and How They Are Attained: ZVI
EVO
Low DO and ORP (< -200 mV)
Immediate onset of bioremediation Microbes
Enhanced bacterial populations; faster degradation

Parallel abiotic degradation ZVI

Elimination of inhibitory contaminants (1,1,1-TCA)

Addresses recalcitrant compounds (DCM, 1,2-DCA)

Can address DNAPL EVO
EVO Microbes
Abundant H2 for biotic degradation ZVI

Complete degradation to ethene

Microbes
ZVI
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Zero Valent Iron: Requirements for Successful Outcomes

Persistence ORP @ 6
Months Post Injection

Rapid Reactivity

Ease of Use

Subsurface
Distribution
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Available Iron Products

Cast/scrap iron: > 1 mm

Far Microscale: ~ 50 mm

Composite Products: (EHC, BOS100)

Z-Loy Products: 2 3 mm

NZVI: < 1 mm
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Characteristics as a Function of Particle Size

Soluble Nano Near-Microscale Far- Microscale Scrap Iron
Fe+2, Bicarb NZVI Z-Loy products, Powdered ZVI
EVO - EDSER EHC, BOS100

0 m 0.2 m 1-4 m 50 m 1 mm
Kinetics

Persistence

Difficulty
Easy Agglomeration Requires mixing/ High pressure/ Soil Mixing/
issues recirculation fracturing trenching
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

How to Apply ZVI?

1990s - Permeable Reactive Barrier / Trenching

Physical application methods Uses coarse ZVI

Used for shallow depths Subject to fouling

Photos: ITRC PRB Report

 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

How to Apply ZVI?

1990s - Soil Mixing

Trenching and soil mixing

methods can be effective
but are highly invasive

Limitations when near

infrastructure

Uses coarse ZVI

Photo: Malcolm Drilling
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

How to Apply ZVI?

1990s to Present - Pneumatic / Hydraulic Fracturing

Uneven distribution is a concern

High pressure can destabilize
the formation ( >150 psi )

Uses far-microscale ZVI

Backpressure is a concern
and can slow down work

Photos: OnMaterials
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

How to Apply ZVI?

2000s - Screened wells

Low pressure injection possible into more

permeable zones
Must use small particle size / soluble material
Good for repeat application

Photos: OnMaterials

New installation can be expensive

Good for deeper contaminants
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

How to Apply ZVI?

2000s - Direct Push

Direct Push Very flexible, small footprint

Photos: OnMaterials

Variety of injection tooling

Methodology can be
used for a wide variety
of applications
Large areas can be
treated quickly
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

How to Apply: Small Particle Size Amendments

Dilute with water / Inject via low pressure (< 50 psi)

Mixing is easy with systems

of mixing / injection tanks

Flexible - application via DPT or

screened wells
Photos: OnMaterials

Often real time data from adjacent

monitoring wells can be an indicator
of influence
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Characteristics and Advantages of Z-Loy Products

Reactivity:

Mechanical grinding
Small particles, metallic surfaces

Chemical surface modification

Enhanced reactivity

Photos: OnMaterials
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Characteristics and Advantages of Z-Loy Products

Persistence: Reaction rates are proportional to surface area

Diameter: ~ 10 x of NZVI Photos: OnMaterials

Surface Area: ~ 1% of NZVI

Reactive Lifetime ~ 100 x of NZVI

Photomicrograph of Z-LoyTM MicroMetal

 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Characteristics and Advantages of Z-Loy Products

Ease of Use:
Easy to pump and pour

Minimal mixing / recirculation

Injection behavior is similar to EVO and soluble products

+ Water =

Photos: OnMaterials
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Z-Loy Product Suite

Z-Loy MicroMetal: Glycerol-based suspension: Ideal for anaerobic

bioremediation projects

AquaMetal ZVI: Waterbased suspension: Ideal for ISCR / abiotic

degradation

MicroEVO-ISCR: Oil-in-water emulsion of AquaMetal ZVI & EDS-ER.

Co-Product makes application easier and cheaper.

EZVI: Hydrophobic water-in-oil emulsion for source zone/DNAPL treatment. Our

engineered approach is superior to legacy EZVI products
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Delivery:
Over the years, we have demonstrated the mobility of
materials by pumping through various sand / soil columns.

Photos: OnMaterials
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

What is Expected During Injection?

Using small particle size amendments saves time and money.
(Large particle size + High viscosity) = High pressure and problems
You do not want to see this on your site:
Photos: OnMaterials

Will it actually go into the ground? Oops! 300 psi caused daylighting in
Eight people (on the clock) are waiting to see! the ditch 100 ft away.
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Our Preferred Methodology

Water miscible AquaMetal ZVI /

Injection through sampler screens for even
Z-Loy MicroMetal
distribution into permeable zones

Efficient multi-point injection Degradation results post -injection

 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Dosing Considerations
Commodity products are typically dosed on a soil mass basis (0.5 1.0
m/m%). Non-uniform emplacement requires overdosing.

Z-Loy products are dosed based on intragranular pore volume; 4.0 to

10.0 g/L about 10-20 percent what is used for commodity iron
products.

Less material required = lower project cost

Photo: OnMaterials
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Dosing Considerations

In-Situ Mix Tank

Site geometry Material Requirements Dose (g/L) Dose (g/L) Mass (lb.)
Length (ft) 60 AquaMetal ZVI 5 51 2500
Width (ft) 60 Buffer 4 41 2020
Treatment Area (sq ft) 3,600 EVO 8 82 4039
Vertical Treatment (ft) 15.0
Treatment Volume (cu ft) 54,000 Liters
Treatment Volume (cu yd) 2,000 Microbes 3.5
Mobile Porosity (%) 15%
Pore Volume (cu ft) 8,100
Pore Volume (gal) 60,588
Injection volume Points (Hex Grid Rows) Material Allocation
Pore Volume (cu ft) 8,100 Treatment Area (sq ft) 3,600 Per point
Pore Replacement (%) 10% ROI (ft) 7.5 Water (gal) 370
Total Injection Volume (gal) 6,059 # of Points (X rows) 4 AquaMetal ZVI (lb) 167
# of Points (Y rows) 5 Buffer (lb) 135
Total Points 15 EVO (lb) 269
Microbes (L) 0.23
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Z-Loy MicroMetal Bioremediation Program

Source: Texas industrial site had a

degreaser which ruptured spilling 100+
gal of TCE. Residual TCE DNAPL with little
natural attenuation

Approach: Amendments were applied Photos: OnMaterials

via screened wells at 5-20 psi.

Amendments:
Z-Loy MicroMetal
EVO
pH modifier, nutrients
Dechlorinating microbes
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Z-Loy MicroMetal Bioremediation Program

Implementation: Injection was done in two

phases based on baseline and monitoring data.

Chlorinated Ethene Concentrations

Souce Zone MW-1
6000
2008 2011 TCE
Program Program c-1,2-DCE
5000
4300
VC
Photos: OnMaterials
uM
5000 uM Ethene
TCE
c-1,2-DCE
3600 uM
4000 Ethene
Conc.
(uM)
Results: 5 year monitoring data
3000 tells an interesting story. A large
spike in ethene shows complete
2000
biotic degradation after 2011
1000 injection event
0
2008 2009 2010 2011 2012 2013
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Z-Loy AquaMetal ZVI Abiotic Reduction

In some cases a straight abiotic approach is desired
No unwanted daughter products
Regulatory approval / previous scope to inject ZVI without organic
The reduction of cis-1,2-DCE without subsequent formation of vinyl chloride is a good
indicator of abiotic degradation. Prior bioremediation efforts had stalled at this site.
Monitoring Well 10
Concentrations (ug/L)
4000
TCE
3500 c-1,2-DCE
VC
3000

2500

2000

1500

1000

500

0
Sep 2015 Dec 2015 Mar 2015
Date Photos: OnMaterials / EA Env.
 Optimization of ZVI Technology for In-Situ
Remediation of Chlorinated Contaminants

Thank You for Your Time!

We offer our Z-LoyTM products as well as:
Remedial design and support
Injection services
Custom mixing, material handling and injection equipment
All personnel hold at least M.S. in Chem. or Env. Engineering discipline
Over 15 years of successful results and expertise in the industry
Partnerships / Private label products with preferred vendors