Technology Z V I

12330: Contaminated sites
April 26th 2019
Annika S. Fjordbøge (asfj@env.dtu.dk)
Zero Valent Iron Technologies
April 26th 2019 DTU Environment

Overview
• Zero valent iron technologies:
– In situ chemical reduction 13:00-13:15
– Permeable reactive barriers 13:15-13:45
– Break 13:45-13:55
– Case (VAPOKON) 13:55-14:15
– Alternative ZVI technologies (injectable nZVI) 14:15-14:35
– Break 14:35-14:45
– Alternative ZVI technologies (ZVI-Clay soil mixing) 14:45-15:00
– Case (Skuldelev) 15:00-15:15
• Exercise N1 15:15-17:00

Scope of lecture
• After the lecture the student should:
– know the principles behind different ZVI technologies incl. main advantages
and limitations of the technologies
– know the principles involved in field application of ZVI technologies incl. the
difference between the technologies (PRB, injection, soil mixing)
– understand the most common processes for ZVI based remediation
(degradation, precipitation, passivation etc.)
– be able to dimension a PRB based on a number of design parameters
– be aware of the importance of particle size (specific surface area, SSA) and
delivery system (contact)

Types of remediation technologies
Ex situ
Excavation followed by
soil treatment
Pump-and-treat
In situ mass transfer In situ mass destruction
Thermal remediation Chemical oxidation
4 Enhanced reductive
Soil vapor extraction Chemical reduction dechlorination 4
In situ chemical reduction (ISCR)
• Zero valent metals are strong reductants
– Zero valent iron (ZVI) is most commonly
Tratnyek et al. 2014
used for in situ remediation
Source Zone
Injection
Soil mixing
• Chemical reduction can also be achieved
with certain iron and/or sulfide minerals
– Natural occurring processes (abiotic
Reactive barrier
MNA) ZVI+Carbon
Biogeochemical
– ”Stimulated” processes (e.g. BiRD,
ISRM)
Redox manipulation Catalyzed
Natural attenuation
April 26th 2019 DTU Environment 5

Plume vs. source zone
• ZVI technologies exist as both plume and source
zone technologies
• Permeable reactive barriers:

– Semi passive technology for plume remediation
• “Alternative” ZVI technologies:

– Nanoscale ZVI (nZVI): Active injection – plume or
source zones
– ZVI-Clay Soil Mixing: Active soil mixing – source
zone remediation

Level of implementation

Recognition of the remedial potential
• Catalyzed metallic iron powder shown to degrade a wide range of halogenated
organic contaminants already in the 1970’s/80’s (waste water).
• Largely overlooked until the late 1980’s, where mainly the University of Waterloo
put in on the remedial map
Reynolds et al. 1990
• ZVI has since been found to be reactive towards many contaminants

Contaminants treated by ZVI
• Organics:
– Chlorinated aliphatics (most are rapidly degraded)
• Chlorinated methanes (e.g. CT)
• Chlorinated ethanes (e.g. TCA)
• Chlorinated ethenes (e.g. TCE)
– Nitroaromatics/energetics (e.g. TNT, RDX)
– Pesticides
• Inorganics:
– Metals (e.g. Cr, As)
– Nitrate, sulfate

The process
• Anaerobic iron corrosion (redox reaction)
• Electron transfer at solid surface (contact needed)
• Initially fast consumption of any dissolved O2
2 → 2
• Hydrogen is formed (possible synergy with biotic processes)

• Hydroxy-ions are formed (pH-increase, risk of precipitates forming)

The process - Dechlorination
• The anaerobic corrosion lowers the redox potential:
→ 2
2 →
→
• Chlorinated solvents are chemically degraded in contact with iron surfaces

• Some compounds/intermediates are NOT readily degraded (DCM, DCA)

Cl Cl
Cl C-C Cl
Cl Cl
HCA
Dechlorination pathways Cl
C=C
Cl
H Cl
Cl Cl Cl C-C Cl
PCE
Cl Cl
• Several pathways are possible H Cl
PCA
Cl C=C Cl C=C H H
• Β-elimination is the dominant Dichloroacetylene
Cl
TCE
Cl Cl C-C Cl
Cl Cl
pathway (>90%) 1,1,2,2TeCA
Cl H
Cl C-C Cl
– Very limited formation of VC H C=C Cl
H
C=C
H H
C=C
Cl H
C=C
Cl
Cl H
Cl Cl Cl H H Cl 1,1,1,2TeCA
Chloroacetylene cDCE tDCE 1,1DCE
H H
H H Cl C-C Cl
H C=C H C=C Cl H
Cl H 1,1,2TCA
Acetylene VC
H H
H H H C-C Cl
C=C Cl H
1,2DCA
H H
Ethene
Hydrogenolysis
Cl H
α-elimination Cl C-C H
β-elimination H H Cl H
H C-C H 1,1,1TCA
Hydrogenation H H
Ethane H H
Cl C-C H
Cl H
1,1DCA

April 26th 2019
Zero Valent Iron Technologies:

Permeable Reactive Barriers
(PRBs)
What is a PRB?
In situ permeable treatment zone designed to intercept and
remediate a contaminant plume
PRB Treated
Groundwater
Source Zone
Contaminated
Groundwater
Physical, chemical and/or biological

processes depending on the material

Zero Valent Iron
Technology acceptance
• Most popular material for PRBs
(around 80% use ZVI) 16
ITRC, 2005
14
• In situ mass destruction

12
• >150 commercial sites:
# Installations
10
– Most in the USA (>100), but 8
also some in Europe (4 in DK),

Canada and Japan 6
0
1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004

Dimensioning - Dechlorination
• The PRB needs to be designed with sufficient residence time for the degradation
to occur:
·
· exp
½·
• Co: outlet concentration (mg/m3)

• Ci: inlet concentration (mg/m3)
• L: thickness of the iron barrier in direction of flow (m)
• T½: half-life of the compound (hours)
• vp: pore water velocity (m/hour)

Dimensioning - Dechlorination
½·
·
• Co: outlet concentration (mg/m3)

• Ci: inlet concentration (mg/m3)
• L: thickness of the iron barrier in direction of flow (m)
• T½: half-life of the compound (hours)
• vp: pore water velocity (m/hour)

Dechlorination half lives
• 1. order kinetics - half-lives are often less than 1 day (typical 0.5-8 hours)
• Half-lives depend on the compound and the ZVI (e.g. the surface area of ZVI type)
Landis et al.(2001)

Exercise
• How thick does the permeable reactive barrier need to be to reduced TCE below
the MCL of 1 µg/L if the maximum groundwater concentration is 4 mg/L, the half-
life of TCE in the PRB is 2 hours and the pore water velocity in the PRB is 180
m/yr

Dimensioning - Byproducts

Dimensioning - Treatment train
• Initial step before MNA
• Polishing step to more aggressive source remediation
TCE concentration
Compliance Point
PRB
Design basis
Cd
Target
concentration
Ct
Distance
Configuration of PRBs
• Main types
– Funnel-and-Gate
– Continuous wall
• Other types:
– Reactive injection zone
– (Passive collection with reactive
cells)
ITRC, 2005

Continuous wall
• Hanging
• Keyed

Funnel-and-Gate

PRB emplacement methods
• Main types
– Conventional excavation (backhoe)
• Unsupported or supported
– Sheet piling (Cofferdam)
– Biopolymer slurry
– Continuous trencher
• Other types
– Caisson / Mandrel
– High pressure grouting (Jetting)
– Hydraulic / Pneumatic fracturing

Conventional excavation
• Intersil site, Sunnyvale, CA, 1995

• 6 m deep, 1.2 m thick
• Trench gate (backhoe) and slurry funnel wall
• Remediation of chlorinated solvents (TCE)
Biopolymer slurry excavation
ITRC, 2011
• Excavation using “guar gum” or similar

• Subsequent removal of “guar gum” by enzymes

Continuous Trencher
• Coast Guard site, Elizabeth City, NC
1996
• 7.5 m deep hanging wall, 0.6 m thick
• Continuous wall using continuous
trencher
• Remediation of chromium and TCE
RTDF, 2001

Excavation methods for PRB installation
Method Depth (m) Thickness (m) # Installations
Unsupported excavation <6 >0.3 3
Supported excavation <6 >0.6 4
Cofferdam (sheet pile) <13 >1 14
Biopolymer slurry <20 >0.6 8
Continuous trenching <11 0.5-0.9 9
ITRC, 2005
Injection methods for PRB installation
Method Depth (m) Thickness (m) # Installations
Hydraulic fracturing <40 <0.2 5
Pneumatic fracturing <60 Variable 4
Jetting: columnar <60 <2 2
Jetting: diaphragms <60 <0.1 1
ITRC, 2005
Example of construction costs
Construction Iron Total
Case
(USD) (USD) (USD)
Backhoe excavation, OH (1999)
•8 ppm TCE
36000 28000 64000
•8 m x 60 m (D x W)
•Flow: 1.1 m/yr
Biopolymer excavation, NH (1999)
•10 ppm cDCE, 5 ppm TCE, 1 ppm VC
200000 130000 330000
•10 m x 45 m (D x W)
•Flow: 33 m/yr
Trench box, WY (1999)
•21 ppm TCE
1400000 600000 2000000
•7 m x 170 m (D x W)
•Flow: 145 m/yr
• The cost of ZVI is significant (generally 30-50 % of the total cost)
PRB longevity – how long does it last?
• Any loss of reactivity depends on several site-specific conditions
– Oldest PRB is around 25 years (Sunnyvale, CA, 1994)
– Generally likely to last 20–40 years before maintenance is needed
• Out of 156 commercial sites only 10 sites were found not to met expectations
– Design issues (e.g. insufficient site characterization)
• Main factors than can affect longevity:

– Geochemical performance
– Microbial performance
– Hydraulic performance

Geochemical performance
• Extremely wide range of geochemical conditions are encountered (site specific)
– Difficult to arrive at generally applicable conclusions regarding long-term
performance
• Precipitation
– Dissolved oxygen or nitrate (Fe hydroxides
precipitation)
– High alkalinity (Fe, Ca, Mg carbonates precipitation)
– Reducible metal content e.g. chromate (low
permeability metal salts)
– Sulfate concentration (sulfide formation on iron
surfaces)
• Iron sulfides can contribute to the degradation

Impacts on longevity from precipitation
• Precipitation on the iron 300
surfaces can reduce the PRB Lowry AFB, Long-term column test with TCE
reactivity 250
– Contaminant half-life
T 1/2 (minutes)
200
changes over time
150
• Extensive precipitation can 100

reduce the porosity of the PRB
– Clogging may impact the 50 Alkalinity ~ 600 mg/L, Calcium ~ 240 mg/L
hydraulic performance 1400 pore volumes is ~ 25 years of field operation

0
0 200 400 600 800 1000 1200 1400
Number of Pore Volumes

PRB – Cape Carnaveral
Advantages of PRBs
• Mass destruction occurs in the subsurface
• An efficient passive plume control technology for reducible
compounds
• Typical treatment is passive
– Potentially lower operation and maintenance costs
PRB – VAPOKON
• Generally few restrictions for the use of the site
– No extensive on-ground installations
– No daily activities
– Allows full economic use of a property

Limitations of PRBs
• High startup costs (construction)
• Difficult to make adjustments after the PRB is constructed
– High requirements to initial site characterization to avoid poor initial design
– Vulnerable to changes in the efficiency with aging of the PRB
• Some (degradation) compounds are not degraded or very slowly degraded
• Application limitations
– Impractical at great depths with ”conventional” techniques
– Difficult to place “precisely” in depths over 10-15 meters
– Infrastructure at the site
• Limited life-time of the PRB?
– Precipitates expected at the increased pH: Can effect the reaction half-lives
and the hydraulic performance
– Groundwater composition is important (be careful in hard water)
Technology implementation case study
(VAPOKON)

Case: The VAPOKON site
• Solvent recovery factory

• Contamination from subsurface tanks
• Various chlorinated solvents

Technology implementation methodology
Conceptual Model
Site Characterization
Treatability Testing
T½  v p  Ci 
L  ln 
PRB Design ln 2  Co 
Full-Scale Emplacement
Monitoring
ITRC, 2005

Conceptual model
• The suitability of a contaminated site for PRB treatment is affected by e.g.:
– Contaminant type
– Groundwater geochemistry
– Plume size and distribution (3 dimensions)
– Groundwater flow characteristics
– Depth to aquitard

Site characterization (design information)
Contaminants Conc (g/L)
• Composition of the groundwater Chloroform (TCM) 770
– Contaminant types and concentrations Trichloroethane (TCA) 37,000
– Geochemistry of groundwater (e.g. pH, DO, ions) Tetrachloromethane (CT) 6.4
Trichloroethylene (TCE) 27,000
• Used to:
Perchloroethylene (PCE) 20,000
– Select the appropriate remediation Vinyl Chloride (VC) 710
– Set up appropriate treatability tests 1,1-DCE 320
Characteristics ppm Characteristics ppm Trans-1,2-DCE (Trans-DCE) 100
Cis-1,2-DCE (Cis-DCE) 20,000
Ca2+ 231 Cl- 47
Dichloromethane (DCM) 33,000
Mg2+ 14 SO42- 167
1,2-Dichloroethane (1,2-DCA) 6,100
NH3-N & NH4+-N 0.28 NO3- 0.07
1,1-Dichloroethane (1,1-DCA) 520
Na+ 31 NO2- 0.02 Benzene 9,800
K+ 3.2 H2 S 0.13 Toluene 11,000
Fe2+ & Fe3+ 13 Conductivity (mS/cm) 0.82 Ethylbenzene 6,200
HCO3- 424 pH 7.3 m + p-xylene 26,900
Site characterization (design information)
• Hydrogeology of the impacted aquifer
– Groundwater flow velocity and direction
– Plume extent (200x80 m)
– Stratigraphy Groundwater velocity:
400-500 m/year
• Used to:
– Set up appropriate treatability tests
– Design the thickness of the wall
Geology:
• Loam & soil filling to 1.5 m bgs
• Water saturated sandy aquifer, 10 m thick
• Clay layer >15 m thick
Treatability testing (design information)
• Batch tests for quick screening of:
– multiple reactive media
– multiple geochemical conditions
• Column tests:
– Final selection of reactive media
– Obtaining design information
• Used to:
– Determine the best suitable reactive media
– Determine reaction kinetics (half-lives)
– Design the thickness of the wall

PRB design:
Funnel-and-Gate
• Upstream drainage to reduce GW flow
– Expected reduced flow velocity of
100 m/year
– Retention time: 70 hours
• Funnel
– Sheet piling
• Gate
– ZVI (80 m3)
– Depth 9m, thickness 0.8m, width 14m

PRB design: Funnel-and-Gate
4590
M10 M5 M6 Geotextile M13
20.85
Sheet piles Sheet piles

(withdrawn) (withdrawn)
Iron filings
Refilled with
aquifer material Gravel
M11
M07
M10
M05
M12
M9
M06
M13
11.9 M8
M02
M04
M03
M01 M14
Clay aquitard 1000 800 1000
M15
Full-scale emplacement
1) Ramming down the sheet piling case 3) Construction of a metal frame for filling of the ZVI
ZVI PRB
9  0.8  14 m (D  T  W)
2) Removal of the soil & 4) Filling of 270 ton
water from the case (80 m3) of ZVI
Monitoring – Contaminant depletion
Muchitsch et al. 2011

Monitoring - Mass discharge reduction
Contaminant Mass discharge (before) Mass discharge (after) Removal
[kg/year] [kg/year] [kg/year]
PCE 2.1 0.02 2.1
TCE 12 0.04 12
1,1,1-TCA 12 0.03 12
Chloroform 0.25 0.12 0.14 Still high cis-DCE
Cis-DCE 19 5.8 14
Trans-DCE 0.04 0.01 0.03
1,1-DCE 0.30 0.02 0.28
1,1-DCA 0.25 0.51 -0.26 Biotic degradation?
1,2-DCA 0.72 0.02 0,70
Vinylchlorid 0.53 0.12 0.42
DCM 0.14 0.05 0.09
Ethen 0.24 0.31 -0.07
Ethan 0.02 0.26 -0.25

Front Front
Monitoring - longevity
Center Virgin
Muchitsch et al. 2011

Experiences from the VAPOKON site
• Effective depletion of the chlorinated solvents
• Some formation of degradation products (still high cis-DCE)
• Uneven contaminant load - heterogeneous performance
• DCM and 1,2-DCA are removed (probably biotic)
• Signs of precipitates, but still acceptable performance after 8 years

April 26th 2019

Alternative ZVI Technologies
(injectable nZVI)
Nanoscale ZVI (nZVI)
• The importance of size
• Diverse product group
– Manufacturing: top-down or bottom-up
– Size: generally <200 nm
– SSA: generally ~30 m2/g
Golder nZVI DTU Nano nZVI
[www.discovernano.northwestern.edu]

Reactivity of nZVI
Large surface area available for reaction Wang & Zhang (1997)
• Enhanced reactivity compared with

coarser ZVI materials
– Complete degradation within hours in lab
– Degradation of greater range of
contaminants
• Catalytic properties of BNPs (Bimetallic
Nano Particles with noble metal e.g. Pd)
• Better selectivity of sulfidated nZVI (less
reaction with water)

Mobility of nZVI (bare vs. coated nZVI)
Small size make the nZVI injectable
• Bare nZVI • Coated nZVI
– Aggregate rapidly nm → µm – Steric and electrostatic repulsion
– Accelerated deposition – Increase mobility (cm → m)
– Reduce SSA and reactivity – Risk of reactivity trade-off
Bare nZVI CMC nZVI
He et al. (2007)

Field applications with nZVI
• Around 40-50 sites reported at the homepage of PEN
(Project of Emerging Nanotechnology)
2011

Sites remediated with nZVI
• Reported field data are limited
• Lower removal efficiencies than in laboratory studies
– Typically 30-90% removal within months in the field
– Contact/delivery issues
– Groundwater geochemistry Metal Test type Contaminant Removal [%] Reference
Fe0/Pd Field; plume TCE 34-95 Elliott & Zhang (2001)
Fe0/Pd Field; plume TCE >90 Glazier et al. (2003)
Fe0 Field; plume TCE; TCA <90 Varadhi et al. (2005)
BNP Field; plume TCE >95 Hains et al. (2008)
Fe0/Pd Field; plume PCE; TCE N/A Bennett et al. (2010)
Fe0/Pd Field; plume VC 20-99 Wei et al. (2010)
Fe0/Pd Field; source TCE; TCA 8-92 Henn & Waddill (2006)
Fe0 Field; source TCE <96 Chang et al. (2010)
Fe0 Field; source TCE; TCA 12-30 Elsner et al. (2010)
Fe0/Pd Field; source PCE; TCE 20-96 He et al. (2010)
Fe0 Field; DNAPL TCE 26-99 Quinn et al. (2005)
Stoichiometric dimensioning
• Same overall reaction processes for all ZVI technologies
• Stoichiometry and delivery/emplacement are important issues for the active
technologies
• Degradation of e.g. 1 mol PCE to ethene requires 4 mol nZVI

4 → 4 8
8 4 → 4
4 4 → 4 4

Exercise
• How many gFe/gPCE is needed for complete degradation of PCE to ethene,
assuming that all nZVI is used for the reaction with the contaminant?
PCE: Mw = 165.8 g/mol; Fe(0): Mw = 55.8 g/mol

Delivery of nZVI
• Plume treatment
– Down-gradient injection of reactive zone
• Source treatment
– Injection in or up-gradient of the source zone
– (DNAPL targeting) Tratnyek & Johnson (2006)
• Injection methods
– Gravity feed
– Fracturing
• Direct push
(Saleh et al. 2007)
• Hydraulic
• Pneumatic
Longevity of nZVI
• Core-shell structure
– Fe0 core / Magnetite (Fe3O4) and maghemite (Fe2O3) shell
Aging
Fe0
R-H
R-Cl
• Longevity depends on the nZVI product and the environment

– Aggregation/filtration of particles (life-time of coatings)
– Depletion of reactivity (competing processes)
– Reactive life-time estimates ranges from a few days to a year
– Rebound of contaminants have been observed

Benefits vs. risks of nZVI
• Possible conflicts between desirable remedial properties and
low risk properties
• Particle optimization
Remedial focus Risk focus

Longevity Persistence
Mobility Spreading
Reactivity Toxicity
• Few studies
– Not basis for expecting a severe toxicity
Auffan et al. (2008)

Advantages of nZVI
• Efficient degradation of an array of chlorinated solvents upon contact
– Fewer toxic intermediate than larger size ZVI, and additional contaminants can
be degraded (catalytic properties)
– Potential for a faster remediation time frame (aggressive treatment)
• Field application possible through injection
(Under constant development to achieve better reactivity, selectivity, mobility and

affinity for contaminants such as DNAPL)

Limitations of nZVI
• High material cost
• The efficiency varies significantly and rebound in groundwater concentrations is
generally a problem
– Several reinjections are likely required for sufficient source mass depletion
• Achieving contact between the contaminant and the reagent can be challenging
– Vulnerable to subsurface heterogeneities (general issue with technologies
based on injection delivery)
– Appropriate mainly at homogeneous sites without DNAPL
• Limited life-time of the particles due to low selectivity (e.g. reaction with water)
• The fate in the environment is primarily based on bench-scale studies under
ideal conditions
– Toxicity uncertain, but no severe apparent risks
– Transport distance uncertain

April 26th 2019

Alternative ZVI Technologies
(ZVI-Clay soil mixing)
ZVI-Clay Soil Mixing
• The importance of contact
• Soil mixing for delivery and contact
• ZVI addition for degradation (mZVI or granular ZVI)
• Clay addition for containment/stabilization
• Contaminant mass discharge reduced by both processes
CCH, CSU

3.5
Contaminants (reactivity)
Concentration [mmol/kg]
3.0
2.5 Control
• Degradation of the same contaminants as in 2.0
CT
CF
DCM
PRBs by the same processes 1.5
1.0
• Dimensioning based on stoichiometry and 0.5
treatability studies 0.0

0 10 20 30 40 50 60 70
Time [d]
1.0
• Half-lives (contaminated soil)
Concentration [mmol/kg]
0.8
– Chlorinated ethenes: weeks Control
PCE
TCE
– Chlorinated ethanes: days-weeks 0.6 DCE
VC
Ethene
– Chlorinated methanes: days 0.4 Ethane
0.2
0.0
0 20 40 60 80 100
Time [d]

Stabilization/containment (clay addition)
• Different properties of clay (non-swelling or swelling clays)
Al3+
Si4+
• Clay facilitates the drilling process and keeps ZVI suspended

– Less material demand and better ZVI suspension with bentonite (swelling clay)
• Hydraulic conductivity reduced 1-5 orders of magnitude
– Primarily from the soil mixing process 1 cm
– Additional contribution from bentonite

• Emulsification of the DNAPL with bentonite

Field applications of ZVI-Clay
• Few sites worldwide
• Different geological settings (sand, clay, peat)
• Down to 14 m
• Different chlorinated compounds (mainly methanes and ethenes)
2011

Sites remediated
• More than 90 % removal within one year achieved on several occasions
– Good correlation with laboratory studies
Iron; Clay [%] Volume [m3] Contaminant Removal [%] Reference

Soil; water
N/A 200 TCE ~90; N/A CSU
2-6; 6 3000 CT >99; N/A Shackelford et al. (2005)
2; 1 5400 PCE 82; 96 Bozzini et al. (2006)
1.5; 1 1700 TCE N/A; ~85 CSU
2; 1 900 PCE; TCE >98; >98 CSU
2; 1 5400 TCE N/A; N/A CSU
2; 4 900 CT; CF; TCA >99; ~90 Ovbey et al. (2010)
2; 3 23000 TCE; TCA 96; 89 Olson et al. 2012
3; 1 200 PCE >99; 76 Fjordbøge et al. 2012

Emplacement (conventional equipment)
• Soil mixing with conventional excavator
• Manufacturing facility, SC
• CF and 1,1,2,2-tetrachloroethane
• 2.5% ZVI, 4% bentonite
• 880 m3; 8 days (0.6 m excavator teeth)
Ovbey et al. (2010)

Emplacement (specialized equipment)
• Soil mixing with specialized auger Olson et al. (2012)
• Camp Lejeune, NC
• TCE and 1,1,2,2-tetrachloroethane (DNAPL)
• 2% ZVI, 3% bentonite
• 23000 m3; 80 days; 515 columns (3 m auger)

Longevity
• The longevity of ZVI-Clay is relatively untested
– Oldest installation around 15 years
– Coarser ZVI products (slower reactivity depletion)
– Sites have currently not been revisited since their one year post-treatment
monitoring campaigns
• Once reactivity is depleted the source is still stabilized by the clay material
(reduced hydraulic conductivity) with expected continued mass discharge
reduction as a result

Advantages of ZVI-Clay soil mixing
• Good contact between contaminant and reagent (soil mixing)
• Appropriate for the more heavily contaminated, heterogeneous source zones
– Source heterogeneities and geology are of lower importance
– Possible to treat DNAPL
– Generally high source zones remediation efficiencies (>80% and often >95%)
• Ideally reduced the mass discharge by both contaminant reduction (ZVI) and
physical stabilization (Clay) of the source
• Typical treatment is aggressive
– Faster remediation time frame

Limitations of ZVI-Clay soil mixing
• High mobilization costs (soil mixing)
• Application limitations
– Infrastructure at the site
• Post-treatment land use
– Soil structure significantly altered by soil mixing
– Post-treatment soil strength varies

Source zone remediation case study (Skuldelev)

The site
• Metal processing with use of PCE until 1983.
• Leakage from the sewer system
• Heavy PCE contamination of soil and ground water (DNAPL)

Site characterization
• Geology
– Fill layer
– Peat/organic silt (variable)
– Sand (secondary aquifer)
– Clay till (aquifer bottom)
• The hydraulic conductivity:

– 0.2-41 m/d
– Varies with the geology
• The hydraulic gradient:

– Approximately 3 ‰

Site contamination
• Several discrete hot spots
• Hot spot V:
– Soil conc. >1000 mg/kg
– High solute concentrations
J2 J3
J1 J4
J7 J8
J6
J5
J9
J11
J12 J13
J10 J14
J16 J17 J18
J15 J20
J19
Well
Multilevel
l

Treatability tests
• Batch test
– PCE contaminated soil
– One ZVI type
– Three ZVI amounts (1-3%)
– Sterile and non-sterile
– Short-term (2 months)
• Batch column test

– PCE contaminated soil
– Three ZVI types
– Three ZVI amounts (1-4%)
– Soil mixing platform
– Longer term (7 months)
Treatability test results
• Low production of chlorinated
intermediates
• Gas production (H2), lower in non-
sterile batches
• Reduced conditions (+100 → -600 mV)
• Chloride production
• Degradation half-lives:
– 2-10 months for PCE (control 47
years)
– No formation of TCE
– Faster with more iron

Full-scale emplacement

Monitoring (iron distribution)
• Significant decrease with depth (0.5 %/m) as a result of the top-down addition
Fe concentration [%]
0 1 2 3 4 5 6 7 8
2.5
Depth [m bgs.]
5.0
7.5

Monitoring (mass depletion)
• Average: >99 % removal within one year
• >95 % of the samples below 5 mg/kg within nine months
• Ethene as the main degradation product 0
57
10000
Time [d]
111
Log(Concentration in mg/kg)
182
1000
279
100 348
0 10 20 30 40 50 60 70 80 90 100
10 PCE TCE DCE VC Ethene Ethane Molar distribution [%]
0.1
0 57 111 182 279 348
Time [d]

Monitoring (mass discharge)
• The solute concentrations decrease
significantly
• 77-98 % of the mass discharge occurred
through <10 % of the down-gradient transect
• The mass discharge of PCE is reduced 76 %
(cDCE increased)

Experiences from the Skuldelev site
• Effective mass depletion of the chlorinated solvents (PCE DNAPL) in the source
zone with >99 % removal
• No significant formation of chlorinated degradation compounds in the source
zone
• Some formation of degradation products (cDCE) down-gradient
• The contaminant mass discharge of PCE decreased (76 %), but the mass
discharge of cDCE increased

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12330: Contaminated sites

April 26th 2019

Annika S. Fjordbøge (asfj@env.dtu.dk)

Zero Valent Iron Technologies

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment

In situ mass transfer In situ mass destruction

Thermal remediation Chemical oxidation

April 26th 2019 DTU Environment 5

• Permeable reactive barriers:

• “Alternative” ZVI technologies:

April 26th 2019 DTU Environment 6

April 26th 2019 DTU Environment 7

Reynolds et al. 1990

• ZVI has since been found to be reactive towards many contaminants

April 26th 2019 DTU Environment

• Hydrogen is formed (possible synergy with biotic processes)

April 26th 2019 DTU Environment

• Chlorinated solvents are chemically degraded in contact with iron surfaces

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment 12

Annika S. Fjordbøge (asfj@env.dtu.dk)

Zero Valent Iron Technologies:

Physical, chemical and/or biological

April 26th 2019 DTU Environment

• In situ mass destruction

• >150 commercial sites:

– Most in the USA (>100), but 8

also some in Europe (4 in DK),

April 26th 2019 DTU Environment 15

• Co: outlet concentration (mg/m3)

April 26th 2019 DTU Environment

• Co: outlet concentration (mg/m3)

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment

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April 26th 2019 DTU Environment 22

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment

• Intersil site, Sunnyvale, CA, 1995

• Excavation using “guar gum” or similar

April 26th 2019 DTU Environment 27

April 26th 2019 DTU Environment 28

Unsupported excavation <6 >0.3 3

Supported excavation <6 >0.6 4

Cofferdam (sheet pile) <13 >1 14

Biopolymer slurry <20 >0.6 8

Continuous trenching <11 0.5-0.9 9

Method Depth (m) Thickness (m) # Installations

Hydraulic fracturing <40 <0.2 5

Pneumatic fracturing <60 Variable 4

Jetting: columnar <60 <2 2

Jetting: diaphragms <60 <0.1 1

• Main factors than can affect longevity:

April 26th 2019 DTU Environment

April 26th 2019 DTU Environment

• Extensive precipitation can 100

hydraulic performance 1400 pore volumes is ~ 25 years of field operation

April 26th 2019 DTU Environment 34