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Postbus 48 4190 CA Geldermalsen
COST Action 22, 6th WorkshopOptimisation and Remediation of Preservatives
September 22-23, 2003 Zagreb, Coatia
– In-situ Electro-Reclamation of soil and groundwater contaminated with Arsenic and heavy metals
– In-situ Electro-bioreclamation of soil and groundwater contaminated with organic species
– Electrokinetic fences to fence off hot spots and remediate and contain groundwater plumes
Reinout Lageman, Lambda Consult / Hak Milieutechniek BV
E-mail: [email protected]: www.lambdaconsult.com
E-mail: [email protected]: www.hakmilieu.nl
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Postbus 48 4190 CA Geldermalsen
In-situ remediation techniques deployed by Hak Milieutechniek BV
Electro-reclamation of inorganic contaminantsElectro-bioreclamation of organic contaminantsElectrokinetic fences and biofences for control, containment and remediation of groundwater plumesGroundwater extraction (Divisio ®)Removal of free product (Skimmio ®)Soil-Vapour ExtractionAir SpargingSteam InjectionNutrient Sparging
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Postbus 48 4190 CA Geldermalsen
Electro-reclamation of Inorganic contaminants– Basic principles, laboratory tests and project
results with arsenic, heavy metals, cyanide,Electro-bioreclamation of organic contaminants– VOCs, aromates, fuel oil, PAH, TNT, creosote etc.
Electrokinetic Fences and Biofences– Basic principles and examples
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Postbus 48 4190 CA Geldermalsen
1. Electroreclamation of inorganics
(ionic and/or polar) contaminantsCurrent type : Direct Current
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Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
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At ∆V/∆x = 40 V/m:
Keo = 0,017 m/day
Kef = 0,01 – 0,0003 m/day
Kel = 0,17 m/day
K gravel = 10 – 1000 m/day
Kcoarse sand = 1 – 500 m/day
Kfine sand = 0,1 – 10 m/day
Kclay = < 0,0009 m/day
Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
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Electrolyte conditioning and purification
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Postbus 48 4190 CA Geldermalsen
Our 3 step closed loop process
1 Contamination must be desorbed from the soil particles• a proton (H+) sweep is used to desorb metals• a hydroxide ion (OH-) sweep is used to desorb nonmetals• H+ and OH- are formed by electrolysis of water
2 Contamination is migrated toward the electrodes• anions (Cl- , SO4
2- ,AsO3-) migrate to the anode• cations (Cu2+ , Zn2+) migrate to the cathode
3 Contamination is captured in the electrolyte• electrolyte management is closed loop
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Postbus 48 4190 CA Geldermalsen
1. Electro-reclamation of inorganics
Laboratory tests
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Postbus 48 4190 CA Geldermalsen
Electrokinetic laboratory setup
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Postbus 48 4190 CA Geldermalsen
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(Stenholtsvang)
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Postbus 48 4190 CA Geldermalsen
Laboratory test Stenholtsvang (DK)
0
500
1000
1500
2000
2500
3000
3500
0 50 100 150 200 250 300
Energy (kWh/m3)
Conc
entra
tion
(mg/
kg)
Average As-concentration Average Cu-concentration
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Postbus 48 4190 CA Geldermalsen
ER laboratory test Ter Apel (NL) (As)
0,0
50,0
100,0
150,0
200,0
250,0
300,0
350,0
400,0
450,0
0 50 100 150 200 250 300
Energy (kWh/m3)
As
- con
cent
ratio
n (m
g/kg
dm
)
computed measured target value
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Postbus 48 4190 CA Geldermalsen
ER laboratory test Hjältevad (DK) (As)
0,0
200,0
400,0
600,0
800,0
1000,0
1200,0
1400,0
0 100 200 300 400 500 600
Energy (kWh/m3)
As-
conc
entr
atio
n (m
g/kg
dm
)
computed measured target value
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Postbus 48 4190 CA Geldermalsen
ER Laboratory test Rijsbergen (NL) (As)
0,0
20,0
40,0
60,0
80,0
100,0
120,0
140,0
160,0
180,0
0 50 100 150 200 250 300
Energy (kWh/m3)
As-
conc
entr
atio
n (m
g/kg
dm
)
computed measured target value
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Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
Soil sample former gasworks
• Duration : 17 days• Energy : 650 kWh/m³
• Current density : 29 A/m²
CN and Phenol are collected in the anolyte. The formation of HCN is avoided by keeping the anolyte alkaline. CN and Phenol are both destroyed at the anode
0,1
1
10
100
1000
10000
100000
0 17Time (days)
Con
cent
ratio
n (m
g/kg
dm
)
CN: 96% decrease Phenol: 73% decrease
As: 38 % decrease Cd: 56% decrease
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200
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Postbus 48 4190 CA Geldermalsen
1. Electro-reclamation of inorganics
Field tests & Project Results
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Postbus 48 4190 CA Geldermalsen
Electroreclamation at Loppersum ArsenicYear 1989Volume 250 m³Type of contamination • As in heavy clay
Concentration at start• Max. 500 mg/kg • Average 115 mg/kg
Concentration at end• Max. 29 mg/kg • Average 10 mg/kg
Energy• 150 kWh/ton
Duration• 80 days of 18 hoursProduct removed• 38 kg As by ER• 14 kg As by excavation
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Postbus 48 4190 CA Geldermalsen
Electroreclamation at Loppersum Arsenic
25 m
Situation at start : 24-01-1989
As > 250 mg/kg100 < As < 250 mg/kg
30 < As < 100 mg/kgAs < 30 mg/kg
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Postbus 48 4190 CA Geldermalsen
Electroreclamation at Loppersum Arsenic
25 m
Situation at end : 28-04-1989
As > 250 mg/kg100 < As < 250 mg/kg
30 < As < 100 mg/kgAs < 30 mg/kg
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Postbus 48 4190 CA Geldermalsen
Large scale field trial (150 ton) Electro-reclamation with soil contaminated with Cyanide and PAH
Calculation of remediation period to target value (5 mg/kg):
Ct = C0 * e at
0,0
20,0
40,0
60,0
80,0
100,0
120,0
0 5 10 15 20 25 30
Time (weeks)
Con
cent
ratio
n (m
g/kg
dm
)
CN calculated CN measured CN target value
020406080
100120
0 5 10 15
Time (weeks)
Con
cent
ratio
n (m
g/kg
)
CN (free) CN (total) PAH (total)
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Postbus 48 4190 CA Geldermalsen
Electroreclamation at Stadskanaal Cadmium
Year 1990-1992
Volume 2.500 m³
Type of contamination
• Cd in fine clayey sandConcentration at start• Cd > 2.000 mg/kg• Average 250 mg/kg
Concentration at end• Cd 5 - 40 mg/kg • Average 11 mg/kg
Energy• 200 kWh/tonDuration• 2 ½ years200
3
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Postbus 48 4190 CA Geldermalsen
Electroreclamation at Woensdrecht Heavy metalsYear 1992-1994Volume 3.500 m³
Energy:• 150 kWh/tonDuration:• 2 years
0
2000
4000
6000
8000
Con
cent
ratio
n (m
g/kg
)
75
80
85
90
95
100
Dec
reas
e (%
)
Start (mg/kg) 7300 2600 860 770 730 660End (mg/kg) 755 860 80 98 108 47Decrease % 90 89 91 87 85 93
Cr Zn Ni Cu Pb Cd
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0 10 m
LegendS-value contour Nicke 0 – 0,5 m -mvI—value countour Nickel 0 – 0,5 m -mv
S-value contour Nickel 0,5 – 1,0 m -mvI-value countour Nickel 0,5 – 1,0 m -mv
S-value contour Nickel 1,5 – 2,0 m -mvI-value contour Nickel 1,5 – 2,0 m -mv
S-value contour Nickel in groundwater I-valuecontour Nickel in groundwater
Sanering Nikkel- & Zinkverontreiniging
Overzicht verontreinigingsituatie nikkel en zink in grond en grondwater
S-value contour Zinc 0 –1,5 m -mvI-value contour Zinc 0 – 1,5 m -mv
Enclosure - 1
A4
RL
0-00-2031, 13-07-0100-2031
00-2031-01
nvt
WP
Van Remmen b.v., ‘s-Heerenberg
Galvanizing plant at 's-Heerenberg Nickel & Zinc
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LegendI-value contour Nickel in groundwater
I-value contour Zinc in ground
Row with anode-electrodes
Row with cathode-electrodes
Enclosure - 2
S-value contour Nickel in groundwater
Van Remmen b.v. ‘s-Heerenberg
Overzicht saneringsaanpak
0 10 m
Remediation containers
Transformer building
Groundwater extraction well
Excavation Zn-contamination
A4
RL
00-2031
00-2031- 02
nvt
WP
0-00-2031, 13-07-01
Sanering Nikkel- & Zinkverontreiniging
Postbus 48 4190 CA Geldermalsen
Galvanizing plant at 's-Heerenberg Nickel & Zinc
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Postbus 48 4190 CA Geldermalsen
2. Electro(bio)reclamation of organicpollutants
Current : Alternating Current (AC)
or in some cases Direct Current (DC)
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Postbus 48 4190 CA Geldermalsen
Some characteristics of DNAPL's (chlorinated hydrocarbons, PAH, Creosote, etc)
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Postbus 48 4190 CA Geldermalsen
Schematic view of CHC spill in soil (Schwille 1988)
Unsaturated zone
Saturated zone
Unsaturated zone
Saturated zone
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Postbus 48 4190 CA Geldermalsen
Two-layer bead medium initially saturated with water. PCE then applied from above
(Schwille, 1988)
Top
Infiltration paths are broader in the finer bead layer
Bottom
PCE dammed up at interface with smaller beads, and entered them only when significant PCE pressure built up in the upper layer
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(Schwille, 1988)
TopBeads initially dry. PCE then dripped in from above. Most of the pore corners contain PCEBottomBeads initially moist. PCE then dripped in from above. Most of the PCE flowed out, leaving isolated drops in the internal portions of the pore spaces
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Postbus 48 4190 CA Geldermalsen
Electricalcurrent
Soil vapour andgroundwaterpurification
Groundwater extraction
Soil vapour extraction
Electrical soil heatingSaturated soil
Electrode ElectrodeUnsaturated soil
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Postbus 48 4190 CA Geldermalsen
Electro(bio)reclamation of organic contaminants
Intensive phase (physico-chemical)– Direct heating of the saturated zone and indirect heating of the
unsaturated zone, combined with groundwater and soil vapour extraction and nutrient injection
Attenuated phase (biological)– Nutrient injection. Air sparging if aerobic conditions are necessary
Monitoring phase– Monitoring and control through periodic sampling and analysis, if clean-
up criteria have not been met completely and there might be risk of recontamination
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Postbus 48 4190 CA Geldermalsen
2. Electro(bio)reclamation of organicpollutants
Some Poject Results
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Postbus 48 4190 CA Geldermalsen
Electro(bio)reclamation Nieuwpoort
Soil VolumeIntensive phase : 4.800 m³ Start : Augustus 1998, Finish : November 2000Extenuated phase : 7.700 m³ Start : Augustus 1998, Finish : October 2001
Product Removed (VOC) : appr. 330 kg
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Electro(bio)reclamation Nieuwpoort
Clay and peat soil
Sandy soil Aquifer
Low CHC concentrations in groundwater
High CHC concentrations in groundwater (free product)Intermediate CHC concentrations in groundwater
Dept
h (m
be lo
w su
r face
)Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
Electro(bio)remediation Nieuwpoort
CHC-Concentrations at 10-12 m depth
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4000
4500
0 50 100 150 200
Time (Days)
Con
cent
ratio
n (u
g/l)
PCE TCE DCE VC CHC total Trendline CHC
2 m
6 m
4 m
8 m
10 m
12 m
Electrode
Monitoring filter
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Postbus 48 4190 CA Geldermalsen
Electro(bio)reclamation Horst Aromates, diesel
• Intensive Phase : Jan ‘98 - Jul ‘99
• Extenuated Phase :Jul ‘99 - Aug ‘00
• Product removed : 21.000 kg
• Temperature : 40 - 83 °C0
5000
10000
15000
20000
prod
uct r
emov
ed (k
g)
Excavation
Free product
Active Carbon
Air stripper
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Postbus 48 4190 CA Geldermalsen
Electro(bio)remediation Maasdam Aromates
0
2000
4000
6000
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10000
12000
0 160 335 472
Intensive Phase (Days)
Soil
& g
roun
dwat
er v
olum
e (m
3)
0
100000
200000
300000
400000
500000
600000
Ener
gy (k
Wh)
Decrease volume of contaminated groundwater Decrease volume of contaminated soil Energy consumption
Electro(bio)remediation (up to 8 m depth) of 11.500 m³ soil and groundwater in 67 weeks
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Postbus 48 4190 CA Geldermalsen
Electro(bio)reclamation Zeist
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Postbus 48 4190 CA Geldermalsen
Electro(bio)reclamation Zeist
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Postbus 48 4190 CA Geldermalsen
2. Electro(bio)reclamation of organicpollutants
Efficiency Curves
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Postbus 48 4190 CA Geldermalsen
0
200
400
600
800
1000
1200
1400
0 10000 20000 30000 40000 50000 60000 70000 80000 90000 100000
Energy (kWh)
Rem
oval
of f
ree
prod
uct (
kg)
Remediation efficiency as a function of energy during the intensive phase
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Postbus 48 4190 CA Geldermalsen
Remediation efficiency as a function of energy cost during the intensive phase
0
20
40
60
80
100
120
140
0 20 40 60 80 100 120 140 160 180
Days after start remediation
Rem
oval
of fr
ee p
rodu
ct (k
g) p
er u
nit c
ost o
f ene
rgy
200
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Postbus 48 4190 CA Geldermalsen
0
20
40
60
80
100
120
140
0 50 100 150 200 250 300 350
Days after start remediation
Rem
oval
of fr
ee p
rodu
ct (k
g) p
er
unit
cost
of e
nerg
y
Intensive phase Extenuated phase
Remediation efficiency as a function of energy cost during the intensive phase and extenuated phase
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Postbus 48 4190 CA Geldermalsen
2. Electro-bioreclamation of organicpollutants
Influence on biodegradation
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Postbus 48 4190 CA Geldermalsen
Changes in VOCs concentrations during electro-bioreclamation Nieuwpoort
0,1
1
10
100
1000
10000
100000
1000000
Months after start remediation
Con
cent
ratio
n (µ
g/l)
pce 110 2200 17000 27 0,2
tce 310 5500 5800 93 0,2
cis-dce 9600 20000 88000 158000 2800
vc 8700 9500 15000 4800 9900
ethene 3800 3100 690 79 8400
toc 13 14 57 350 97
0 9 13 17 24
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1st order degradation constants from literature• k1 = 0.0023• k2 = 0.0033• k3 = 0.0038• k4 = 0.0015
1st order degradation constants duringElectro(bio)reclamation
• k1 = 0.221 - 0,361• k2 = 0.193 - 0,317• k3 = 0.051 - 0,09• k4 = 0.0062 - 0,051
Electro(bio)reclamation Nieuwpoort
0 1 2 3 40
40008000
1.21041.61042 1042.41042.81043.21043.61044 104
.CvinxtMvin
t365
0 5 10 15 200
300060009000
1.21041.51041.81042.11042.41042.71043 104
.CvinxtMvin
t365
k1 k2 k3 k4
Per Tri Cis VC Ethene
Time (Years) Time (Years)
Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
3. Electrokinetic Fences and Biofences
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Postbus 48 4190 CA Geldermalsen
Electrokinetic Fence to fence off, contain and remediate Groundwater Plumes
contaminated with inorganic compounds(heavy metals, Cyanide, Arsenic etc)
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Postbus 48 4190 CA Geldermalsen
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• Heavy metals and other polar contaminants are captured in the electrolytes and periodically removed
• No contamination downstream of the fence area and no disturbance of the groundwater flow regime
Postbus 48 4190 CA Geldermalsen
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Postbus 48 4190 CA Geldermalsen
Electrokinetic Biofence to fence off, contain and remediate Groundwater Plumes
contaminated with organic compounds
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Electrokinetic Biofence for organic Contaminants
Enhancement of biodegradation inside and downstream of the fence area:
• Inducement of nutrients
• Homogeneous dispersion of nutrients
• Temperature increase
Infiltration wells for nutrients
Source of Contamination
Direction of groundwater flow
Electrokinetic Biofence area
Contaminated groundwater plume
Aquifer
Anode & Cathodeelectrodes
Postbus 48 4190 CA Geldermalsen
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Flow paths of nutrients without an electrical DC-field
Direction of groundwater flow
Contaminated groundwater plume
Cathode Anode
Infiltration wells with nutrients
Postbus 48 4190 CA Geldermalsen
Electrokinetic Biofence
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Electrokinetic Biofence
Direction of groundwater flow
Flow paths of nutrients influenced by an electrical DC field
Negative charged nutrients
Contaminated groundwater plume
Infiltration wells
Positive charged nutrients
AnodeCathode
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AnodeCathode
Infiltration wells
Electroreclamation source area
Electrokinetic Biofence
Wildervank
Pilotproef Electrokinetisch bioscherm + Electroreclamatie deel brongebied
Provincie Groningen
Overgenomen uit Nader bodemonderzoek fase-1, figuur 4, IWACO maart 1999.B
Project Electrokinetic Biofence at Wildervank (VOC)
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Year: 2001-2004Fence data:
• Length: 30 m, • Width: 3 m, • Depth: 10 m • Volume: 900 m³• A-C distance: 5 m• Infiltration wells: 24• Power: 30A/20V• GW flow: 7 m/year
Type of contamination: • PCE, TCE, CIS, VC
Duration:• 3 years
Project Electrokinetic Biofence at Wildervank (VOC)
ElectrodesInfiltration wells
Postbus 48 4190 CA Geldermalsen
2003