Postbus 48 4190 CA Geldermalsen

COST Action 22, 6th Workshop

Optimisation 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: lageman@lambdaconsult.com
Web: www.lambdaconsult.com

E-mail: lageman@hakmilieu.nl
Web: www.hakmilieu.nl
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In-situ remediation techniques deployed by

Hak Milieutechniek BV
Electro-reclamation of inorganic contaminants
Electro-bioreclamation of organic contaminants
Electrokinetic fences and biofences for control, containment and
remediation of groundwater plumes
Groundwater extraction (Divisio ®)
Removal of free product (Skimmio ®)
Soil-Vapour Extraction
Air Sparging
Steam Injection
Nutrient Sparging

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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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1. Electroreclamation of inorganics
(ionic and/or polar) contaminants
Current type : Direct Current

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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
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Electrolyte conditioning
and purification

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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- , SO42- ,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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1. Electro-reclamation of inorganics
Laboratory tests

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Electrokinetic laboratory setup

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(Stenholtsvang)

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Laboratory test Stenholtsvang (DK)

Average As-concentration Average Cu-concentration

3500

3000
Concentration (mg/kg)

2500

2000

1500

1000

500

0
0 50 100 150 200 250 300
Energy (kWh/m3)

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ER laboratory test Ter Apel (NL) (As)

computed measured target value

450,0

400,0
As - concentration (mg/kg dm)

350,0

300,0

250,0

200,0

150,0

100,0

50,0

0,0
0 50 100 150 200 250 300
Energy (kWh/m3)

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ER laboratory test Hjältevad (DK) (As)

computed measured target value

1400,0
As-concentration (mg/kg dm)

1200,0

1000,0

800,0

600,0

400,0

200,0

0,0
0 100 200 300 400 500 600
Energy (kWh/m3)

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ER Laboratory test Rijsbergen (NL) (As)

computed measured target value

180,0
As-concentration (mg/kg dm)

160,0

140,0

120,0

100,0

80,0

60,0

40,0

20,0

0,0
0 50 100 150 200 250 300
Energy (kWh/m3)

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Soil sample former gasworks

100000

10000

Concentration (mg/kg dm)

1000

• Duration : 17 days 100

• Energy : 650 kWh/m³ 10

• Current density : 29 A/m² 1

CN and Phenol are collected in the anolyte. 0
Tim e (days)
17
The formation of HCN is avoided by 0,1
keeping the anolyte alkaline. CN: 96% decrease Phenol: 73% decrease
CN and Phenol are both destroyed at the As: 38 % decrease Cd: 56% decrease
anode
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1. Electro-reclamation of inorganics
Field tests & Project Results

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Electroreclamation at Loppersum Arsenic

Year 1989
Volume 250 m³
Type of contamination
• As in heavy clay
Concentration at start
• Max. 500 mg/kg
• Average 115 mg/kg
Concentration at end
• Max. 29 mg/kg Duration
• Average 10 mg/kg • 80 days of 18 hours
Energy
Product removed
• 150 kWh/ton • 38 kg As by ER
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• 14 kg As by excavation
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Electroreclamation at Loppersum Arsenic

Situation at start :
24-01-1989
As > 250 mg/kg
100 < As < 250 mg/kg
25 m 30 < As < 100 mg/kg
As < 30 mg/kg

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Electroreclamation at Loppersum Arsenic

Situation at end :
28-04-1989
As > 250 mg/kg
100 < As < 250 mg/kg
25 m 30 < As < 100 mg/kg
As < 30 mg/kg

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CN (free) CN (total) PAH (total)

Concentration (mg/kg)
120
Large scale field trial (150 ton) 100
80
Electro-reclamation with soil 60

contaminated with Cyanide and 40

20

PAH 0
0 5 10 15
Time (weeks)

CN calculated CN measured CN target value

Calculation of remediation 120,0

Concentration (mg/kg dm)

period to target value (5 mg/kg): 100,0

80,0

60,0

Ct = C0 * e at 40,0

20,0

0,0
0 5 10 15 20 25 30
Time (weeks)
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Electroreclamation at Stadskanaal Cadmium

Year 1990-1992
Volume 2.500 m³
Type of contamination
• Cd in fine clayey sand
Concentration at start
• Cd > 2.000 mg/kg
• Average 250 mg/kg
Concentration at end Energy
• Cd 5 - 40 mg/kg • 200 kWh/ton
• Average 11 mg/kg Duration
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Electroreclamation at Woensdrecht Heavy metals

Year 1992-1994
Volume 3.500 m³

8000 100
C oncentration (m g/kg)

95

D ecrease (% )
6000
90
4000
85
2000 80
0
Cr Zn Ni Cu Pb Cd
75
Energy:
Start (mg/kg) 7300 2600 860 770 730 660 • 150 kWh/ton
End (mg/kg) 755 860 80 98 108 47
Decrease % 90 89 91 87 85 93
Duration:
• 2 years
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Galvanizing plant at 's-Heerenberg Nickel & Zinc

Legend
S-value contour Nicke 0 – 0,5 m -mv
I—value countour Nickel 0 – 0,5 m -mv

S-value contour Nickel 0,5 – 1,0 m -mv

I-value countour Nickel 0,5 – 1,0 m -mv

S-value contour Nickel 1,5 – 2,0 m -mv 0 10 m

I-value contour Nickel 1,5 – 2,0 m -mv

S-value contour Nickel in groundwater

I-valuecontour Nickel in groundwater
Enclosure - 1
S-value contour Zinc 0 –1,5 m -mv
I-value contour Zinc 0 – 1,5 m -mv nvt
Van Remmen b.v., ‘s-Heerenberg A4
RL
Sanering Nikkel- & Zinkverontreiniging WP
0-00-2031, 13-07-01
Overzicht verontreinigingsituatie 3000-2031
200 nikkel en zink in grond en grondwater 00-2031-01
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Galvanizing plant at 's-Heerenberg Nickel & Zinc

Remediation containers

Transformer building
Legend
I-value contour Nickel in groundwater

I-value contour Zinc in ground

S-value contour Nickel in groundwater

0 10 m

Excavation Zn-contamination

Groundwater extraction well

Enclosure - 2
Row with anode-electrodes
nvt
Van Remmen b.v. ‘s-Heerenberg A4
Row with cathode-electrodes
RL
Sanering Nikkel- & Zinkverontreiniging WP
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0-00-2031, 13-07-01

Overzicht saneringsaanpak 00-2031

00-2031- 02
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2. Electro(bio)reclamation of organic
pollutants
Current : Alternating Current (AC)
or in some cases Direct Current (DC)

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Some characteristics of DNAPL's

(chlorinated hydrocarbons, PAH, Creosote, etc)

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Schematic view of CHC spill in soil (Schwille 1988)

Unsaturated zone

Saturated zone

Unsaturated zone

Saturated zone

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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
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(Schwille, 1988)

Top
Beads initially dry. PCE then
dripped in from above. Most
of the pore corners contain
PCE
Bottom
Beads 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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Soil vapour and

Electrical groundwater
current purification

Electrode Electrode
Unsaturated soil

Soil vapour extraction

Electrical soil heating

Saturated soil

Groundwater extraction

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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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2. Electro(bio)reclamation of organic
pollutants
Some Poject Results

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Electro(bio)reclamation Nieuwpoort

Soil Volume
Intensive phase : 4.800 m³ Start : Augustus 1998, Finish : November 2000
Extenuated phase : 7.700 m³ Start : Augustus 1998, Finish : October 2001

Product Removed (VOC) : appr. 330 kg

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Electro(bio)reclamation Nieuwpoort
Depth (m below surface)

Clay and peat soil Low CHC concentrations in

groundwater
High CHC concentrations in
groundwater (free product)
Intermediate CHC
concentrations in groundwater

Sandy soil Aquifer

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Electro(bio)remediation Nieuwpoort

CHC-Concentrations at 10-12 m depth

PCE TCE DCE VC CHC total Trendline CHC

2m

4500

4000
4m
3500
Concentration (ug/l)

3000

6m 2500

2000

1500
8m
1000

Electrode 500

10 m 0
0 50 100 150 200
Monitoring
Time (Days)
filter
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Electro(bio)reclamation Horst Aromates, diesel

Excavation

20000 • Intensive Phase : Jan ‘98 - Jul ‘99

product removed (kg)

Free product
15000 • Extenuated Phase :Jul ‘99 - Aug ‘00
10000 Active Carbon
• Product removed : 21.000 kg
5000
Air stripper • Temperature : 40 - 83 °C
0

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Electro(bio)remediation Maasdam Aromates

Decrease volume of contaminated groundwater
Decrease volume of contaminated soil
Energy consumption
12000 600000

Soil & groundwater volume (m3)

10000 500000

8000 400000

Energy (kWh)
6000 300000

4000 200000

2000 100000

0 0
0 160 335 472
Intensive Phase (Days)

Electro(bio)remediation (up to 8 m depth) of 11.500 m³ soil and groundwater in 67 weeks

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Electro(bio)reclamation Zeist

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Electro(bio)reclamation Zeist

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2. Electro(bio)reclamation of organic
pollutants
Efficiency Curves

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Remediation efficiency as a function of energy during the

intensive phase
Removal of free product (kg)

1400

1200

1000

800

600

400

200

0
0 10000 20000 30000 40000 50000 60000 70000 80000 90000 100000

Energy (kWh)

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Remediation efficiency as a function of energy cost

during the intensive phase

140
Removal of free product (kg) per

120
unit cost of energy

100

80

60

40

20

0
0 20 40 60 80 100 120 140 160 180 200

Days after start remediation

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Remediation efficiency as a function of energy cost

during the intensive phase and extenuated phase

140
Intensive phase Extenuated phase
120
Removal of free product (kg) per

100
unit cost of energy

80

60

40

20

0
0 50 100 150 200 250 300 350
Days after start remediation
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2. Electro-bioreclamation of organic
pollutants
Influence on biodegradation

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Changes in VOCs concentrations during electro-

bioreclamation Nieuwpoort
1000000

100000
Concentration (µg/l)

10000

1000

100

10

0,1
0 9 13 17 24

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
e the ne 3800 3100 690 79 8400
toc 13 14 57 350 97

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Electro(bio)reclamation Nieuwpoort
k1 k2 k3 k4
Per Î Tri Î Cis Î VC Î Ethene Î
1st order degradation constants from literature 1st order degradation constants during
• k1 = 0.0023 Electro(bio)reclamation
• k2 = 0.0033 • k1 = 0.221 - 0,361
• k3 = 0.0038 • k2 = 0.193 - 0,317
• k4 = 0.0015 • k3 = 0.051 - 0,09
• k4 = 0.0062 - 0,051
4
3 10 4
4 4 10
2.710 4
4 3.610
2.410 4
4 3.210
2.110 4
4 2.810
1.810 4
.
CvinxMvin 4 . 2.410
t 1.510 CvinxMvin2 104
4 t 4
1.210 1.610
9000 4
1.210
6000 8000
3000 4000
0 0
0 5 10 15 20 0 1 2 3 4
t t
Time (Years) Time (Years)
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3. Electrokinetic Fences and Biofences

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Electrokinetic Fence to fence off, contain and

remediate Groundwater Plumes
contaminated with inorganic compounds
(heavy metals, Cyanide, Arsenic etc)

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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
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Electrokinetic Biofence to fence off, contain

and remediate Groundwater Plumes
contaminated with organic compounds

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Electrokinetic
Electrokinetic Biofence for Biofence area
organic Contaminants Infiltration wells for
nutrients

Source of
Enhancement of Contamination
biodegradation
inside and
downstream of the
fence area: Contaminated
groundwater plume

• Inducement of Direction of groundwater flow

Anode & Cathode
nutrients electrodes
• Homogeneous
dispersion of nutrients
• Temperature increase
Aquifer

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Electrokinetic Biofence Infiltration wells with nutrients

Flow paths of Contaminated

groundwater plume
nutrients
without an
electrical DC-
field Cathode Anode

Direction of
groundwater flow

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Electrokinetic Biofence
Infiltration wells

Flow paths of Contaminated

groundwater plume Negative
nutrients charged
nutrients
influenced by Positive charged
nutrients
an electrical
DC field Cathode Anode

Direction of
groundwater flow

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Project Electrokinetic Biofence at Wildervank (VOC)

ce
i ofen
B
kinetic
ctro
Ele Anode
Cathode
Infiltration wells

Electroreclamation source area

Provincie Groningen

Wildervank

Pilotproef Electrokinetisch
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Overgenomen uit Nader bodemonderzoek fase-1, figuur 4, IWACO maart 1999. bioscherm + Electroreclamatie deel
brongebied B
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Project Electrokinetic Biofence at Wildervank (VOC)

Year: 2001-2004
Fence 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 Infiltration wells Electrodes 64
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