Hakmilieu

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: lageman@lambdaconsult.comWeb: www.lambdaconsult.com

E-mail: lageman@hakmilieu.nlWeb: www.hakmilieu.nl

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

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

1. Electroreclamation of inorganics

(ionic and/or polar) contaminantsCurrent type : Direct Current

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

Electrolyte conditioning and purification

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

1. Electro-reclamation of inorganics

Laboratory tests

Electrokinetic laboratory setup

(Stenholtsvang)

Laboratory test Stenholtsvang (DK)

0 50 100 150 200 250 300

Energy (kWh/m3)

Average As-concentration Average Cu-concentration

ER laboratory test Ter Apel (NL) (As)

0 50 100 150 200 250 300

Energy (kWh/m3)

computed measured target value

ER laboratory test Hjältevad (DK) (As)

1000,0

1200,0

1400,0

0 100 200 300 400 500 600

Energy (kWh/m3)

ER Laboratory test Rijsbergen (NL) (As)

0 50 100 150 200 250 300

Energy (kWh/m3)

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

100000

0 17Time (days)

CN: 96% decrease Phenol: 73% decrease

As: 38 % decrease Cd: 56% decrease

1. Electro-reclamation of inorganics

Field tests & Project Results

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

Electroreclamation at Loppersum Arsenic

Situation at start : 24-01-1989

As > 250 mg/kg100 < As < 250 mg/kg

30 < As < 100 mg/kgAs < 30 mg/kg

Electroreclamation at Loppersum Arsenic

Situation at end : 28-04-1989

As > 250 mg/kg100 < As < 250 mg/kg

30 < As < 100 mg/kgAs < 30 mg/kg

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 5 10 15 20 25 30

Time (weeks)

CN calculated CN measured CN target value

020406080

100120

0 5 10 15

Time (weeks)

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

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

Electroreclamation at Woensdrecht Heavy metalsYear 1992-1994Volume 3.500 m³

Energy:• 150 kWh/tonDuration:• 2 years

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

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

0-00-2031, 13-07-0100-2031

00-2031-01

Van Remmen b.v., ‘s-Heerenberg

Galvanizing plant at 's-Heerenberg Nickel & Zinc

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

00-2031

00-2031- 02

0-00-2031, 13-07-01

Sanering Nikkel- & Zinkverontreiniging

Galvanizing plant at 's-Heerenberg Nickel & Zinc

2. Electro(bio)reclamation of organicpollutants

Current : Alternating Current (AC)

or in some cases Direct Current (DC)

Some characteristics of DNAPL's (chlorinated hydrocarbons, PAH, Creosote, etc)

Schematic view of CHC spill in soil (Schwille 1988)

Unsaturated zone

Saturated zone

Unsaturated zone

Saturated zone

Two-layer bead medium initially saturated with water. PCE then applied from above

(Schwille, 1988)

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

(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

Electricalcurrent

Soil vapour andgroundwaterpurification

Groundwater extraction

Soil vapour extraction

Electrical soil heatingSaturated soil

Electrode ElectrodeUnsaturated soil

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

Some Poject Results

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

Clay and peat soil

Sandy soil Aquifer

Low CHC concentrations in groundwater

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

r face

)Postbus 48 4190 CA Geldermalsen

Electro(bio)remediation Nieuwpoort

CHC-Concentrations at 10-12 m depth

0 50 100 150 200

Time (Days)

PCE TCE DCE VC CHC total Trendline CHC

Electrode

Monitoring filter

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

Excavation

Free product

Active Carbon

Air stripper

Electro(bio)remediation Maasdam Aromates

0 160 335 472

Intensive Phase (Days)

100000

200000

300000

400000

500000

600000

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

Electro(bio)reclamation Zeist

Efficiency Curves

0 10000 20000 30000 40000 50000 60000 70000 80000 90000 100000

Energy (kWh)

Remediation efficiency as a function of energy during the intensive phase

Remediation efficiency as a function of energy cost during the intensive phase

0 20 40 60 80 100 120 140 160 180

Days after start remediation

0 50 100 150 200 250 300 350

Days after start remediation

Intensive phase Extenuated phase

Remediation efficiency as a function of energy cost during the intensive phase and extenuated phase

2. Electro-bioreclamation of organicpollutants

Influence on biodegradation

Changes in VOCs concentrations during electro-bioreclamation Nieuwpoort

100000

1000000

Months after start remediation

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

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

0 1 2 3 40

40008000

1.21041.61042 1042.41042.81043.21043.61044 104

.CvinxtMvin

0 5 10 15 200

300060009000

1.21041.51041.81042.11042.41042.71043 104

.CvinxtMvin

k1 k2 k3 k4

Per Tri Cis VC Ethene

Time (Years) Time (Years)

3. Electrokinetic Fences and Biofences

Electrokinetic Fence to fence off, contain and remediate Groundwater Plumes

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

• 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

Electrokinetic Biofence to fence off, contain and remediate Groundwater Plumes

contaminated with organic compounds

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

Flow paths of nutrients without an electrical DC-field

Cathode Anode

Infiltration wells with nutrients

Electrokinetic Biofence

Flow paths of nutrients influenced by an electrical DC field

Negative charged nutrients

Infiltration wells

Positive charged nutrients

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)

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

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