|\ COMMITTEE ON EPA 542-R-02-001
THE CHALLENGES OF January 2002
MODERN SOCIETY www.epa.gov/tio
www.clu-in.org
www.nato.int/ccms
NATO/CCMS Pilot Study
Evaluation of Demonstrated and
Emerging Technologies for the
Treatment of Contaminated Land
and Groundwater (Phase
2001
ANNUAL REPORT
Number 250
NORTH ATLANTIC TREATY ORGANIZATION
-------
2001
Annual Report
NATO/CCMS Pilot Study
Evaluation of Demonstrated and Emerging
Technologies for the Treatment and Clean Up
of Contaminated Land and Groundwater
(Phase III)
Liege, Belgium
September 9-14, 2001
January 2002
-------
NOTICE
This Annual Report was prepared under the auspices of the North Atlantic Treaty
Organization's Committee on the Challenges of Modern Society (NATO/CCMS) as a service
to the technical community by the United States Environmental Protection Agency (U.S.
EPA). The report was funded by U.S. EPA's Technology Innovation Office. The report was
produced by Environmental Management Support, Inc., of Silver Spring, Maryland, under
U.S. EPA contract 68-W-00-084. Mention of trade names or specific applications does not
imply endorsement or acceptance by U.S. EPA.
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CONTENTS
Introduction 1
Projects Included in the NATO/CCMS Phase III Pilot Study 3
Summary Table 4
Project 1: Bioremediation of Oil-Polluted Loamy Soil 7
Project 2: Pilot Test on Decontamination of Mercury-Polluted Soil 16
Project 3: Permeable Treatment Beds 19
Project 4: Rehabilitation of Land Contaminated by Heavy Metals 22
Project 5: Application of Bioscreens and Bioreactive Zones 28
Project 6: Rehabilitation of a Site Contaminated by PAH Using Bio-Slurry Technique 32
Project 7: Risk Assessment for a Diesel-Fuel Contaminated Aquifer Based on Mass
Flow Analysis During Site Remediation 34
Project 8: Obstruction of Expansion of a Heavy Metal/Radionuclide Plume Around a
Contaminated Site by Means of Natural Barriers Composed of Sorbent Layers 39
Project 9: Solidification/ Stabilization of Hazardous Wastes 44
Project 10: Metal-Biofilm Interactions in Sulphate-Reducing Bacterial Systems 59
Project 11: Predicting the Potential for Natural Attenuation of Organic Contaminants
in Groundwater 65
Project 12: Treatability Test for Enhanced In Situ Anaerobic Dechlorination 69
Project 13: Permeable Reactive Barriers for In Situ Treatment of Chlorinated Solvents 80
Project 14: Thermal Cleanup Using Dynamic Underground Stripping and Hydrous
Pyrolysis/Oxidation 84
Project 15: Phytoremediation of Chlorinated Solvents 91
Project 16: In-Situ Heavy Metal Bioprecipitation 102
Project 17: Gerber Site 107
Project 18: SAFIRA 109
Project 19: Succesive Extraction-Decontamination of Leather Tanning Waste Deposited Soil Ill
Project 20: Innovative Treatment Technologies: A Summary of Work Completed on a
DNAPL Site at Cape Canaveral, Florida 113
Project 21: Development and Use of a Permeable Adsorptive Reactive Barrier System
for Ground Water Cleanup at a Chromium Contaminated Site 121
Project 22: Thermal In-situ Remediation of the Unsaturated Zone by Steam Injection 124
Project 23: Bioremediation of Pesticides 127
Project 24: Surfactant-Enhanced Aquifer Remediation 132
Project 25: Liquid Nitrogen Enhanced Remediation (LINER): A New Concept for the
Stimulation of the Biological Degradation of Chlorinated Solvents 136
Project 26: SIREN: Site for Innovative Research on Monitored Natural Attenuation 142
Project 27: Hydro-Biological Controls on Transport and Remediation of Organic Pollutants
for Contaminated Land 147
Project 28: Demonstration of a Jet Washing System for Remediation of Contaminated Land 150
Project 29: Automatic Data Acquisition and Monitoring System for Management of
Polluted Sites 152
Project 30: Approved Biological Treatment Technologies for the Sustainable Cleanup of
TNT-Contaminated Soil 156
Project 31: Phytoremediation Evaluation of Petroleum Hydrocarbon in Surface Soil 159
Project 32: Remediation of Chlorinated Solvents in Groundwater by Chemical Reduction
Using Zero-Valent Iron, Pneumatic Fracturing, and Reagent Atomization 163
Project 33: Chemical Ozidation and Natural Attenuation at the Camden County Landfill 166
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Country Tour De Table Presentations 169
Armenia 170
Austria 175
Belgium 177
Canada 181
Czech Republic 185
Finland 188
France 193
Germany 200
Greece 203
Italy 205
Japan 208
Latvia 212
Lithuania 216
The Netherlands 221
Norway 227
Romania 228
Slovenia 235
Spain 244
Switzerland 248
Turkey 251
United Kingdom 254
United States of America 262
Country Representatives 269
Attendees List 272
Pilot Study Mission 278
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
INTRODUCTION
The Council of the North Atlantic Treaty Organization (NATO) established the Committee on the
Challenges of Modern Society (CCMS) in 1969. CCMS was charged with developing meaningful
programs to share information among countries on environmental and societal issues that complement
other international endeavors and to provide leadership in solving specific problems of the human
environment. A fundamental precept of CCMS involves the transfer of technological and scientific
solutions among nations with similar environmental challenges.
The management of contaminated land and groundwater is a universal problem among industrialized
countries, requiring the use of existing, emerging, innovative, and cost-effective technologies. This
document reports on the fourth meeting of the Phase III Pilot Study on the Evaluation of Demonstrated
and Emerging Technologies for the Treatment and Clean Up of Contaminated Land and Groundwater.
The United States is the lead country for the Pilot Study, and Germany and The Netherlands are the Co-
Pilot countries. The first phase was successfully concluded in 1991, and the results were published in
three volumes. The second phase, which expanded to include newly emerging technologies, was
concluded in 1997; final reports documenting 52 completed projects and the participation of 14 countries
were published in June 1998. Through these pilot studies, critical technical information was made
available to participating countries and the world community.
The Phase III study focuses on the technologies for treating contaminated land and groundwater. This
Phase is addressing issues of sustainability, environmental merit, and cost-effectiveness, in addition to
continued emphasis on emerging remediation technologies. The objectives of the study are to critically
evaluate technologies, promote the appropriate use of technologies, use information technology systems
to disseminate the products, and to foster innovative thinking in the area of contaminated land. The Phase
III Mission Statement is provided at the end of this report.
The first meeting of the Phase III study was held in Vienna, Austria, on February 23-27, 1998. The
meeting included a special technical session on treatment walls and permeable reactive barriers. The
proceedings of the meeting and of the special technical session were published in May 1998. The second
meeting of the Phase III Pilot Study convened in Angers, France, on May 9-14, 1999, with represent-
atives of 18 countries attending. A special technical session on monitored natural attenuation was held.
This report and the general proceedings of the 1999 annual meeting were published in October 1999. This
third meeting was held in Wiesbaden, Germany from June 26-30, 2000. The special technical session
focused on decision support tools. The reports were published in January 2001. Most recently, the fourth
Phase III meeting was held September 9-14, 2001 in Liege, Belgium. The topic of this year's special
session was validation of in situ remediation performance.
This and many of the Pilot Study reports are available online at http: //www .nato. int/ccms/ and
http://www.clu-in.org/intup .htm. General information on the NATO/CCMS Pilot Study may be obtained
from the country representatives listed at the end of the report. Further information on the presentations in
this decision support tools report should be obtained from the individual authors.
Stephen C. James
Walter W. Kovalick, Jr., Ph.D.
Co-Directors
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
THIS PAGE IS INTENTIONALLY BLANK
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
PROJECTS INCLUDED IN NATO/CCMS PHASE III PILOT STUDY
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
SUMMARY TABLE
PROJECT
1 . Bioremediation of Oil-Polluted
Loamy Soil
2. Pilot Test on Decontamination of
Mercury-Polluted Soil
3. Permeable Treatment Beds
4. Rehabilitation of Land
Contaminated by Heavy Metals
5. Application of BioScreens and
Bioreactive Zones
6. Rehabilitation of a Site
Contaminated by PAH Using
Bio-Slurry Technique
7. Risk Assessment for a
Diesel-Fuel Contaminated
Aquifer Based on Mass Flow
Analysis During Site
Remediation
8. Obstruction of Expansion of a
Heavy Metal/Radionuclide
Plume Around a Contaminated
Site by Means of Natural
Barriers Composed of Sorbent
Layers
9. Solidification/Stabilization of
Hazardous Wastes
10. Metal-Biofilms Interactions in
Sulfate-Reducing Bacterial
Systems
1 1 . Predicting the Potential for
Natural Attenuation of Organic
Contaminants in Groundwater
12. Treatability Test for Enhanced In
Situ Anaerobic Dechlorination
13. Permeable Reactive Barriers for
In Situ Treatment of Chlorinated
Solvents
14. Thermal Cleanup Using
Dynamic Underground Stripping
and Hydrous Pyrolysis/Oxidation
COUNTRY
Belgium
Czech Rep.
Germany
Greece
Netherlands
Sweden
Switzerland
Turkey
Turkey
UK
UK
USA
USA
USA
MEDIUM
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CONTAMINANT
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NOTES
PAHs, munitions
chemieals
Hg, metals, PAHs,
TPH •
PAHs, BTEX, TCE,
PCE •
Pb, Zn, Cd, As, H+,
S04=
Chlorinated
pesticides, BTEX,
TPH, HCH, PCE, TCE
PAHs, cyanides,
metals, ammonium
compounds •
PHC
Pb, As, Cr, Cu, Cd,
Hg, Ni, Zn; 137Cs, 9°Sr,
J38|J .
PCBs, AOX,«metals
Metals (Cu, Zn, Cd),
radionuclides (Lab-
scale)
Coal tars, phenols,
creosol, xylenols,
BTEX;NH4+«
TCE, DCE, VC, PCE
PCE, TCE, BCE
PAHs, fuels, gasoline,
chlorinated solvents,
pentaohlorophenol
COMPLETE
•
• •
•. .
•
• •
•
• •
• •
•
•• .
•• .
• •
• •
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
PROJECT
15. Phytoremediation of Chlorinated
Solvents
16. I n-Situ Heavy Metal
Bioprecipitation
17. GERBERSite
18. SAFIRA
19. Successive Extraction -
Decontamination of Leather
Tanning Waste Deposited Soil
20. Interagency DNAPL
Consortium Side-by-Side
Technology Demonstrations at
Cape Canaveral, Florida
21 . Development and Use of a
Permeable Adsorptive
Reactive Barrier System for
Ground Water Clean-up at a
Chromium-Contaminated Site
22. Thermal In-Situ Using Steam
Injection
23. Bioremediation of Pesticides
24. Surfactant-Enhanced Aquifer
Remediation
25. Liquid Nitrogen Enhanced
Remediation (LINER)
26. SIREN: Site for Innovative
Research on Monitored Natural
Attenuation
27. Hydro-Biological Controls on
Transport and Remediation of
Organic Pollutants for
Contaminated Land
28. Demonstration of a Jet
Washing System for Remed-
iation of Contaminated Land
29. Automatic Data Acquisition
and Monitoring System for
Management of Polluted Sites
COUNTRY
USA
Belgium
France
Germany
Turkey
USA
Switzerland
Germany
USA
USA
Netherlands
UK
UK
UK
Italy
MEDIUM
'o
03
•
•
•
• •
•
• •
•
Groundwater
•
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•
• •
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CONTAMINANT
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Pesticides/PCBs
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NOTES
TCE, TCA, DCE,
PCE, xylenes, methyl
chloride, TMB
Heavy Metals (Zn, Cd,
As, Pb, Cr, Ni, Cu,
sulfate)
Chlorinated solvents,
BTEX, PCBs,
phenols, phthalates,
Pb, Zi>
Complex contamina-
tion, chlorobenzene
Tanning wastes •
DNAPLs
Chromium (VI)
TCE, BTEX
Chlordane, DDT,
ODD, DDE, dieldrin,
molinate, toxaphene
PCE
Chlorinated
hydrocarbons
Organic solvents
PAHs, phenols,
substituted benzenes
Tars, petroleum
hydrocarbons
TPH, BTEX
COMPLETE
• •
•
• •
• •
• •
• •
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
30. Biological Treatment
Technologies for the Cleanup
of TNT-Contaminated Sites
31 Phytoremediation Evaluation
for Petroleum Hydrocarbons in
Surface Soil
32. Remediation of Chlorinated
Solvents in Groundwater by
Chemical Reduction Using
Zero-Valent Iron, Pneumatic
Fracturing, and Reagent
Atomization
33. Chemical Oxidation and
Natural Attenuation at the
Camden County Landfill
Germany
USA
USA
USA
• •
• •
•
•
•
•
•
•
•
•
•
•
TNT
Petroleum, RAHs
TCE
Chlorinated ethenes
KEY:
AOX = adsorptive organic halogens
BTEX = benzene, toluene, ethylbenzene,
and xylenes
DCE = dichloroethene
HCH = hexachlorocyclohexane
PAHs = polycyclic aromatic hydrocarbons
PCBs = polychlorinated biphenyls
PCE = tetrachloroethene
PHCs = petroleum hydrocarbons
SVOCs = semivolatile organic compounds
1MB = trimethylbenzene
TCA = trichloroethane
TCE = trichloroethene
TNT = trinitrotoluene
VC = vinyl chloride
VOCs = volatile organic compounds
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 1
Bioremediation of Oil-Polluted Loamy Soil
Location
"van Oss" site,
former fuel storage depot,
Neder-Over-Heembeeck
Technical contact
Ecorem nv
Dr. Walter Mondt
ir. Serge Van Meerbeeck
Wayenborgstraat 2 1
2800 Mechelen
Tel: 015/29.49.29
Fax: 015/29.49.28
E-mail: EcoremiSglo.be
Project Status
Interim Report
Project Dates
accepted 1994
final report 1997
Costs Documented?
yes
Media
loamy soil
Contaminants
mineral oil
Technology Type
bioremediation
Project Size
full-scale
(proposed future pilot project)
Progress on this project is current as of January 2002.
1. INTRODUCTION
Name of the technology: Bioremediation of oil polluted loamy soil.
Status of the technology: Highly innovative and reasonable costs. Further experiments are required to
evaluate different bioremediation techniques for the decontamination of loamy soil.
Project Objectives: Decontamination of oil polluted loamy soil by an in-situ activated biorestoration
system, composed of a bioventing and a biostimulation system.
Following the good decontamination results on the van Oss site, this project is considered as a first step
towards a more general and more effective application of bioremediation of contaminated loamy soils. In
collaboration with the ULB (Universite libre de Bruxelles) Ecorem proposed a pilot project to NATO,
with objective to examine which bioremediation techniques could efficiently be used in the
decontamination of loamy soils polluted with hydrocarbons.
2. SITE DESCRIPTION
The van Oss site is a former fuel storage depot in Neder-over-Heembeek, contaminated with mineral oil.
A topographical situation of the site is shown on Figure 1.
3. DESCRIPTION OF THE PROCESS
Based upon a reconnoitring soil examination, it was proven that the soil as well as the groundwater of the
former fuel storage depot van Oss was seriously contaminated with mineral oil. Compared to the
contamination with this parameter, the presence of other components present was negligible.
The volume of contaminated soil (unsaturated zone) was estimated, based on the reconnoitering soil
examination, at 3.500 m3. Proceeding with these data, selective excavation of the contaminated zones was
a first option to be considered.
In order to draw up a detailed proposal for decontamination, Ecorem proposed an elaborated analysis
campaign based on a sample grid.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Based on the analytical results and the positioning of the grid the volume of contaminated soil was
assessed. Table 1 gives an overview of the volumes of contaminated soil. In Figure 3 the horizontal
spreading of the mineral oil contamination in the soil is represented.
Table 1: Overview of the volumes of contaminated soil (mineral oil)
Depth (cm)
0-200
0-250
0-300
9231m3
14,770 tons
10,997m3
17,995 tons
12,763 m3
20,420 tons
6284 m3
10,054 tons
6997 m3
11, 196 tons
7711m3
12,338 tons
943m3
15 09 tons
1050m3
1680 tons
1156m3
1850 tons
The cubing shows that the volumes of contaminated soil were considerably higher than estimated at first.
As a result, Ecorem proposed an alternative decontamination technique, i.e., an in-situ activated
biorestoration system composed of a bioventing and a biostimulation system. Bioventing consists of a
forced air flushing of the unsaturated soil with as main objective the supply of oxygen in order to
stimulate the biodegrading activity of the microorganisms present in the soil. The biostimulation in this
project consisted of mixing the contaminated ground with compost and wood flakes, in order to obtain a
porous matrix, and the addition of nutrients to enhance microbial activity.
Decontamination of the unsaturated zone consisted of the following stages:
A. Excavation of the Hot Spots
Hot spots (areas with severe contamination - here areas where the concentration of mineral oil
>5000mg/kg DS) are secondary sources of contamination, and can therefore inhibit the efficient
functioning of an in-situ decontamination technique. It is thus essential that these secondary sources of
contamination be removed, for the in-situ decontamination technique to have any chance of success.
B. Biodegradation
The efficiency of the biodegradation system strongly depends on soil characteristics. In order to obtain a
good biological degrading, the oxygen level and level of nutrients need to be established in optima forma.
A good supply of oxygen can only be realised in porous soils. Soils with limited air permeability, such as
loamy soils, therefore need to be mixed with structure amelioration additives. Oxygen is necessary for
hydrocarbon degradation, as this is done aerobically. Oxygen limitation leads to slowing down and
discontinuing of the degradation kinetics. The creation of good air permeability is also of crucial
importance for the bioventing.
A second parameter, the nutrient supply is just as essential for a good biodegradation. In order to optimise
the feeding pattern the soil should be mixed with bioactivating substrates.
C. Soil Air Extraction
The efficiency and the design of the soil air extraction strongly depend on the soil characteristics, as these
have an important effect on the movement and transportation of soil air (gas). The most important
determining soil characteristics are: soil structure, stratigraphy, porosity, grain size, water level, residual
contamination, and presence of macro pores.
The air permeability of the soil represents the effect of these different soil characteristics. The air
permeability indicates to what extent fumes can float through a porous environment.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Air permeability and airflow velocity are linearly dependent. The higher the air permeability and the
airflow velocity, the greater the chances of an effective soil air extraction.
Taking into account that the loamy/clayey unsaturated zone at the van Oss site is heterogeneously built,
the air transportation throughout the soil is prevented and the airflow velocity is relatively small. A
solution to break this heterogeneity was to mix this oil with structure-enhancing additives till the depth of
0.5 m above ground water level. This also enlarged the porosity of the soil, which was favourable for air
transportation.
In order to get a large zone of influence, the placement of horizontal injection and withdrawal drains was
chosen. Placement of drains was performed in layers, the soil mixed with structure-enhancing additives
being completed (Figure 2)
The withdrawn air was purified in an air treatment establishment, consisting of following units:
Air/Water Separator and Air Filter
This separator and filter eliminates soil damp (water) and fine particles that may damage the mechanical
equipment, and might disrupt further air treatment. The water discerned needs to be collected and, if
contaminated, purified.
Vacuum Pump
The vacuum pump causes the suction in the underground. The compression heat in the pump causes a
temperature increase and a corresponding decrease of the relative humidity of the airflow when leaving
the blower.
Air Cleaning Unit
The pumped up air was treated by means of biofiltration and active carbon filtration.
Measure Devices
By measuring the different parameters the air treatment and soil air extraction could constantly be
monitored and adjusted.
The above mentioned decontamination concept has a double advantage:
• It avoids transportation of considerable volumes of contaminated soil (approx. 12.000 tons with a
concentration higher than lOOOmgkg DM) to an adapted dumping-ground;
• It relocates the problem of the desired quality from a problem of volume to a problem of time. The
final quality of the soil is function of the time period in which the system is applied.
The complete decontamination setting is represented in Figure 2.
4. RESULTS AND EVALUATION
The bioremediation of the unsaturated zone was started in October 1995, after the hot spots had been
excavated and the remaining soil had been mixed with compost and wood flakes. After two months a first
analysis campaign was executed. The results have been visually represented in Figure 3. Further analysis
campaigns were executed after 5 and after 10 months. These results have been represented in Figure 4 and
Figure 5. Based on the visual representation of the horizontal spread of the contamination in the different
figures it has become clear that the bioremediation technique is successful.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
After ten months the mean concentration of mineral oil was less than 490 ppm, while the decontamination
objective imposed by the BIM was a concentration of 900 ppm.
From these results it is clear that bioremediation techniques can be efficient on loamy soil on short term,
so that further examination for possible bioremediation techniques on finer textures offers quite a lot of
perspective.
5. COSTS
The bioremediation technique was also a favourable concept regarding the cost of decontamination. The
total cost for bioremediation of the unsaturated area amounted to about 20 million franks. A selective
excavation of the contaminated grounds would have easily exceeded a 30 million franks' cost price.
6. PROPOSAL OF A PILOT PROJECT ON BIOREMEDIATION OF LOAMY SOIL
Following the decontamination at the van Oss site, Ecorem proposed to NATO a pilot project, with
objective to verify which bioremediation techniques are effective in the decontamination of contaminated
loamy soils.
In order to dimension the different technologies to be tested in the scope of this pilot project, the
following activities are planned prior to the experimental stage:
Characterisation of the Soil to be Treated
This stage consists of the analysis of the soil to be treated, regarding the most relevant organic and
inorganic parameters. Therefore, a number of samples will be taken. A good characterisation is necessary
because certain pollutants, even in low concentrations, have a certain inhibiting effect on the microbial
activity. Complementary to these analyses a certain number of general parameters such as grain size, the
C/N relation and the degree of humidity will be determined as well.
Determination of Initial Microbial Activity
The determination of initial microbial activity is performed based on the classical techniques used in soil
microbiology, such as microscopical research (countings), determination of the biomass by fumigation
and extraction, respiration measurements (CO2 production) and ATP determinations.
Determination of the Maximum Potential Biodegradability of the Contamination Present
In order to determine the maximum degradability of the pollutants, column tests with lysimeters are being
executed. Therefore optimal conditions for microbial growth and degradation are created by means of
addition of water, nutrients, air, microorganisms and other additives. During the column tests the
pollutant concentration, the use of oxygen and the CO2 production are continuously monitored in order to
obtain an accurate image of the biodegradability of the pollutants.
The preparatory stages will result in a first indication of the potential applicability of bioremediation as a
decontamination technique for loamy soils that were contaminated with hydrocarbons.
Based on the results and conclusions of the preparatory stages a number of decontamination concepts and
configurations will be tested on a lab scale. Regarding the in-situ decontamination techniques, this is only
executed with the help of column studies based on soil column lysimeters. Regarding the ex-situ
decontamination techniques, mainly bioreactor tests will be executed.
Soil column lysimeters are simple but efficient means to verify the possibilities to what extent the soil can
be in-situ decontaminated with the help of bioremediation techniques. In Figure 6 a schematic
representation of the test setting is given. Different soil columns are being equipped as represented in
10
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Figure 6. In the test setting fluid solutions can be put in with the help of a time-directed system that is
established on top of each column. Furthermore, air fumes can be added in each column. Before entering
the column, the fumes are lead through a shaft filled with glass pearls to enable a uniform separation.
Different column tests will be performed simultaneously to monitor the microbial activity and the
evolution of the contaminants under different circumstances and feedings. The liquid solutions will
mainly consist of nutrient mixtures containing nitrogen sources, phosphates and oligo-elements. For each
column the effluent is collected and analysed on pH, conductivity and nutrient concentrations. In order to
measure microbial activity in the column, the production of CO2 produced is determined. On the columns
following treatments will be performed: control setting without specific treatment; only addition of water,
addition of water and nutrients, addition of water + nutrients + microorganisms; addition of water + air +
nutrients; addition of water + microorganisms + air + nutrients.
Such soil column lysimeters are extremely well equipped to verify whether contaminated sites can be
decontaminated in-situ with the help of bioremediation techniques. In addition, the column tests will be
used for the evaluation of ex-situ decontamination techniques, during which the contaminated soil will be
submitted to different preliminary treatments (e.g., mixing with compost). Different compost formulas
and relationships in the process will be tested.
Based on the results of the experiments on a lab scale, the most appropriate concepts will be tested on a
larger scale, in order to obtain a more realistic idea. Therefore the ex-situ decontamination techniques will
be tested in the soil-recycling centre. Regarding the in-situ decontamination techniques, the different
contaminated zones in different sites will be isolated civil-technically in order to prevent a horizontal
spreading of the contamination. The volume of isolated cells will amount to approximately 50m3. In order
to prevent spreading towards the ground water, a pump and injection system are established around
different cells. If possible slots will be dug to the depth of 2 to 3 m around the cells. From these slots
horizontal perforated tubes will be installed under the cells to enable monitoring of the groundwater as
well as of the soil vapour. With this sampling system the heterogeneity of the soil can be optimally
studied.
This decontamination experiments will be conducted on the future soil-recycling centre of s.a. Ecoterres
in Brussels. This centre will be built on the van Oss site, owned by the G.O.M.B. Figure 7 gives an
impression of the future soil-recycling centre.
11
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Figure 1
* - - -i; X;'-- >tf
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FIG. 1: OF VAN ON THE MAP
Figure 2
UNIT
UNIT
FIG. 2: LAY-OUT OF TOE
RMS
12
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Figure 3
Sioremediatlon zone
Excavation zone
1
.. 1400ppm
i^. I200ppm
,800ppm
lOOppm
Oppm
OF 2 OF
of in DM)
Figure 4
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-20-
-40-
•50-
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Stefentedlatlon zone
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13
-------
NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2002
Figure 5
isne Excavation
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14
-------
NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Figure 7
-~^
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OF THE
15
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 2
Pilot Test on Decontamination of Mercury-Polluted Soil
Location
Spolchemie a.s.,
Usti nad Labem,
Czech Republic
Technical Contact
Marek Stanzel
KAP, Ltd.
Trojska92
171 00 Prague 7
Czech Republic
Tel: (00-420-2) 83 09 06 14
Fax: (00-420-2) 83 09 06 58
E-mail:
nLstanzel^21BJ5§&iCz
Project Status
Final report
Project Dates
Accepted 1999
Final Report 2000
Costs Documented?
Yes
Contaminants
Metallic mercury
Technology Type
Wet gravity
separation
Media
Soil
Project Size
Pilot test - 1 m3 (2 tons)
Results Available?
No
Project 2 was completed in 2000.
1. INTRODUCTION
The pilot test on decontamination of mercury-polluted soil consisting of excavation of mercury-polluted
soil and on-site wet gravity separation was conducted at the area of Spolchemie located in the center of
the city Usti nad Labem in northwest Bohemia. The pilot test was conducted with the aim to demonstrate
the recovery efficiency and possibility to fulfill the objective limit for decontamination, i.e., 70 ppm of Hg
in treated soil.
2. BACKGROUND
In 1998, the investigation of pollution and risk assessment was finished in the area of Spolchemie, a large
chemical plant located in the center of Usti nad Labem in northwest Bohemia. High-grade elemental Hg
pollution of soil was found in areas adjacent to former and current buildings of the mercury-cell process
for producing caustic soda, caustic potash, hydrogen, and chlorine. Maximum concentrations of mercury
often reach up to hundreds of thousands ppm. Total calculated amount of metallic Hg is 267-445 tons in
222.740 m3 of polluted soil. The mercury is present in the form of visible drops or softly dispersed in the
soil. The scale and character of the pollution was presented in detail in previous papers. A scale of the
cleanup project has not been decided yet, but it looks very probable that the main volume of polluted soil
will be excavated and decontaminated and the lower level of pollution will be monitored only. The
feasibility study evaluating decontamination methods used worldwide was performed.
Because of a lack experience in decontamination of mercury-polluted soils in the Czech Republic, a
project was conducted in 1998 for identification and laboratory tests for decontamination. The project
aimed to select the most suitable method for decontamination of soils with massive pollution by mercury.
For a large quantity of contaminated material the thermal method (used worldwide) is not considered
suitable for our case because of high-energy costs. Regarding the laboratory tests, the experts of KAP
decided to solve this problem by means of wet gravity separation, taking advantage of mercury's specific
physical and chemical properties. On the basis of laboratory tests, the Pilot Test Project for
Decontamination of Mercury-Polluted Soil was elaborated and accepted in 1999.
The main aim and tasks of the pilot test was to solve the following problems in semi-industrial scale:
• to check recovery efficiency of the proposed gravity separation on 1 - 3 m3 of polluted material;
• to check possible adsorption of Hg on clay minerals and its influence on the decontamination
efficiency;
16
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
• to test the dewatering of treated material;
• to specify the energy consumption and total costs of decontamination;
• to design the optimal decontamination unit that could be maintained and operated effectively under
the conditions of the local economy and infrastructure.
The Pilot Test was funded by the Czech National Property Fund. The total cost was 0.5 M CZK (13,000
USD).
3. TECHNICAL CONCEPT
The decontamination unit set up for the pilot test consists of the following devices:
steel container— excavated material was loaded into steel container where the material was blunged by
hydromonitor— this device blunges and feeds the treated material to
gravity storage bin— from this tank the suspended material was pumped to
hydrocyclone— the first stage of separation - classifying into two fractions - mud and sand (in this
fraction, the metallic mercury is concentrated and the mud is dewatered and backfilled into the excavation
hole)
centrifugal concentrator— the second stage of separation, the pre-concentrate is finally treated
sedimentation basins— wastewater from hydrocyclone and centrifugal concentrator is pre-treated
(sedimentation of mud)
centrifuge— dewatering of mud from hydrocyclone and sedimentation basins.
During the processing of polluted soil the important points of tested technology was sampled:
polluted soil— this represents a problem because of the highly variable Hg concentration in the material
(due to occurrence of Hg in drops and/or finely disseminated), analyzed concentrations vary from XOO to
120,000 ppm in the feed (i.e., polluted soil);
waste from hydrocyclone (mud) — determined values of Hg concentration did not exceed 10 ppm;
pre-concentrate from hydrocyclone (sandy fraction) — due to high specific weight of Hg it is also
complicated to collect representative samples;
waste from centrifugal concentrator— due to high specific weight of Hg it is also complicated to collect
representative samples— determined Hg concentration was in order X ppm;
concentrate, i.e., separated mercury— this output was not sampled because it is represented by metallic
mercury with admixture of sand, in frame of conducted Pilot Test about 9 ml of mercury (i.e.,
approximately 121.5 g) was separated.
process water— determined concentration of Hg were under the detection limit (<0.003 mg/1) so during
the decontamination process the Hg does not dissolve in processing water.
The test for dewatering of treated soil was successful. The determined moisture in treated soil shows that
it is possible to backfill this material into the excavation because the moisture in dewatered material is
only about 5% higher than in natural soil.
4. ANALYTICAL APPROACH
During the pilot test, the excavated material, feed, and outputs were sampled and analyzed for mercury
concentration, as well as the process water. The total concentration of Hg, as well as the concentration of
metallic, organic, and inorganic form of Hg, was analyzed. The concentration of accompanying pollutants
was also monitored (i.e., CHCs, heavy metals). Analyses were carried out in accredited laboratories by
relevant analytical methods.
17
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
5. RESULTS
The conducted pilot test approved the excellent recovery efficiency of wet gravity separation of the
mercury from polluted soil. Concentration of mercury in the feed reached values over 100,000 ppm.
Analyzed concentration in output (i.e., treated "clean" soil) did not exceed 10 ppm (i.e., in conditions of
The Bohemian Massif value only slightly exceeding the natural background).
On the basis of results of the pilot test a final proposal on decontamination of mercury polluted soil was
elaborated. Proposed treating technology is consisting of accessible technology.
6. HEALTH AND SAFETY
Regarding the mercury's specific physical and chemical properties and wet treating process, no
extraordinary personal protection clothing or devices were used.
7. ENVIRONMENTAL IMPACTS
Conducted pilot test had no impact on the environment. Treated (i.e., clean) soil was backfilled into the
space of excavation. Process water was pre-treated in sedimentation basins and released to the plant's
sewerage system and subsequently to the wastewater treating plant. The quality of both treated soil and
wastewater was monitored. Content of metallic mercury in treated soil was below 10 ppm. Concentration
of Hg in wastewater was under the detection limit (<0.003 mg/1).
8. COSTS
The total project cost was 0.5M CZK (13,000 USD). The cost breakdown was as follows:
Personnel cost (managing, supervision, consultant) - 49%
Pilot Test operation (excavation, treating, dewatering, sampling) - 41%
Laboratory cost -7%
Transportation - 2%
Miscellaneous - 1%
9. CONCLUSIONS
In the frame of the successfully conducted pilot test, the mercury contaminated soil was excavated and
blunged, and by the means of gravity separation the mercury was recovered. Treated soil was dewatered
by centrifuge. During the pilot test all the feed and outputs, as well as processing water, were sampled and
analyzed.
The pilot test approved excellent recovery efficiency of wet gravity separation of metallic mercury using
normally accessible technology. On the basis of the results, the proposal on gravity decontamination
technology for remediation in the area of Spolchemie was elaborated. This proposal is assessed by The
Czech Environmental Inspectorate.
10. REFERENCES
1. Sedlacek M.: Risk Analysis Update - Pollution of Rock Environment and Groundwater by Mercury in
the Area of Spolchemie a.s. in Usti nad Labem. KAP, Ltd., Prague, 1998.
2. Sedlacek M.: Report on Laboratory Testing of Decontamination of Mercury Polluted Soil., KAP,
Ltd., Prague, 1999.
3. Sedlacek M.: Report on Pilot Test on Decontamination of Mercury Polluted Soil. KAP, Ltd., Prague,
2000.
18
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 3
Permeable Treatment Beds
Location
Former solvent blending plant,
Essen, Germany
Technical Contact
Eberhard Beitinger
WCI Umwelttechnik GmbH
Sophie-Charlotten-StraBe 33
14059 Berlin
Tel: +49-7(0)30-32609481
Fax: +49-(0)30-32609472
E-mail: exbeitiOiSwcc.com
Project Status
Field tests
finalized in 1999
Project Dates
Accepted 1997
Completed 1999
Costs
Documented?
Cost estimation is
available
Contaminants
Chlorinated and non-
chlorinated solvents,
BTEX-aromates, TCE,
PCE
Technology Type
Permeable reactive
barrier as in situ
groundwater
remediation
technology
Media
Groundwater
Project Size
Full-scale
Results Available?
Field test results
available
Project 3 was completed in 1999.
1. INTRODUCTION
A pilot groundwater treatment plant was installed at a former industrial site in Essen, Germany, where
organic solvents had been stored and processed in a small chemical plant for several decades. Leakage
and handling losses caused significant soil and groundwater contamination, mainly by BTEX and CHC.
The contaminated aquifer has low hydraulic conductivity and is only 2-3 m thick. The aquifer is covered
by 4-11 m of thick, silty and clayey covering layers (loess). During investigations and conceptual
remediation design, it was determined that the site was suitable to install adsorbent walls since
conventional remediation and contamination control measures cannot be applied in a cost-efficient
manner.
Subsequently, WCI and IWS studied and reported on various technical variants to install an adsorbent
wall in a feasibility study. The study also established which data were necessary to arrive at the
dimensions of the adsorbent wall. The feasibility study recommended that pilot tests be conducted on the
site for this purpose.
The objective of the pilot tests was to obtain precise information on the adsorption potential for the
contaminants at the site, the type and quantity of the required adsorbent material, the functioning of filters
at different flow speeds, and the long-term effectiveness and attendant risks, if any, of installing an
adsorbent wall.
Conducting the pilot tests involved the following principal tasks:
• Selecting a suitable adsorbent for the tests depending on water quality and the relevant contaminant
concentrations at the site;
• Structural design and planning of the pilot plant;
• Operating and taking samples from the pilot plant, as well as carrying out laboratory analyses;
• Assessment of the pilot tests.
2. BACKGROUND/SITE DESCRIPTION
From 1952 to 1985, a chemical factory was located on an area of about 10,000 m2 in a city in the Ruhr
area. Mostly solvents, like hydrocarbons, volatile chlorinated hydrocarbons, PAHs, petroleum, turpentine
oil substitute, ketones, monoethyleneglycol, and alcohols were handled, stored, and processed. Today, a
residential building is left on the site while underground and above ground tanks are demolished.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
The ground was filled up 2.0 m over silty soil (approx. 4 to 11 m thick). Below the silt, a layer of sand
and gravel (0.8 to 7.4 m) and marly sands (7.0 to 16.3 m below the top) have been detected. The marly
sands are the first waterproof layer.
The first aquifer is about 1.0 to 3.2 m thick and the flow velocity is very slow (kf = 6.6 x 10"6 m/s). The
concentrations of main contaminants in groundwater are petrol hydrocarbons 23.6 mg/1 to 164.0 mg/1,
volatile chlorinated hydrocarbons 27.0 mg/1 and aromatic hydrocarbons 153.0 mg/1. Furthermore, higher
concentrations of manganese and iron are present.
The project is funded by the city of Essen and the state; Nordrhein-Westfalen, the former owner, went
bankrupt.
3. DESCRIPTION OF THE PROCESS
The pilot plant was fed with groundwater, which was pumped directly from the aquifer into the front
column. Two dosing pumps located behind a gravel bed in the front column fed groundwater into
columns 1 and 2. The gravel filter served to hold back sediments as well as to eliminate iron and
manganese.
Column 1 contained:
• 45 cm gravel filter (size: 2 to 3.15 mm)
• 5 cm activated carbon ROW 0.08 supra
• 5 cm gravel filter (gravel size: 2 to 3.15 mm)
• 65 cm activated carbon ROW 0.08 supra
The thickness of the activated carbon bed in Column 1 corresponded to the recommended thickness of the
activated carbon bed of the adsorbent wall in the feasibility study.
Column 2 contained:
• 100 cm activated carbon ROW 0.08 supra
The treated water was led via an overflow into a trough located outside the container.
Groundwater analyses were based on the contamination at the site; their scope was determined by the
feasibility study to install an adsorbent wall. The analyses covered field parameters, general parameters
and parameters to quantify BTEX and volatile CHC contamination.
The analyzed general parameters included sum parameters for organic compounds as well as the
parameters iron and manganese. A sum parameter for organic compounds was used in order to study
whether it could serve as a substitute for analyses of individual substances. Moreover, the sum parameters
were also used to check whether the results of individual analyses were plausible. Iron and manganese
contents were determined in order to check whether precipitation of these substances would block the
adsorbent wall.
Separate analyses were carried out for BTEX and volatile CHC. The number of analyzed parameters (16)
was deliberately large so as to also cover important decomposition products such as vinyl chloride.
Contaminant retention by the activated carbon was determined in two ways. First, contaminant
concentrations were continuously monitored at the inlet, in the columns, and at the column outlets.
Secondly, following the conclusion of tests, the columns were disassembled and individual partitions of
carbon samples were analyzed for contaminant content. Tests were carried out to determine whether iron
and manganese precipitation or microbial activity in the activated carbon could block the adsorbent wall.
20
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Water samples collected on 11 days were tested for numerous parameters; on the whole, over 1,600
individual results were obtained for water samples taken during pilot operation. The determined
concentrations for dissolved organic carbons (DOC) ranged between 80 and 160 mg/1 at the inlet. The
DOC values correlate well with the CSB and TOC concentrations. No contaminant breakthrough was
detected in samples from the outlets of the two columns over a period of almost half a year.
The pilot tests with Columns 1 and 2 confirm that putting up an adsorbent wall is feasible.
With respect to contaminant retention, results of the pilot tests indicate that the long-term effectiveness
would be much higher than the estimated period of 30 years in the feasibility study.
4. RESULTS AND EVALUATION
The pilot tests confirm the findings of the feasibility study, to the effect that the site is suited to put up an
adsorbent wall. The following statements can be made with respect to the present tests:
The pilot tests show good contaminant retention in the activated carbon, in fact much higher than what
was assessed in the feasibility study. Contaminant breakthrough for toluene and trichloroethylene was
determined at sampling point S2P50 (i.e., after flow through 50 cm), Column 2, only at the end of the 5-
month pilot test operation. By this time, throughput had reached 600 times the bed volume.
The pilot tests indicate that the durability of the wall given a 70 cm-thick activated carbon layer would be
much higher than the 30 years estimated in the feasibility study. The thickness of the carbon layer should
therefore be reduced when the wall is put up.
The DOC concentrations established during the pilot tests can almost entirely be traced to the
contaminants detected at the site. It is therefore to be expected that the adsorbing potential of the activated
carbon will not be impaired by natural organic compounds, such as human.
Data pertaining to the contaminant breakthrough suggest that the depletion of the adsorbing capacity of
the activated carbon is accompanied by a sharp peak in the concentration of volatile substances. A
suitable monitoring system should therefore be set up when the adsorbent wall is erected.
The fact that the activated carbon could be regenerated after disassembling the plant suggests economic
operation of the adsorbent wall.
Laboratory analyses of the water and activated carbon samples indicate that iron and manganese
precipitation will be insignificant and will not block the adsorbent wall.
Microbial activity could not be detected in the gravel filter or in the activated carbon; it may be concluded
that under the given site conditions, the build-up of bacterial film does not pose a risk.
Preliminary laboratory tests to determine the choice of activated carbon as well as pilot tests must be
carried out in all cases prior to setting up an adsorbent wall given the variance in site conditions.
5. COSTS
The costs for conducting the field tests have been EURO 50.000,--. The overall costs to erect the wall
system and then fill it with activated carbon are estimated to be EURO 750.000,--. Included are additional
costs for monitoring the water quality for 30 years, which is as long as the minimum performance time of
one single filling will be.
In comparison with traditional pump-and-treat groundwater remediation costs, the proposed permeable
reactive barrier system will be at least 25% less expensive.
6. REFERENCE
Eberhard Beitinger and Eckart Biitow. Machbarkeitsstudie zum Einsatz einer Adsorberwand -
"Schonebecker Schlucht" in Essen, Internal Report, WCI, Wennigsen, 1997 (not published)
21
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 4
Rehabilitation of Land Contaminated by Heavy Metals
Location
Lavrion, Kassandra (Greece)
Sardinia (Italy)
Estarreja (Portugal)
Technical Contact
Prof. loannis Paspaliaris,
Dr. Anthimos Xenidis
National Technical University of Athens
9, Iroon Polytechneiou str.
15780Zografou
Greece
Tel: +30/1-772-2176
Fax: +30/1-772-2168
Project Status
3rd Progress Report
Project Dates
Accepted 1997
Final Report 2002
Costs Documented?
No
Contaminants
Lead, zinc, cadmium,
arsenic, acidity, sulfates
Technology Type
Alkaline
additives
Surface barriers
Chemical
fixation and
immobilization
Soil leaching
Media
Mining tailings and waste rock, Pyrite
cinders, Soil
Project Size
Laboratory,
Demonstration-scale
Results Available?
Yes
1. INTRODUCTION
Polymetallic sulfide mining and processing operations result in the generation of millions of tons of
mining, milling, and metallurgical wastes, most of them characterized as hazardous. Improper
environmental management in the past, but to some degree in current operations, has resulted in intensive
in terms of concentration and extensive in spatial terms pollution of land and waters by heavy metals and
toxic elements which migrate from the wastes. The project aims at developing (a) innovative, cost-
effective and environmentally acceptable industrial technologies for the rehabilitation of land
contaminated from sulfide mining and processing operations and (b) an integrated framework of
operations that will allow for environmentally sustainable operation of the mining and processing
industries.
Rehabilitation technologies under development include:
Preventive
1. Application of alkaline additives to prevent acid generation from sulfidic wastes.
2. Formation of surface barriers with bentonite, zeolite or other additives to prevent pollutant
migration from the pyrite cinders and calamina residues.
3. Chemical stabilization of the heavy metals in situ in oxidic wastes and soils.
Remedial
Removal of heavy metals from soils by leaching techniques.
The status of the technologies is bench and demonstration scale. One particular technology involving the
application of ground limestone to inhibit acid generation has been applied in full-scale for the
rehabilitation of a 150,0001/2,500 ha sulfidic tailings dam in Lavrion.
2. SITES
The research is of a generic nature and the results applicable to a wide number of cases. The sites
examined as case studies are given below:
22
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Site
Lavrion, GR
Stratoni, GR
Montevecchio,
Monteponi, Sardinia, IT
Estarreja, PT
Description
Redundant polymetallic sulfide mine
(argentiferous, galena, sphalerite, pyrite)
Active polymetallic sulfide mines (galena-
sphalerite-pyrite) with a mining history of
more than 2.500 years.
Extensive Pb-Zn historic mining area.
Currently, there is one operating and many
redundant mines.
Chemical industrial site. Production of
sulfuric acid by roasting of pyrites in the
period 1952-1991.
Material tested
Sulfidic and oxidic
tailings, soils
Waste rock
Sulfidic tailings,
calamina red mud,
soils
Pyrite cinders
3. DESCRIPTION OF THE PROCESSES-RESEARCH ACTIVITY
3.1 Preventive Technologies to Inhibit the Spread of Pollution from the Active Sources
Processes for the prevention of pollutant migration, which were investigated in laboratory scale and are
being evaluated in field scale, include:
A. Limestone or Fly Ash Addition to Prevent Acid Generation from Sulfidic Wastes
The technical objective is the development of a process for the inhibition of acid generation from sulfidic
wastes by making beneficial use of the oxidation-dissolution-neutralization-precipitation reactions so as
to achieve: on a microscale, precipitation of reaction products around the pyrite grains, inhibiting further
oxidation and/or on a macroscale, formation of a hard pan that will drastically reduce the permeability of
wastes to water and oxygen. By achieving these goals, the required limestone or other alkaline additive
will be only a fraction of the stoichiometric requirements; therefore, the cost of application will be
significantly lower compared to the current practice of adding near-stoichiometric quantities.
An extensive laboratory kinetic testwork was carried out using limestone, a low cost and commonly found
at mine sites alkaline material, and fly ash, a by product of Greek-lignite powered electricity plants with
significant neutralization potential and cementitious properties. Kinetic tests using columns or humidity
cells were carried out for a period of 270-600 days. After 270 days of operation a selected number of
columns as well the humidity cells were dismantled and a detailed geotechnical and geochemical
characterization of the solid residues was performed.
Based on the laboratory test results, field tests were constructed in Lavrion and Stratoni, for the
remediation of sulfidic tailings and waste rock respectively, which have been run for a period of sixteen
months.
B. Formation of Surface Barriers for the Pyrite Cinders and Calamina Residues
The technical objective is to develop an innovative, cost-effective process for the inhibition of the toxic
leachate generation from these wastes by modification of the top surface layer with bentonite or
bentonite-zeolite additives. The aim is to achieve very low permeability of the surface layer in order to
inhibit water infiltration and subsequent leaching of contaminants.
The laboratory work performed include: a) selection of the stabilizing agents (bentonites and/ or zeolites
and/ or other materials) having certain properties (proper sediment volume, swelling index, yield, filtrate
loss and high cation exchange capacity), b) short term leaching tests to preliminarily determine
parameters including mode of application and addition rates of the stabilizing agents and c) lysimeter
kinetic tests. Following laboratory testing, field scale tests were conducted to evaluate the performance of
low permeability layers including: a) a sand-bentonite mixture to cover pyrite cinders at the Estarreja site,
23
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
and b) an alumina red mud stabilized with gypsum and calamina red mud mixture to cover calamina
residues and Montevecchio oxidic tailings.
C. Chemical Stabilization of Metals in Oxidic Wastes and Soils
The technical objective is to develop a process for the in-situ immobilization of heavy metals that exist in
toxic and bioavailable speciations by transforming them into less soluble and bioavailable species using
calcium oxyphosphates or other low cost additives.
A number of stabilizing agents including phosphates, alumina red mud, fly ash, peated lignite and
biological sludge were tested on Lavrion and Montevecchio oxidic tailings and soils by conducting pot
experiments. Stabilization was examined by chemical extraction tests and verified by actual biological
tests. Chemical extraction tests included toxicity characterization using the EPA-TCLP test and
determination of the bioavailable-phytotoxic fraction using a combination of EDTA, DTPA and NaHCO3
leaching tests. The biological tests involved plant growth tests using dwarf beans (Phaseolus vulgaris
starazagorski) as plant indicator. The morphological parameters of the plants (root weight, leaf area,
length and weight of aerial parts) were measured. Samples from the roots and leaves were collected for
the determination of the metal concentrations. Based on the laboratory test results, alumina red mud
stabilized with gypsum was proven to be a successful stabilizing agent for Montevecchio soils and was
tested under field conditions. On the other hand a mixture of phosphates and peated lignite was selected
and is tested in field scale for the stabilization of Lavrion oxidic tailings and soils.
3.2 Development of Remedial Industrial Technologies for the Clean-up of Contaminated Sites
Remedial measures for rehabilitation of contaminated soils include removal of contaminants by either
chemical or physical means with operations, which can be applied either in-situ or ex-situ. The technical
objective is to develop process/processes for the removal of heavy metals from soils by leaching
techniques.
Leaching Methods for the Clean-up of Contaminated Soils
The work performed comprised the following stages: a) evaluation of alternative leaching reagents, i.e.
oxalic acid, acetic acid, citric acid, Na2H2EDTA, Na2CaEDTA and an acidic brine consisting of HC1-
CaCl2, b) development of two integrated leaching processes based on the use of Na2CaEDTA and HC1-
CaCl2 reagents, with the investigation of all the required treatment stages, i.e. removal of metals from the
pregnant solution, regeneration of reagents for recycling, polishing of effluents for discharge etc., c)
comparative evaluation of the above processes on representative soil samples from Montevecchio and
Lavrion sites. The integrated HCl-CaCl2 and Na2CaEDTA processes were also evaluated with column
experiments, in order to define crucial operating parameters for the application of heap leaching
techniques on Montevecchio (MSO) and Lavrion (LSO) soils.
4. RESULTS AND EVALUATION
4.1 Limestone or Fly Ash Addition to Prevent Acid Generation from Sulfidic Wastes
Mixing of the pyrite with limestone at rates corresponding to only 15% of the stoichiometric quantity was
effective both in preventing the generation of acidic drainage and reducing the hydraulic conductivity.
Furthermore, mixing of pyrite or Lavrion tailings with 18-20 % w/w fly ash resulted in the formation of a
cemented layer that reduced the permeability by two orders of magnitude as compared with the control
inhibiting the downward migration of acidic leachates. Based on the experimental work, field tests were
constructed in Lavrion. The field test area was divided into 4 quadrants of 100 m2 (10 x 10m) where the
alkaline materials were homogeneously mixed with Lavrion tailings and applied either to the entire mass
of tailings or only to the upper layers. Referring to the Stratoni waste rock, the separation of the sulfide
rich -4 mm size fraction and its placement after mixing with 14% limestone on top of the coarse was
24
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
proven effective in preventing acid generation even under acidic conditions. Based on the laboratory
results, field tests (4 testing areas) were constructed in the Stratonion site. The remediation scheme
investigated involves separation of the fine from the coarse fraction, mixing of the fine fraction with
limestone and placement of the mixture on top of the coarse fraction. Field tests are currently in progress.
However, the monitoring results obtained so far indicated that the investigated remediation scheme
decreased significantly the drainage volume and improved the leachates quality.
4.2 Formation of Surface Barriers for the Pyrite Cinders and Calamina Residues
Laboratory tests showed that mixing of pyrite cinders or calamina red mud with bentonite would not
reduce drastically the hydraulic conductivity, so that to achieve the formation of a low permeability layer,
i.e. k: <10~7 cm/sec. Alternative materials such as alumina red mud stabilized with gypsum and a sand-
bentonite mixture are currently evaluated under field scale for the rehabilitation of calamina red muds and
pyrite cinders respectively. Preliminary results showed that covering of the pyrite cinders with a sand-
10% bentonite layer, 30 cm thick, reduced the volume of leachates by 72%. The reduction in the
cumulative mass of metals dissolved was 90% for iron, copper and zinc, 83% for arsenic and 75% for
lead.
4.3 Chemical Stabilization of Metals in Oxidic Wastes and Soils
For Lavrion oxidic tailings, phosphates, fly ash and biological sludge, added to amounts 0.9, 8 and 10 %
w/w, were proven to be efficient stabilizers reducing Pb and Cd leachability well below the regulatory
limits. The most successful additives for Lavrion soils were phosphates, lime, red mud and fly ash at a
dose of 1.4, 5, 5 and 7.5% w/w respectively. Alumina red mud stabilized with 5% gypsum was proven to
be a successful stabilizing agent for Montevecchio soils.
Given that inorganic materials, e.g. phosphates, fly ash, lime, do not support plant growth, whereas the
application of organic materials, e.g. biological sludge, peated lignite, has a beneficial effect on the
production of biomass, the rehabilitation scheme currently tested under field scale involves mixtures of
inorganic and organic materials including phosphates and peated lignite. The field test results indicated
that treatment of soils and oxidic tailings with phosphates and peated lignite improved the leachates
quality and plants growth and reduced metals uptake by plants.
4.4 Leaching Methods for the Clean-up of Contaminated Soils
The HCl-CaCl2 process was selected as the most efficient treatment option for Montevecchio soils, due to
their low calcite content, whereas the Na2CaEDTA process was considered as best alternative for the
calcareous soils of Lavrion. The results indicated that it is possible to achieve a high extraction of heavy
metals, e.g., Pb 93-95%, Zn 78-85%, Cd 71-95% etc. The contaminants are recovered in a solid residue,
corresponding to approximately 76 kg per ton soil on a dry basis. Finally, fresh water required for the
final washing of treated soil was estimated to be approximately 1.6 m3 per ton soil.
5. COSTS
Cost estimates of rehabilitation technologies examined will be available upon evaluation of field scale test
results.
6. REFERENCES
1. Cambridge, M. et al, 1995: "Design of a Tailing Liner and Cover to Mitigate Potential Acid Rock
Drainage: A Geochemical Engineering Project" presented at the 7995 National Meeting of the
American Society for Surface Mining and Reclamation, Gillette, Wyoming.
2. Daniel, D.E., Koerner, R.M., 1993: Cover systems in geotechnical practice for waste disposal, ed.
D.E. Daniel, Chapman and Hall, London, pp. 455-496.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
3. Elliot, H.A., Brown, G.A. & Shields, G.A., Lynn, J.H., 1989. Restoration of metal-polluted soils by
EDTA extraction. In Seventh International Conference on Heavy Metals in the Environment, Geneva,
vol.2, pp. 64-67.
4. Hessling, J.L., M.P. Esposito, R.P. Traver, & R.H. Snow, 1989. Results of bench-scale research
efforts to wash contaminated soils at battery recycling facilities. In J.W. Patterson & R. Passino
(eds.), Metals Speciation, Separation and Recovery, Chelsea Lewis Publishers Inc., vol.2, pp. 497-
514.
5. Jenkins, R.L., B.J. Sceybeler, M.L. Baird, M.P. Lo & R.T. Haug, 1981. Metals removal and recovery
from municipal sludge. Journal WPCF, vol. 53, pp. 25-32.
6. Kontopoulos, A., Komnitsas, K., Xenidis, A., Papassiopi, N., 1995: Environmental characterization
of the sulfidic tailings in Lavrion. Minerals Engineering, vol.8, pp. 1209-1219.
7. Kontopoulos, A., Komnitsas, K., Xenidis, A., Mylona, E., Adam, K., 1995: Rehabilitation of the
flotation tailings dam in Lavrion. Part I: Environmental characterization and development studies, ///
International Conference and Workshop on Clean Technologies for the Mining Industry, Santiago,
Chile.
8. Kontopoulos, A., Komnitsas, K., Xenidis, A., 1995: Rehabilitation of the flotation tailings dam in
Lavrion. Part II: Field application, III International Conference and Workshop on Clean Technologies
for the Mining Industry, Santiago, Chile.
9. Kontopoulos, A., Adam, K., Monhemius, J., Cambridge, M., Kokkonis, D., 1996: Integrated
environmental management in polymetallic sulphide mines, Fourth International Symposium on
Environmental Issues and Waste Management in Energy and Minerals Production, Cagliari, Italy.
10. Kontopoulos, A., Papassiopi, N., Komnitsas, K., Xenidis, A., 1996: Environmental characterization
and remediation of tailings and soils in Lavrion. Proc. Int. Symp. Protection and Rehabilitation of the
environment, Chania.
11. Kontopoulos, K. Komnitsas, A. Xenidis, 1998: Heavy metal pollution, risk assessment and
rehabilitation at the Lavrion Technological and Cultural Park, Greece. SWEMP '98 Conference,
Ankara.
12. Kontopoulos, A. and Theodoratos, P., 1998: Rehabilitation of heavy metal contaminated land by
stabilization methods. In: M.A. Sanchez, F. Vegara and S.H. Castro, (eds.) Environment and
innovation in mining and mineral technology. Univ. of Conception-Chile.
13. Krishnamurthy, S., 1992: Extraction and recovery of lead species from soil. Environmental Progress,
vol. 11, pp. 256-260.
14. Leite, L. et al., 1989: Anomalous contents of heavy metals in soils and vegetation of a mine area in
S.W. Sardinia, Italy. Water, Air and Soil Pollution, vol. 48, pp. 423-433.
15. Xenidis, A., Stouraiti, C. and Paspaliaris, I., 1999: Stabilization of highly polluted soils and tailings
using phosphates", in Global Symposium on Recycling, Waste Treatment and Clean Technology,
REWAS '99,1. Gaballah, J. Hager, R. Solozabal, eds., San Sebastian, Spain, pp. 2153-2162.
16. Xenidis, A., Stouraiti, C., and Paspaliaris, I., 1999: Stabilization of oxidic tailings and soils by
addition of calcium oxyphosphates: the case of Montevecchio site (Sardinia, Italy), Journal of Soil
Contamination, 8(6), pp. 681-697.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
17. Papassiopi, N., Tambouris, S., Skoufadis, C. and Kontopoulos, A., 1998: Integrated leaching
processes for the removal of heavy metals from heavily contaminated soils, Contaminated Soil 98,
Edinburg.
18. Peters, R.W. & L. Shem, 1992: Use of chelating agents for remediation of heavy metal contaminated
soil. In ACS Symposium Series Environmental Remediation: 70-84.
19. Roche, E.G., J. Doyle & C.J. Haig, 1994: Decontamination of site of a secondary zinc smelter in
Torrance California. In IMM, Hydrometallurgy '94: 1035-1048. London: Chapman & Hall
20. Royer, M.D., A. Selvakumar & R. Gaire, 1992: Control technologies for remediation of contaminated
soil and waste deposits at superfund lead battery recycling sites. J. Air & Waste Management
Association, pp. 970-980.
21. Shikatani, K.S., Yanful, E.K., 1993: An Investigation for the Design of Dry Covers for Mine Wastes,
in Proceedings of the International Symposium on Drying, Roasting, Calcining and Plant Design and
Operation. Part II Advances in Environmental Protection for Metallurgical Industries, eds: A. J.
Olivier, W. J. Thornburn, R. Walli, 32nd Annual Conference of Metallurgists of CIM, Quebec, Aug.
29-Sep.2, pp. 245-258.
22. Theodoratos, P., Papassiopi, N., and Kontopoulos, A., 1998: Stabilization of highly polluted soils,
Contaminated Soil 1998, Edinburg.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 5
Application of Bioscreens and Bioreactive Zones
Location
Rademarkt (former dry cleaning site)
Rotterdam Harbour (oil refinery site)
Rural Area (natural gas production site)
Akzo Nobel (chlorinated pesticides site)
Technical Contact
Herco Van Liere/Huub Rijnaarts/Sjef Staps
TNO Institute of Environmental Sciences,
Energy Research and Process Innovation
Laan van Westenenk 501
7334DTApeldoorn
The Netherlands
Tel: +31 555493380
Fax: +3 155 5493410
E-mail: H.H.M.Riiiiaartsfa;mcp.tno.iil
SJItaEs^m^ixtna.!!!
Project Status
Final report
Project Dates
Accepted 1998
Costs Documented?
Yes
Contaminants
Oil, BTEX,
chlorinated solvents,
chlorinated pesticides,
and benzenes
Technology Type
In situ
bioremediation
Media
Groundwater
Project Size
Pilot to full-scale
Results Available?
Yes
Project 5 was completed in 2000.
1. INTRODUCTION
Name of the technology: Biowalls/Bioscreens/Biobarrier/Treatment zones
Status of the technology: bench, pilot to full scale; emerging and innovative
Project objectives: To develop and demonstrate the technical and economical feasibility of various
biowall/bioscreen configurations for interception of mobile groundwater contaminants, as a more cost-
effective and groundwater resources saving alternative for currently used pump-and-treat approaches.
2. SITE DESCRIPTIONS
Chlorinated solvent site. The Rademarkt Site (Groningen, The Netherlands) is contaminated with
perchloroethylene (PCE) and trichlorethylene (TCE). It concerns an unconfmed aquifer with a clay
aquitard at a depth of 9 m. The plume is located at a depth of 6 - 9 m and 150 m long and 30 to 60 m
wide, and has mixed redox conditions, i.e. separate reducing and oxidising zones. Transformation rates of
especially vinylchloride as observed in the field (and in the laboratory) are too slow to prevent migration
of this hazardous compound to areas to be protected. Source remediation and plume interception are
therefore required.
Oil refinery site. At this site in the Rotterdam Harbour area, it is required to manage a plume of the
dissolved fraction of a mineral oil/gasoline contamination (80% of the compounds belong to the C6 - C12
fraction).
Aromatic hydrocarbon (BTEX) sites. At three sites in the north part of the Netherlands, deep anaerobic
aquifers contaminated with Benzene, Toluene, Ethylbenzene or Xylenes (BTEX) have been investigated.
Under the existing sulfate-reducing conditions, the intrinsic biodegradation of toluene and ethylbenzene
could be demonstrated in the field and in microcosm studies. Benzene was shown to be persistent.
Managing the benzene plumes, i.e. by enhanced in-situ bioprocesses, is therefore required.
Chlorinated pesticides site. Hexachlorocyclohexane (HCH) isomers are important pollutants introduced
by the production of lindane (gamma HCH). Natural degradation of all HCH-isomers was demonstrated
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
at the site of investigation. Interception of the HCH/Chlorobenzene/benzene plume is needed to protect a
canal located at the boundary of the site.
3. DESCRIPTION OF PROCESS
Chlorinated solvent site. Laboratory experiments identified that a mixture of electron-donors is most
suitable to enhance the in situ reductive dechlorination. In situ full-scale demonstration of enhanced
anaerobic degradation in the source zone designed for complete reductive dechlorination is currently
performed. The same technology is considered to be applied later at the head of the plume in terms of a
treatment zone.
Oil refinery site. Bench scale experiments have been finished and established: i) optimal grain-size and
packing density for the porous media used in the trench, ii) optimal oxygen supply rates to sufficiently
initiate aliphatic hydrocarbon biodegradation and to minimise clogging with iron (III) oxides. Three
different technologies are being tested at pilot scale: two gravel filled reactive trenches with biosparging
units and one biosparging fence, without excavation of the soil. Each pilot application has a length of 40
m, and a depth of 4 meters.
Aromatic hydrocarbon (BTEX) sites. Microcosms were used to investigate possibilities to stimulate
biodegradation of benzene and TEX compounds. Especially, addition of nitrate and low amounts of
oxygen to the anaerobic systems appears to be the appropriate way to create down-stream biostimulated
zones. Pilot demonstration tests are currently performed. One pilot test is a biostimulated zone with
dimensions of 10 to 10 meters.
Chlorinated pesticide site. A bioactivated zone as an alternative to conventional large-scale pump-and-
treat is currently being investigated. Laboratory process research indicated that a combination of
anaerobic-microaerophilic in-situ stimulation in a bioactivated zone is the most feasible approach.
Preparations are being made to incorporate the installation of the biotreatment zone in new building
activities ate the site.
4. RESULTS AND EVALUATION
The status of most projects is that they recently have entered a pilot or a full-scale phase. First
evaluations of technology performance are to be expected at the end of 1999.
5. COSTS
In a separate cost-analyses project, the costs of investment and operation of various bioscreen
configurations (i.e. the funnel-and-gate™, the reactive trench and the biostimulated zone configuration) is
being evaluated for various sites. The results indicate that biotreatment zones are in most cases the
cheapest and most flexible approach, whereas funnel-and-gate™ systems and reactive trenches have a cost
level comparable to conventional pump-and-treat. Biotreatment zones have therefore the greatest market
perspective, whereas funnel-and-gate™ systems and reactive trenches can be used when a high degree of
protection is required or when these approaches can be integrated with other building activities planned at
the site.
6. REFERENCES AND BIBLIOGRAPHY
1. Bosnia, T. N. P., Van Aalst, M.A., Rijnaarts, H.H.M., Taat, J., & Bovendeur, J. (1997) Intrinsic
dechlorination of 1,2-dichloroethane at an industrial site monitoring of extensive in-situ
biotechnological remediation. In: In Situ and On Site Bioremediation, the 4th International
Symposium, New Orleans, Louisiana, April 28-May 1.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
2. Brunia, A., Van Aalst-van Leeuwen, M.A., Bosma, T.N.P., & Rijnaarts, H.H.M. (1997) Feasibility
study on the in situ bioremediation of chlorinated solvents using in situ electrochemical generation of
hydrogen (In Dutch) Internal TNO-report.
3. De Kreuk, H., Bosma, T.N.P., Schraa, G., & Middeldorp, P. (1998) Complete in situ biodegradation
of perchloroethylene and trichloroethylene under anaerobic conditions. CUR-NOBIS, Gouda, The
Netherlands, Nobis report, project no 95-2-19
4. Gerritse, J., Alphenaar, A., & Gottschal, J.C. (1998) Ecophysiology and application of dechlorination
anaerobes. ASCE Conference on Environmental Engineering, 6-10 June, Chicago.
5. Gerritse, J., Borger, A., van Heiningen, E., Rijnaarts, H.H.M., Bosma, T.N.P. 1999, in press.
Presented at the In situ and on-site Bioremediation, the fifth international symposium, San Diego,
USA, April 19-22, 1999.
6. Gerritse, J., Schraa, G., & Stams, F. (1999). Dechlorination by anaerobic microorganisms. 9th
European Congress of Biotechnology (ECB9), July 11-15, Brussels.
7. Griffioen, J., Rijnaarts, H.H.M., van Heiningen, E., Hanstveit, B., & Hiddink, H. (1998) Benzene
degradation under strongly reducing conditions (In Dutch, with English summary) CUR-NOBIS,
Gouda, The Netherlands. Nobis project no. 96-3-05 (in press)
8. Koene, J. J. A., Rijnaarts, H.H.M. 1996. In-situ activated bioscreens: a feasibility study (in Dutch,
with English summary) R 96/072. TNO-MEP.
9. Langenhoff, A. A. M., van Liere, H.C., Harkes, M.H., Pijls, C.G.J.M., Schraa, G., Rijnaarts, H.H.M.
1999, in press. Combined Intrinsic and Stimulated In Situ Biodegradation of Hexachlorocyclohexane
(HCH). Presented at the In situ and on-site Bioremediation, the fifth international symposium, San
Diego, USA, April 19-22, 1999.
10. Nipshagen, A., Veltkamp, A. G., Beuming, G., Koster, L.W., Buijs, C.E.H.M., Griffioen, J., Kersten,
R.H.B., & Rijnaarts, H.H.M. (1997). Anaerobic degradation of BTEX at the sites Slochteren and
Schoonebeek 107, (In Dutch, with English abstract). CUR-NOBIS, Gouda, The Netherlands, Nobis
report project no. 95-1-43.
11. Rijnaarts, H. H. M. (1997). Data requirements for in-situ remediation. NICOLE-workshop "Site
assessment & characterisation", TNO-MEP, Apeldoorn, 22-23 January.
12. Rijnaarts, H. H. M. & Sinke, A. (1997). Development and acceptance of guidelines for safe
application of natural attenuation. NICOLE-workshop, Compiegne/France, 17-18 April.
13. Rijnaarts, H. H. M., Brunia, A., & Van Aalst, M.A. (1997). In-situ bioscreens. In: In situ and on-site
bioremediation, the 4th International Symposium, New Orleans, Louisiana, April 28 - May 1.
14. Rijnaarts, H. H. M., De Best, J.H., Van Liere, H.C., & Bosma, T.N.P. (1998) Intrinsic biodegradation
of chlorinated solvents: from thermodynamics to field. Nobis/TNO report. CUR-NOBIS, Gouda, The
Netherlands, NOBIS project no. 96004
15. Rijnaarts, H. H. M., Van Aalst-van Leeuwen, M.A., Van Heiningen, E., Van Buijsen, H., Sinke, A.,
Van Liere, H.C., Harkes, M., Baartmans, R., Bosma, T.N.P., & Doddema, H.J. (1998b). Intrinsic and
enhanced bioremediation in aquifers contaminated with chlorinated and aromatic hydrocarbons in the
Netherlands. 6th International FZK/TNO Conference on Contaminated soil, Edinburgh, 17-21 May.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
16. Rijnaarts, H.H.M. (1998) Application of biowalls/bioscreens. NATO-CCMS Pilot Project on
Contaminated Land and Groundwater (Phase III), annual report no. 228, EPA/542/R-98/002,
p. 19-20.
17. Rijnaarts, H.H.M. (1998) Bioprocesses in treatment walls. NATO-CCMS Pilot Study on
Contaminated Land and Groundwater (Phase III), Special session Treatment walls and Permeable
Reactive Barriers, report no. 229, EPA/542/R-98/003, p. 44 - 47.
18. Schippers, B. P. A., Bosma, T.N.P., Van den Berg, J.H., Te Street, C.B.M., Van Liere, H.C.,
Schipper, L., & Praamstra, T.F. (1998) Intrinsic bioremediation and bioscreens at dry cleaning sites
contaminated with chlorinated solvents. (In Dutch, with English abstract). CUR-NOBIS, Gouda, The
Netherlands, NOBIS-report project no. 96-2-01
19. Van Aalst-van Leeuwen, M. A., Brinkman, J., Keuning, S., Nipshagen, A.A.M., & Rijnaarts, H.H.M.
(1997) Degradation of perchloroethene and trichloroethene under sequential redox conditions Phase
1, partial results 2-6: Field characterisation and laboratory studies. (In Dutch, with English abstract)
CUR-NOBIS, Gouda, The Netherlands, Nobis report project no. 95-1-41
20. Van Eekert, M.H.A., Staps J.J.M., Monincx J.F., Rijnaarts H.H.M. (1999) Bitterfeld: Bioremediation
of contaminated aquifers. Partial report 1 of the TNO-NOBIS participation in the SAFIRA project,
Bitterfeld, Germany. TNO-MEP Apeldoorn, The Netherlands, Report no. TNO-MEP-R99/106, pp
43.
21. van Heiningen, E., Nipshagen, A.A.M., Griffioen, J., Veltkamp, A.G., Rijnaarts, H.H.M. 1999, in
press. Intrinsic and enhanced Biodegradation of Benzene in strongly reduced aquifers. Presented at
the In situ and on-site Bioremediation, The fifth international symposium, San Diego, april 19-22,
1999.
22. Van Liere, H. C., Van Aalst-van Leeuwen, M.A., Pijls, C.G.J.M., Van Eekert, M.H.A., & Rijnaarts,
H.H.M. (1998) In situ biodegradation of hexachlorocyclohexane (HCH). 5th International HCH and
Pesticides Forum IHOBE, 25-27 June 1998, LEIOA.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 6
Rehabilitation of a Site Contaminated by PAH Using Bio-Slurry Technique
Location
Former railroad unloading
area, Northern Sweden
Technical Contact
Erik Backlund
Eko Tec AB
Nasuddsvagen lo
93221 Skelleftehamn
Sweden
Tel: +46/910-33366
Fax: +46/910-33375
E-mail:
erik.backlundiffiebox.tninet.se
Project Status
Interim
Project Dates
Accepted 1996
Final Report 2001
Costs Documented?
No
Contaminants
Coal tars, phenols,
cyanides, metals,
ammonium compounds
Technology Type
Ex situ
bioremediation
Media
Soil
Project Size
Full-scale (3,000 tons)
Results Available?
Yes
Information in this project summary is current as of May 1998.
1. INTRODUCTION
Eko Tec AB is a Swedish environmental engineering company dealing with problems posed by hazardous
wastes, soil, and water pollution. Main clients are the oil industry, Swedish National Oil Stockpile
Agency, and the Swedish State Railways.
In 1995, Eko Tec was contracted for bioslurry remediation of approximately 3,000 tons of creosote-
contaminated soil and ditch sediments from a railway station area in the northern part of Sweden. A
clean-up criterion of 50 ppm total-PAH was decided by the environmental authorities. For the specific
PAH compounds benzo(a)pyrene and benzo(a)anthracene, a cleanup criterion of 10 ppm was decided.
Full-scale treatment has been preceded by bench- and pilot-scale treatability studies carried out at the Eko
Tec treatment plant in Skelleftehamn, Sweden.
2. SITE DESCRIPTION
Not available
3. DESCRIPTION OF THE PROCESSS
3.1 Pretreatment
The contaminated soil was initially treated to reduce volume. Stones and boulders were separated from
the rest of the soil. In the next step, the soil was screened in a 10 mm sieve. Soil with a grain size less than
10 mm was mixed with water and later pumped to wet-screening equipment, in which particles >2 mm
were separated from the process. The remaining soil fraction (<2 mm) was pumped to a 60 m3 slurry-
phase bioreactor for further treatment. The volume of the treated soil fraction (<10 mm) was
approximately 25 m3. Samples were taken from the soil before water was added.
3.2 Slurry-Phase Bioreactor Treatment
Slurry-phase treatment was carried out in a 60 m3 Biodyn reactor. During treatment, the soil/water
mixture was continuously kept in suspension. In order to optimize the degradation rate, an enrichment
culture containing microorganisms that feed on PAH was added to the slurry, together with nutrients and
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
soil activators. During the treatment phase, dissolved oxygen, nutrient concentration, temperature, and pH
were monitored continuously.
After 27 days of treatment, the cleanup criteria were met and the slurry-phase treatment process was
closed. The slurry was pumped to a concrete basin where the treated soil was separated from the water by
sedimentation. The waster was stored for reuse in the text treatment batch. The treated soil will be reused
as fill material.
3.3 Monitoring Program
In order to determine the initial PAH concentration, a soil sample was taken from the soil fraction <10
mm. During the wet screening process, a soil sample was taken from the separated soil (<2 mm fraction).
Samples were also taken from the slurry phase during treatment. Soil samples were stored by freezing,
and then sent to the laboratory. The same accredited laboratory was used during the project period.
4. RESULTS
Cleanup criteria were met in 14 days. The initial PAH concentration (total PAH) was 219.9 ppm. Final
concentration after 27 days of treatment was 26.97 ppm, which is well below the cleanup criterion of 50
ppm. PAH compounds benzo(a)pyrene and benzo(a)anthracene were occurring in concentrations below
the cleanup criterion of 10 ppm.
5. COSTS
Not yet available.
33
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 7
Risk Assessment for a Diesel-Fuel Contaminated Aquifer Based on
Mass Flow Analysis During Site Remediation
Location
Menziken/Studen, Switzerland
Technical Contact
Mathias Schluep
Frohburgstrasse 184
8057 Zurich
Switzerland
Tel: +41-79-540-5557
mathias(rt)schlucp.ch
Christoph Munz
BMG Engineering Ltd
Ifangstrasse 11
8057 Schlieren
Switzerland
Tel: +41-1-732-9277
Fax: +41-1-730-6622
E-mail: christoph.munz^bmgcng.ch
Josef Zeyer
Soil Biology
Inst. of Terrestrial Ecology ETFiZ
Grabenstrasse 3
8952 Schlieren
Switzerland
Tel: +41-1-633-6044
Fax:+41-1-633-1122
E-mail: zever[a]MoM]nv^
Project Status
Final
Project Dates
Accepted 1997
Final Report 2000
Costs Documented?
No
Media
Groundwater
Technology Type
In situ
bioremediation
Contaminants
Petroleum hydrocarbons (diesel fuel,
heating oil)
Project Size
Results Available?
Yes
Project 7 was completed in 2000.
1. INTRODUCTION
The studies were aimed to give a scientific basis for an evaluation procedure, allowing us to predict the
treatability of a petroleum hydrocarbon (PHC) contaminated site with in situ bioremediation technologies
[1]. This includes the description of the risk development with time and the quantification of the
remediation efficiency by identifying critical mass flows. The focus of the project was set on the
modeling of movement and fate of compounds typically found in non-aqueous phase liquids (NAPLs)
such as PHCs in the subsurface.
2. SITE DESCRIPTION
At the Menziken site [2] the contaminated aquifer was remediated based on the stimulation of indigenous
microbial populations by supplying oxidants and nutrients (biorestoration). Detailed investigations were
made from 1988 until 1995. The engineered in situ bioremediation took place from 1991 - 1995.
At the Studen site [3] no engineered remedial actions were taken. The investigations started in 1993 and
led to a better understanding of the biological processes occurring in the aquifer. It could be shown that
intrinsic bioremediation is a major process in the removal of PHC at this site.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
3. DESCRIPTION OF THE RESEARCH ACTIVITY
PHC contain benzene, toluene, ethylbenzene, and xylenes (BTEX) and polycyclic aromatic hydrocarbons
(PAH), which are regulated hazardous compounds. These substances potentially dissolve into
groundwater in relevant concentrations at petroleum release sites, posing risks to drinking water supplies.
Understanding this process is important, because it provides the basis to perform initial remedial actions
and plan a long term remedial strategy for contaminated sites. Fortunately the dissolved BTEX and PAH
compounds are degradable under various conditions in aquifers. The biodegradation process leads to a
reduction of total mass of PHCs. Therefore the evaluation of the effectiveness of the biodegradation
processes is another key step in applying in situ remediation techniques to reduce risks. These processes
were studied in a laboratory system consisting of the following sequence (Figure 1): dissolution of PHCs
into the aqueous phase (section A), anaerobic (section B) and aerobic biodegradation (section C) of the
dissolved compounds.
Figure 1: Experimental setup of the laboratory study on dissolution of diesel fuel compounds into sterile
groundwater (section A) and biodegradation in two laboratory aquifer columns under denitrifying (section
B) and aerobic (section C) conditions
section A
diesel fuel
flow/through
reactor
section B
denitrifying column
section C
aerobic column
4. RESULTS AND EVALUATION
4.1 Dissolution of NAPL Compounds in a Batch System
The purpose of the first study was to develop a modeling approach for the quantification of mechanisms
affecting the dissolution of NAPLs in the aqueous phase using the slow stirring method (SSM) and thus to
provide a tool for the interpretation of experimental data regarding the interaction between NAPLs and
water [4]. Generally, mass transfer from the NAPL to the aqueous phase increases with the stirring rate.
This can be interpreted as a decrease of the thickness of the aqueous stagnant layer at the water/NAPL
interface across which diffusion occurs. Therefore, the time to reach saturation depends on the mechanical
agitation and the aqueous diffusion coefficient of the chemical. This is only true as long as transport
within the NAPL does not control the overall mass transfer of the different NAPL components. It is
known that NAPL viscosity can influence the dissolution kinetics of PAHs. The phenomenon was
attributed to transport limitation within the NAPL of constituents with high viscosity. Thus, the existence
of a depletion zone in the NAPL phase (which in the SSM is not directly stirred) was postulated.
An analytical model was developed to provide a qualitative understanding for the different processes that
determine the temporal evolution of the combined NAPL/aqueous phase system. For situations were the
employed quantitative approximations are no longer valid a short recipe how the equations can be solved
numerically and without restrictions regarding the relative size of certain terms was presented. The
theoretical framework was validated with experimental data. The experiment was performed by running
section A of the laboratory setup (Figure 8) in batch mode.
With focus on the applicability of the preparation of water soluble fractions in slow stirring batch system
the results can be summarized as follows: Once equilibrium is reached in the system a fraction of a
35
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
compound will be transferred from the NAPL phase into the aqueous phase leading to a lower
concentration in the NAPL phase. Equilibrium concentrations in the aqueous phase therefore will be
lower compared to calculations based on initial concentrations in the NAPL phase. This effect is only
relevant for relatively soluble substances like benzene and in the presence of small NAPL volumes and is
independent of the NAPLs viscosity. The relative diffusivities of the NAPL compounds govern the
dissolution kinetics in terms of mass transfer limitations within the NAPL phase. Thus, in low viscosity
NAPLs, the depletion process is controlled by diffusion within the NAPL layer of relatively soluble
substances like benzene, whereas in high viscosity NAPLs, even the dissolution of relatively insoluble
substances like Naphthalene may be diffusion-limited. With the theoretical framework presented the
mechanisms affecting the dissolution of NAPLs into the aqueous phase in slow stirring batch systems can
be quantified. The models allow us to predict the errors in equilibrium concentrations and the time frame
to reach saturation.
4.2 Dissolution of NAPL Compounds in a Flow Through System
The objective of the second study was twofold: First the dynamic changes of NAPL-water equilibria as
the soluble compounds deplete from a complex NAPL mixture was studied. Second an easy to use model
based on Raoult's law to predict such dissolution patterns with respect to time varying NAPL mass and
composition was developed [5].
The experimental setup consisted of a flow through vessel containing deionized water and diesel fuel
(Figure 8, section A). The resulting concentrations in the water were measured in the effluent of the
vessel. The results were compared with the calculated aqueous concentrations based on Raoult's law for
supercooled liquid solubilities. The model considers the dynamic changes of the diesel fuel / water
equilibrium due to continuous depletion of the soluble compounds from diesel fuel.
It could be shown that Raoult's law is valid during dynamic dissolution of aromatic compounds from
complex NAPL mixtures (e.g., diesel fuel) in non-disperse liquid/liquid systems (in this case the SSM).
This is true as long as a significant depletion of substances is observable. At low concentrations in the
NAPL phase non-equilibrium effects probably play a major role in the dissolution behavior, resulting in
underestimation of the aqueous concentration. However deviations at these concentration levels are not
important from a risk point of view. The quality of predictions was improved by considering time varying
NAPL mass. Although the model could be confirmed in an idealized laboratory system, it can not be
applied to complex field situations with the same accuracy. However this study provides a simple method
to assess contaminated sites on an "initial action" basis and supports the planning of long term remedial
strategies at such sites.
4.3 Biodegradation of Dissolved NAPL Compounds
The effluent of the flow through vessel was fed into two columns filled with quartz sand which were
operated in series [6]. The first column was operated under enhanced denitrifying conditions whereas the
second column was operated under aerobic conditions (Figure 1, section B and C). The two columns
represent two degradation zones downstream of a contamination plume under different redox conditions
as it is commonly found in contaminated aquifers. As an example of the measured BTEX and PAH
compounds observed benzene and ethylbenzene concentration curves in the effluent of the flow through
reactor (section A), the denitrifying column (section B) and the aerobic column (section C) respectively
are drawn in Figure 2. Degradation under denitrifying conditions only occurred in the case of
ethylbenzene, whereas benzene seems to be persistent to denitrification. The slight decrease of benzene
concentrations in the effluent of the denitrifying column is attributed to small amounts of oxygen intruded
into the system at the beginning of the experiment. Under aerobic conditions benzene and ethylbenzene
were rapidly degraded. Based on these results a mass balance was performed for each compound as well
as for the total amount of diesel constituents after each section of the experimental setup (Figure 1) and
compared with the depletion of the electron acceptor. Results indicate that the fate of lexicologically
relevant compounds is predictable by measuring inorganic compounds.
36
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
The development of risk with time was calculated after each section of the experiment (Figure 1) using the
corresponding concentrations of the relevant compounds as well as their toxicological properties. The
non-carcinogenic risk (FigureS) as well as the carcinogenic risk (data not shown) is dominated by
benzene, which is depleted from the NAPL rapidly. Since benzene is not readily degraded under
anaerobic conditions the risk is not significantly reduced under these conditions. However, after the
introduction of oxygen as it occurs in the field due to groundwater mixing, the risk is instantly reduced to
acceptable levels.
Figure 2: Benzene and ethylbenzene concentration
curves in the effluent of the flow through reactor
(section A), the denitrifying column (section B) and
the aerobic column (section C) respectively of the
continuous flow-through experiment.
400
§300
o concentration of the dissolved
compound (section A)
-a- - concentration after anaerobic
degradation (section B)
—•»— concentration after aerobic
degradation (section C)
ethylbenzene
Figure 3: Development of the toxicological risk
(hazard index) after the dissolution of single
compounds from diesel fuel into the aqueous phase
and after anaerobic and aerobic degradation
respectively. The hazard index was calculated as the
additive risk of the single BTEX and PAH
compounds.
to ..!_.
-^ C
re
.2 N
x ra
O.C
risk after dissolution
(section A)
risk after anaerobic
degradation (section B)
risk after aerobic
degradation (section C)
_accerjtable_risk_
20 40 60
water flow through [I]
80 100
20 40 60
water flow through
100
4.4 Correlation with Field Data
Results from the laboratory studies including the mathematical models finally were applied at the field
sites in Studen and Menziken in order to perform a risk assessment [7-9]. Several assumptions to simplify
the complex field situation and to acquire unknown parameters had to be made. This lead to the following
findings:
Using the composition data of diesel fuel or heating oil, the maximal concentrations of lexicologically
relevant compounds expected in the groundwater can be predicted (worst case scenario).
The efficiency of in situ bioremediation techniques can be assessed. With a mass balance calculation of
the inorganic species (oxygen, nitrate, etc.) measured in the Studen groundwater it could be determined
that about 200 kg of PHC were biodegraded within the time frame of 5 years. Comparing this result with
a theoretical calculation based on the mathematical dissolution model it could be shown that the removal
of 200 kg PHC through the dissolution process alone would take about 50 years. This indicates that
biological processes enhance the depletion of PHC, and hence shorten the time for PHC removal from the
subsurface.
37
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Based on mass flows the duration of a site-remediation can be estimated at the level of single compounds.
Modeling the dissolution and biodegradation processes of the heating oil spill in Studen, we can predict
that aqueous benzene concentrations drop below detection limit and therefore is expected to be depleted
from the NAPL phase after 3 years, ethylbenzene after 30 years, and naphthalene after 130 years. These
results correlate well with concentrations measured in groundwater samples of the five years old spill.
The impact of the remediation process on the risk development can be predicted. The risk in Studen and
Menziken was calculated to have been above acceptable levels during the first two years after the spill
happened. As soon as the more soluble compounds such as benzene are dissolved completely the risk
drops below unacceptable levels. At "older" hazardous sites involving diesel fuel or heating oil spills, the
risk therefore may be already significantly reduced.
5. CONCLUSIONS
The remediation of PHC contaminated sites usually occurs naturally without engineered remediation
activities mainly through the biodegradation of compounds dissolved in the groundwater. Since every site
has its own geochemical and biological characteristic the decision whether additional actions have to be
taken in order to reduce risks for human and the environment has to be made on a site-by-site basis. Using
simple tools such as mass balances and distribution models the applicability and efficiency of in situ
bioremediation technologies at PHC spill sites can be assessed.
6. REFERENCES AND BIBLIOGRAPHY
1. Schluep M. 2000. Dissolution, biodegradation and risk in a diesel fuel contaminated aquifer —
modeling and laboratory studies. Dissertation No. 13713, Swiss Federal Institute of Technology ETH,
Zurich, Switzerland.
2. Hunkeler D, Hoehener P, Bernasconi S, Zeyer J. 1999. Engineered in situ bioremediation of a
petroleum hydrocarbon contaminated aquifer: Assessment of mineralization based on alkalinity,
inorganic carbon and stable isotope balances. J Contam Hydrol 37:201-223.
3. Bolliger C, Hoehener P, Hunkeler D, Haeberli K, Zeyer J. 1999. Intrinsic bioremediation of a
petroleum hydrocarbon contaminated aquifer and assessment of mineralization based on stable carbon
isotopes. Biodegradation 10:201-217.
4. Schluep M, Imboden DM, Gaelli R, Zeyer J. 2000. Mechanisms affecting the dissolution of non-
aqueous phase liquids into the aqueous phase in slow stirring batch systems. Environ Tox Chem,
20(3).
5. Schluep M, Gaelli R, Imboden DM, Zeyer J. 2000. Dynamic equilibrium dissolution of complex non-
aqueous phase liquid mixtures into the aqueous phase, in preparation.
6. Schluep M, Haner A, Galli R, Zeyer J. 2000. Bioremediation of petroleum hydrocarbon contaminated
aquifers: laboratory studies to assess risk development, in preparation.
7. Kreikenbaum S, ScerpellaD. 1999. Risikobewertung eines Heizoelschadenfalls. Diplomarbeit
Eidgenoessische Technische Hochschule ETH, Zurich, Switzerland.
8. Schluep M, Galli G, Munz C. 1999. Mineralolschadenfalle - wie weiter. TerraTech 6:45-48
9. Wyrsch B, Zulauf C. 1998. Risikobewertung eines mit Dieselol kontaminierten Standortes.
Diplomarbeit Eidgenoessische Technische Hochschule ETH, Zurich, Switzerland.
38
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 8
Obstruction of Expansion of a Heavy Metal/Radionuclide Plume Around a
Contaminated Site by Means of Natural Barriers Composed of Sorbent Layers
Location
Istanbul University
Project Status
Interim Report
Contaminants
Heavy metals (Pb, Cu,
Cd) and radionuclides
(137Cs, 90Sr, 238U),
textile dyes
Technology Type
In situ adsorption
and stabilization/
solidification
Technical Contact
Re sat Apak
Istanbul University
Avcilar Campus, Avcilar
34850 Istanbul, Turkey
Tel: 90/212-591-1996
Fax: 90/212-591-1997
E-mail:
rapak@istanbul.cdu.tr
Project Dates
Accepted 1998
Final Report 1999
Media
Soil and ground-water (unconventional sorbents
e.g., red muds and fly ashes, simulate hydrous
oxide-like soil minerals; kaolinite and feldspar
represent clay minerals)
Costs Documented?
No
Project Size
Bench-scale
Results Available?
Partly
Project 8 was completed in 1999.
1. INTRODUCTION
When a spill or leakage of a heavy metal/radionuclide contaminant occurs, in situ soil and groundwater
technologies are generally preferred to cope with the contaminants and to prevent their dispersion outside
the site. Barrier wall technologies employ immediate action that restricts the expansion of the
contaminant plume. Thus, this project involves a laboratory-scale investigation of the use of metallurgical
solid wastes and clay minerals as barrier materials to adsorb toxic heavy metals and radionuclides from
water (a fixation or stabilization process) followed by solidification of the metal-loaded mass in a cement-
based block totally resistant to atmospheric weathering and leaching conditions.
2. BACKGROUND
Metals account for much of the contamination found at hazardous waste sites. They are present in the soil
and groundwater (at approximately 65% of U.S. Superfund sites) coming from various metal processing
industrial effluents. Turkey also has metal (Pb, Cd, Cu, Cr, U, etc.) contaminated sites due to effluents
predominantly from battery, electroplating, metal finishing, and leather tanning industries, and mining
operations.
Cesium-137 and strontium-90, with half-lives of 30 and 28 years, respectively, pose significant threats to
the environment as a result of fallout mainly from power plant accidents. In Turkey, 137Cs became a
matter of public concern after the Chernobyl accident, especially contaminating the tea plant harvested in
the Black Sea Coast of the country. On the other hand, milk products and other biological materials
containing Ca were extensively investigated for possible 90Sr contamination. Land burial of low-level
radioactive wastes also pose a contamination risk to groundwater.
Physical/chemical treatment processes specific to metals/radionuclides include chemical precipitation, ion
exchange, electrokinetic technologies, soil washing, sludge leaching, membrane processes, and common
adsorption. When adsorption is employed, there is an increasing trend toward substitution of pure
adsorbents (e.g., activated carbon, alumina, and other hydrated oxides) with natural by-products, soil
minerals or stabilized solid waste materials (e.g., bauxite waste red muds and fly ashes). These substances
also serve as barrier material for passive wall technologies utilized around a heavy metal spill site or
shallow-land burial facility of low-level radioactive wastes. Once these contaminants are stabilized within
barrier walls, it is also desirable to fix them in an environmentally safe form by performing in situ
stabilization/solidification by way of adding cement—and pozzolans if necessary—to obtain a durable
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
concrete mass. The host matrix for metals and radionuclides, i.e., red muds, fly ashes, and clay minerals,
may serve as inexpensive pozzolanic binders to be used along with cement for solidification.
The aim of this Pilot Study project is to develop unconventional cost-effective sorbents for basically
irreversible fixation of heavy metals/radionuclides; these sorbents should show high capacities and fast
retention kinetics for the so-called contaminants. The determination of conditions affecting
stabilization/solidification of the loaded sorbents by adding pozzolans and cement is also aimed.
Durability and leachability of the final concrete blocks have to be tested. Modeling of sorption of heavy
metals/radionuclides onto the tested materials has to be made in order to extend the gained knowledge to
unforeseen cases. Finally a reasonable unification of in situ physical/chemical treatment technologies
applicable to a spill/leakage site will be accomplished.
3. TECHNICAL CONCEPT
The effect of various parameters (sorbent grain size, pH, time of contact, contaminant concentration,
metal speciation, etc.) affecting the adsorption/desorption behavior of the selected heavy metals onto/from
the sorbents has been investigated. The sorption capacity (batchwise and dynamic column capacities) and
leachability of the sorbents in terms of heavy metals/radionuclides have been estimated by the aid of
batch contact, column elution and standard leaching (simulating groundwater conditions) tests. Possible
interferents (e.g., inert electrolytes as neutral salts) have been incorporated in the synthetic contaminant
solutions so as to observe any incomplete adsorption or migration of contaminants that may occur under
actual field conditions. The sorption data have been analyzed and fitted to linearized adsorption
isotherms. New mathematical models have been developed to interpret equilibrium adsorption data with
simple polynomial equations.
Red muds and fly ashes, after being loaded to saturation with Pb(II), Cd(II) and Cu(II), were solidified to
concrete blocks that should not pose a risk to the environment. The setting and hardening characteristics
of mortars, as well as the flexural and mechanical strengths of the solidified specimens, were optimized
with respect to the dosage of natural and metal-loaded solid wastes. Extended metal leaching tests were
carried out on the solidified samples.
These treatment steps actually serve the perspective of unification of seemingly separate
physical/chemical technologies for the removal of heavy metals/radionuclides in environmentally safe
forms. The developed barrier materials in a way resemble iron hydroxides and oxyhydroxides that are
currently developed from low-cost iron waste streams by DuPont (Hapka, 1995). In the meantime,
although not directly fitting with the project title, the usage of iron fillings as potential barrier material has
been tested for the management of textile dyeing wastes, e.g., as a restricting agent for an uncontrolled
expanding plume from a permeable storage lagoon or pond where textile wastes are collected.
4. ANALYTICAL APPROACH
The metallurgical solid wastes used as sorbents were supplied from Turkish aluminium and thermal (coal-
fired) power plants, and characterized by both wet chemical and X-ray (diffraction and fluorescence)
analysis. They were subjected to chemical treatment (water and acid washing) for stabilization, and
classified with respect to size when necessary. Their surface areas were determined by BET/N2 surface
area analysis, and their surface acidity constants (pKa) by potentiometric titration.
After equilibrating the sorbents with the metal solutions, all metal determinations in the centrifugates
were made with flame atomic absorption spectrometry (AAS) using a Varian SpectrAA FS-220
instrument. The beta activities of the Cs-137 and Sr-90 radioisotope containing centrifugates were
counted by an ERD Mullard Geiger Muller tube type MX 123 system with halogen extinction. The batch
and dynamic adsorption and desorption tests were carried out in thermostatic shakers and standard Pyrex
glass columns, respectively.
40
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
A mortar-mixing mechanical apparatus, ASTM Vicat apparatus, steel specimen moulds (4x4x16 cm3),
tamping-vibrating apparatus, and testing equipment for flexural and compressive strength tests were used
for following the solidification process and the mechanical strength of the final concrete blocks.
The textile dyes used for modeling textile wastes were analyzed by UV/visible spectrophotometry.
The adsorption isotherms conforming to Langmuir, Freundlich, B.E.T. and Frumkin isotherm equations
were evaluated by linear regression and non-linear curve fitting of experimental data.
5. RESULTS
The distribution coefficients of metals (as log KD) between the solid (red mud, fly ash, etc.) and solution
phases varied between 1-3 and showed a gradual decrease with increasing equilibrium concentration of
the metal remaining in solution.
The Langmuir saturation capacities of the sorbents (in the units of mg metal per g sorbent as red mud-fly
ash, in this order) for the metals averaged at approximately 50-200 mg Cd.g-1, 40-100 mg Cu.g-1, and
100-350 mgPb.g-1.
The adsorption isotherms were somewhat S-shaped B.E.T. type isotherms showing layered sorption at the
natural pH of equilibration, but saturation of the sorbent was attained at a definite concentration enabling
an approximated Langmuir evaluation of equilibrium data in operational sense.
The order of hydrolysable divalent metal cation retention on the selected sorbents was as follows in terms
of molar saturation capacities: Cu > Pb > Cd for fly ashes and Cu > Cd > Pb for red muds. The degree of
insolubility of the metal hydroxides approximately followed the same order. The simulation of CO2-
injected groundwater conditions were achieved by saturated aqueous CO2 (pH 4.8) and carbonic
acid/bicarbonate buffer (pH 7.0) solutions. The heavy metals (Cu, Pb, Cd) retained on the sorbents were
not leached out by these carbonated leachant solutions.
Heavy metal adsorption onto red muds, either as free metal ion or in chelated metal-EDTA forms, has
been effectively modeled for (M+M-EDTA) mixtures. The adsorption data could be theoretically
generated by using simple quadratic equations in terms of covalently- and ionically- adsorbed metal
concentrations in the sorbent phase, once the total metal concentration prior to equilibration and final
solution pH were known.
As for solidification of the metal-loaded solid wastes, when these loaded wastes were added up to 20% by
mass to Portland cement-based formulations, the fixed metals did not leach out from the solidified
concrete blocks over extended periods, with the exception of Cu(II), which reached a concentration of 0.4
ppm after 8 months in a water leachate of pH 8-9. 2% setting accelerator Ca3(PO4)2"added improved
formulations could bear only 10% of lead-loaded fly ash, while this tolerance could be raised to 20% fly
ash by incorporating (3% Ca3(PO4)2+l% CaCl2) mixed additive.
The studied radionuclides did not show a significant temperature dependency in adsorption. Especially
radiostrontium retention increased with pH. These observations are in accord with ion exchange
mechanism of sorption. Radiocesium adsorption is maximal around neutral pH, which is specific for most
natural waters.
Of the textile dyes tested, acid blue and acid yellow showed 75-90% and 60-80% removal, respectively,
when passed through a granular iron bed at an initial concentration of 10-100 ppm dye containing 0.10 M
HC1 in solution.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
6. HEALTH AND SAFETY
The primary components of the unconventional sorbent suspensions, i.e., red muds and fly ashes
containing Fe2O3, A12O3, SiO2, TiO2, and some aluminosilicates, to be used as barrier material are
essentially non-toxic. The tested heavy metals, either as free ions or in chelated forms, i.e., Cd2+, Pb2+
(and partly Cu2+) and Cd-EDTA2~, Pb-EDTA2~, Cu-EDTA2~, were toxic, so care should be exercised
especially in solidification/ stabilization processes using the heavy metal-loaded sorbents in dry form
where small particles could be inhaled by workers. Also working with radionuclide solutions, even in
very dilute forms, needs special pipettes and glassware to be used under a hood on a stainless steel
workbench, and special laboratory practice with workers wearing radiation dosimeters. All waste
solutions, even at very low-level activity, should be properly collected and submitted to the nuclear
energy authority for waste storage and stabilization.
7. ENVIRONMENTAL IMPACTS
Prior acid or water leaching of the sorbents before adsorption experiments did not effectively increase the
specific surface area or chemical adsorption power of these sorbents, but rather these sorbents were
stabilized so as not to leach out any micropollutants to water at the time of heavy metal adsorption. It is
also indicated in literature that iron oxyhydroxide based grouts as barrier material can be made from low
cost industrial by-products, which should be tested for safety and effectiveness on a case-by-case basis
(Hapka et al., 1995). Thus these criteria should be judged for red muds and fly ashes.
Stabilization/solidification of the metal-loaded solid wastes puts these wastes and incorporated toxic
metals into environmentally safe (mechanically strong, durable and unleachable) forms. The matrix
disrupting effect of Pb was eliminated by using relatively small amounts of sodium aluminate or calcium
phosphate to improve the setting, hardening and mechanical properties of the final concrete blocks. It was
environmentally safe to observe that the matrix-held metals (either as a result of irreversible adsorption or
solidification) did not leach out by carbonate or carbonic acid solutions ensuring the chemical stability of
these solid wastes under changing groundwater conditions.
8. COSTS
Because iron-based grouts (without relatively expensive additives such as citric acid, urea, and urease)
can be prepared from inexpensive by-products, the primary costs involved come from transportation and
additives (Jet grouted, 25% grout) roughly around 50 USD per m2 for 1m thick wall, i.e., or 50 USD for 1
cubic meter. The overall cost data have not yet been obtained.
9. CONCLUSIONS
In investigation of the possibility of usage of metallurgical solid wastes as cost-effective sorbents in
heavy metal (Pb, Cu, Cd) and radionuclide (Cs-137 and Sr-90) removal from contaminated water, red
muds and especially fly ashes have been shown to exhibit a high capacity. Extensive modeling of heavy
metal sorption—either as free metal ions or in the form of EDTA-chelates—has been performed by
simple quadratic equations in terms of the retained metal concentration in the sorbent phase. These
modeling efforts enable the prediction of heavy metal adsorption in different media over a wide pH and
concentration range. The developed iron- and aluminum-oxide based sorbents may be used as barrier
material as cost-effective grout for the prevention of expansion of a heavy metal contaminant plume.
Heavy metal-loaded solid wastes have been effectively solidified by adding cement, sand, and water. The
setting and mechanical properties of concrete specimens obtained by optimal dosage of waste addition
were satisfactory. The fixed heavy metals did not leach out appreciably into water over extended periods.
The usage of iron fillings as potential barrier material has been successfully tested for the management of
textile dyeing wastes, i.e., acid blue and acid yellow.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
A unified passive technological process for the in situ sorption of heavy metals, radionuclides, and textile
wastes using iron oxide-, alumina- and silica-based metallurgical solid wastes functioning as barrier
material in conjunction with granular metallic iron is on the way of development. The presumed process
is planned to be finished with in situ stabilization/solidification.
10. REFERENCES
1. S. Arayici, R. Apak and V. Apak, "Equilibrium modeling of pH in environmental treatment
processes," J. Environ. Sci. and Health, Pt. A-Environ. Sci. and Eng., 31 (1996) 1127-1134.
2. R. Apak, G. Atun, K. Giiclii, E. Tiitem and G. Keskin, "Sorptive removal of cesium-137 and
strontium-90 from water by unconventional sorbents. I. Usage of bauxite wastes (red muds)," J. Nucl.
Sci. Technol., 32 (1995) 1008-1017.
3. R. Apak, G. Atun, K. Giiclii and E. Tiitem, "Sorptive removal of cesium-137 and strontium-90 from
water by unconventional sorbents. II. Usage of coal fly ash," J. Nucl. Sci. Technol., 33 (1996) 396-
402.
4. F. Kilinckale, S. Ayhan and R. Apak, "Solidification-stabilization of heavy metal-loaded red muds
and fly ashes," J. Chem. Technol. Biotechnol., 69 (1997) 240-246.
5. R. Apak, E. Tiitem, M. Hiigiil and J. Hizal, "Heavy metal cation adsorption onto unconventional
sorbents (red muds and fly ashes)," Water Research, 32 (1998) 430-440.
6. R. Apak, "Heavy metal and pesticide removal from contaminated groundwater by the use of
metallurgical waste sorbents," NATO/CCMS International Meeting, 18-22 November 1991,
Washington, DC, USA.
7. R. Apak, "Uranium(VI) adsorption by soil in relation to speciation," Mediterranean Conference on
Environmental Geotechnology, 24-27 May 1992, Cesme, Turkey.
8. E. Tiitem and R. Apak, "The role of metal-ligand complexation equilibria in the retention and
mobilization of heavy metals in soil," Contaminated Soil'95 Proceeding of the Fifth International
FZK/TNO Conference on Contaminated Soil, 30 Oct.-3 Nov. 1995, Maastricht, Netherlands, W. J.
van den Brink, R. Bosnian and F. Arendt (eds.), Kluwer Academic Publishers, Vol. I, 425-426.
9. R. Apak, "Sorption/solidification of selected heavy metals and radionuclides from water,"
NATO/CCMS Pilot Study International Meeting on 'Evaluation of Emerging and Demonstrated
Technologies for the Treatment of Contaminated Land and Groundwater', 17-21 March 1997, Golden
Colorado, USA.
10. K. Giiclii, unpublished Ph.D. thesis (Supervisor: R. Apak), "Investigation and modeling of heavy
metal adsorption dependent upon pH and complexing agents," Department of Chemistry, Faculty of
Engineering, Istanbul University, 1999, Istanbul.
11. M. Hapka, J. S. Thompson and J. M. Whang, "Method for precipitating a solid phase of metal," 1995,
provisional patent application.
12. R. R. Rumer and J. K. Mitchell, "Assessment of barrier containment technologies," International
Containment Technology Workshop, 29-31 Aug. 1995, Baltimore, Maryland: Proceedings, pp. 221-
223.
13. K. Giiclii and R. Apak, "Investigation of adsorption office- and bound- EDTA onto red muds for
modeling the uptake of metal-organic complexes by hydrated oxides," 19th International Meeting on
Organic Geochemistry, 6-10 Sept. 1999, Istanbul (accepted as presentation).
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 9
Solidification/ Stabilization of Hazardous Wastes
Location
Middle East Technical
University, Ankara, Turkey
Technical Contact
Kahraman Unlii
Middle East Technical
University
Environmental Engineering
Dept.
06531 Ankara
Turkey
Tel: 90-3 12-210-5869
Fax:90-312-210-1260
E-mail: kuoMi^McM^MJl
Project Status
Near Completion
Project Dates
Accepted 1998
Final Report 2001
Costs Documented?
No
Contaminants
PCBs, AOX
(adsorbable
organic halides),
heavy metals
Technology Type
Solidification/
Stabilization
Media
Soil, mining waste and wastewater and
sludge from pulp and paper industry
Project Size
Bench Scale
Results Available?
Yes
1. INTRODUCTION
Solidification and stabilization are treatment processes designed to either improve waste handling and
physical characteristics, decrease surface area across which pollutants can transfer or leach, or limit the
solubility or to detoxify the hazardous constituents (EPA, 1982). They also refer to techniques that
attempt to prevent migration of contaminated material into the environment by forming a solid mass.
Although solidification and stabilization are two terms used together, they have different meanings.
Solidification refers to techniques that encapsulate the waste in a monolithic solid of integrity. The
encapsulation may be of fine waste particles (microencapsulation) or of a large block or container of
wastes (macroencapsulation). Solidification does not necessarily involve a chemical interaction between
the wastes and the solidifying reagents, but may mechanically bind the waste into the monolith.
Contaminant migration is restricted by vastly decreasing the surface area exposed to leaching and/or by
isolating the wastes within an impervious capsule. Stabilization refers to techniques that reduce the hazard
potential of a waste by converting the contaminants into their least soluble, mobile, or toxic form. The
physical nature and handling characteristics of the waste are not necessarily changed by stabilization
(Conner and Hoeffner, 1998).In practice, many commercial systems and applications involve a
combination of stabilization and solidification processes. Solidification follows stabilization to reduce
exposure of the stabilized material to the environment through, for example, formation of a monolithic
mass of low permeability (Smith, 1998). This project focuses on investigating the effectiveness of
solidification/stabilization (S/S) technology by conducting bench scale treatability tests with contaminated
soils and various types of hazardous waste materials. The major objectives of the project are (i) to
investigate the effectiveness and reliability of the S/S technology for the safe disposal of hazardous
wastes containing metal and organic contaminants, and (ii) to determine the appropriate technical criteria
for applications based on the type and composition of hazardous wastes
2. BACKGROUND
With the enforcement of the Hazardous Wastes Control Regulation in August 1995, the direct or indirect
release of hazardous wastes into the receiving environment in such a manner that can be harmful to
human health and the environment is banned in Turkey. The main purpose of the regulation is to provide
a legal and technical framework for the management of hazardous wastes throughout the nation. In this
regard, the regulation is applicable not only to hazardous wastes to be generated in the future, but also
concerns with the existing hazardous wastes and their safe disposal in compliance with the current
regulation. The S/S technology is recognized by the Turkish Hazardous Wastes Control Regulation
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
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(THWCR) as a promising new emerging technology for the safe disposal of hazardous wastes. This
recognition by the regulation plays a major role for the initiation of this project.
3. TECHNICAL CONCEPT
The following technical criteria is considered for the evaluation of the effectiveness of the S/S technology
for the safe disposal of hazardous wastes containing metal and organic contaminants: (i) determining the
mobility of contaminants in the waste via conducting leaching and permeability tests on
solidified/stabilized samples; and (ii) determining the strength of solidified samples against deformation
and deterioration via conducting unconfmed compressive strength tests on solidified samples.
In this study, for metals a residue material from gold mining, for organics PCB contaminated soil and
AOX containing sludge and wastewater from pulp and paper industry were used. Although mining waste
has relatively high heavy metal content, use of mining waste with very high metal content was considered
to serve better for the purpose of assessing the performance of S/S technology. Concentrated mining
waste was obtained by the addition of heavy metal salts of chromium nitrate, cadmium nitrate, lead
nitrate, copper sulfate and zinc sulfate. Water content of wastewater sludge was initially very high; thus it
was dried in an oven at 60°C to remove water and then ground into powder before S/S process. Initial
analysis of the PCB-contaminated soil showed that it did not contain significant quantities of PCBs.
Therefore, transformer oil containing PCBs was added to the soil at the rate of 5 ml of oil to 100 grams of
soil, which yielded oil concentration of 43000 ppm in the soil. Particle size distribution of the soil was
approximately 33% silt, 60% sand and 7% gravel and soil was classified as "silty-sand".
For solidification of waste and encapsulation of contaminants, portland cement as a binding agent was
mixed with waste materials at different ratios. This ratio was determined based on particle size
distribution of waste materials. In general, as the fraction of fine particles in the waste increases the
amount of portland cement to be used decreases. On the other hand, as the fraction of coarse particles in
the waste increases, the strength of solidified waste against deformation increases at the same ratio of
portland cement and waste material mixture. Waste material and portland cement mixing ratios were
determined considering these general facts. For mining residue, two samples representing fine, and coarse
particle size distribution were prepared. In order to prepare the coarse particle size distribution, sand was
added to the waste. The mixing ratio of sand to waste + cement + moisture was 1:1. For each waste
material representing a given particle size distribution class, two different portland cement mixing ratio
was used. The objectives were to determine the effects of binding agent ratio and particle size distribution
of waste material on S/S process and the metal retention efficiency of portland cement as a binding agent.
Mixing ratios for different waste groups are given in Table 1.
Table 1: Waste material and portland cement mixing ratios
Waste Material
Waste material from gold mining (fine texture)
Waste material from gold mining (coarse texture)
Wastewater from pulp and paper industry
Sludge from treatment of pulp and paper industry wastewater
PCB-contaminated soil
Cement Addition
(% by weight)
10 and 20%
10 and 20%
83 and 88 %
30 and 50 %
20 and 35 %
4. ANALYTICAL APPROACH
Prior to S/S process, physical and rheological characteristics of waste materials were determined. For
mining waste and PCB-contaminated soil, maximum dry density, optimum moisture content, Atterberg
limits, specific gravity and particle size distribution were determined. For AOX containing sludge, only
maximum dry density and optimum moisture content were determined. Particle size distributions of
mining waste and PCB-contaminated soil were determined using hydrometer and sieving methods,
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
respectively. Standard Proctor Compaction Test was performed to determine maximum dry density and
optimum moisture content. In order to test ability of solidified/stabilized waste samples to withstand
overburden loads, unconfmed compressive strength tests were performed on samples using Compression
Test Equipment. Hydraulic conductivity of solidified/stabilized waste samples was measured using a
flexible wall permeameter under a hydraulic gradient of 113.
All waste and cement mixtures were prepared by adding optimum moisture content and then compacted
to corresponding maximum dry density in cylindrical molds having a height of 71 mm and a diameter of
36 mm. After compaction, cylindrical samples were removed from the molds and placed in a 95 %
humidity room for 28 day-curing. At the end of the 28-day cure period, duplicate samples of
solidified/stabilized waste were used for strength and hydraulic conductivity tests. Prior to the
performance of leaching tests, solidified samples were crushed and passed through sieves for fractionation
to aggregate sizes between 1-2 mm and >2 mm. Then, duplicates of crashed waste samples from each
aggregate size fraction were subjected to leaching test. Based on the physical tests and chemical
compositions of leachate obtained from leaching tests, the effectiveness of S/S in terms of contaminant
encapsulation was assessed for each waste type and cement ratio combination.
The level of effectiveness of S/S process in terms of reducing contaminant mobility is evaluated through
hydraulic conductivity and leaching tests. In this study, as leaching test Toxicity Characteristic Leaching
Procedure (TCLP) of the U.S. Environmental Protection Agency (U. S. EPA) and Distilled Water
Leaching Procedure (DWLP) of THWCR were used. TCLP and DWLP were applied using 2 and 3
grams of duplicate waste samples from each aggregate size fraction, between 1-2 mm and >2 mm.
Prior S/S process, initial metal composition of mining waste and portland cement were determined by
acid (HNO3-HF) digestion method (Infante and Acosta, 1988). The leachate of solidified waste samples
obtained from TCLP were analysed for various metals (Cr2+, Zn2+, Pb2+, Cd2+, Ni2+, Cu2+, Ca2+, Mg2+, Na+,
and K+) and anions (Cl~ ,SO4, CO32" and PO43") using standard methods (AWWA-APHA, 1989). For the
analyses of metals, except for sodium and potassium, Flame Atomic Absorption Spectrophotometer was
used; analyses of sodium and potassium were carried out by Flame Photometer. Sulfate and phosphate
were measured by spectrophotometer. The measurement of sulfate was based on turbidimetric method.
For the measurement of phosphate, ascorbic acid method was used. Chloride and carbonate analyses were
based on titrimetric methods. AOX analyses were done based on German DIN-3849 method using
Euroglas BV microcoulometer equipment. Measurement of PCB was based on microwave-assisted
solvent extraction method 3546 and gas chromatography method 8080 of EPA SW-846.
5. RESULTS
5. 1 Mining Waste
A. Chemical Analyses for Waste-Cement Mixtures
Prior to 28-day cure period, initial metal composition of the mining waste was determined. Because
portland cement, as binding agent, was mixed with waste material, metal composition of portland cement
was also determined to see any contribution to the metal content of waste. The results of total metal
compositions of mining waste material and portland cement are given in Table 2. As seen in the table,
main constituents of portland cement used in this study were calcium, magnesium, aluminium and iron as
expected. Initial total metal analyses of mining waste material showed that heavy metal (Cd, Cr, Cu, Pb,
and Zn) concentrations were relatively high except for cadmium.
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Table 2: Metal Compositions of Portland Cement and Mining Waste Material Before (Initial) and After
(Final) Metal Salt Addition
Metals
Cd
Cu
Cr
Pb
Zn
Fe
Al
Ca
Mg
Portland Cement
(mg/kg)
BDLa
30
500
BDL
40
15630
29070
276310
8240
Waste (Initial)
(mg/kg)
40
2410
350
3480
2380
29700
30890
440
1150
Waste (Final)
(mg/kg)
970
3640
2410
4380
3760
32210
30090
640
1570
"BDL: Below detection limit (for Cd, 0.05 mg/1)
Table 3 provides an overview of various cleanup goals based on total metal concentrations. If these values
are exceeded, the soil or waste will be classified as "contaminated". Therefore, initial total metal
concentrations of mining waste should be much higher than these standards in order to be classified as
hazardous. Upon comparing these cleanup values (Table 3) with Table 2, it can be seen that initial total
metal concentrations of mining waste do not exceed cleanup goals much except for copper and lead. In
order to assess the performance of S/S technology effectively, presence of much higher heavy metal
concentrations in the mining waste may serve better for the purpose.
To increase metal concentration levels, solutions of nitrate or sulfate salts of five heavy metals (Cd, Cr,
Cu, Pb, and Zn) were added to the mining waste. The added salts were chromium nitrate, cadmium
nitrate, lead nitrate, copper sulfate and zinc sulfate. Final metal composition of mining waste material is
given in Table 2. By the addition of metal salts, metal concentrations in the waste reached the desired
high levels and original concentrations for each metal, except for Cr, increased approximately by 1000
mg/kg. The low Cr concentration may result form non-homogeneous mixing of the waste material and
metal salts.
Table 3: Various Cleanup Goals for Total Metals
Total Metal Cleanup
Goals
Superfund Site Goals
From Technical Resource
Document
California Total
Threshold Limit
Concentration
Louisiana Cleanup
Standards For
Contaminated Soil
Cd
(mg/kg)
3 to 20
100
20
Cr
(mg/kg)
6.7 to 375
500
100
Pb
(mg/kg)
200 to 500
1000
100
Cu
(mg/kg)
a
a
1500
Zn
(mg/kg)
a
a
2800
a not specified among the goals
In addition to the initial metal compositions of mining waste material and portland cement, total metal
analyses of samples of waste-cement mixtures at the end of 28-day cure period were performed. The
purpose was to obtain the chemical composition of these waste samples before leaching tests. The results
are given in Table 4. As seen from the table, metal concentrations of coarse waste samples were diluted
due to addition of sand, which shifted the texture of waste from silt (fine) to sand (coarse). Moreover,
since coarse waste mixed with 20% portland cement contained less original waste compared to the one
mixed with 10% portland cement, total metal concentrations were the lowest in coarse textured waste
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containing 20% portland cement. All waste samples also have very high concentrations of Fe, Al, Ca and
Mg due to high concentrations of these metals in the portland cement.
Table 4: Chemical composition of fine and coarse mining waste and cement mixtures
Metals
(1)
Cd
Cu
Cr
Pb
Zn
Fe
Al
Ca
Mg
K
Na
10% cement
Fine
(mg/kg)
(2)
1250
3330
3060
3090
1900
13500
26130
7830
1710
21550
27780
10% cement
Coarse
(mg/kg)
(3)
850
1690
1920
1420
1350
10470
11170
15540
3100
9950
7150
20% cement
Fine
(mg/kg)
(4)
1000
2550
2140
2320
1990
13310
24360
17720
2490
12950
20000
20% cement
Coarse
(mg/kg)
(5)
750
1250
1770
1210
1050
8780
8250
19400
1560
9000
21000
B. Physical Analyses
Prior to S/S, some physical characteristics, such as Atterberg limits, maximum dry density, optimum
moisture content, specific gravity and particle size distribution of mining waste and cement mixtures were
determined. Among these, values of optimum moisture content and corresponding maximum dry density
were used to determine for each case the volume of water to be added to waste-cement mixture and the
mass at which waste-cement mixture to be compacted. Results are given in Table 5. As seen from the
table, coarse textured waste-cement mixtures have higher dry densities and corresponding low optimum
moisture contents. Soil classification of the samples in Table 5 was made based on their plasticity index
and particle size distribution. Addition of sand to waste-cement mixture changed soil classification of fine
waste samples from ML (silt-low plasticity) to SM (silty sands) and decreased liquid limit values of
coarse waste-cement mixtures.
C. TCLP Leaching Tests
TCLP provides a measure of metal concentration that leach from the solid phase of a waste sample when
extracted in an acetic acid solution. It is designed to simulate leaching conditions to which a waste
disposed in a landfill may be exposed (Pritts et al., 1999). Therefore, one of the most important technical
criteria for testing the effectiveness of S/S process is the quality of TCLP leachate. At the end of 28-day
cure period, TCLP was applied and leachate obtained for each waste group (fine and coarse waste, 10%
and 20% cement; crashed solidified sample aggregate size between 1-2 mm and > 2mm) was analyzed for
heavy metals and some ions. The results of these analyses are given in Table 6. In general, at the same
cement ratio, fine waste samples produced leachate having lower metal concentrations than coarse waste
samples. Therefore, when initial waste characterization is taken into consideration, waste samples having
finer textures will result in better S/S process. Despite slight difference between initial metal
compositions of cement-waste mixtures, increasing cement ratio from 10% to 20% did not have any
considerable effect on metal concentrations in the leachate of the same fine or coarse textured waste.
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Table 5: Physical characteristics of fine and coarse mining waste and cement mixtures
Characteristics
(1)
Dry density (gem"
3)
Optimum
moisture content
Liquid limit (%)
Plastic limit (%)
Plasticity index
Soil classification
Specific gravity
Particle size
distribution
10% cement
Fine
(2)
1.77
15
28
18
10
ML (silt-low
plasticity)
2.72
18% clay
55% silt
27% sand
20% cement
Fine
(3)
1.78
17
28
20
8
ML(silt-low
plasticity)
2.73
22% clay
52% silt
26% sand
10% cement
Coarse
(4)
2
10
22
17
5
SM (silty sands)
2.67
12% clay
29% silt
59% sand
20% cement
Coarse
(5)
2
11
22
16
6
SM(silty sands)
2.75
13% clay
29% silt
5 8% sand
Table 6: The chemical compositions of TCLP and DWLP leachates obtained from mining waste
solidified at different cement ratios
Ions
Cd
Cu
Cr
Pb
Zn
Fe
Al
Ca
Mg
K
Na
SO42
PO43
cr
CO32
10% cement, fine
1-2 mm
TCLP
mg/L
1.85
0.31
0.37
0.39
0.71
ND
ND
94.6
17
58
152.2
149.9
0.31
150
1854
DWLP
mg/L
0.23
ND
ND
ND
0.24
ND
ND
83.39
6.31
19
36
76.5
25.02
274.9
4320
>2 mm
TCLP
mg/L
3.89
0.44
ND
0.23
1.85
ND
ND
93.5
18.31
30.5
385
143.8
0.58
208.3
1320
DWLP
mg/L
ND
ND
ND
ND
0.31
ND
ND
80.83
4.95
19
28
78.1
8.94
224.9
1440
20% cement, fine
1-2 mm
TCLP
mg/L
0.47
0.41
0.59
0.58
0.5
1.94
ND
172.1
21.98
45.5
760.7
36.7
0.88
495.3
1110
DWLP
mg/L
0.12
0.12
0.55
0.45
0.07
0.84
ND
114.5
4.25
19
7.7
4.47
0
574.8
2370
>2 mm
TCLP
mg/L
0.58
0.38
0.58
0.48
0.35
1.09
ND
161.3
23.63
43
773.7
26.96
1.12
482.9
300
DWLP
mg/L
0.08
0.07
0.59
0.39
0.02
0.51
ND
117.5
6.35
19
6.45
16.3
0
524.8
4020
10% cement, coarse
1-2 mm
TCLP
mg/L
2.0
0.92
1.71
1.12
0.96
3.69
ND
288
30.7
21.5
266
53.58
1.44
386.4
2940
DWLP
mg/L
0.29
0.51
0.60
0.51
0.33
3.08
ND
162.1
8.31
20
10.35
8.77
0
418.9
1350
>2 mm
TCLP
mg/L
2.41
0.68
0.76
0.76
1.04
2.2
ND
286.6
29.25
21.5
260
66.29
0
623.8
1500
DWLP
mg/L
0.13
0.27
0.19
0.35
0.15
0.70
ND
170.4
8.76
20
8.4
0
0
468.9
630
20% cement, coarse
1-2 mm
TCLP
mg/L
0.73
0.91
2.22
1.38
0.77
2.35
ND
218.4
3.16
20
995
17.12
2.14
605.3
495
DWLP
mg/L
0.16
0.51
1.03
0.55
0.24
2.18
ND
144.2
0.227
11.5
19.3
4.6
2.2
320.9
780
>2 mm
TCLP
mg/L
0.19
0.29
0.95
0.22
0.17
0.78
ND
215.4
5.73
19.75
1001
19.63
0.08
555.3
735
DWLP
mg/L
0.12
0.22
0.68
0.13
0.05
0.62
ND
136.7
0.36
12.5
25.6
2.3
4.57
220.9
150
ND: Concentration is below the detection limit (for Cd, 0.05 mg/1; Cu, 0.05 mg/1; Cr 0.1 mg/1; Pb 0.1 mg/1; Fe, 0.5 mg/1 and Al, 5 mg/1)
For metals, the U.S. EPA defines toxicity characteristic limits based on metal concentrations measured in
the TCLP leachates (U. S. EPA, 1997). These toxicity characteristic limits, which are given in Table 7 for
metals studied in this work, mean that wastes containing metal concentrations in their TCLP extract
exceed the listed concentrations are considered to be characteristically hazardous and said to have the
toxicity characteristic. When the results of TCLP in Table 6 were compared with EPA toxicity
characteristic limits, given in Table 7, it is observed that only Cd concentrations in the leachates of fine
and coarse waste samples mixed with 10% cement exceeded the regulated level. All the other metal
concentrations in the leachate were much lower than these regulated levels. This higher Cd concentration
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in TCLP leachate of 10% cement-waste samples may be due to somewhat lower leachate pH, which was
around 6, of 10% cement-waste samples. This slightly acidic leachate condition probably caused
dissolution of Cd, for which lower pH limit to precipitate is 6.8 (Table 7), and thus prevented its
precipitation within the cement matrix. Results of Cioffi et al. (1998) support this observation by stating
that cadmium is retained within the matrix provided that pH does not drop to the acid range. Overall, from
a regulatory perspective leachate quality indicates that S/S process is effective for all (fine and coarse
textured wastes mixed with 10% and 20% cement) cases of the mining waste.
Table 7: The pH range for the quantitative precipitation and U.S. EPA toxicity characteristic limits of
metals
Metals
(1)
Cd
Cr
Cu
Fe
Pb
Zn
pH range for precipitation
(2)
6.8-12.0
5.4-10.0
5.4-12.0
2.3-12.0
6.0-9.0
5.3-9.0
U.S. EPA toxicity characteristic
(mg/L)
(3)
limits
1.0
5.0
130.0
30.0
5.0
500.0
For heavy metals, pH dependent precipitation reactions (i.e., hydroxides, carbonates, sulfates) are often an
important stabilization mechanism. The pH of TCLP extraction fluid used for the mining waste was
around 4.93, but after shaking fractionated solidified waste samples together with the extraction fluid, the
final pH of TCLP leachates were within the range of 6.05 and 6.80. The pH of the extraction fluid, as
expected, affected the final pH of leachates and also the alkalinity present in the cement leads to higher
leachate pH values. Table 7 gives the pH range for the precipitation of heavy metals cadmium, chromium,
lead, copper, iron, and zinc considered in this study (Porteus, 1985). At high pH, many metals reach their
lowest solubility and precipitate as their respective insoluble hydroxides, carbonates, phosphates and etc.
(LaGrega, 1994). Moreover, major aqueous components of cement such as Na+, K+, Ca2+, Mg2+, OH" and
SO42" are potentially available ions to react with wastes and make insoluble precipitates of heavy metals
(Glasser, 1997). Most of the metals in the mining waste are converted to insoluble precipitates during S/S
process within the observed final pH range of TCLP leachates and are subsequently trapped within the
pores of cement matrix.
With regard to aggregate size effect, results in Table 6 showed that crashing the solidified samples into
aggregate size classes 1-2 mm and >2 mm did not affect the metal concentrations in the TCLP leachate.
Increase in the leachate concentration with the decrease in the aggregate size was observed only for
coarse waste sample with 20 % cement addition. Wiebusch et al. (1998) investigated much larger
aggregate size classes (20-50 mm, 2-20 mm and <2 mm) obtained from solidified fly ash and found that
leachate concentrations of heavy metals in samples with aggregate size <2 mm were 2.5 times greater
than those in samples with aggregate size in the range of 20-50 mm.
Following TCLP extractions, percentages of metals retained in the solidified/stabilized mining waste were
calculated to determine the amount of metals released into the leachate and in turn, to assess the
effectiveness of S/S process. The following formula was used to calculate the retention efficiency, i.e.,
percent retention (% RT):
%RT =
MT-(VL)(CL)
MT
xlOO
where MT is the total initial mass of a given metal in the waste-cement mixture, mg; VL is the volume of
leachate, L; and CL is the concentration of metal in the leachate, mg/L. For example, %RT=90 means that
10% of the metal initially present in the waste-cement mixture transferred into the leachate while 90% of
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the metal still remained in the solidified waste. Thus, high values of %RT imply high degree effectiveness
of S/S process. Values of %RT calculated for TCLP and DWLP are given in Table 8 and 9, respectively.
According to these tables, S/S applications for all cases resulted in high degree of effectiveness. Although
fine waste samples mixed with 10% cement had initially the highest metal concentrations among the
others, the effectiveness of S/S was also high for this case. In general, the finer the waste texture and
higher the cement ratio, the higher the value of %RT and greater the effectiveness of S/S process. Despite
very high %RT values (>94%) for all metals, Cd concentration in TCLP leachate of 10% cement-waste
mixture exceeded the U. S. EPA regulatory limit when initial Cd concentration in the waste is high (> 850
mg/kg).
D. Unconfined Compressive Strength and Hydraulic Conductivity Tests
In addition to leaching tests conducted to determine the amount of contaminant that can be leached from
the solidified wastes, the effectiveness of S/S process can also be assessed by testing the unconfined
compressive strength and hydraulic conductivity of solidified/stabilized samples (Porteous, 1985). These
tests have been adopted in order to evaluate the physical integrity and engineering properties of solidified
and stabilized product in actual field conditions (Lagrega et al., 1994). Unconfined compressive strength
and hydraulic conductivity tests were performed on duplicate cylindrical solidified samples of each
treatment at the end of 28 days-cure period. These results are given in Table 10.
Table 10: Unconfined compressive strength (qu) and hydraulic conductivity (K) values for mining waste
samples solidified at different cement ratios
Property
(1)
qu, kPa
K,m/s
10% Cement,
Fine
(2)
1153.46
2.1xlO'9
20% Cement,
Fine
(3)
2520.4
1.09 xlO'9
10% Cement,
Coarse
(4)
1019
1.84 xlO'9
20% Cement,
Coarse
(5)
3250
1.04 xlO'9
Solidified and stabilized wastes must have adequate strength to be able to support the loads of materials
placed over them. In general for any given S/S agent, the stronger the solidified waste, the more effective
S/S process (LaGrega et al., 1994). In this study, results of both fine and coarse textured wastes showed
that unconfined compressive strength also increases with increasing cement ratio in the waste. The U.S.
EPA defines a minimum unconfined compressive strength value of 350 kPa for the disposal of solidified
hazardous wastes in landfills (U. S. EPA, 1992). Unconfined compressive strength values measured for
all treatments considered in this study are well above this limiting value. Therefore, these solidified
samples can easily be disposed of in landfills.
Solidified fine and coarse waste materials at the same cement ratio had similar hydraulic conductivity
values. As the cement ratio increased hydraulic conductivity values decreased both for fine and coarse
textured waste samples. As shown in Table 10, hydraulic conductivity values measured for all treatments
were in the order of 10"9 m/s although higher cement addition (20%) results in somewhat lower
conductivity values. Measured conductivity values are two orders of magnitude lower than the value of
10"7 m/s recommended by U.S. EPA for land-burial of stabilized wastes (U. S. EPA, 1989). Therefore, in
terms of hydraulic conductivity criterion, mining waste can be disposed of in a landfill.
5.2 AOX Containing Pulp and Paper Wastewater and Sludge
For S/S of AOX containing sludge from pulp and paper industry, the same procedure was followed as in
the case of mining waste. Since the samples were compacted into cylindrical molds at their optimum
moisture content yielding maximum dry density, in terms of initial physical characterization, only
optimum moisture content and corresponding maximum dry density values were measured. The results
for sludge mixed with 30% and 50% portland cement are given in Table 11, which show a slight increase
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
in the optimum moisture content of sludge samples with increasing portland cement addition and in turn,
an increase in the corresponding dry density.
Table 11: Optimum moisture content and maximum dry density values for AOX-containing pulp and
paper sludge
Material
(1)
30% Cement-Sludge
50% Cement-Sludge
Optimum moisture content
(%)
(2)
18
19
Maximum dry density
(g/cm3)
(3)
1.27
1.32
A. AOX Analyses
Prior to S/S of samples, initial AOX concentrations of wastewater and sludge were measured as39 mg/L
and 400 mg/kg, respectively. Following the 28 day-S/S cure period, TCLP were applied to the solidified
samples crashed to aggregate sizes between 1-2 mm and >2 mm. The results of AOX analyses in TCLP
and DWLP leachates are given in Table 12 and 13 for wastewater and sludge, respectively. Results show
that the cement-mixing ratio and aggregate size of the crashed solidified samples did not have any
considerable effect on the AOX concentration in the leachate. AOX concentrations in the leachate
decreased slightly with increase in the cement addition. Based on TCLP and DWLP results, AOX
retention efficiency for solidified wastewater and sludge samples were determined as 90% and 85%,
respectively.
Table 12: AOX concentrations in TCLP and DWLP leachates of wastewater solidified at different
cement ratios
Wastewater:
Cement Ratio
1:6
1:8
AOX Concentration (mg/1)
1-2 mm
TCLP
3.24
3.20
Water
3.22
3.19
> 2mm
TCLP
3.35
3.33
Water
3.30
3.14
Table 13: AOX concentrations in TCLP and DWLP leachates of pulp and paper sludge solidified at
different cement ratios
% Cement added
to sludge
30%
50%
AOX Concentration (mg/1)
1-2 mm
TCLP
3.37
3.11
Water
3.43
3.21
> 2mm
TCLP
3.22
3.20
Water
3.45
3.01
Unlike U. S. EPA, Turkish Hazardous Waste Control Regulation defines a specific hazardous waste
criteria range of 0.6 to 3 mg/L for AOX in the leachate. If AOX concentration of a waste is within this
range, then that waste is considered to be hazardous waste and need to be disposed of in a hazardous
waste landfill without any pre-treatment before landfilling. But, if AOX concentrations exceed the upper
limit, then waste should be treated before landfilling. Although application of S/S process to AOX
containing sludge yielded high retention efficiency, concentrations of AOX in the TCLP leachates were
above the regulated levels. That is, wastes having similar AOX concentrations as of these sludges do not
seem to be disposed of directly in landfills.
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B. Unconfined Compressive Strength and Hydraulic Conductivity Tests
At the end of the 28-day cure period, hydraulic conductivity and unconfined compressive strength tests
were performed on duplicates of solidified/stabilized sludge samples. The results of these tests, which are
given in Table 14, indicate that as expected, increase in the cement ratio increased the strength of
solidified/stabilized samples. Unconfined compressive strength values measured for both 30% and 50%
cement cases are well above U. S. EPA limiting value of 350 kPa for the disposal of solidified hazardous
wastes in landfills.
Table 14: Unconfined compressive strength (qu) and hydraulic conductivity (K) values for AOX-
containing pulp and paper sludge samples solidified different cement ratios
Property
(1)
qu, kPa
K,m/s
30% Cement
(2)
2990
2.6 xlO'9
50% Cement
(3)
3605
1.8X10'9
There was a decrease in hydraulic conductivity with higher cement addition. When the measured
conductivity values were compared with the value of 10"7 m/s recommended by U.S. EPA for land-burial
of stabilized wastes (EPA, 1989), measured values were two orders of magnitude lower than the
recommended value of EPA. Therefore, in terms of hydraulic conductivity criterion, these samples can be
disposed of in landfills.
5.3 PCB-Contaminated Soil
A. Physical Analyses
Prior to S/S of PCB-contaminated soil, Atterberg limits and particle size distribution of soil were
determined. In addition, optimum moisture content and corresponding maximum dry densities of soil-
cement mixtures were determined. Results are presented in Table 15. Although there was no change in the
optimum moisture content, maximum dry density increased with high cement addition. Atterberg limits of
the contaminated soil showed that the soil is non-plastic. Based on particle size distribution analysis, the
soil consists of approximately 33% silt, 60% sand and 7% gravel.
Table 15: Optimum Moisture Content and Maximum Dry Density Values for PCB-Contaminated Soil
Material
(1)
20% Cement-Soil
50% Cement-Soil
Optimum moisture content
(%)
(2)
21
21
Maximum dry density
(g/cm3)
(3)
1.38
1.42
B. PCB Analyses
Because the contaminated soil initially did not contain significant PCB concentration, transformer oil was
added to the soil at the ratio of 5 ml of oil to 100 grams of soil to increase initial PCB concentration in the
soil. The density of transformer oil was approximately 0.86 g/cm3. Therefore, the concentration of oil in
the soil was around 43,000 mg/kg. Oil concentration was high in the soil, so it was expected that PCB
concentration of the soil would also be high. However, the analyses of the transformer oil yielded 39.6
mg/kg PCB as arochlor 1254. Some records of PCB analyses for a number of transformer oil showed that
PCB concentration differs considerably.
Initial PCB concentrations in the soil were measured by gas chromatograph following microwave assisted
solvent extraction based on U. S. EPA method 3546. In order to determine which arochlors exist in the
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
soil as PCB, the standard solutions of arochlor 1016, 1221, 1232, 1242, 1248, 1254 and 1260 were
injected. Results showed that the soil has arochlor 1254 as PCB and initial PCB concentration (Arochlor
1254) in the soil is 1.74 mg/kg.
The results of PCB analyses in TCLP and DWLP leachates are given in Table 16. As expected, arochlor
1254 was seen in the leachates as PCB. Higher cement addition resulted in less PCB concentrations in the
leachates implying that application of S/S process to PCB-contaminated soil will be more effective with
higher cement addition. Moreover, the effect of aggregate size on leachate quality was observed. Samples
with finer aggregate sizes yielded higher concentrations in the leachates due to the increased surface area
exposed to the leachant in the crushed samples. Thus, it was seen that the only effective mechanism for
S/S of PCB was physical entrapment rather than chemical reactions. The U. S. EPA regulations allow
wastes containing 50 to 500 ppm PCB to be disposed of in landfills. Such landfill sites must have
hydraulic conductivity of liner or underlying soil less than 10"7 cm/s, attenuation layer at the bottom of the
landfill and above the historical high groundwater table at least 15m thick, and monitoring wells and
leachate collection system. Landfilling of wastes with PCB levels of less than 50 ppm is not currently
regulated. That is, these wastes can be disposed of in landfills permitted under Resource Conservation and
Recovery Act (RCRA) or even solid waste landfills (Freeman, 1988).
Table 16: PCB concentrations in TCLP and DWL leachate of PCB-contaminated soil solidified at
different cement ratios
Cement Ratio
20%
35%
PCB Concentration (ug/1)
1-2 mm
TCLP
30
22
Water
14
11
> 2mm
TCLP
18
11
Water
6
5
In order to assess leachate quality, the Drinking Water Standard of PCB, being 0.5 ug/L (Watts, 1998),
was used. Following the U. S. EPA guidelines, i.e., using the magnifying factor of 100 to drinking water
standard, gives maximum allowable concentration of PCB in the TCLP leachate as 50 ug/L. PCB
concentrations measured in TCLP leachate (Table 14) are lower than this value, but 20 to 60 times higher
than the drinking water standard. Calculated percent retention efficiency of PCB in the
solidified/stabilized soil after TCLP and DWLP extractions are given in Table 17. Higher retention
efficiencies were obtained with higher cement addition and samples of larger aggregate size.
Table 17: Percent retention efficiency of PCB concentration in S/S soil samples after TCLP and DWLP
Cement Ratio
20%
35%
Retained (%)
1-2 mm
TCLP
66
75
Water
84
87
> 2mm
TCLP
79
87
Water
93
94
C. Unconfined Compressive Strength and Hydraulic Conductivity Tests
Both hydraulic conductivity and unconfined compressive strength tests were performed on duplicate
solidified/stabilized samples of PCB-contaminated soil. The results of these tests are given in Table 18.
Results showed that PCB affected the strength development of portland cement, because the values of
unconfined compressive strength values were much lower than those for mining waste and AOX
containing sludge. Especially, unconfined compressive strength of solidified soil with 20% cement was
just above the U. S. EPA standard of 350 kPa. Therefore, 20% cement addition was not enough for
effective applications of S/S for PCB-contaminated soil. It seems that PCB in the soil interferes with the
strength development or hydration reaction of cement. However, the unconfined compressive strength
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
value of solidified soil with 35% cement added satisfies the U.S. EPA standard of 350 kPa recommended
for disposal in landfills.
Table 18: Unconfined compressive strength (qu) and hydraulic conductivity (K) values for PCB-
contaminated soil samples solidified at different cement ratios
Property
(1)
qu, kPa
K,m/s
20% Cement
(2)
373
l.lxlO'9
35% Cement
(3)
1340
4.4X10'10
As in the case of other waste types, hydraulic conductivity values of solidified PCB-contaminated soil
decreased with higher cement addition. These conductivity values were lower than the U. S. EPA
standard of 10"7 m/s required for disposal in landfills.
6. HEALTH AND SAFETY
Not applicable.
7. ENVIRONMENTAL IMPACTS
Not applicable.
8. COSTS
Not available.
9. CONCLUSIONS
S/S of mining waste was investigated for four cases: combinations of two different portland cement ratios
(10% and 20%) and two different particle size distribution of plane waste (fine and coarse). For all cases
of metals it was shown that the application of S/S produced acceptable results from a regulatory
perspective. Unconfined compressive strength values were in the range of 1019 to 3250 kPa and hydraulic
conductivity in the range of 1.04 x 10"9 to 2.1 x 10"9 m/s, which were below the U. S. EPA regulated
values for landfilling. The effect of aggregate size on TCLP leachate quality was also investigated using
in TCLP tests solidified samples crashed into two different aggregate sizes. Test results showed that S/S
produced metal retention efficiencies in the solidified mass greater than 94%. In terms of the effect of
particle size distribution of the plane mining waste, as a general trend, at the same cement-waste ratio
leachate concentrations of fine waste samples were lower than those of coarse waste samples.
Technical criteria for the performance assessment of S/S require low leachate concentrations, low
permeability and high unconfined compressive strength. For metal containing mining waste, since all
cases produced acceptable unconfined compressive strength and hydraulic conductivity values in terms of
regulatory compliance, leachate concentrations seem to be the most critical factor in assessing the
effectiveness of S/S technology. Therefore, overall results indicate that the most suitable conditions for
S/S of metal containing hazardous wastes occur when 10% cement is mixed with the plane waste
consisting of nearly 75 % fine (silt and clay size) particles. However, the application of S/S for cadmium
was not successful because leachate concentrations of cadmium exceeded the regulatory limits of the U.
S. EPA. Therefore, for effective applications of S/S to the mining wastes containing high cadmium
concentration (-1000 mg/kg), cement addition should be greater than 10%.
For the S/S of AOX containing pulp and paper sludge, it was observed that portland cement was highly
effective in retaining AOX within solid matrix. Percent retention efficiency of solidified/stabilized AOX
was 85%. However, AOX concentrations in the leachate were slightly above the regulated levels.
Cement-mixing ratio and crashing the solidified samples into different aggregate sizes did not affect AOX
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
concentration in leachate. There was only a slight decrease in leachate AOX concentrations with
increasing cement addition. When the other technical criteria (unconfined compressive strength and
hydraulic conductivity) were taken into consideration, they were consistent with the U.S. EPA standards.
For successful application of S/S to pulp and paper sludge containing AOX concentration greater than
400 mg/kg, the cement ratio can be increased beyond 50% or other additives as adsorbent must be used
besides portland cement.
S/S of PCB-contaminated soil gave questionable results. Despite low initial PCB concentration in soil
(1.74 mg/kg), PCB concentrations in TCLP leachate from solidified/stabilized soil samples were
relatively high (in the range of 11-30 |lg/L). Percent retention efficiency of PCB in S/S samples ranged
between 66% and 87% for different treatments. Higher PCB concentrations in the TCLP leachates of
solidified samples with finer aggregate sizes indicated that the physical entrapment in the pores is the
major retention mechanism for solid matrix and therefore chemical fixation of PCB is not taking place. At
low cement additions, unconfined compressive strength of PCB-contaminated soil was much lower than
those of mining waste and AOX containing sludge. So, it can be concluded that PCB oil had an inhibitory
effect on the strength development of portland cement when cement ratio is low. Overall result indicate
that the effective applications of cement-based S/S to PCB contaminated coarse textured soils are highly
unlikely especially at PCB concentration levels as high as 50 to 500 ppm range and at cement ratios less
than 35%. In this regard, higher cement ratio or other additives, such as industrial adsorbents, together
with portland cement can be applied in order to obtain better leachate quality and thus more effective S/S
of PCB in soils.
10. REFERENCES
1. AWWA-APHA. (1989). Standard Methods for the Examination of Water and Wastewater, 17th
edition, USA.
2. Conner J. R. and Hoeffner S. L. (1998). "The History Of Stabilization/Solidification Technology",
Critical Reviews in Environmental Science and Technology, 28(4), 325-396.
3. Freeman, H. M. (1988). Standard Handbook of Hazardous Waste Treatment and Disposal. McGraw-
Hill, New York.
4. Glasser, F. P. (1997). "Fundamental aspects of cement solidification and stabilization", Journal of
Hazardous Materials, 52, 151-170.
5. Infante, R. N., and Acosta, I. L. (1988). "Comparison of extraction procedures for the determination
of heavy metals in airborne particulate matter by inductively coupled plasma-atomic emission
spectroscopy", Atomic Spectroscopy, 9(6), 191-194.
6. LaGrega, M. D., Buckingham, P. L., and Evans, J. C. (1994). Hazardous Waste Management,
McGraw Hill, New York.
7. Porteus, A. (1985). Hazardous Waste Management Handbook. Butterworths & Co Publishers,
London.
8. Smith M.A. (1998). Evaluation of Demonstrated and Emerging Technologies for the Treatment and
Clean Up of Contaminated Land and Ground Water, NATO/CCMS Pilot Study, Phase II, Final
Report.
9. U.S. EPA. (1982). "Guide To The Disposal Of Chemically Stabilized And Solidified Waste", SW-
872, Office of Water and Waste Management, Washington DC.
10. U. S. EPA. (1989). "International Waste Technologies/Geo-Con In-Situ Solidification/ Stabilization,
Applications Analysis Report".
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
11. U. S. EPA. (1992). "Silicate Technology Corporations Solidification/Stabilization Technology for
Organic and Inorganic Contaminants in Soils, Applications Analysis Report".
12. Watts, R. J. (1998). Hazardous Wastes, Sources, Pathways, Receptors. John Wiley and Sons,
New York.
13. Wiebusch, B., Ozaki, M., Watanabe, H., and Seyfried, C. F. (1998). "Assessment of leaching tests on
construction material made of incinerator ash (sewage sludge): investigations in Japan and Germany",
Water Science and Technology, 38(7), 195-205.
57
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 10
Metal-Biofilm Interactions in Sulphate-Reducing Bacterial Systems
Location
Under development in
consortium's laboratories
Technical Contact
Prof. Harry Eccles
BNFL,
Research & Technology,
Springfields,
Preston,
Lancashire PR4 OXJ,
United Kingdom
Tel: 44 1772 762566
Fax: 44 1772762891
E-mail hajj^brifLcom
Project Status
Final Report
Project Dates
Project accepted 1998
Final project report 1999
Costs Documented?
No
Contaminants
Metals
Technology Type
Biological treatment
Media
Effluents and ground water
Project Size
Laboratory
Results Available?
Yes
Project 10 was completed in 1999.
1. INTRODUCTION
Sulphate-reducing bacteria (SRB) were developed to remove toxic heavy metals and radionuclides from
liquid effluents and/or contaminated ground waters. The technology is currently at the laboratory scale to
provide fundamental data to enable engineers to design better bioreactors. SRB technology for the
removal of toxic heavy metals has been used on a limited number of occasions. In general, the bioreactors
have been over-engineered thus increasing both the capital and operational costs and consequently the
technology is not perceived as competitive. With intrinsic bioremediation, under anaerobic conditions,
such as wetlands technology, SRB plays a key role in the sequestration of metals. It is not fully
understood if this SRB role is complementary or pivotal. If the latter function predominates then
understanding SRB-metal precipitation mechanisms could enable the wetlands to be better
engineered/controlled leading to more effective in-situ treatment.
The aim of this project was to generate new fundamental data by:
1. Employing a purpose designed biocell
2. Generating fundamental metal precipitation data from this biocell
3. Investigating factors affecting growth of sulphate-reducing bacterial (SRB) biofilms
4. Quantification of important biofilm parameters on metal immobilization
2. SITE DESCRIPTION
The studies were carried out in the consortium's laboratories.
3. DESCRIPTION OF THE PROCESS
Biological processes for the removal of toxic heavy metals are presently less favored than their chemical/
physicochemical counterparts. Reasons for this are several; one of which is the inability to intensify the
technology due to the lack of fundamental data. BNFL and its partners used a novel biofilm reactor to
provide such information that can be used by the consortium's biochemical engineers and biofilm
modelers to design better, smaller and more efficient bioreactors incorporating SRB technology.
These bacteria are capable of reducing sulphate ions in liquid waste streams to hydrogen sulphide, which
with many toxic heavy metals will precipitate them from solution as their insoluble sulphides.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
As the solubility products of these sulphides are very small the final treated effluent will meet the most
stringent specification. Equally as the biological system is an active metabolic one the initial metal
concentrations can be comparatively high i.e., a few hundred ppm.
The project commenced on the 1 April 1996 and was completed on the 31 March 1999.
4. RESULTS AND EVALUATION
At the outset of this project it was appreciated that consistent, reproducible transferable results were
required from both of the laboratories (Westlakes Scientific Consulting [WSC] and the University of
Dundee [UOD]) involved in the project. Equally biofilm characterization protocols needed to be
developed/modified so that the SRB biofilms grown under a variety of conditions and challenged with
several toxic heavy metals could be comprehensively examined.
A. Biocell Design and Operation
A key component of the project was the provision of sound laboratory data in reasonable time-frames. To
satisfy these and other criteria a purpose designed biocell was constructed by a local specialist
engineering company. Prior to manufacture the design of the biocell with respect to flow regimes for a
variety of liquor flow-rates was simulated using CFD and subsequently verified by both WSC and UOD.
Laminar flow was achieved throughout (>95%) of the biocell biofilm active region.
The biocell comprised of two chambers separated by a membrane. In some experiments a porous
membrane was employed thus allowing a variety of experiments to be carried out which included
for example:
1. The separation of carbon source, or sulphate or heavy metal from the SRB biofilm.
2. Transfer, by pressure manipulation, of carbon source, or sulphate through the membrane into the
biofilm with the generated sulphide subsequently coming into contact with the metal solution.
3. The reverse of the above.
The biocell units were constructed in two sizes (lengths), a larger one (500 mm biofilm active length) and
a smaller unit (100 mm biofilm active length). The longer biocell was largely used for growing the initial
SRB biofilm on an appropriate membrane and dissected into lengths that could be accommodated by the
smaller unit. Most of the metal precipitation studies were undertaken in these units.
The philosophy for this arrangement was the period for biofilm growth was not less than 14 days whereas
metal precipitation studies took no more than 2 days to complete.
Factors Affecting Biofilm Growth
A major variable was the identity of the carbon/energy source used for culture. In general sulphate
reduced per mol of carbon source consumed was in the order: lactate > ethanol > acetate. Organic
nitrogen (e.g., a defined vitamin solution) also stimulated yield. However, a complex organic nitrogen
source e.g., yeast extract did not further stimulate yield. The structure of the support material also affected
biomass yield. Pore size stimulated yield between pore sizes of 20-100 |im. This appeared to primarily
affect the area available for attachment.
Temperature (maximum growth at 30°C), and the substrate concentration also affected growth and
sulphate reduction significantly and Km values were determined. No effect was observed due to phosphate
concentration, inorganic N concentration or support material or hydrophobicity. Prolonged culture led to
deeper biofilms but the maximum active depth (shown by fluorescein diacetate-staining) remained at
approximately 500 |im with deeper material appearing to be inactive.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
B. Substrate Utilisation
The biofilm flow cell (biocell) was a key element in this project. It allowed a defined area of biofilm to be
incubated under defined conditions of rheology and nutrient supply by recirculating medium from a
reservoir and samples of the recirculating medium can be removed for assay. Substrate-utilization was
studied in the biocell as a closed system where a fixed quantity of medium was circulated and the
substrate was depleted over time by the metabolic activities of the biofilm.
This system permitted measurement of the concentration and rate of use of substrates. Sodium lactate was
rapidly utilized, producing acetate. Varying the concentrations over a 10- to 20-fold range and allowed
determination of lactate utilization kinetics, this was carried out by personnel engaged on process
modeling (K m @ 1,4 mM). Acetate was utilized very slowly by the biofilm culture and accumulated
during experiments on lactate utilization as it was produced by SRB metabolizing lactate.
When acetate was supplied as the sole carbon/energy source, its rate of utilization and the accompanying
sulphate reduction were almost undetectable so that no kinetic parameters could be determined. The low
acetate utilization appeared to result from absence of acetate-degrading organisms from the mixed culture,
probably as a result of selection by maintaining the culture on lactate as sole carbon/energy source. An
acetate-utilizing mixed SRB culture was obtained, combined with the lactate-utilizing culture and the
combined culture was maintained on mixed lactate and acetate as carbon/energy source. This combined
culture utilized acetate considerably faster than the lactate-grown culture alone. However, it was not
possible to fit a single set of kinetic parameters to the data.
As the addition of an acetate-utilizing culture led to increased acetate utilization, it appears that the very
low rate of acetate utilization in the original culture was due to the absence of acetate-degrading
organisms.
Effects of Metal Uptake on Biofilm Growth
Biofilms exposed to Cd or Cu in the growth medium accumulated the metal sulphides. Metal sulphide
uptake was accompanied by increased content of protein and polysaccharide content of the biofilm as
well as its increased thickness. The increase in polysaccharide was considerably greater than of protein,
so that it appeared that extracellular polysaccharide was secreted in response to the accumulation of metal
sulphides in the biofilm. The accumulated metal sulphides were concentrated in the upper part of the
biofilm and resulted in increased biofilm thickness, but the depth of active (fluorescein diacetate-staining)
biofilm remained the same (approximately 500 |im) in metal-loaded biofilms. Metal sulphide deposits
could, however, overlie the active cells in metal-loaded biofilms, which indicates that these deposits did
not obstruct diffusion of nutrients to the biofilm.
5. METAL PRECIPITATION STUDIES
5.1 Metal (Cd and Cu) Bioprecipitation
The kinetics and metal mass-balances of Cd and Cu bioprecipitation were studied using the biocell
system. After flushing sulphide from the system, the appearance of soluble sulphide in the medium was
rapid in the absence of metals but was delayed, in the presence of Cd or Cu. The apparent "shortfall" of
sulphide was stoichiometric with the metal added to the medium, which was consistent with metal
sulphide formation. However, not all of the metal sulphide formed was immediately precipitated, as some
remained dispersed as colloidal material. A method of fractionating the metal into soluble, colloidal and
precipitated fractions was developed and the time-course of formation and transformation of these
fractions was investigated, this indicated that colloid flocculation to form precipitated solids was
relatively slow compared to sulphide formation and appeared to be rate-limiting for the overall
bioprecipitation process. Data on sulphate reduction, sulphide formation and colloid flocculation was used
to parameterize and test a mathematical model that confirmed the rate-limiting nature of the flocculation
step. In continuous culture, with a hydraulic residence time of 5 h, both Cd and Cu were precipitated. At
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
metal concentrations used in batch experiments (250 |iM), almost all metal was precipitated with a small
colloidal phase and almost no remaining dissolved metal At 500 and 1000 |iM metal a similar result was
observed but with more of the metal remaining in solution and a similar percentage (approximately 5-
10%) in the colloidal phase. It therefore appeared that the processes occurring in a continuous culture
system were similar to those occurring in batch culture and that the residence time allowed significant
flocculation of the colloidal material to take place. Although it is clearly an important component, the
occurrence of a significant colloidal phase in metal sulphide bioprecipitation is a novel observation that
does not appear to have been previously reported.
5.2 Iron Precipitation
The degree of iron sulphide formation by the biofilm (not previously exposed to FeSO4) was found to
depend upon the initial FeSO4 loading of the medium, with a saturating concentration 0.5mM FeSO4.
Under these conditions 0.86mg/cm2 of Fe was taken up by the biofilm, but this represented only 16% of
that in the system the rest precipitated in the system tubing and reservoir because of the biogenic S" in
solution.
6. MEMBRANE STUDIES
6.1 Permeable Membrane
Investigations into the flow characterization of the 2.5mm sintered polyallomer PorvairTM permeable
membrane showed that a 20-day-old (mature) biofilm made the membrane less permeable, but there was
sufficient fluid flow to allow the biocell to be effective at metal removal. Copper sulphate was used as the
test heavy metal, fed through the membrane along with the lactate for biofilm metabolism. At high flow
rates through the permeable membrane (>0.05mil/min/cm2) copper sulphide formed a suspension and
appeared in the waste stream, whereas at lower flow rates, where the contact time between the metal and
biofilm was increased, the amount of copper sulphide in the waste stream was reduced to insignificant
levels.
6.2 Cross Flow Operation Using a Permeable Membrane
The biocell was set up with two channels for recirculating liquor separated by a permeable membrane,
which supported the growing biofilm. The two recirculating liquor streams were only connected via the
permeable membrane. Two main processes were envisaged to transport material between these streams
bulk- phase transvection due to a pressure difference between the sides of the biocell and diffusion.
Experiments varying the pressure difference across the membrane showed that solutes supplied in the
bulk-phase liquor were transported proportionally to the exchange of volume, implying that transvection
was the main mechanism. However, sulphide produced by the biofilm was approximately equally
distributed between both sides of the biocell even at low-pressure differentials, which produced no bulk-
phase movement. This indicated that the sulphide was transported out of the biofilm in both directions by
diffusion. When a metabolically-active biofilm was grown on one side of the biocell and metal (Cd)
solution was supplied on the other (sterile) side of the biocell, bioprecipitation of the Cd occurred,
removing it from solution. Cd was not detected on the biofilm side of the cell so this arrangement, with
the biofilm separated from the metal-containing stream by a membrane, permits separation of the metal-
containing and nutrient streams reducing any environmental risks from discharge of BOD in the form of
nutrients or of toxicity to the biofilm from unprecipitated metals.
7. MODELING STUDIES
7.1 Biofilm
A model of the biological phenomena occurring within the sulphate reducing bacterial biofilms, has been
developed. The model is based upon the Generalized Repository Model (GRM) developed by BNFL. The
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
mechanistic model takes into account a complex microbiology based upon Monod type Kinetic, and
incorporates chemical speciation based on the PHREEQE geochemical speciation package. The biofilm
code allows the modeling of eight bacterial groups. All microbial groups in each biofilm layer are subject
to growth and decay. Microbial growth is modeled via two groups of reactions, energy generating
reactions and biomass generating reactions. Bacterial growth and substrate removal is modeled using
Monod kinetics, in which substrate removal is related to biomass growth through the yield coefficient.
Changes to the bulk chemistry due to microbial activity within the code are utilized as input data by the
chemical speciation component of the code, PHREEQE.
The main roles of PHREEQE are the modeling of mineral precipitation and dissolution, speciation of
dissolved species, and calculation of the ambient pH. The PHREEQE database has been modified to
include lactate and acetate species, which are of specific interest to this project. Species diffuse into the
biofilm and an equilibrium is reached between adjacent compartments, (i.e., another biofilm layer or, in
the case of the upper biofilm layer, the bulk liquid phase). Microbial degradation changes the
concentration of species in the biofilm layers, and compounds diffuse in and out of the layers tending
towards equilibrium. Whilst this is occurring the speciation component of the code determines the
reaction path of the released species.
Speciation is carried out in the bulk liquid phase, and each of the individual biofilm layers. The rate at
which microbial degradation and speciation occur determines the compartment in which the minerals
precipitate Species which become incorporated in a mineral phase, by precipitation, remain in that
compartment and are not subject to diffusion. The inclusion of advection allows a series of model cells to
be connected, allowing a range of experimental and environmental situations to be modeled. After each
time step (time taken for speciation, diffusion, and microbiology), species are able to enter and leave the
model cells, via adjacent model cells, or an external route.
Microbial growth within each layer is dependent on the diffusion of substrate. The model is based upon a
single, or series of model cells, containing a gas phase, bulk liquid phase, biofilm and a substratum.
The model has been success fully applied to results produced by the University of Dundee. It was possible
to model the utilization of lactate and sulphate within the biofilm, and the precipitation of cadmium
sulphide with a high degree of success. At present the model has had a limited application, as modeling
the BNFL biocell experiments has not utilized the bulk of the models capabilities.
A number of biofilm models are reported in current literature, however none include an extensive
microbiology and such a comprehensive speciation component. The model may be applied to further
modeling tasks in the future, taking advantage of the full extent of it capabilities.
7.2 Bioreactor Configuration
From the point of view of engineering design, the project has disclosed the following new information:
A. Kinetics
At the start of the project, only one paper was available on tentative reaction kinetics in SRB systems.
This project has shown that:
1. Sulphide production is zero order in sulphate concentration and exhibits a Monod rate dependence on
carbon substrate composition (ignoring complications from acetate utilization),
2. The biofilm kinetics do not alter substantially as the film grows, supporting modeling work presented
in the literature on non-SRB systems that there is a constant, active biofilm thickness,
3. Sulphide production rate does not appear to be affected by the adsorption of insoluble sulphides, and
kinetics are dependent on intrinsic kinetics with little effect of diffusional mass transfer in the film,
4. As a consequence of the above, a simple form for the local kinetics at a point in a reactor is possible,
thereby reducing the computational complexity of previous literature models.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
B. Metal Precipitation
The form of the precipitation of metal sulphide is very important as it exerts a profound effect on reactor
performance and the design of ancillaries to remove insolubles from the reactor outlet stream. This was
not realized at the outset of the project and has not, hitherto, been discussed or analyzed in the literature.
Nonetheless, the experimental and theoretical work in the project has:
1. Allowed estimates of the rate of flocculation of colloidal material to be made (which do not appear to
be substantially affected by the presence of the biofilm),
2. Allowed estimates of the rate of biofilm capture of colloidal material to be made, and
3. Has shown the conditions under which metal precipitation occurs predominantly either within the
biofilm or in the free solution outside the film.
C. Reactor Modeling
The few reactor models for SRB systems in the literature have used very complex biofilm kinetics and
have not considered practical issues such as flocculation and precipitation. A simple reactor model has
been constructed which could be used immediately to interpret the results from a pilot-scale reactor. It
demonstrates that very careful process control is important in order to achieve the stringent targets with
regard to both soluble sulphide concentration and soluble metal concentration in the discharged stream.
The model indicates the great sensitivity of the quality of the discharged stream to changes in key
parameters.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 11
Predicting the Potential for Natural Attenuation of Organic Contaminants in Groundwater
Location
Operational coal tar processing and
organic chemicals manufacturing plant,
West Midlands, U.K.
Project Status
Final report
Media
Groundwater
Technology Type
Intrinsic
bioremediation, natural
attenuation
Technical Contact
Dr. Steve Thornton,
Groundwater Protection & Restoration
Group,
Dept. of Civil & Structural Engineering,
University of Sheffield, Mappin St.,
SHEFFIELD SI 3JD
United Kingdom
Tel: 01142225744
Fax: 0114 222 5700
E-mail: iyFjIiMmiteifaMlS^^
Project Dates
Accepted
Final Report
1998
1999
Contaminants
Coal tars, phenol, cresols, xylenols,
BTEX
Costs Documented?
Not applicable
Project Size
Not applicable
Results Available?
Yes
Project 11 was completed in 1999.
1. INTRODUCTION
Natural attenuation is an emerging technology, which uses natural biological and chemical processes
occurring in aquifers to reduce contaminants to acceptable levels. The technology has been used
successfully in shallow North American aquifers but has not been developed for the deep, fractured,
consolidated aquifer systems found in the U.K. Technical protocols are available which provide a basis
for the performance assessment of monitored natural attenuation schemes (Buscheck and O'Reilly, 1995;
OSWER, 1997). These have primarily evolved from studies of petroleum hydrocarbon and chlorinated
solvent spills at sites in North America. However, there is little provision within these protocols for
interpretation of natural attenuation within the hydrogeological settings and range of contaminated sites
found in the UK and elsewhere in Europe. The U.K. has a legacy of contaminated industrial sites located
on deep, consolidated, dual-porosity aquifers and groundwater pollution from these sites often results in
the development of complex plumes.
The application of natural attenuation technology requires that there is a framework in place for the robust
assessment of its performance at individual sites. This framework needs to incorporate appropriate
strategies for monitoring natural attenuation processes in situ and predicting the potential for natural
attenuation at field scale.
Coal-gasification plants are an important source of soil and groundwater pollution in the U.K. Pollutant
streams from these facilities typically contain a wide variety of organic and inorganic compounds (e.g.,
phenolic compounds and NFL^, usually at very high concentration. These phenolic compounds are
normally biodegradable under a range of redox conditions (Suflita et al, 1989; Klecka, et al, 1990;
Rudolphi, et al., 1991). However, in comparison with other groups of organic pollutants our
understanding of the fate of pollutants from coal-gasification plants in U.K. aquifers is poor.
2. BACKGROUND
The research site is an operational coal-tar processing and phenols manufacturing plant, constructed in
1950, and situated in the U.K. West Midlands. The plant is located on a deep, unconfined, fractured,
Permo-Triassic sandstone aquifer and has contaminated the groundwater with a range of phenolic
compounds, including phenol, cresols, xylenols and BTEX, some at concentrations up to 12,500 mg I"1.
The aquifer is naturally aerobic, calcareous at depth and contains abundant Fe and Mn oxides as grain
coatings. Groundwater levels are shallow (typically <5 mbgl) and the aquifer is 250 m thick in the
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
vicinity of the site. Groundwater flow is 4-11 m y"1. The current volume of the plume is about 3 million
m3. The total concentration of organic compounds in the plume source area is presently 24,800 mg I"1,
including 12,500 mg I"1 phenol. Site history and groundwater flow patterns suggest that spillages started
soon after construction of the plant, that is, the plume is 50 years old. These spillages include mixtures of
organic compounds and mineral acids, the latter giving rise to a SO4 plume with concentrations up to 449
mg I"1. There is no information to indicate when spillages stopped, although the plume remains anchored
by a strong source. The only receptor at risk is a public supply borehole, located approximately 2 km west
of the plant and >100 y travel time from the present plume.
The project objectives are (a), to understand processes controlling the natural attenuation of a complex
mixture of organic pollutants in a U.K. sandstone aquifer, (b), to develop practical techniques to estimate
the potential for natural attenuation and (c), to understand the value of intervening to increase attenuation.
The key research issues are (a), estimating the timing and duration of degradation, (b), understanding the
degradation processes and potential inhibitors, (c), quantifying the role of mineral oxidants in
degradation, (d), assessing the supply of soluble electron acceptors from dispersion and diffusion at the
plume fringe, and (e), assessing the contribution of fermentation to degradation.
The project is funded primarily by the UK Engineering and Physical Sciences Research Council and
Environment Agency, with additional contributions from the UK Natural Environment Research Council
through affiliated projects. The project began in September 1996, in collaboration with the British
Geological Survey, Institute of Freshwater Ecology and University of Leeds, and is 3 years duration.
Industrial collaborators include Laporte Inspec, BP, SAGTA and Aspinwall & Co.
3. TECHNICAL CONCEPT
Simultaneous field investigations, laboratory studies and reactive transport modeling have been initiated
and are ongoing. The field studies have focused on characterization of the baseline groundwater
hydrochemistry and microbiology in the plume. This was undertaken to identify spatial and temporal
variations in the distribution of contaminants, redox processes, dissolved gases, microbial population
activity and diversity. Two comprehensive groundwater quality surveys have been completed for the suite
of 25 monitoring boreholes installed by consultants responsible for the site investigation (Aspinwall &
Co., 1992). A basic conceptual process model of contaminant attenuation was developed with this data.
High-resolution multilevel groundwater samplers (MLS) have been developed and installed in the plume
at 130 m and 350 m from the site, to depths of 30 m and 45 m below ground level, respectively. These
devices provide a vertical profile through contaminated and uncontaminated sections of the aquifer at a
level of detail unobtainable with the existing borehole network. The MLS boreholes have been used to
quantify solute fluxes, degradation rates, redox processes, and identify environmental controls on
degradation in the plume. The MLS have been sampled at quarterly intervals over a year to monitor
changes in plume redox conditions and microbial population dynamics in response to water table
fluctuations in the aquifer. A rock core was recovered anaerobically from the aquifer, adjacent to one of
the MLS boreholes, to provide material as inoculum for laboratory process studies, for examination of
microbial ecology, for analysis of metal oxide and silicate mineralogy, and for stable isotope
characterization of reduced sulphide and carbonate minerals.
Laboratory microcosm studies using acclimated groundwater and aquifer sediment are in progress to
examine the degradation rates of phenolic mixtures under the range of redox and environmental
conditions found in the plume. The scope of these process studies is wide and includes an assessment of
degradation coupled to different aqueous and solid phase oxidants, identifying the contribution of
fermentation to degradation and understanding the broad controls on degradation (e.g., oxidant
bioavailability and contaminant toxicity). Different redox systems were established in the microcosms
under different contaminant concentrations in order to understand the timing and extent of degradation.
Initially, aquifer sediment incubated under different redox conditions in boreholes at the site was used as
inocula in the microcosms. Additional process studies are now in progress using rock core material
recovered from the aquifer. These will examine the spatial variability in aquifer degradation potential, and
quantify the bioavailability of mineral oxidants in degradation along a vertical profile through the plume.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Microbiological analysis of groundwater and aquifer sediment samples has focused on understanding the
spatial and temporal variability in the diversity and activity of indigenous microbial populations. These
variations have been compared for the range of redox conditions and contaminant concentrations found in
the plume, to refine the process model developed from the hydrochemical data and to understand the
broad environmental controls on microbial ecology and aquifer potential for contaminant degradation.
Reactive transport modeling of biodegradation processes in the plume is ongoing. An initial modeling
study was undertaken with the biodegradation code, BIOREDOX, to test the conceptual process model of
the plume and to identify additional modeling objectives. Further transport modeling is now underway in
collaboration with the University of Waterloo in Canada, using a more advanced code. The necessary
parameter values, rate data and processes required for modeling are obtained from the laboratory and field
studies. This will provide an independent assessment of the utility of the approach in predicting
contaminant fate at field scale.
4. ANALYTICAL APPROACH
Groundwater samples have been collected, anaerobically, for analysis of organic contaminants, dissolved
gases (e.g., N2, CO2, CFLj), major cations, major anions, organic and inorganic (e.g., total inorganic
carbon, Fe2+, Mn2+, S2") metabolites of phenolic compound degradation, nutrients, 34S/32S-SO4,34S/32S-S2",
13C/12C-CO32", 18O/16O-SO4, organically-complexed and organically-uncomplexed Fe, and micro-
biological parameters. Samples have been collected concurrently for analysis of these determinands on
each groundwater survey, to provide time-series data for comparison. Geochemical modeling of the
groundwater quality data has been completed to identify potential sinks for inorganic products of
biodegradation and to refine a carbon mass balance for the plume.
Microbiological analysis has included enumeration of total and culturable bacteria. Direct measures of in
situ degradation potential have been made on groundwater and aquifer sediment samples by stimulation
with NO3 and addition of radiolabeled phenol compounds and other aromatic hydrocarbons. Microbial
diversity has been assessed after inoculation of samples with different nutritional tests.
Rock core samples have been analyzed for oxidation capacity (OXC) and mineral phases (e.g., iron
sulphides, metal oxides, carbonates and aluminosilicates). Permeameter tests and analyses of mineral
phase 34S/32S-S2" and 13C/12C-CO32- stable isotopes have also been performed on core samples.
5. RESULTS
The range of redox and microbial processes identified in the plume has demonstrated the aquifer potential
for aerobic and anaerobic degradation of the organic contaminants. Contaminant degradation is occurring
under aerobic, nitrate-reducing, iron/manganese-reducing, sulphate-reducing, and methanogenic
conditions, at contaminant concentrations up to 24,000 mg L"1. Degradation rates and microbial activity
are highly variable and are correlated with contaminant concentrations and electron acceptor availability
in the plume. There is increased microbial activity, diversity and degradation at the plume fringe, in
response to the increased flux of dissolved oxygen and nitrate from the background groundwater and
dilution of contaminant concentrations. The supply of aqueous oxidants and dilution of contaminants are
controlled by mechanical dispersion at the plume fringe. The mixing zone over which this dispersion
occurs is relatively small (2 m) for the plume under study. A carbon and electron acceptor mass balance
for the plume has constrained the plume source term and suggests that degradation has not been
significant within much of the plume (Thornton et al., 1998). The mass balance suggests that dissolved
oxygen and nitrate, supplied by dispersion, are more important for contaminant mass turnover in the
plume than other degradation processes. The stable isotope studies show that a contaminant threshold
concentration exists for the initiation of sulphate reduction in the plume, although other degradation
processes appear relatively insensitive to the organic pollutant load.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
6. HEALTH AND SAFETY
Not available.
7. ENVIRONMENTAL IMPACTS
Not available.
8. COSTS
Not available.
9. CONCLUSIONS
A combination of methodologies has been developed to assess the potential for natural attenuation of
organic contaminants at this site. These methodologies include theoretical approaches and practical, field-
based, technology which provides an improved framework for understanding the behaviour of complex
plumes in aquifers. Contaminant fate in this aquifer system is controlled by a complex plume source
history and spatial variations in the aquifer degradation potential, as influenced by contaminant
concentration and the bioavailability of oxidants. Source history has a greater impact on contaminant
concentrations in this aquifer than degradation processes. The field and laboratory studies show that
contaminant mass loss can be demonstrated for the range of environmental conditions found in the plume.
However, although the phenolic compounds are biodegradable and the aquifer is not oxidant limited, the
plume is likely to grow under the present conditions. This is because contaminant concentrations remain
toxic to degradation in much of the plume core and the supply of aqueous oxidants, via mixing with
uncontaminated groundwater, is insufficient to meet the demand from the plume. Natural attenuation of
these organic pollutants in this system is therefore likely to increase only after increased dilution of the
plume.
10. REFERENCES
1. Aspinwall & Co. (1992). Site Investigation at Synthetic Chemicals Limited, Four Ashes: Phase 6
Report
2. Borden, R. C., Gomez, C. A. and Becker, M. T. (1995). Geochemical indicators of intrinsic
bioremediation. Ground Water, 33, 180-189.
3. Buscheck, T. and O' Reilly, K. (1995). Protocol for monitoring intrinsic bioremediation in
groundwater. Chevron Research and Technology Company, pp. 20.
4. Klecka, G. M., Davis, J. W., Gray, D. R. and Madsen, S. S. (1990). Natural bioremediation of organic
contaminants in ground water: Cliff-Dow Superfund site. Ground Water, 28, 534-543.
5. OSWER (1997). Use of Monitored Natural Attenuation at Superfund, RCRA Corrective Action, and
Underground Storage Tank Sites, Directive 9200.4-17, USEPA.
6. Rudolphi, A., Tschech, A. and Fuchs, G. (1991). Anaerobic degradation of cresols by denitrifying
bacteria. Archives of Microbiology, 155, 238-248.
7. Suflita, J. M., Liang, L. and Saxena, A. (1989). The anaerobic biodegradation of o-, m- and p-cresol
by sulfate-reducing bacterial enrichment cultures obtained from a shallow anoxic aquifer. Journal of
Industrial Microbiology, 4, 255-266.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 12
Treatability Test for Enhanced In Situ Anaerobic Dechlorination
Location
Cape Canaveral Air Station, FL
Naval Air Station Alameda, CA
Fort Lewis, WA
Camp Lejeune, SC
Project Status
Demonstration
complete
Demonstration
complete
Demonstration
complete
Demonstration in
progress
Media
Groundwater
Technology Type
In situ
bioremediation
Technical Contact
Capt. Dave Kempisty
AFRL/MLQ
139 Barnes Drive, Suite 2
Tyndall AFB, FL 32403
Tel: 850-283-6126
Fax: 850-283-6064
E-mail:
david.kcmpistv@tvndall.af.mil
Project Dates
Accepted
Final Report
1999
2002
Contaminants
Tetrachloroethylene (PCE),
trichloroethylene (TCE),
dichloroethene (DCE), vinyl chloride
Costs Documented?
Spring 2002
Project Size
Field
Treatability
Testing
Andrea Leeson
DoD SERDP/ESTCP
Cleanup Program Manager
901 N. Stuart Street, Suite 303
Arlington, VA 22203
Tel: (703)696-2118
Fax:(703)696-2114
E-mail: aiidrea.lecsoiif«;osd.mil
Results Available?
Spring 2002
1. INTRODUCTION
Chloroethene compounds, such as tetrachloroethene (PCE) and trichloroethene (TCE), have been widely
used for a variety of industrial purposes. Past disposal practices, accidental spills, and a lack of
understanding of the fate of these chemicals in the environment have led to widespread contamination at
U.S. Department of Defense (DoD) and industrial facilities. Enhanced anaerobic dechlorination is a very
promising bioremediation treatment approach for remediating chlorinated ethene-contaminated
groundwater. The goal of this effort is to develop and validate a comprehensive approach for conducting a
treatability test to determine the potential for applying reductive anaerobic biological in situ treatment
technology (RABITT) at any specific site. A treatability protocol has been written (Morse, 1998) and will
be applied to five DoD chlorinated solvent contamination sites in the United States. Based on the field
test results, the protocol will be revised as needed upon completion of the effort.
2. BACKGROUND
Because both PCE and TCE are stable compounds that resist aerobic degradation or require the presence
of an electron-donating co-contaminant for anaerobic transformation, these compounds tend to persist in
the environment. However, in reductive systems, highly oxidized contaminants (e.g., PCE) can be utilized
as electron acceptors. RABITT attempts to stimulate this reductive pathway by supplying excess reduced
substrate (electron donor) to the native microbial consortium. The presence of the substrate expedites the
exhaustion of any naturally occurring electron acceptors. As the natural electron acceptors are depleted,
microorganisms capable of discharging electrons to other available electron acceptors, such as oxidized
contaminants, gain a selective advantage.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
The reductive dechlorination of PCE to ethene proceeds through a series of hydrogenolysis reactions
shown in Figure 1. Each reaction becomes progressively more difficult to carry out.
Figure 1: Reductive Dechlorination of PCE
The selection of an appropriate electron donor may be the most important design parameter for
developing a healthy population of microorganisms capable of dechlorinating PCE and TCE. Recent
studies have indicated a prominent role for molecular hydrogen (H2) in the reductive dechlorination
process (Holliger et al., 1993; DiStefano et al, 1992; Maymo-Gatell et al, 1995; Gossett et al., 1994;
Zinder and Gossett, 1995). Most known dechlorinators can use H2 as an electron donor, and some can
only use H2. Because more complex electron donors are broken down into metabolites and residual pools
of H2 by other members of the microbial community, they may also be used to support dechlorination
(Fennell et al., 1997; Smatlak et al., 1996; DiStefano et al., 1992).
The rate and quantity of H2 made available to a degrading consortium must be carefully engineered to
limit competition for hydrogen from other microbial groups, such as methanogens and sulfate-reducers.
Competition for H2 by methanogens is a common cause of dechlorination failure in laboratory studies. As
the methanogen population increases, the portion of reducing equivalents used for dechlorination quickly
drops and methane production increases (Gossett et al., 1994; Fennel et al., 1997). The use of slowly
degrading nonmethanogenic substrates will help prevent this type of system shutdown.
Because of the complex microbial processes involved in anaerobic dechlorination, thorough site
characterization and laboratory microcosm testing are an important part of the RABITT protocol. The
protocol presents a phased or tiered approach to the treatability test, allowing the user to screen out
RABITT in the early stages of the process to save time and cost. The protocol guides the user through a
decision process in which information is collected and evaluated to determine if the technology should be
given further consideration. RABITT would be screened out if it is determined that site-specific
characteristics, regulatory constraints, or other logistic problems suggest that the technology will be
difficult or impossible to employ, or if competing technology clearly is superior.
The first phase of the treatability test includes a thorough review of existing site data to develop a
conceptual model of the site. The protocol contains a rating system that can be used to assess the
suitability of a site for RABITT testing. The rating system is based on an analysis of the contaminant,
hydrogeologic, and geochemical profiles of the site. The decision to proceed with the RABITT screening
process should be supported by data indicating that the site meets the requirements for successful
technology application. The second phase of the approach involves selecting a candidate test plot location
within the plume for more detailed site characterization. Characterization activities will examine
contaminant, geochemical, and hydrogeologic parameters on a relatively small scale to determine the
selected location's suitability as a RABITT test plot. Based on the information generated during the
characterization of the test plot, a decision is made to proceed to phase three of the treatability study,
which consists of conducting laboratory microcosm studies. The microcosm studies are conducted to
determine what electron donor/nutrient formulation should be field-tested to provide optimum biological
degradation performance. If the results from the microcosm testing indicate that reductive dechlorination
does not occur in response to the addition of electron donors and/or nutrients, the technology is eliminated
from further consideration. The fourth and final phase of the treatability test entails field testing the
electron donor/nutrient formulation determined in the laboratory microcosm tests to be most effective for
supporting biologically mediated reductive dechlorination. The data from this phased treatability test
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
indicate the potential for the microbiological component of RABITT and are used to make the decision to
proceed to pilot-scale or full-scale implementation of RABITT.
This effort consists of applying the protocol to five chlorinated solvent contamination sites. Currently the
field treatability test systems are operating at two locations, Cape Canaveral Air Station, FL, and Naval
Air Station Alameda, CA. Microcosm studies will begin in August 1999, using contaminated aquifer
material from a site at Ft Lewis, WA which is the proposed location for site number three. The fourth and
fifth field locations are yet to be determined.
3. ANALYTICAL APPROACH
A summary of soil and groundwater analytes is presented here. For detailed information on sample
collection techniques or analytical methods, please refer to Morse, et al. 1998.
A. Site Characterization Activities
Soil cores are visually examined for soil type and stratigraphy. In addition, soil core subsamples are sent
to an off-site laboratory and analyzed for VOCs, TOC, and Total Iron. Groundwater samples are analyzed
for the following parameters: dissolved oxygen, temperature, pH, Fe+2, conductivity, chloroethenes,
dissolved organic carbon, ammonia, CFL,, C2H4, C2H6, NO3, NO2, SO4, Cl, Br, alkalinity, and total iron.
B. Performance Monitoring of the Field Test Cell
Table 1 presents the performance monitoring parameters and their measurement frequency during field-
testing.
Table 1: Performance Monitoring Parameters
Parameter
TCE, cis-DCE, VC, ethene
Volatile Fatty Acids (electron
donor)
Bromide
Dissolved Oxygen
PH
Conductivity
T^ +2
Fe
CFL,, C2FL,, C2Hg
NO3, NO2, SO4, Cl
Alkalinity
Measurement
Site
Lab
Lab
Field and Lab
Field
Field
Field
Field
Lab
Lab
Lab
Measurement Frequency
Initial, baseline, and biweekly
Initial, baseline, and biweekly
Initial, baseline, and biweekly
Initial, baseline, and biweekly
Initial, baseline, and biweekly
Initial, baseline, and biweekly
Initial, baseline, and biweekly
Baseline and monthly
Baseline and monthly
Baseline and monthly
4. RESULTS
4.1 Site 1: Cape Canaveral Air Station, FL
Description. Facility 1381, the Ordnance Support Facility at Cape Canaveral Air Station, contains a
shallow, 110-acre volatile organic compound (VOC) plume consisting primarily of TCE, DCE, and VC.
Improper disposal of solvents used for cleaning and degreasing operations contributed to this groundwater
contamination plume. Field data suggest that TCE is naturally being dechlorinated to DCE and
subsequently to VC. Each of these contaminants has been detected in a surface water body adjacent to the
site.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
The geology at the site is characterized by poorly sorted coarse to fine sands and shell material from
ground surface to approximately 35 ft below ground surface (bgs). From approximately 35 to 50 ft bgs,
sands show a decrease in grain size and the silt and clay content increases. From 48.5 to 51 ft bgs, a
continuous clay unit appears to underlie the entire area at Facility 1381. Groundwater at the site is very
shallow, generally ranging between 4 and 7 ft bgs. The hydraulic conductivity for the shallow
groundwater has been determined to be approximately 88.7 ft/day. The pH of the groundwater ranged
from 6.87 to 8.14 and conductivity readings ranged from 464 to 5,550 |imhos/cm. The groundwater flow
velocity has been calculated to be 0.21 ft/day. The suspected source area contains high levels of TCE (up
to 342 mg/L), but TCE concentrations drop off quickly and only DCE and VC are detected towards the
edges of the plume.
A. Microcosms
Microcosm studies at Cape Canaveral showed that all organic electron donors evaluated (lactate, butyrate,
propionate, benzoate, and yeast extract amendment) promoted enhanced dechlorination of the 2 mg/L
TCE, 10 mg/L cDCE and 1.5 mg/L VC present in the site groundwater. Lactate was selected for the
electron donor to be used in the field-testing.
Figure 2 illustrates lessons learned from conducting microcosm studies. Upon the addition of lactate and
vitamin Bi2 with no yeast extract, levels of TCE and cDCE show no significant signs of reduction.
Alternatively, the addition of yeast extract along with lactate and vitamin B12 facilitated the onset of and
completion of the dechlorination process.
Figure 2: Degradation of Chlorinated Compounds under Various Conditions: Cape Canaveral Air Station
Aquifer Material
CCAS Microcosm 5C-II (GPW09/10) Lactate + Bn
nors and Products
M
OJ
1
W
s~
"o
CO
cr1
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
B. Field Study
The standard RABITT design was modified for the site at Cape Canaveral Air Station in order to meet the
State of Florida Underground Injection Control regulatory requirements. This regulation does not allow
for reinjection of contaminated groundwater. The objective of the modified system was to allow for
effective delivery and distribution of nutrients and electron donors and to provide for extensive
monitoring and hydraulic control, without pumping groundwater aboveground. The modified system was
installed at Facility 1381 in March 1999 and operated for six months.
The modified design consisted of two communicating wells, a series of 13 tri-level groundwater
monitoring probes, and upgradient and downgradient monitoring wells. The system wells are a dual
screen design, with one operating in an upflow mode and the other in a downflow mode. Each well was
screened within two distinct zones (10-12.5 and 17.5-20 ft bgs). The wells are placed close enough to
affect each other with the effluent from one well feeding the other. This results in groundwater circulation
that can be used to mix and distribute the electron donor/nutrient formulation. Tri-level monitoring points
were screened in three zones that covered similar depths and an intermediate zone. The monitoring probes
were positioned around the treatment cell to provide three-dimensional data that was required to track the
tracer and added electron donor/nutrients, calculate mass reductions during treatment, and evaluate gains
and losses from the treatment cell through background groundwater migration. The monitored plot
dimensions were 39 ft by 10 ft.
After initial tracer testing established the site hydrological conditions, lactic acid was injected into the
communicating well system to maintain an initial groundwater concentration of 3 mM lactate. The total
system pumping rate was approximately 2,880 gal/day (7.6 L/ min).
Figure 3: Degradation of Chlorinated Compounds during Field Testing at Cape Canaveral
120
100
=
o
U
10 20 30 40 50 60 70
80 90 100
Time (Days)
110 120 130 140 150 160 170 180
Cape Canaveral field-testing showed rapid dechlorination of TCE and cDCE to VC, followed by slower
subsequent dechlorination to ethene under the established sulfate reducing to methanogenic conditions
(Figure 3). Molecular probing indicated the presence of a dechlorinating organism similar to
Dehalococcoides ethenogenes, an organism that has been shown to promote complete dechlorination with
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
slow removal of VC. The treatment demonstrated reduction of TCE, cDCE, and VC by 88.7%, 90.6%,
and 66.3%, respectively. The ethene concentration increased significantly to approximately 0.04 mM, but
good molar balances were not possible due to diffusion. Overall, there was reasonable agreement between
laboratory microcosm and field results.
4.2 Site 2: Naval Air Station Alameda, CA
A. Site Description
Building 360 (Site 4) at Naval Air Station Alameda was selected for the second demonstration. This
building has been used as an aircraft engine repair and testing facility, and consisted of former machine
shops, cleaning areas, as well as plating and welding shops and parts assembly areas. Solvents used in the
cleaning shop of Building 360 have included a mixture of 55% PCE and other chemicals such as
dichlorobenzene, methylene chloride, toluene and 30 to 70% solutions of sodium hydroxide. Site
characterization activities performed by the facility revealed elevated levels of chlorinated solvents,
primarily TCE (24 mg/L), DCE (8.6 mg/L), and VC (2.2 mg/L), between 5.5 and 15.5 feet bgs.
Depth to groundwater in the Building 360 area ranges between 4.4 feet and 6.5 feet bgs. Aquifer testing
yielded hydraulic conductivity values from 1.22 x 10"3 to 3.86 x 10"3 cm/sec. The estimated groundwater
flow is very low at only 1.1 x 10"5 cm/sec or 11.4 ft/year. It appears that groundwater in this area is very
nearly stagnant.
B. Microcosms
Microcosms showed that all electron donors tested except benzoate promoted enhanced dechlorination of
TCE. Butyrate was chosen for field injection because of a shorter lag time associated with stimulating
dechlorinating activity. TCE was rapidly dechlorinated to ethene under the established sulfate reducing to
methanogenic conditions when supplied with a constant 3 mM supply of butyrate in the injected
groundwater obtained from the supply well. Molecular probing to date has been negative for D.
ethenogenes; however, recent data indicates that a closely related species may be present at the site.
C. Field Study
After baseline sampling and tracer testing, injection of butyric acid began in June 1999 using a flow
through system. The field test involved an upgradient injection well and downgradient extraction well
with aboveground recirculation. The injection well was supplemented with TCE-contaminated
groundwater from a separate supply well outside the influence of the 3-ft by 15-ft monitored plot. The
injection, extraction, and nine monitoring wells were all screened between 24 and 27 ft bgs. The total
pumping rate for the system was 236 gal/day (0.62 L/min). Butyric acid and yeast extract were added to
maintain initial in situ concentrations of 3mM and 20 mg/L respectively.
Injected groundwater contained average TCE, cDCE, and VC concentrations of 81.7 |iM, 7.0 |iM, and 3.4
|lM respectively. By the end of the demonstration the average TCE concentration observed in the
treatment zone had been reduced by 94% despite the continuing input of TCE (Figure 4). In addition, both
cDCE and VC were on the decline; ethene levels were steadily increasing and accounted for
approximately half of the total chloroethene concentration. On average, 87% of injected chloroethenes
could be accounted for during sampling events. Good agreement between microcosm and field results
was also observed for the Alameda site.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Figure 4: Degradation of Chlorinated Compounds during Field Testing atNAS Alameda
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230
Time (Days)
4.3 Site 3: Fort Lewis, WA
A. Site Description
The East Gate Disposal Yard (EGDY) covers approximately 29 acres at Ft Lewis, WA. Aerial
photographs indicate that between 1940 and 1971 the EGDY was used as a storage and disposal site for
various solid and liquid wastes. The photographic evidence shows that the wastes were disposed of in
large trenches and pits and that, on occasion, the waste materials were burned. Waste materials disposed
of at the EGDY include TCE and petroleum, oil, and lubricant wastes from equipment cleaning and
degreasing activities conducted at the Fort Lewis Logistics Center.
The depth to groundwater at the EGDY Site is approximately 10 feet bgs. Background groundwater
velocities across the EGDY are in the range of 0.25 to 0.75 feet per day in the field test location. TCE,
cDCE, VC, and BTEX constituents have been detected in groundwater samples from the EGDY Site. Of
these, TCE and cDCE are most prevalent. Data from a previous investigation indicated that reductive
dechlorination may be occurring in the area, but that the process is held up at cDCE.
B. Microcosms
Dechlorination in the Ft. Lewis microcosms was markedly slower than anticipated based on previous
results with samples collected from Alameda Point and Cape Canaveral (Figure 5). The initial dose of
TCE was removed from all of the amended, biotic reactors; however, formation of VC and complete
conversion to ethene occurred in only a few bottles after 292 days of monitoring. The two amendments
that did result in complete conversion to ethene in two of the three replicates were butyrate and high
concentrations of yeast extract. Because the observed degradation of butyrate is slow, it appears to
provide a relatively steady, long-term supply of electron equivalents for use.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
The single, most important factor influencing dechlorination—both lag and extent—was probably the low
native levels of TCE in the materials from which these microcosm sets were created. In the majority of
bottles, there was a consistently long lag time observed prior to the initiation of cDCE dechlorination.
However, once cDCE dechlorination activity began, it was generally followed by concurrent
transformation of VC to ethene. These patterns suggest that the transformation of TCE was mediated by
different organisms than those responsible for cDCE and VC dechlorination. This type of pattern is
consistent with the presence of a dechlorinating population in which Dehalococcoides ethenogenes is not
the dominant member.
Figure 5: Microcosm Results, Ft. Lewis, WA
Ft. Lewis Microcosm 6-II + YE + 812
«, 3
a s
w
12000
Butyric Acid
Acetic Acid
Isobutyric Acid
40
80
120 160 200
Time (Day)
240
280
C. Field Study
A conventional RABITT test system (shown in Figure 6.1 on page 54 of the draft RABITT protocol) was
installed at Fort Lewis, with the exception that the gradient well was removed from the design based on
the results of the tracer test and the measured gradient in the selected area. The three injection wells are
spaced approximately 2 feet apart and the distances between the injection wells and each row of
monitoring wells are 10 feet for a plot dimension of approximately 4 feet by 30 feet. A background
monitoring well was installed upgradient of the plot to monitor any naturally occurring changes in
background contaminant and geochemical profiles. An existing well in a contaminated area was used to
provide the required supply of contaminated groundwater for injection into the test plot. The injected fluid
imparts a gradient, which drives the flow of groundwater through the system.
Initial TCE concentrations ranged across the test plot from 11.0 to 47.9 uM (1,450 to 6,300 ppb). Injected
groundwater initially contained moderately higher levels that tended to increase over the first 13 weeks of
the demonstration from a low of 39.6 uM (5,200 ppb) at system startup to 148 uM (19,400 ppb) at 13
76
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
weeks. TCE concentrations remained within this range until Week 24 when concentrations spiked
dramatically to 1,286 uM (169,000 ppb). Concerns that TCE levels of this magnitude would prove toxic
to the microorganisms catalyzing the dechlorination reaction proved unwarranted as the conversion of
TCE to cDCE continued unimpeded.
After 8 weeks of electron donor injection, the influent concentration of TCE was reduced 99.94% from 65
uM (8,500 ppb) to an average concentration of 0.04 uM (5 ppb) by the time it reached the first row of
monitoring wells approximately 50 hours later. Assuming pseudo-first order kinetics apply, this rate of
TCE removal translates into a half-life of 4.7 hours (k = -0.1488 h"1). This rate of removal remained
constant when the influent concentration of TCE increased to 1,286 uM (169,000 ppb) during Week 24.
The concentration in the injected water once it reached nearby MW-3 was only 0.53 uM (69.4 ppb),
which translates into a half-life of 4.4 hours (k = -0.155 h"1).
The dramatic reduction in TCE concentrations contributed to the accumulation of cDCE during the
demonstration. Increases in vinyl chloride levels suggest that cDCE was being dechlorinated, but at a
significantly slower rate than TCE. The maximum VC concentration was only 3.5 uM (217 ppb) and
comprised a very small percentage of the overall chloroethene mass. Ethene and ethane concentration
remained at or near detection limits throughout most of the demonstration.
4.4 Site 4: Marine Corps Base Camp Lejeune, NC
A. Site Description
The contamination at Site 88, Marine Corps Base Camp Lejeune, occurred as a result of past operating
procedures at the Base Dry Cleaners as well as due to leaking underground storage tanks at the site. The
surficial aquifer was encountered at depths of 6 to 15 feet bgs. The aquifer consists of a series of
sediments, primarily sand and clay, which commonly extend to depths of 75 feet. The principal water
supply for the base is found in the series of sand and limestone beds that occur between 50 and 300 feet
bgs. This series of sediments generally is known as the Castle Hayne Formation, associated with the
Castle Hayne Aquifer. The top of the Castle Hayne Aquifer was found at a depth of 40 to 60 feet bgs.
Clay layers occur in both of the aquifers. However, the layers are thin and discontinuous in most of the
area, and no continuous clay layer separates the surficial aquifer from the Castle Hayne Aquifer. Thin,
discontinuous layers and lenses of silt, clay, and/or peat are scattered throughout the sand. The hydraulic
conductivity values estimated for the upper portion of the surficial aquifer ranged from 0.4 feet/day to
29.7 feet/day. The hydraulic conductivity values estimated for the lower portion of the surficial aquifer
ranged from 56.4 feet/day to 85.5 feet/day.
B. Microcosms
Core samples were taken from Camp Lejeune for microbial analysis in November 2000. Because
previous site characterization indicated varying contaminant and geochemical profiles at increasing
depths, two distinct microcosm sets were constructed. The first set was assembled using core material and
groundwater from 15 to 19 feet bgs, while the second used core material and groundwater from 45 to 49
feet bgs. The construction of two microcosm sets was undertaken to more fully assess the potential for
stimulating dechlorinating activity in the area. Transferring material between two microcosms from
different depths should provide information about potential inhibitory conditions at the site, as well as an
indication of the promise of implementing a recirculating system in the field study. Monitoring of the
Camp Lejeune microcosms is currently in-progress.
C. Field Study
A conventional RABITT test system consisting of 3 injection wells and an array of 9 monitoring wells
was installed at Camp Lejeune in April 2001. The wells were installed to a depth of 48 ft bgs and covered
an area approximately 4 ft wide by 30 ft long. Existing wells are being used to monitor background
groundwater characteristics and supply groundwater for the demonstration. Injection of contaminated
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
groundwater amended with butyric acid and yeast extract commenced in June 2001, with a total system
pumping rate of approximately 0.65 L/min. The expected completion date for the field demonstration is
December 2001.
Preliminary results show groundwater at the site is anaerobic, highly reduced (-200 mV), and PCE
concentrations within the testing zone average about 33 |iM (5,500 ppb). Other chloroethenes are present,
but at considerably lower concentrations. The average concentrations of TCE, cDCE and VC within the
testing zone are 2.9 |iM, 0.8 |iM, and <0.1 |lM, respectively.
5. HEALTH AND SAFETY
Activities conducted during RABITT system installation and operation that could potentially cause health
and safety hazards include drilling with hollow-stem augers or direct push methods, soil and groundwater
sample collection, and replenishing concentrated stock solutions (tracer, nutrient, electron donor
solutions). Potential hazards include exposure to organic contaminants and other chemicals used in stock
solutions, exposure to organic vapors, objects striking feet or eyes, and electrical shock. Appropriate
safety precautions and protective equipment is utilized to minimize or eliminate health and safety hazards.
6. ENVIRONMENTAL IMPACTS
Because the contaminants are biologically transformed in situ into non-hazardous compounds (e.g.,
ethene), the RABITT treatability test does not produce a process waste stream. Characterization and
sampling activities generate a small amount of contaminated soil and groundwater that must be properly
disposed of.
7. COSTS
Detailed costs for all phases of the RABITT treatability approach will be presented in the final report.
8. CONCLUSIONS
To date RABITT demonstrations have been completed at three Department of Defense Facilities, Cape
Canaveral Air Station, FL; Alameda Point, CA; and Ft. Lewis, WA. The fourth and final facility, Camp
Lejeune, NC, has been initiated and will be completed by the end of the year.
Microcosm studies were conducted at each demonstration site to gauge the probability of enhancing
reductive dechlorination and to examine a suite of electron donors for efficacy. In all four cases the
electron donor butyric acid demonstrated results equal or superior to all other donors tested. This
assessment is based on the percentage of reducing equivalents used for dechlorination and on the rate and
degree of dechlorination.
The design and operation of each RABITT field demonstration system was tailored to site-specific
characteristics. The site's hydrogeology, regulatory environment, and results from microcosm testing all
influenced the design and operation of the system. An overview of each system's design is outlined in
Table 2. Despite differences in site characteristics and system design, each of the three completed
demonstrations showed rapid reduction of TCE to cDCE. At Cape Canaveral and Alameda this reduction
proceeded to ethene. The demonstration at Ft. Lewis was exposed to extraordinarily high concentrations
of TCE (169,000 ppb), but no slowdown in microbial activity was observed and dechlorination continued
at a remarkable pace. The high-rate dechlorination observed at Ft. Lewis did lead to an accumulation of
cDCE, but increases in the VC concentration suggest that dechlorination was proceeding past cDCE.
Results from field demonstrations were generally in agreement with microcosm test results. Results from
Camp Lejeune are still pending.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Table 2: Hydrogeology, Regulatory Environment and Results from Microcosm Testing
Design Parameter
System flow rate
Flow pattern
Surface dimensions
Depth
Sampling locations
Demonstration duration
Electron donor
Yeast extract3
Sodium bicarbonate3
Units
L/min
NA
ft.
ft. bgs
number
Days
NA
mg/L
mg/L
Cape Canaveral
7.5
Circulation
10x34
10-20
49
169
Lactic acid
None
None
Alameda Point
0.6
Linear flow-
through
3x15
24-27
12
194
Butyric acid
20
None
Ft. Lewis
1.5
Linear flow-
through
4x30
26-29
12
179
Butyric acid
20
279
Camp Lejeune
0.6
Radial flow-
through
4x30
45-48
12
ongoing
Butyric acid
20
None
NA - not applicable.
a - target in situ concentration.
9. REFERENCES
1. DiStefano, T.D., J.M. Gossett, and S.H. Zinder. 1991. "Reductive Dechlorination of High
Concentrations of Tetrachloroethene to Ethene by an Anaerobic Enrichment Culture in the Absence
of Meihanogenesis" Applied and Environmental Microbiology 57(8): 2287-2292.
2. DiStefano, T.D., J.M. Gossett, and S.H. Zinder. 1992. "Hydrogen as an Electron donor for
Dechlorination of Tetrachloroethene by an Anaerobic Mixed Culture." Applied and Environmental
Microbiology 58(11): 3622-3629.
3. Fennell, D.E., J.M. Gossett, and S.H. Zinder. 1997. "Comparison of Butyric Acid, Ethanol, Lactic
Acid, and Propionic Acid as Hydrogen Donors for the Reductive Dechlorination of
Tetrachloroethene. " Environmental Science & Technology 31: 918-926.
4. Gossett, J.M., T.D. DiStefano, and M.A. Stover. 1994. Biological Degradation of
Tetrachloroethylene in Methanogenic Conditions. U.S. Air Force Technical Report No. AL/EQ-TR-
1983-0026, USAF Armstrong Laboratory, Environics Directorate, Tyndall AFB, FL.
5. Holliger, C., G. Schraa, A.J.M. Stams, and A.J.B. Zehnder. 1993. "A Highly Purified Enrichment
Culture Couples the Reductive Dechlorination of Tetrachloroethene to Growth" Applied and
Environmental Microbiology 59(9): 2991-2997'.
6. Maymo-Gatell, X., V. Tandoi, J.M. Gossett, and S.H. Zinder. 1995. "Characterization of an H2-
Utilizing Enrichment Culture that Reductively Dechlorinates Tetrachloroethene to Vinyl Chloride and
Ethene in the Absence of Methanogenesis and Acetogenesis. " Applied and Environmental
Microbiology 6\(U): 3928-3933.
7. Morse, J. J., B.C. Alleman, J.M. Gossett, S.H. Zinder, D.E. Fennell, G.W. Sewell, C.M. Vogel. 1998.
Draft Technical Protocol - A Treatability Test for Evaluating the Potential Applicability of the
Reductive Anaerobic Biological In Situ Treatment Technology (RABITT) to Remediate
Chloroethenes. DoD Environmental Security Technology Certification Program. Document can be
downloaded from www.estcp.org.
8. Smatlak, C.R., J.M. Gossett, and S.H. Zinder. 1996. "Comparative Kinetics of Hydrogen Utilization
for Reductive Dechlorination of Tetrachloroethene and Methanogenesis in an Anaerobic Enrichment
Culture." Environmental Science and Technology 30(9) 2850-2858.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 13
Permeable Reactive Barriers for In Situ Treatment of Chlorinated Solvents
Location
Dover Air Force Base,
Delaware, USA
Project Status
Final Report
Media
Groundwater
Technology Type
In situ abiotic
destruction of
contaminants
Technical Contacts
Charles Reeter
U.S. Navy
1100 23rd Ave., Code 412
PortHueneme, CA 93043
Tel: (805) 982-4991
Fax: (805)982-4304
E-mail:
reetercvffivfesc.navv.mil
Project Dates
Accepted 1999
Final Report 2000
Contaminants
Chlorinated solvents: PCE, TCE, and cis-
1,2-DCE
Catherine Vogel
DoD SERDP/ESTCP
Cleanup Program Manager
901 N. Stuart Street, Suite 303
Arlington, VA 22203
Tel: (703)696-2118
Fax:(703)696-2114
E-mail: YQgelo@aM.,osd,mjl
Costs Documented?
Yes
Project Size
Field demonstration
Pilot-scale
Results Available?
Yes
Project 13 was completed in 2000.
1. INTRODUCTION
A permeable reactive barrier (PRB) was installed at Dover Air Force Base (AFB) in January 1998 to
capture and treat a portion of a chlorinated solvent plume. The PRB consisted of a funnel-and-gate system
with two permeable gates containing reactive media and impermeable funnel walls to achieve the required
groundwater capture. This PRB was installed was installed to a depth of almost 40 ft using an innovative
installation technique involving the use of caissons. The PRB was monitored periodically since
installation and is performing satisfactorily in terms of contaminant degradation and groundwater capture
(Battelle, 2000).
2. BACKGROUND
The Air Force Research Laboratory (AFRL), Tyndall Air Force Base (AFB), Florida contracted Battelle,
Columbus, Ohio in April, 1997 to conduct a demonstration of a pilot-scale field PRB at Area 5, Dover
AFB, Delaware. The Area 5 aquifer is contaminated with dissolved chlorinated solvents, primarily
perchloroethene (PCE). The U.S. Department of Defense (DoD) Strategic Environmental Research and
Development Program (SERDP) and the Environmental Security Technologies Certification Program
(ESTCP) provided funding for this project. The primary objective of this demonstration was to test the
performance of two different reactive media in the same aquifer, under uncontrolled field conditions. A
secondary objective of the demonstration was to facilitate technology transfer through by documenting
and disseminating the lessons learned regarding PRB design, construction, and monitoring.
The U.S. Environmental Protection Agency (EPA) National Exposure Research Laboratory (NERL) was
funded separately by SERDP to conduct long-term above-ground column tests with groundwater from
Area 5 of the Dover AFB to evaluate and select suitable pre-treatment and reactive cell treatment and
media for the field demonstration. Members of the Remediation Technologies Development Forum
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
(RTDF) Permeable Barriers Group and the Interstate Technologies Regulatory Cooperation (ITRC)
Permeable Barriers Subgroup provided document review support for this demonstration.
3. TECHNICAL CONCEPT
A PRB consists of permeable reactive media installed in the path of a contaminant plume. The natural
groundwater flow through the permeable portion of the PRB brings the contaminants into contact with the
reactive media. The contaminants are degraded upon contact with the media and treated groundwater
emerges from the downgradient side of the PRB. Sometimes, impermeable "funnel" walls are installed
next to the permeable "gate(s)" containing the media; the funnel helps to capture additional groundwater
and channel it through the gate(s). A PRB design guidance document prepared by Battelle for AFRL
describes the concept, design, construction, and installation of PRB systems in considerable detail
(Gavaskar et al., 2000).
Based on column tests conducted with several alternative reactive media and Area 5 site groundwater, US
EPA-NERL reported that a pyrite-and-iron combination ranked the best (U.S. EPA, 1997). Because of its
potential for scrubbing oxygen and controlling pH in the iron-groundwater system, pyrite was expected to
provide the benefits of enhanced kinetics of CVOC degradation and reduced precipitation of inorganic
constituents. Precipitation of inorganic constituents, such as dissolved oxygen, carbonates, calcium, and
magnesium, in the reactive medium is generally anticipated to be a probable cause for any loss of
reactivity or hydraulic performance that the iron may encounter during long term operation. Precipitates
could potentially coat the reactive surfaces of granular iron and reduce reactivity and hydraulic
conductivity over time. Based on the U.S. EPA (1997) recommendation for the use of pyrite and iron to
control precipitation, Battelle designed and installed a funnel-and-gate type PRB with two gates. Both
gates have a reactive cell consisting of 100% granular iron. In addition, Gate 1 also incorporates a pre-
treatment zone (PTZ) consisting of 10% iron and sand; Gate 2 incorporates a PTZ consisting of 10%
pyrite and sand. The exit zone in both gates consists of 100% coarse sand. The construction of the PRB
was completed in January 1998.
The location and design of the barrier was also determined by detailed Area 5 site characterization and
modeling conducted in June 1997 to support the PRB and monitoring system design (Battelle, 1997). The
groundwater treatment targets forthis project are 5 (ig./L of PCE and TCE, 70 (ig/L ofcis-1,2
dichloroethene (cis-1,2 DCE), and 2 (ig/L of vinyl chloride (VC); these targets correspond to the U.S.
EPA-recommended maximum contaminant levels (MCLs) for the respective chlorinated volatile organic
compounds (CVOCs). An innovative construction technique involving caissons was used to install the
two gates down to about 40 ft bgs, which is beyond the reach of conventional backhoe installation.
4. ANALYTICAL APPROACH
Following installation, the reactive (geochemical) and hydraulic performance of the PRB were evaluated
primarily through two comprehensive monitoring events in July 1998 and June 1999 (Battelle, 2000a).
Monitoring events were conducted periodically throughout the demonstration to monitor a limited
number of operating parameters. At the end of 18 months of operation, core samples of the gate and
surrounding aquifer media were collected and analyzed for precipitate formation.
5. RESULTS
Monitoring results show that, to date, the PRB is functioning at an acceptable level in terms of capturing
groundwater, creating strongly reducing conditions, and achieving treatment targets. The treatment targets
at Dover AFB are 5 (ig/L of PCE and TCE, 70 (ig/L of cis 1,2-dichloroethene (DCE), and 2 (ig/L of vinyl
chloride (VC); DCE and VC are typical byproducts of PCE and TCE degradation process. The PTZs in
both gates succeeded in removing dissolved oxygen from the groundwater before it entered the reactive
cell. In addition, the use of pyrite did result in some degree of pH control while the groundwater was in
the PTZ of Gate 2. However, once the groundwater entered the reactive cell, the tendency of the iron to
raise the pH of the system overwhelmed any pH control effect achieved by the pyrite. Magnesium, nitrate,
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
and silica were the main inorganic species precipitating out of the low-alkalinity groundwater as it flowed
through the gates.
6. HEALTH AND SAFETY
A health and safety plan was prepared before construction started and was reviewed by Dover AFB and
all contractors. A pre-construction meeting was held at the site to discuss safety issues. Level D safety
measures and personal protective equipment (PPE) were used to address the minimal safety hazards
during construction. These consisted of a hard-hat and steel-toed shoes for workers at the site. When the
vibratory hammer was used to drive the caissons into the ground, workers used earplugs to protect
potential hearing loss. Entry of workers into the excavation was avoided by using a pre-fabricated frame
holding the monitoring well array that was inserted from the ground into the excavated gates. The
granular iron was placed in the gates with a tremie tube. No health and safety incidents occurred during
construction.
7. ENVIRONMENTAL IMPACTS
A photo-ionization detector was used to monitor ambient organic vapors during construction. Because of
the very low levels of organic contaminants present in the groundwater and soil at the location of the
PRB, there were no real concerns about environmental impacts. Extracted soil from the caisson was
transported to a nearby construction site for reuse.
8. COSTS
The initial capital investment incurred the pilot-scale PRB at Dover AFB Area 5 was a total of
US$739,000, including US$47,000 for the granular iron media and US$264,000 for the on-site
construction; site characterization, column testing, design, site preparation, and procurement accounted
for the rest of the cost. A long-term life cycle analysis of a full-scale PRB (expanded funnel-and-gate
system with four gates) and an equivalent pump-and-treat (P&T) system was conducted for the site.
Assuming that the iron medium would sustain its reactivity and hydraulic properties for at least 30 years,
the discounted net present value (NPV) of the long-term savings over 30 years of operation was estimated
to be approximately US$800,000, compared with using the P&T system. Given that the solvent plume is
likely to last for several decades or even centuries, the longer-term savings are significant.
9. CONCLUSIONS
A pilot-scale PRB was successfully designed and installed at Dover AFB to capture and treat a
chlorinated solvent plume to meet the desired clean up targets. The caisson method of installation was
found to be suitable for installing a PRB at relatively greater depths and in the midst of underground
utility lines. Monitoring shows that the PRB continues to meet its targets. One significant unknown is the
longevity of the PRB, that is, for how long will the iron medium continue to sustain it reactive and
hydraulic performance. Precipitates were found to be forming in the iron cell due to the level of inorganic
constituents measured in the groundwater. In the absence of longevity information, the cost analysis
described above was repeated assuming that the iron would have to be replaced every 5, 10, 20, or 30
years. This economic analysis showed that as long as the iron does not have to be replaced for at least 10
years, the PRB would be a less costly option compared to an equivalent P&T system at Area 5. Dover
AFB is currently considering an expansion of the system to capture more of the plume.
10. REFERENCES AND BIBLIOGRAPHY
1. Battelle, 2000. Design, Construction, and Monitoring of the Permeable Reactive Barrier in Area 5 at
Dover Air Force Base. Final report prepared for the Air Force Research Laboratory by Battelle,
Columbus, Ohio, USA on March 31, 2000.
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2. Battelle, 1997. Design/Test Plan: Permeable Barrier Demonstration at Area 5, Dover AFB. Prepared
for Air Force Research Laboratory by Battelle, Columbus, Ohio.
3. Gavaskar, A., N. Gupta, B. Sass, R. Janosy, and J. Hicks. Design Guidance for the Application of
Permeable Reactive Barriers for Groundwater Remediation. Prepared for Air Force Research
Laboratory by Battelle, Columbus, Ohio on March 31, 2000.
4. U.S. EPA, 1997. Selection of Media for the Dover AFB Field Demonstration of Permeable Barriers
to Treat Groundwater Contaminated with Chlorinated Solvents. Preliminary report to U.S. Air Force
for SERDP Project 107. August 4, 1997.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 14
Thermal Cleanup Using Dynamic Underground Stripping and Hydrous Pyrolysis/Oxidation
Location
LLNL Gasoline Spill Site,
Livermore, CA.
Visalia Pole Yard, Visalia, CA.
Project Status
Final Report
Contaminants
PAHs, diesel and
pentachlorophenol
(Visalia)
Gasoline (LLNL)
(TCE, solvents and fuels
at other sites)
Technology Type
Dynamic
underground
stripping and
hydrous pyrolysis/
oxidation
Technical Contacts
Robin L. Newmark
Lawrence Livermore National
Laboratory
L-208, P.O. Box 808
Livermore, Ca., 94550
United States
Tel: (925)-423-3644
Fax: (925)-422-3925
E-mail: newmark@llnl.gov
Paul M. Beam
U.S. Department of Energy
19901 Germantown Road
Germantown, MD 20874-1290
United States
Tel: 301-903-8133
Fax: 301-903-3877
E-mail:
Project Dates
Accepted 1998
Final Report 1999
Media
Groundwater and soil
Costs Documented?
Yes
Project Size
Full-scale:
Livermore: 100,000yd3
(76,000 m3)
Visalia: 4.3 acres, >130
ft deep (app. 600,000
m3)
Results Available?
Yes
Project 14 was completed in 1999.
1. INTRODUCTION
In the early 1990s, in collaboration with the School of Engineering at the University of California,
Berkeley, Lawrence Livermore National Laboratory developed dynamic underground stripping (DUS), a
method for treating subsurface contaminants with heat that is much faster and more effective than
traditional treatment methods. More recently, Livermore scientists developed hydrous pyrolysis/oxidation
(HPO), which introduces both heat and oxygen to the subsurface to convert contaminants in the ground to
such benign products as carbon dioxide, chloride ion, and water. This process has effectively destroyed all
contaminants it encountered in laboratory tests.
With dynamic underground stripping, the contaminants are vaporized and vacuumed out of the ground,
leaving them still to be destroyed elsewhere. Hydrous pyrolysis/oxidation technology takes the cleanup
process one step further by eliminating the treatment, handling, and disposal requirements and destroying
the contamination in the ground. When used in combination, HPO is especially useful in the final
"polishing" of a site containing significant free-product contaminant, once the majority of the
contaminant has been removed.
2. BACKGROUND
A. Lawrence Livermore National Laboratory (LLNL) Gasoline Spill Site:
LLNL recently completed the cleanup and closure of a moderate-sized spill site in which thermal cleanup
methods, and the associated control technologies, were used to remediate nearly 8,000 gallons (30,000 L)
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of gasoline trapped in soil both above and below the standing water table. The spill originated from a
group of underground tanks, from which an estimated 17,000 gallons (64,000 L) of gasoline leaked
sometime between 1952 and 1979. The gasoline penetrated the soil, eventually reaching the water table,
where it spread out. Gasoline trapped up to 30 ft (9 m) below the water table was there due to a rise in the
water table after the spill occurred, with the gasoline held below water by capillary forces in the soil.
Groundwater contamination extended about 650 ft (200 m) beyond the central spill area. The soils at the
site are alluvial, ranging from very fine silt/clay layers to extremely coarse gravels, with unit
permeabilities ranging over several orders of magnitude. The site was prepared for long-term groundwater
pump-and-treat with vapor extraction; recovery rates prior to thermal treatment were about 2.5 gal/day 9.5
L/day).
B. Visalia Pole Yard:
In 1997, DUS and HPO were applied for cleanup of a 4.3 acre (17,000 m2) site in Visalia, California,
owned by Southern California Edison Co. (Edison). The utility company had used the site since the 1920s
to treat utility poles by dipping them into creosote, a pentachlorophenol compound, or both. By the 1970s,
it was estimated that 40-80,000 gallons (150,000-300,000 L) of DNAPL product composed of pole-
treating chemicals (primarily creosote and pentachlorophenol) and an oil-based carrier fluid had
penetrated the subsurface to depths of approximately 100 ft (30 m), 40 ft (12 m) below the water table.
Edison had been conducting pump and treat operations at the site for nearly 20 years. While this activity
had successfully reduced the size of the offsite groundwater contaminant plume, it was not very effective
at removing the NAPL source. Prior to thermal treatment, about 10 Ib. (4.5 kg) of contaminant was being
recovered per week. Bioremediation of the free-organic liquids is expected be prohibitively slow
(enhanced bioremediation was predicted to take at least 120 years).
3. TECHNICAL CONCEPT
A. Dynamic Underground Stripping (DUS): Mobilization and Recovery
Dynamic Underground Stripping combines two methods to heat the soil, vaporizing trapped
contaminants. Permeable layers (e.g., gravels) are amenable to heating by steam injection, and
impermeable layers (e.g., clays) can be heated by electric current. These complementary heating
techniques are extremely effective for heating heterogeneous soils; in more uniform conditions, only one
or the other may be applied. Once vaporized, the contaminants are removed by vacuum extraction. These
processes - from the heating of the soil to the removal of the contaminated vapor - are monitored and
guided by underground imaging, which assures effective treatment through in situ process control.
B. Hydrous Pyrolysis/Oxidation (HPO): In Situ Destruction
At temperatures achieved by steam injection, organic compounds will readily oxidize over periods of
days to weeks. By introducing both heat and oxygen, this process has effectively destroyed all petroleum
and solvent contaminants that have been tested in the laboratory. All that is required is for water, heat,
oxygen, and the contaminant to be together; hence the name. After the free organic liquids are gone, this
oxidation will continue to remove low-level contamination. The oxidation of contaminants at steam
temperatures is extremely rapid (less than one week for TCE and two weeks for naphthalene) if sufficient
oxygen is present. In HPO, the dense, nonaqueous-phase liquids and dissolved contaminants are
destroyed in place without surface treatment, thereby improving the rate and efficiency of remediation by
rendering the hazardous materials benign by a completely in situ process. Because the subsurface is
heated during the process, HPO takes advantage of the large increase in mass transfer rates, such as
increased diffusion out of silty sediments, making contaminants more available for destruction.
C. Underground Imaging: process control
Most subsurface environmental restoration processes cannot be observed while operating. Electrical
Resistance Tomography (ERT) has proven to be an excellent technique for obtaining near-real-time
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images of the heated zones. ERT gives the operator detailed subsurface views of the hot and cold zones at
their site on a daily basis. Heating soil produces such a large change in its electrical properties that it is
possible to obtain images between wells (inverted from low voltage electrical impulses passed between)
of the actual heated volumes by methods similar to CAT scans. Combined with temperature
measurements, ERT provides process control to ensure that all the soil is treated.
D. LLNL Gasoline Spill Site: DUS
The DUS application at the LLNL Gasoline Spill Site was designed to remove free-product NAPL. The
targeted volume was a cylinder about 120 ft (36 m) in diameter and 80 ft (24 m) high, extending from a
depth of 60 ft (18 m) to a depth of 140 ft (43 m). The water table is located at 100 ft (30 m). Due to the
presence of relatively thick clay-rich zones, both electrical heating and steam injection were required to
heat the target volume.
E. Visalia Pole Yard: DUS + HPO
Thermal treatment (DUS steam injection and vacuum extraction) was chosen for removal of the free
product contaminant. The overall objectives of thermal remediation of the Visalia Pole Yard are to
remove a substantial portion of the DNAPL contaminant at the site, thereby enhancing the bioremediation
of remaining contaminant. This is expected to significantly shorten the time to site closure as well as
improve the accuracy of the prediction of time to closure. As part of the final removal process, Edison is
also implementing hydrous pyrolysis (HPO), an in situ method of destroying organic contaminants using
small amounts of supplemental air or oxygen. The primary use of HPO at this site is for destruction of
residual pentachlorophenol, which will not readily steam strip due to high solubility and low vapor
pressure. The combination of rapid recovery and thermal destruction is expected to permit Edison to
achieve their cleanup goals, which included termination of groundwater treatment.
A series of noble gas tracer tests were conducted to verify the extent of HPO under field conditions.
Evidence of hydrous pyrolysis/oxidation came from the disappearance of dissolved oxygen, the
appearance of oxidized intermediate products, the production of CO2, and the distinct isotopic signature
of the carbon in the CO2 produced, indicating contaminant origin. These results constrain the destruction
rates throughout the site, and enable site management to make accurate estimates of total in situ
destruction based on the recovered carbon using the system-wide contaminant tracking system being used
on the site.
4. ANALYTICAL APPROACH
Standard laboratory analyses were performed on all samples unless noted specifically in the references.
5. RESULTS
A. LLNL Gasoline Spill Site:
During 21 weeks of thermal treatment operations conducted over about a year, DUS treatment removed
more than 7600 gallons (29,000 L) of an estimated 6200 gallons (23,000 L) of gasoline trapped in soil
both above and below the water table. Prior to thermal treatment, separate phase contamination extended
to >120 ft (37 m) deep. Approximately 100,000 yd (76,000 m3) were cleaned. The maximum removal
rate was 250 gallons (950 L) of gasoline a day. The process was limited only by the ability to treat the
contaminated fluids and vapors on the surface.
Dynamic underground stripping removed contaminants 50 times faster than with the conventional pump-
and-treat process. The cleanup, estimated to take 30 to 60 years with pump-and-treat, was completed in
about one year. As of 1996, following removal of more than 99% of the contaminant, and achievement of
Maximum Contaminant Limit (MCL) levels in groundwater for five of the six contaminants, the site is
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being passively monitored under an agreement with the California Regional Water Quality Control Board
(RWQCB), California EPA's Department of Toxic Substances Control (DTSC), and the Federal EPA
Region 9. These regulatory agencies declared that no further remedial action is required.
The initial objective of the LLNL DUS demonstration was to remove the separate phase gasoline from the
treatment area. Not only was the separate phase gasoline removed, but the groundwater contamination
was reduced to or near the regulatory limits. Thermal treatment under these conditions did not sterilize the
site, and instead led to the establishment of flourishing indigenous microbial ecosystems at soil
temperatures up to 90°C. The very positive response of regulators, who provided quick closure
authorization for the site, indicates that these methods will be accepted for use.
B. Visalia Pole Yard:
During the first six weeks of thermal remediation operations, between June and August 1997,
approximately 300,000 pounds (135 metric tons) of contaminant was either removed or destroyed in
place, a rate of about 46,000 pounds (22 metric tons) per week. That figure contrasts sharply with the 10
pounds (0.003 metric ton) per week that Edison had been removing with conventional pump and treat
cleanup methods. In fact, the amount of hydrocarbons removed or destroyed in place in those six weeks
was equivalent to 600 years of pump-and-treat, about 5,000 times the previous removal rate.
Edison achieved their initial goal of heating over 500,000 yd3 (380,000 m3) to at least a temperature of
100 °C by the beginning of August 1997. Uniform heating of both aquifer and aquitard materials was
achieved. At this point, about 20,000 gallons (76,000 L) of free-product liquid had been removed. Vapor
and water streams continued to be saturated with product. Continued destruction by HPO was indicated
by high levels of carbon dioxide (0.08 - 0.12% by volume) removed through vapor extraction. Initial
destruction accounted for about 300 Ib/day 136 kg/day) of contaminant being destroyed via HPO.
Operations were changed to a huff and puff mode, where steam is injected for about a week, and then
injection ceases for about a week while extraction continues. Maximum contaminant removal is obtained
during this steam-off period as the formation fluids flash to steam under an applied vacuum.
In September, 1997, following the initial contaminant removal by steam injection and vacuum extraction,
air was injected along with the steam to enhance hydrous pyrolysis of the remaining contaminant. In situ
destruction rates increased to about 800 Ib/day (360 kg/day). Recovery/destruction rates matched
expectations. By the summer of 1998, decreasing contaminant concentrations indicated that the bulk of
the contaminant had been removed from the main treatment volume. Groundwater concentrations
indicated that the site was being cleaned from the periphery inward, with all but two wells showing
contaminant concentrations similar to the pre-steam values by September 1998. Active thermal
remediation of this zone was nearing completion. At this point, Edison chose to begin injecting steam into
a deeper aquifer to heat and remove the remaining contamination that had leaked into the overlying silty
aquitard, which represented the "floor" of the initial treatment zone. Contaminant is being recovered from
this aquitard today.
In the ensuing months, recovery rates have remained high. As of March 1999, over 960,000 Ib (440,000
kg) or 116,000 gallons of contaminant had been removed or destroyed. About 18% of the total has been
destroyed in situ via HPO. Contaminant concentrations in the recovery wells are decreasing.
Edison plans to continue steam injection through the end of June 1999. This will be followed by
groundwater pumping, vacuum extraction and air injection to enhance HPO and bioremediation.
Monitoring of groundwater concentrations is expected to continue for a period of 2 to 5 years.
6. HEALTH AND SAFETY
This high-energy system needs to be handled in accordance with standard safety procedures. Monitoring
of air emissions has revealed low emissions with no worker safety or public health impacts.
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7. ENVIRONMENTAL IMPACTS
Permits were required for water discharge (treated effluent) and NOX emissions from the boilers. The site
is being remediated under a state-lead Remedial Action Plan (RAP). Vapor is destroyed in the boilers
under air permit from the regional air board. Standard regional groundwater monitoring is conducted to
ensure public health protection.
8. COSTS
A. DUS at the LLNL Gasoline Spill Site
The first application of dynamic underground stripping at the Livermore gasoline spill site in 1993 cost
about $110 per cubic yard ($140 per cubic meter); removing the additional research and development
costs suggested the project could have been repeated for about $65 per cubic yard ($85 per cubic meter).
The alternatives would have been significantly higher. Because contamination at the gasoline spill at the
Livermore site had migrated downward over 130 ft (40 meters), digging up the contaminated soil and
disposing of it would have cost almost $300 per cubic yard ($400 per cubic meter). Soil removal and
disposal costs are more typically in the range of $100 to $200 per cubic yard ($130 to $260 per cubic
meter); pump-and-treat method costs are as high as or higher than soil removal costs.
B. DUS and HPO at the Visalia Pole Yard
Use of DUS and HPO in combination can permit huge cost savings because HPO eliminates the need for
long-term use of expensive pump and treat treatment facilities by converting some contaminants to benign
products in situ and mobilizing other contaminants. Site operators can adjust process time to enhance
removal DUS or in situ destruction through HPO. Because the treatment is simple, it can be readily
applied to large volumes of earth.
Edison has projected the life-cycle cost of steam remediation at the Visalia pole yard to be under $20
million, which includes all construction, operation and monitoring activities. The total treatment zone
includes about 800,000 yd3 (600,000 m3) of which about 400,000 yd3 (300,000 m3) contained DNAPL
contamination. Approximately $4.2 million was spent on capital engineering, design, construction, and
startup. In addition, about $12 million had been spent on operations, maintenance, energy (gas and
electric), monitoring, management, engineering support, and regulatory interface by the end of 1998.
Since Edison (the site owner) has acted as primary site operator for the cleanup, the aforementioned
project costs do not reflect a profit in the overhead costs. Post-steaming operations will consist of the
operation of the water treatment system for an expected duration of two to five years to demonstrate
compliance with the California State EPA Remediation Standards. The annual operations and
maintenance costs for the water treatment plant is $1.2 million. The previously-approved cleanup plan of
pump and treat with enhanced bioremediation was expected to cost $45 million (in 1997 US dollars) for
the first 30 years; it was expected to take over 120 years to complete the cleanup.
The Visalia pole yard cleanup is the only commercial application of this method to date, but indications
are that large-scale cleanups with hydrous pyrolysis/oxidation may cost less than $25 per cubic yard
($33/m3), an enormous savings over current methods. Perhaps the most attractive aspect of these
technologies is that the end product of a DUS/HPO cleanup with bioremediation as a final step is
expected to be a truly clean site.
9. CONCLUSIONS
Breakthrough cleanups of seemingly intractable contaminants are now possible using a combined set of
thermal remediation and monitoring technologies. This "toolbox" of methods provides a rapid means to
clean up free organic liquids in the deep subsurface. Previously regarded as uncleanable, contamination of
this type can now be removed in a period of 1-2 years for a cost less than the many-decade site
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
monitoring and pumping methods it replaces. The groundwater polishing by HPO provides the means to
completely clean serious NAPL-contaminated sites.
The gasoline spill demonstration clearly showed that thermal methods can quickly and effectively clean a
contaminated site. With respect to the Visalia Pole Yard cleanup, tremendous removal rates have been
achieved. More than 970,000 Ib. of contaminants was removed or destroyed in about 20 months of
operations; previous recovery amounted to 10 Ib/week. Contaminant concentrations are dropping in the
extraction wells; the site is cleaning from the periphery inward. Site management plans to terminate active
thermal treatment soon, returning to pumping and monitoring the site. The expectations are that
groundwater treatment will no longer be necessary after a few years.
The Visalia field tests confirmed in situ HPO destruction in soil and ground water at rates similar to those
observed in the laboratory, under realistic field remediation conditions. HPO appears to work as fast as
oxygen can be supplied, at rates similar to those measured in the laboratory. The predictive models used
to design HPO steam injection systems have been validated by using conservative tracers to confirm
mixing rates, oxygen consumption, CO2 release, and effects of real-world heterogeneity. Accurate field
measurements of the critical fluid parameters (destruction chemistry, oxygen content, steam front
location) were demonstrated, using existing monitoring wells and portable data systems with minimal
capital cost.
Several sites are designing DUS/HPO applications similar to Visalia. These include both solvent and
pole-treating chemical contaminated sites, ranging in depth from relatively shallow (<40 ft (10 m)) to
relatively deep (>185 ft (56 m)). In January 1999, steam injection began at a relatively shallow (>35 ft (11
m)) site in Ohio in which DNAPL TCE is being removed.
10. REFERENCES AND BIBLIOGRAPHY
1. Aines, R.D.; Leif, F.; Knauss, K.; Newmark, R.L.; Chiarappa, M.; Davison, M.L.; Hudson, G.B.,
Weidner, R.; and Eaker, C.; Tracking inorganic carbon compounds to quantify in situ oxidation of
polycyclic aromatic hydrocarbons during the Visalia Pole Yard hydrous pyrolysis/oxidation field test,
1998 (in prep).
2. Cummings, Mark A.; Visalia Steam Remediation Project: Case Study of an Integrated Approach to
DNAPL Remediation. Los Alamos National Laboratory Report, LA-UR-9704999; 1997; 9pp.
3. Knauss, Kevin G.; Aines, Roger D.; Dibley, Michael J.; Leif, Roald N.; Mew, Daniel A.; Hydrous
Pyrolysis/Oxidation: In-Ground Thermal Destruction of Organic Contaminants. Lawrence Livermore
National Laboratory, Report, UCRL-JC 126636, 1997; 18pp.
4. Knauss, Kevin G.; Dibley, Michael J.; Leif, Roald N.; Mew, Daniel A.; Aines, Roger D. "Aqueous
Oxidation ofTrichloroethene (TCE): A Kinetic and Thermodynamic Analysis". In Physical, Chemical
and Thermal Technologies, Remediation of Chlorinated and Recalcitrant Compounds, Proceeding of
the First International Conference on Remediation of Chlorinated and Recalcitrant Compounds;
Wickramanayake, G.B., Hinchee, R.E., Eds.; Battelle Press, Columbus, OH, 1998a;pp359-364. Also
available as Lawrence Livermore National Laboratory, Report, UCRL-JC-129932, 1998; 8 pp.
5. Knauss, Kevin G.; Dibley, Michael J.; Leif, Roald N.; Mew, Daniel A.; Aines, Roger D. "Aqueous
Oxidation ofTrichloroethene (TCE): A Kinetic analysis. " Accepted for Publication, Applied
Geochemistry; 1998b.
6. Knauss, Kevin G.; Dibley, Michael J.; Leif, Roald N.; Mew, Daniel A.; Aines, Roger D. "Aqueous
Oxidation ofTrichloroethene (TCE) and Tetrachloroethene (PCE) as a Function of Temperature and
Calculated Thermodynamic Quantities, Submitted to Applied Geochemistry; 1998c.
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7. Leif, RoaldN.; Chiarrappa, Marina; Aines, Roger D.; New mark Robin L.; andKnauss, Kevin G. "In
Situ Hydrothermal Oxidative Destruction ofDNAPLS in a Creosote Contaminated Site. " In Physical,
Chemical and Thermal Technologies, Remediation of Chlorinated and Recalcitrant Compounds,
Proceeding of the First International Conference on Remediation of Chlorinated and Recalcitrant
Compounds; Wickramanayake, G.B., Hinchee, R.E., Eds.; BattellePress, Columbus, OH, 1998;pp
133-138. Also available as Lawrence Livermore National Laboratory, Report, UCRL-JC-129933,
1998a; 8pp.
8. Leif, RoaldN.; Knauss, Kevin G.; and Aines, Roger D.; Hydrothermal Oxidative Destruction of
Creosote and Naphthalene, Lawrence Livermore National Laboratory, Report, UCRL-JC, 1998b 21
pp (in prep).
9. Leif, Roald N.; Aines, Roger D.; Knauss, Kevin G. Hydrous Pyrolysis of Pole Treating Chemicals: A)
Initial Measurement of Hydrous Pyrolysis Rates for Naphthalene and Pentachlorophenol; B)
Solubility ofFlourene at Temperatures Up To 150°C; Lawrence Livermore National Laboratory,
Report, UCRL-CR-129938, 1997a; 32pp.
10. Leif, RoaldN.; Knauss, Kevin G.; Mew, Daniel A.; Aines, Roger D. Destruction of 2,2', 3-
Trichlorobiphenyl in Aqueous Solution by Hydrous Pyrolysis / Oxidation (HPO). Lawrence
Livermore National Laboratory, Report, UCRL-ID 129837, I997b; 21 pp.
11. MSB Technology Applications, Inc., "Dynamic Underground Stripping and Hydrous
Pyrolysis/Oxidation Cost Analysis", report prepared for the U.S. Department of Energy, HMP-44,
June, 1998.
12. Newmark, R.L., ed., Dynamic Underground Stripping Project: LLNL Gasoline Spill Demonstration
Report; Lawrence Livermore National Laboratory, Report UCRL - ID - 116964, July, 1994 (1600
pages).
13. Newmark, Robin L.; Aines, Roger D.; Dumping Pump and Treat: Rapid Cleanups Using Thermal
Technology. Lawrence Livermore National Laboratory, Report, UCRL-JC 126637, 1997; 23 pp.
14. Newmark, R.L., R. D. Aines, G. B. Hudson, R. Leif, M. Chiarappa, C. Carrigan, J. Nitao, A. Elsholz,
C. Eaker, R. Weidner and S. Sciarotta, In Situ destruction of contaminants via hydrous pyrolysis/
oxidation: Visalia field test, Lawrence Livermore National Laboratory, Report UCRL-ID-132671,
1998; 45 pp.
15. Newmark, R.L., R. D. Aines, G. B. Hudson, R. Leif, M. Chiarappa, C. Carrigan, J. Nitao, A. Elsholz,
and C. Eaker, 1999. An integrated approach to monitoring a field test of in situ contaminant
destruction, Symposium on the Application of Geophysics to Engineering and Environmental
Problems (SAGEEP) '99, Oakland, CA, March 15-18, 1999, 527-540.
16. Ramirez, A.L., W. D. Daily and R. L. Newmark, Electrical resistance tomography for steam injection
monitoring and process control, Journal of Environmental and Engineering Geophysics, (July, 1995),
v. 0,no.l, 39-52.
17. Udell, K and McCarter, R (1996) Treatability Tests of Steam Enhanced Extraction for the Removal of
Wood Treatment Chemicals from Visalia Pole Yard Soils, University of California, Report to
Southern California Edison. ()
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January 2002
Project No. 15
Phytoremediation of Chlorinated Solvents
Location
Aberdeen Proving Grounds, Edgewood
Area J-Field Site, Edgewood, MD
Edward Sears Site,
New Gretna, NJ
Carswell Air Force Base,
Fort Worth, TX
Project Status
Final Report
Media
Groundwater
Technology Type
Phytoremediation
Technical Contacts
Harry Compton (Aberdeen Site)
U.S. EPA, ERT(MSIOI)
2890 Woodbridge Avenue
Edison, NJ 08837-3679
Tel: 732-321-6751
Fax: 732-321-6724
E-mail: compton.harry@epa.gov
Steve Hirsh (Aberdeen Site)
U.S. EPA, Region 3 (3HS50)
1650 Arch Street
Philadelphia, PA 19103-2029
Tel: 215-814-3352
E-mail: hirsh.stcvcn@cpa.gov
George Prince (Edward Sears Site)
U.S. EPA, ERT(MSIOI)
2890 Woodbridge Avenue
Edison, NJ 08837-3679
Tel: 732-321-6649
Fax: 732-321-6724
E-mail: prince.george@epa.gov
Greg Harvey (Carswell AFB Site)
U.S. Air Force, ASC/EMR
1801 10th Street - Area B
Wright Patterson AFB, OH
Tel: 93 7-25 5-7716 ext. 302
Fax: 937-255-4155
E-mail: Gregory.Harvey@wpafb.af.mil
Project Dates
Accepted 1998
Contaminants
Chlorinated solvents: TCE, 1,1,2,2-
TCA, PCE, and DCE
Costs Documented?
Yes (preliminary)
Project Size
Full-scale field
demonstration
Results Available?
Yes (preliminary)
Project Reports
Available upon completion of projects. When available,
these reports can be obtained from the National Service
Center for Environmental Publications (NCEPI), P.O. Box
42419, Cincinnati, OH 42542-8695; tel: (800) 490-9198, or
(513)489-8695.
Project 15 was completed in 1999.
1. INTRODUCTION
The efficacy and cost of phytoremediation to clean up shallow groundwater contaminated with
chlorinated solvents (primarily trichloroethylene), is being evaluated at the field scale in demonstration
projects at Aberdeen Proving Grounds Edgewood Area J-Field Site in Edgewood, Maryland, the Edward
Sears site in New Gretna, New Jersey, and Carswell Air Force Base in Fort Worth, Texas. These projects
will demonstrate the use of hybrid poplars to hydraulically control the sites and ultimately to remove the
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volatile organic compounds (VOCs) from the groundwater. When completed, these projects will allow a
comparison of phytoremediation at three sites under varied conditions within different climatic regions.
2. SUMMARY AND LATEST OBSERVATIONS
At the Aberdeen Proving Ground site, a process called deep rooting is being used to achieve hydraulic
influence. Hybrid poplar trees were initially planted in the spring of 1996 at five to six feet below ground
surface to maximize groundwater uptake. The field demonstration and evaluation will be for a five year
period. The U.S. Geological Survey has estimated that hydraulic influence will occur when 7,000 gallons
of water per day are removed from the site.
Several trees were excavated in the fall of 1998 to determine root growth. The tree roots were found to be
confined to the hole in which they were placed. In an attempt to increase root depth and width, new trees
were planted in holes of varying sizes and depths.
The latest field data indicates that hydraulic influence is occurring. Current tree uptake is 1,091 gallons
(4,129 liters) per day and is expected to increase to 1,999 gallons (7,528 liters) at the end of 30 years.
Contaminant uptake is minimal at this time but is expected to improve as the trees mature. Groundwater
sampling indicates that the contaminated plume has not migrated off-site during the growing season and
sampling data showed non-detectable emissions from transpiration gas. There are several on-going
studies to determine if deleterious compounds retained in the leaves and soil could pose risks to
environmental receptors.
At the Edward Sears site, deep rooting was also used to maximize groundwater uptake. Beginning in
December 1996, hybrid poplar trees were planted nine feet below ground surface. In addition, some trees
were planted along the boundary of the site at depth of only 3 feet to minimize groundwater and rainwater
infiltration from off-site. Groundwater monitoring will continue in 2000. A November sampling is
scheduled to determine if contaminant concentrations recover during the dormant season.
There were substantial reductions in dichloromethane and trimethylbenzene concentrations during the
1998 growing season. For example, dichloromethane was reduced to 615 parts per billion (ppb) from
490,000 ppb at one location and to a non-detect level from up to 12,000 ppb at another location;
trimethylbenzene was reduced to 50 ppb from 1,900 at one location. There is also indication of anaerobic
dechlorination in the root zone as the level of PCE dropped and TCE increased.
There seems to have been an adverse impact on tree growth in areas with high VOCs concentrations
during the initial two growing seasons. However, in the third growing season, the rate of growth has
increased significantly but the trees have yet to achieve the height and diameter of trees planted in
uncontaminated areas. Evapotranspiration gasses were collected in sampling bags during the hottest
periods of the day and were analyzed for target compounds. Only low levels of toluene (8 to 11 ppb) were
detected. Soil gas flux measurements indicated that no contaminants are released into the air from the soil.
At the Carswell Air Force Base site, the phytoremediation system is a low-cost, low-maintenance system
that is consistent with a long-term contaminant reduction strategy. Trees were planted in trenches as a
short rotation woody crop employing standard techniques developed by the U.S. Department of Energy.
The phytoremediation system was designed to intercept and remediate a chlorinated ethene contaminant
plume. The system relies on two mechanisms to achieve this goal: hydraulic removal of contaminated
groundwater through tree transpiration and biologically mediated in-situ reductive dechlorination of the
contaminant. The tree root systems introduce organic matter into the aquifer system, which drives the
microbial communities in the aquifer from aerobic to anaerobic communities that support this reductive
dechlorination.
The first three growing seasons resulted in a remediation system that reduced the mass of contaminants
moving through the site. The maximum observed reduction in the mass flux of TCE across the
downgradient end of the site during the three-year demonstration period was 11 percent. Increases in
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hydraulic influence and reductive dechlorination of the dissolved TCE plume are expected in out years,
and may significantly reduce the mass of contaminants. Modeling results indicate that hydraulic influence
alone may reduce the volume of contaminated groundwater that moves offsite by up to 30 percent. The
decrease in mass flux that can be attributed to in situ reductive dechlorination has yet to be quantified.
3. SITE DESCRIPTION
Aberdeen Proving Grounds, Maryland
The site is located at the tip of the Gunpowder Neck Peninsula, which extends into the Chesapeake Bay.
The Army practiced open trench (toxic pits) burning/detonation of munitions containing chemical agents
and dunnage from the 1940s to the 1970s. Large quantities of decontaminating agents containing solvents
were used during the operation. The surficial groundwater table had been contaminated with solvents
(1,1,2,2-TCA, TCE, DCE) at levels up to 260 parts per million (ppm). The contamination is 5 to 40 ft (3.5
to 13 m) below ground surface. The plume is slow-moving due to tight soils and silty sand. The impacted
area is a floating mat-type fresh water marsh approximately 500 ft (160 m) southeast. A low
environmental threat is presented by the contaminant plume.
Edward Sears Site, New Jersey
From the mid-1960s to the early 1990s, Edward Sears repackaged and sold expired paints, adhesives,
paint thinners, and various military surplus materials out of his backyard in New Gretna, NJ. As a result,
toxic materials were stored in leaky drums and containers on his property for many years. The soil and
groundwater were contaminated with numerous hazardous wastes, including dichloromethane (up to
490,000 ppb), tetrachloroethylene (up to 160 ppb), trichloroethylene (up to 390 ppb), trimethylbenzene
(up to 2,000 ppb), and xylenes (up to 2,700 ppb). There is a highly permeable sand layer from 0 to 5 ft ( 0
to 1.6 m) below ground surface (bgs). Below that exists a much less permeable layer of sand, silt, and
clay from 5 to 18 (1.6 to 6 m) ft bgs. This silt, sand, and clay layer acts as a semi-confining unit for water
and contaminants percolating down toward an unconfined aquifer from 18 to 80 ft (6 to 26 m) bgs. This
unconfmed aquifer is composed primarily of sand and is highly permeable. The top of the aquifer is about
9 ft (3 m) bgs, which lies in the less permeable sand, silt, and clay layer. The top of the aquifer is
relatively shallow and most of the contamination is confined from 5 to 18 ft 1.6 to 6 m) bgs.
Carswell AFB, Texas
The U.S. Air Force Plant 4 (AFP4) and adjacent Naval Air Station, Fort Worth, Texas, has sustained
contamination in an alluvial aquifer through the use of chlorinated solvents in the manufacture and
assembly of military aircraft. Dispersion and transport of TCE and its degradation products have
occurred, creating a plume of contaminated groundwater. This project is led by the U.S. Air Force
(USAF) and is being conducted as part of the Department of Defense's (DOD's) Environmental Security
Technology Certification Program (ESTCP), as well as the U.S. Environmental Protection Agency's
(U.S. EPA's) Superfund Innovative Technology Evaluation (SITE) Program. Planting and cultivation of
Eastern Cottonwood (Populus deltoides) trees above a dissolved TCE plume in a shallow (under 12 ft)
aerobic aquifer took place in spring 1996. The trees were planted as a short rotation woody crop
employing standard techniques developed by the U.S. Department of Energy (DOE) to grow biomass for
energy and fiber. Data are being collected to determine the ability of the trees to perform as a natural
pump-and-treat system.
4. DESCRIPTION OF THE PROCESS
Aberdeen Proving Grounds, Maryland
Phytoremediation was selected to provide both hydraulic influence of the groundwater plume and mass
removal of contaminants.
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January 2002
The plantation area being monitored is approximately 2034 m2 and contains 156 viable poplars. 1,1,2,2-
TCA and TCE are 90 percent of the contaminants (total approximately 260 ppm solvents). USGS
estimated 7000 gals/day removal would achieve hydraulic influence. The duration of evaluation will be
five years.
Process Description —
After agronomic assessment, two-year-old hybrid poplar 510 trees were planted 5 to 6 ft (1.6 to 2 m) deep
in the spring of 1996. Surficial drainage system was installed to remove precipitation quickly and allowed
trees to reach groundwater.
Various sampling methods were employed during the 1998 growing season to determine if project
objectives are being met. The methodologies which yielded the most valuable data include: groundwater
sampling; sap flow monitoring; tree transpiration gas and condensate sampling; and exposure pathway
assessments. In addition to field sampling activities, new trees were planted on the site in October 1998 to
increase the phytoremediation area and assess the usefulness of native species for phytoremediation.
Figure 1: Aberdeen Proving Grounds, Maryland
\>Go/f Cart Path
WJEGTA512
WJEGTA510
* :
WJEGTA511
*
Meters
EXPLANATION
• MONITORING WELL:
Well number indicates well
was sampled throughout the
entire location
D STREAM-STAGE
GAGE
D TENSIOMETER
NEST
MONITORING WELL
WITH WATER-LEVEL
RECORDER
WEATHER
STATION
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Edward Sears Site, New Jersey
In December 1996, 118 hybrid poplar saplings (Populus charkowiiensis x incrassata, NE 308) were
planted in a plot approximately one-third of an acre in size.
Poplar trees that were left over after the deep rooting was completed were planted to a depth of 3 ft (1 m),
or shallow rooted. These trees were planted along the boundary of the site to the north, west, and east
sides of the site. These trees will minimize groundwater and rainwater infiltration from off-site.
Process Description—
The trees were planted 10 ft (3 m) apart on the axis running from north to south and 12.5 ft (4 m) apart on
the east-west axis. The trees were planted using a process called deep rooting: 12-ft (4 m) trees were
buried nine feet under the ground so that only about 2 to 3 ft (0.6 to 1 m) remained on the surface. This
was done to enhance deep rooting of poplar trees in the zone of contamination, and to maximize uptake of
groundwater compared to surface water.
Monitoring of the site includes semi-annual analysis of groundwater, soils, soil gas, and
evapotranspiration gas. Continued growth measurements will also be made as the trees mature. Site
maintenance also involves fertilization, and control of insects, deer and unwanted vegetation.
Carswell AFB, Texas
This demonstration investigated eastern cottonwood trees planted as a short rotation woody crop to help
remediate shallow aerobic TCE-contaminated groundwater in a subhumid climate.
The study determined the ability of the planted system to hydraulically control the migration of
contaminated groundwater, as well as biologically enhance the subsurface environment to optimize in situ
reductive dechlorination of the chlorinated ethenes.
In addition to investigating changes in groundwater hydrology and chemistry, the trees were studied to
determine important physiological processes such as rates of water usage, translocation and volatilization
of volatile compounds, and biological transformations of chlorinated ethenes within the plant organs.
Since planted systems may require many years to reach their full remediation potential, the study also
made use of transpiration and hydrologic predictive models to extrapolate findings to later years.
A mature cottonwood tree (about 20 years old) and section of the underlying aquifer located proximal to
the study area were investigated to provide evidence of transpiration rates and geochemical conditions
that eventually may be achieved at the site of the planted trees.
This project was evaluated for its ability to reduce the mass of TCE that is transported across the
downgradient end of the site (mass flux). The following performance objectives were established: (1)
there would be a 30 percent reduction in the mass of TCE in the aquifer that is transported across the
downgradient end of the site during the second growing season, as compared to baseline TCE mass flux
calculations; and (2) there would be a 50 percent reduction in the mass of TCE in the aquifer that is
transported across the downgradient end of the site during the third growing season, as compared to
baseline TCE mass flux calculations. To evaluate the primary claim, groundwater levels were monitored
and samples were collected and analyzed for TCE concentrations over the course of the study.
Secondary objectives were addressed to help understand the processes that affect the downgradient
migration of TCE in the contaminated aquifer at the site, as well as to identify scale-up issues. These
secondary objectives include: determine tree growth rates and root biomass; analyze tree transpiration
rates to determine current and future water usage; analyze the hydrologic effects of tree transpiration on
the contaminated aquifer; analyze contaminant uptake into plant organ systems; evaluate geochemical
indices of subsurface oxidation-reduction processes; evaluate microbial contributions to reductive
dechlorination; collect data to determine implementation and operation costs for the technology; and
determine plant enzyme levels for various mature trees in the local area.
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Process description —
In April 1996, the U.S. Air Force planted 660 eastern cottonwoods in a one acre area. The species P.
deltoides was chosen over a hybridized species of poplar because it is indigenous to the region and has
therefore proven its ability to withstand the Texas climate, local pathogens, and other localized variables
that may affect tree growth and health.
Two sizes of trees were planted: whips and 5-gallon (20 L) buckets. The 5-gallon bucket trees are
expected to have higher evapotranspiration rates due to their larger leaf mass.
Site managers plan to increase monitoring at the site to include a whole suite of water, soil, air, and tree
tissue sample analysis. Some of the more unique data colleted (in relation to the other case study sites) are
analyses of microbial populations and assays of TCE degrading enzymes in the trees.
5. RESULTS AND EVALUATION
Aberdeen Proving Grounds, Maryland
1. Examination of groundwater level data revealed an area of depression within the poplar plantation
indicating that hydraulic influence is occurring. Currently, the trees are removing approximately
1,091 gallons per day (4,129 L/day) and at the end of 30 years are expected to remove approximately
1,999 gallons per day (7,528 L/day).
2. Groundwater sampling indicated that the contaminated plume has not migrated off-site during the
growing seasons.
3. There are no ecological impacts that are attributable to the plantation area. Sampling data have shown
non-detectable off-site migration of emissions from transpiration gas.
4. Peak transpiration is estimated to occur in approximately 10 to 15 years.
5. Limitations include depth of contamination, but there are no limitations for concentrations of up to
260 ppm for solvents. Weather and growing season are the most influential factors.
6. Contaminant uptake is minimal at this time but is expected to improve as the trees mature.
7. A groundwater model is under development to quantify the degree of containment generated by the
trees. The model requires an accurate estimate of water withdrawal rates by the trees to determine if
phytoremediation will work as a remedial alternative for the site.
8. This demonstration project is on-going and will be further evaluated for efficacy and costs.
Groundwater samples and elevations were collected, seasonally from the on-site wells to determine VOC
concentrations and if trees were facilitating hydraulic influence of the plume. Results indicated that an
area of drawdown exists within the tree zone during the spring and summer when tree transpiration is the
greatest. In 1998, additional wells were installed using a Geoprobe® in order to more accurately assess
VOC concentrations and groundwater elevation. A groundwater model is currently being developed to
predict potential VOC removal by the trees and when complete hydraulic influence may be attained.
Given the success of the groundwater sampling, sampling objectives for 1999 included groundwater
elevation monitoring and sampling and a continued effort to refine the groundwater model.
Sap flow monitoring was performed to determine the amount of water being removed by individual trees.
In order to increase monitoring accuracy, new sap flow probes were purchased which are placed directly
into the tree tissue as opposed to resting on the trunk of the tree. Comparison of new equipment with
previous methods indicates that the new methodology provides an even more accurate estimation of net
transpiration rate with less data interference or "noise." Future sampling objectives for the site include
continued seasonal sap flow monitoring for the purposes of estimating transpiration rates.
Seasonal tree transpiration gas and condensate sampling continued in the 1998 sampling season to assess
the release of VOCs from the trees. Previous methods consisted of placing a 100-liter Tedlar® bag over a
section of branch and then sampling the gas and any condensate trapped within the bag. This method was
modified in 1998 with the addition of a cold trap which would potentially remove excess moisture from
the bag and keep the leaves in a more ambient temperature. Comparison of the two methods, with and
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without cold trap, indicates that the cold trap apparatus may not be powerful enough to sufficiently cool
the temperature within the bag. Future transpiration gas monitoring was planned for the 1999 sampling
season with the addition of a modified cold trap attachment.
Several studies were designed which examined exposure pathways. Leaves and soil were collected from
the phytoremediation area and a reference area for a leaf degradation study. The study is designed to
determine whether or not there are deleterious compounds retained within the study leaves or within the
associated soil which could pose risk to an environmental receptor. The results of this study are still being
analyzed. Additional studies involved nematode analyses which examined the trophic assemblage of the
nematode community. Data collected in 1997 indicated that the nematode community was enhanced in
the phytoremediation area as compared with data collected prior to the tree planting.
No trees were planted in the 1999 sampling season. The objectives were: 1) to assess the phyto-
remediation capabilities of native Maryland species, tulip trees and silver maples, in addition to hybrid
poplar trees; 2) to increase the area of hydraulic influence; 3) to diversify the age of trees to ensure
continued containment and contaminant removal; and 4) to assess new planting methods. The last
objective relates to the three tree excavations performed in the fall of 1998. Three trees were excavated
and replanted in their same areas on the site to examine root depth and structure and whether or not the
trees were utilizing groundwater. Examinations revealed that most tree roots appeared to be confined to
the hole in which they were placed and did not appear to radiate extensively from this area. It did appear
however, that the tree roots were deep enough to access the groundwater. Three new planting methods
(i.e., hole sizes and widths) were employed for the new trees in an attempt to provide the tree roots with
either increased depth, increased width or a combination of increased width and depth. Monitoring of
these new trees during the 1999 sampling season attempted to discern the phytoremediation capabilities of
the native species versus the hybrid poplars and to assess the growth of the new trees given the various
planting methods employed for each.
Edward Sears Site, New Jersey
Over 40 direct push microwells were installed to monitor groundwater instead of temporary direct push
wells. This will enabled frequent, seasonal monitoring of groundwater, at specific locations for
comparable costs.
Substantial reductions in dichloromethane identified after the second growing season in August 1998
have been sustained as of August 1999. Concentrations at four locations were reduced from 490,000
down to 615 ppb, 12,000 ppb to ND, 680 ppb to ND, and 420 to 1.2 ppb. At one location PCE dropped
from 100 to 56 ppb, while TCE increased from 9 to 35 ppb. This may be indicative of anaerobic
dechlorination in the root zone. At other locations TCE concentrations remained stable over the past three
years, although a decrease from 99 to 42 ppb was noted at one well point. Trimethylbenzene (TMB) was
reduced from 147 to 2 ppb, 246 to ND, 1900 to 50 ppb, and 8 to 1 ppb at four microwell points in the
treated area. At another well point within the treated area, concentrations of TMB were relatively
unaffected, 102 ppb in August 1997 compared to 128 in August 1999. Xylenes were also unaffected or
slightly increased at this same location, 26 ppb in August 1997 compared to 34 ppb in August 1999. At
two other locations, xylene concentrations dropped from 590 to 17 ppb, and from 56 to 1.4 ppb.
The groundwater monitoring program will continue in 2000, with samples being collected in May,
August and November. November sampling is being added to see if concentrations recover slightly
during the dormant season.
Sampling of evapotranspiration gases was conducted by placing Tedlar bags over branches on 6 selected
trees. Five trees were in areas where groundwater was contaminated with different concentrations of
target contaminants. The sixth tree was in an area known to be free of contamination. Evapotranspiration
gasses were collected on an hourly basis, for four hours during the hottest period of the day. Low levels of
toluene 8 to 11 ppb were detected in three of four samples from one tree and one of four discrete gas
samples from another tree. No other target compounds were detected (DL of 8 ppb/v) in any other
samples.
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Soil gas flux measurements were collected in conjunction with the evapotranspiration gas study. Samples
collected indicated no contaminants being released to the air from the soils.
During the initial two growing seasons, tree height and diameter were substantially lower in areas
containing high concentrations of VOCs in groundwater. This adverse impact appears to have been
reduced during the third (1999) growing season. Rate of growth increased significantly in the
contaminated areas, however these trees have yet to achieve the overall height and diameter of trees
planted in uncontaminated areas. Overall the trees in August 1998 averaged 17 ft (22 m) in height with a
range from 3.5 to 25 ft (1 to 8 m).
Carswell AFB, Texas
Root biomass and extent were examined in September of 1997 in the whip and caliper-tree plantations.
Four trees from each plantation were evaluated for fine root biomass and length, coarse root biomass.
Coarse root mass was significantly greater in the caliper trees in the 3.0 to 10 mm range; 458 g per tree
compared to 240 g per tree. Although the coarse root mass in the > 10 mm range was also greater in the
caliper trees than in the whips, the difference was not statistically significant. Differences in the fine root
biomass between the plantations were not statistically significant: 288 g/m2 for whips compared to 273
g/m2 for caliper trees in the <0.5 mm range; 30 g/m2 for whips compared to 36 g/m2 for the caliper trees
in the 0.5 to 1.0 mm range; and 60 g/m2 for the whips compared to 91 g/m2 for the caliper trees in the 1.0
to 3.0 mm range. Fine root length density in the upper 30 cm of soil was statistically greater in the caliper
trees as compared.
In the second growing season (September 1997), the roots of both the whips and caliper trees had reached
the water table (275 cm for the whips and 225 cm for the caliper trees), and the depth distribution of the
roots was quite similar. The more expensive planting costs of the caliper trees did not appear to impart
any substantial benefit with regard to root depth and biomass. Observed differences between the whips
and the caliper trees were reported to be due as much to inherent genotypic differences as to the different
modes of establishment.
The trees in both the whip and caliper-tree plantations at the demonstration site began to use water from
the aquifer and measurably decrease the volumetric flux of contaminated groundwater leaving the site
during the period of demonstration. The maximum reduction in the outflow of contaminated groundwater
that could be attributed to the trees was approximately 12 percent and was observed at the peak of the
third growing season. The reduction in the mass flux of TCE across the downgradient end of the treatment
system at this time was closer to 11 percent because TCE concentrations were slightly higher during the
third growing season than at baseline. The maximum observed drawdown of the water table occurred near
the center of the treatment system at this time and was approximately 10 centimeters. A groundwater flow
model (MODFLOW) developed by the USGS indicates that the volume of water that was transpired from
the aquifer during the peak of the third growing season was probably closer to 20 percent of the initial
volume of water that flowed through the site because there was an increase in groundwater inflow to the
site due to an increase in the hydraulic gradient on the upgradient side of the drawdown cone.
Tree-growth and root-growth data collected from the demonstration site are consistent with the observa-
tions of hydraulic influence of the trees on the contaminated aquifer. Trees in the whip plantation, which
were planted approximately 1.25 m apart, were starting to approach canopy closure by the end of the third
growing season. This observation indicates that the trees were transpiring a significant amount of water at
this time. (A plantation approaches its maximum transpiration potential once it achieves a closed canopy
because a closed canopy limits leaf area.)
The caliper trees were planted 2.5 m apart and although the plantation was not as close to achieving a
closed canopy, individual caliper trees transpired just over twice the water that individual whips
transpired. As a result, the volume of water that was transpired by the two plantations was similar because
there were only half as many caliper trees as whips.
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The physiologically based model PROSPER, which was used to predict out-year transpiration rates at the
demonstration site, indicates that there will be little difference in the amount of water that the whip and
caliper tree plantations will transpire. Transpiration for each plantation is predicted to range from 25 to 48
cm per growing season depending on climatic conditions, soil moisture, and root growth. Forty-eight to
fifty-eight percent of this predicted evapotranspiration is predicted to be derived from the contaminated
aquifer (saturated zone) regardless of the plantation.
Since the phytoremediation system had not achieved maximum hydraulic control during the period of
demonstration, the groundwater flow model was used to make predictions with regards to out-year
hydraulic control. The groundwater flow model indicates that once the tree plantations have achieved a
closed canopy, the reduction in the volumetric flux of contaminated groundwater across the downgradient
end of the site will likely be between 20 and 30 percent of the initial amount of water that flowed through
the site. The actual amount of water that will be transpired from the aquifer by the tree plantations will be
closer to 50 to 90 percent of the volume of water that initially flowed through the site. The discrepancy
between the reduction in the volumetric outflow of groundwater and the volume of water transpired from
the aquifer can be attributed to the predicted increase in groundwater inflow to the site and the release of
water from storage in the aquifer. No hydraulic control was observed during the dormant season from
November to March for the demonstration site.
The amount of hydraulic control that can be achieved by phytoremediation is a function of site-specific
aquifer conditions. A planted system can be expected to have a greater hydrologic affect on an aquifer at a
site that has an initially low volumetric flux of groundwater than at a site where the flux of contaminated
groundwater is significantly greater. The parameters of hydraulic conductivity, hydraulic gradient,
saturated thickness, and aquifer width in the treatment zone all contribute to the volumetric flux of
groundwater through a site. The horizontal hydraulic conductivity at the demonstration site in Fort Worth,
Texas is approximately 6 m/day. The natural hydraulic gradient is close to two percent and the saturated
thickness of the aquifer is between 0.5 and 1.5 m. Volume of water in storage in an aquifer will also affect
system performance.
When designing for hydraulic control during phytoremediation, it is important to keep the remediation
goals in mind. In other words, it may not be desirable to achieve full hydraulic control at a site if full
control would adversely affect the groundwater/surface-water system downgradient of the site. At the
demonstration site in Texas, the receptor is Farmers Branch Creek, which has very low flow (less than 1
ftVsec or 3 cm3/s) during the summer months (period of peak transpiration). The optimal performance at
such a site may be to keep the plume from discharging into the creek without drying up the creek,
particularly since hydraulic control is only one mechanism that contributes to the cleanup of a
groundwater plume by phytoremediation. A groundwater flow model of a potential site is ideal for
addressing such design concerns.
With respect to the fate of the contaminants that were taken up into the planted trees, TCE and its
daughter products were commonly detected in tissue samples of roots, stems and leaves. Generally, there
was an increase over time in the percentage of planted trees in which the compounds were detected. Stem
tissue generally exhibited the greatest diversity and concentration of chlorinated compounds. A research
team investigated the kinetics of transformation of TCE for leaf samples collected from seven trees
(cedar, hackberry, oak, willow, mesquite, cottonwood whip, cottonwood caliper tree). Each of the plant
species investigated appears to have properties that are effective in degrading TCE. Specifically, all leaf
samples showed dehalogenase activity. Pseudo first-order rate constants were determined for the samples.
The average and standard deviation for all seven rate constants is 0.049±0.02 per hour. This corresponds
to a half life of 14.1 hours. These kinetics are fast relative to other environmental transport and
transformation processes with the exception of volatilization for TCE. As a result, it is unlikely that
degradation within the trees will be the rate limiting step during phytoremediation. These data suggest
that it may better to use species that are native to a proposed site rather than genetically altered plants that
are designed to enhance metabolism of TCE.
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With respect to biologically induced reductive dechlorination, there is evidence that the aquifer beneath
the planted trees was beginning to support anaerobic microbial communities capable of biodegradation of
TCE within three years of planting. Specifically, microbial data from soil and groundwater samples
indicate that the microbial community beneath the planted trees had begun to move towards an
assemblage capable of supporting reductive dechlorination during the demonstration period. In addition,
dissolved oxygen concentrations had decreased and total iron concentrations had increased at the southern
end of the whip plantation where the water table is closest to land surface. The ratio of TCE to cis-1,2-
DCE had also decreased at this location beneath the whip plantation, which suggests that the shift toward
anaerobic conditions in this part of the aquifer was beginning to support the biodegradation of TCE.
Significant contaminant reduction by this mechanism, however, had not occurred across the
demonstration site by the end of the demonstration period.
Data from the aquifer beneath a mature cottonwood tree near the planted site support the conclusion that
reductive dechlorination can occur beneath cottonwood trees with established root systems. The ratio of
TCE to cis-l,2-DCE beneath the mature tree was typically one order of magnitude less than elsewhere at
the site during the demonstration. The microbial population in the area of the mature cottonwood tree
included a vibrant community that supported both hydrogen oxidizing and acetate fermenting
methanogens. This active anaerobic population is assumed to be responsible for the decrease in TCE
concentration and the generation of daughter products beneath the mature cottonwood tree.
Preliminary field data collected during the fifth dormant season (January 2001) indicate that the trees
were finally beginning to have a widespread effect on the geochemistry of the ground water. During this
season, dissolved oxygen concentrations were above 4.5 mg/L in water from all upgradient wells and one
well between the tree plantations (well 522). Whereas, they were below 3.5 mg/L in water from all other
wells at the demonstration site, including wells that are over 50 m downgradient of the planted area. The
mean dissolved oxygen concentration in water from all wells, excluding the upgradient wells and well
522, was 1.76 mg/L. The dissolved oxygen concentration in several wells beneath the planted trees was
less than 1 mg/L. In addition, preliminary field data indicate that ferrous iron and/or sulfide
concentrations were elevated in several locations beneath and immediately downgradient of the tree
plantations. These data add to the body of evidence that the planted trees at the demonstration site can
stimulate microbial activity that results in the depletion of dissolved oxygen in the aquifer and the
creation of local anaerobic conditions conducive to microbial reductive dechlorination (Eberts, et al., In
press). These data also support the conclusion that the ground-water system was still in a state of
transition after 5 years. Hansen (1993) reports that soil carbon is significantly related (positive) to tree age
and that there is a net addition of soil carbon from plantations older than about 6 to 12 years of age.
Even though reductive dechlorination has been observed around the mature tree, the presence of TCE
daughter products, as well as residual TCE, indicate that the reductive dechlorination process has not fully
mineralized the contaminants of concern to innocuous compounds. There is no field evidence from this
study that suggest complete in situ biodegradation of TCE and its daughter products can be achieved.
6. COSTS
Aberdeen Proving Grounds, Maryland
Site Preparation (?): $5,000
Capital: $80,000 for UXO clearance of soil during planting; $80/tree.
Operation and maintenance: $30,000 due to no established monitoring techniques
Edward Sears Site, New Jersey
Site Preparation: $24,000
Planting: $65,700
Maintenance: $15,300
Total: $105,000
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1997 Maintenance: $26,000
1998 Maintenance: $14,000 (Maintenance cost will drop substantially after trees are established)
Monitoring/analysis: 50 groundwater stations, soil gas, soils, hydrogeological parameters, weather,
transpiration gas, reports, etc. Monitoring costs should also reduce annually as study techniques become
more refined.
1997: $72,800
1998: $61,600
1999: $42,000
Carswell AFB, Texas
Preparatory Work
Site Characterization: $12,000
Site Design: $10,000
Site Work:
Monitoring (research level) well installation: $90,000
Development of Plantations -1 acre (includes landscaping costs): $41,000
Weatherstation: $3,100
Survey: $25,000
Purchase of Trees
Whips ($0.20 each): $100
Five-gallon buckets ($18 each): $2,000
Installation of Irrigation System: $10,000
Yearly O&M:
Landscaping: $2,000
Groundwater, soil, vegetation, transpiration, climate, soil moisture, and water-level monitoring (research
level): $250,000
The planting costs at Carswell are significantly less than proprietary planting techniques employed by the
vendors that involve auguring down to the capillary fringe and other engineered methods for individual
tree planting.
After Treatment: None
7. REFERENCE
Eberts, S., G. Harvey, S. Jones, and S. Beckman, In press. A Multiple Process Assessment of
Phtoremediation of a Chlorinated Solvent Plume at a Subhumid Field Site, John Wiley and Sons.
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January 2002
Project No. 16
In-Situ Heavy Metal Bioprecipitation
Location
Industrial site in Belgium
Technical Contact
Dr. Ludo Diels
Dr. Leen Bastiaens
Dr. D. van der Lelie
Flemish Institute for
Technological Research
(Vito)
Boeretang 200
B-2400 Mol
Belgium
Tel: +32 143351 00
Fax: +32 14 58 05 23
Project Status
Interim
Project Dates
Accepted 1999
Final report 2002
Costs Documented?
No
Contaminants
Heavy metals (zinc,
cadmium, arsenic, lead,
chromium, nickel,
copper), sulphate
Media
Groundwater
Project Size
Laboratory,
Pilot/full-scale
Technology Type
In-situ
bioremediation
(reactive zone or
biobarrier)
Results Available?
Yes
1. INTRODUCTION
The industrial world is facing many problems concerning soils and groundwater with heavy metal
pollution. This pollution is mainly due to mining activities and non-ferrous activities by metal refining,
metal processing, and surface treatment industries. Immobilization followed by phytostabilization has
been shown to be effective for treating polluted soil in order to reduce the risk of heavy metals being
spread around by wind erosion or leaching from the soil into the groundwater (Van der Lelie et al., 1998).
But what about groundwater that already has been contaminated with heavy metals?
When dealing with dissolved inorganic contaminants, such as heavy metals, the required process
sequence in a "pump & treat" system to remove the dissolved heavy metals present in the groundwater
becomes very complex and costly. In addition, the disposal of the metallic sludge, in most cases as a
hazardous waste, is also very cost prohibitive. Therefore, in situ treatment methods capable of achieving
the same mass removal reactions for dissolved contaminants in an in situ environment are evolving and
gradually gaining prominence in the remediation industry.
In this project, a relatively innovative technique will be studied for in situ treatment of groundwater-
containing heavy metals. Through stimulation of sulfate reducing bacteria (SRBs) in aquifers and
groundwater, heavy metals can be bioprecipitated, hereby reducing the risk of further spreading of the
metals. The feasibility of this technique will be evaluated for two different industrial sites in Belgium. In-
situ bioprecipitation of heavy metals can be implemented as a biological reactive zone or biowall. The
concept of in situ reactive zones is based on the creation of a subsurface zone where migrating
contaminants are intercepted and permanently immobilised into harmless end products.
2. SITE DESCRIPTION
On industrial site 1 (metal smelter), high concentrations of zinc (10-150 mg/1), cadmium (0.4-4 mg/1) and
arsenic (20-270 (ig/1) are present in the groundwater. Also relatively high concentrations of sulfate (400-
700 mg/1) were measured, which is favorable for SRB-activities. Groundwater samples taken further
away from the source have lower metals and sulfate concentrations.
Industrial site 2 (surface treatment) has serious chromium (up to 8300 (ig/1), zinc (up to 78 mg/1), lead (up
to 72 (ig/1), nickel (up to 3500 (ig/1), copper (92 mg/1), and cadmium (up to 17 mg/1) problems in the
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
groundwater. Very high sulfate (up to 3000 mg/1) concentrations are also present. This groundwater has
also a very low pH (between 2 and 4).
3. DESCRIPTION OF THE PROCESS
Bioprecipitation Process:
In-situ precipitation of heavy metals and sulfates is a method based on stimulation of SRBs by
supplementing an appropriate electron donor. Addition of extra nutrients (N and P) might also be required
for good growth of the bacteria. In the presence of a suitable electron donor (for instance acetate), SRBs
reduce sulfates to sulfites and further to sulfides, which then form stable and rather insoluble metal
sulfides:
CH3COOH + SO42- ==> 2 HCO3- + HS- + H+
H2S + Me++ ==> MeS + 2 H+
A good in situ bioprecipitation process, however, only can be obtained under the following conditions:
Sulfate reducing bacteria (SRBs) must be present in the aquifer. In case no SRBs are present among the
autochthonous micro-population in the aquifer, appropriate microorganisms have to be introduced in the
aquifer.
Sulfate should be available. Also nutrients and an appropriate electron donor such as methanol, ethanol,
molasses, acetate, or lactate are required.
No oxygen should be present and a low redox potential (Eh) is necessary.
The applicability of in-situ bioprecipitation of heavy metals on sites should therefore be evaluated case by
case.
Outline of the Project:
1. Preliminary study
2. Site evaluation
3. Lab-scale treatability testing in batch and column experiments
4. The presence of SRBs in the aquifers will be examined by microbial countings, measurements of
SRB-activity, and PCR-technology.
5. Selection of a suitable organic substrate
6. Determination of optimal physico-chemical conditions: required concentration of the electron donor,
nutrients requirement, sulfate requirements, influence of temperature, etc.
7. As the effectiveness of a reactive zone is determined, largely by the relationship between the kinetics
of the target reactions and the rate at which the mass flux of contaminants passes through it with the
moving groundwater, kinetics of metal removal from groundwater will be examined.
8. The stability of the formed metal sulfides will be checked.
9. Further is clogging due to biomass production and metal precipitates an important issue that has to be
evaluated.
10. Field demonstration on pilot or full scale
11. Monitoring
4. RESULTS/COSTS
The first preliminary studies and site investigations were done. Afterwards, groundwater and
(undisturbed) aquifer material samples were taken and investigated in batch systems under different
conditions in order to follow redox potential and the reduction of the dissolved metals. Special attention
was paid to the isolation of SRBs and the identification with special probes (study under way). In the
project, acetate was chosen as the carbon source (no explosion danger like methanol, not contaminated by
other impurities like molasses). Different concentrations of acetate were added and the SRB
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January 2002
Desulfovibrio desulfuricans Dd8301 was added as a positive control. The results for the removal of Zn at
the first site are presented in Table 1. It can be concluded that without addition of a carbon source or by
inhibiting the bacterial activity (addition of HgC12), nearly no Zn removal could be obtained. The
addition of a low concentration of acetate leads to a reduction of Zn from 10700 (ig/1 to 213 (ig/1. In the
same groundwater, As and Cd also were removed and precipitated. The addition of too high
concentrations of acetate did not lead to metal removal because the methanogenic bacteria dominated the
scene (very high gas production was observed). The addition of a specific SRB could in some cases only
reduce the lag time of the bacterial growth. In the last condition no groundwater was used, only aquifer in
water. It was observed that some metals from the aquifer material were solubilised and afterwards
precipitated by the added Desulfovibrio desulfuricans Dd8301. Metals were removed only in those
conditions where the redox potential was below -220 mV.
At site 1, the metal removal of a lower contaminated groundwater (further away from the source) was
evaluated too. The sulfate concentrations were also quite low and this showed not to be favorable for the
SRB-bacteria. Only in the case of added SRBs could the metals be removed.
Table 1: Zn Removal by In-situ Bioprecipitation Under Different Conditions for Site 1
aquifer + groundwater
aquifer + groundwater
+ 0.5 mM HgCl2
aquifer + groundwater
+ 1 ml K-acetate
(25%)
aquifer + grondwater +
5 ml K-acetate (25%)
aquifer + grondwater +
1 ml K-acetate (25%)
+ Dd8301
aquifer + grondwater +
5 ml K-acetate (25%)
+ Dd8301
aquifer + Postgate C
medium + Dd8301
TO
Total
100,000
107,000
107,000
101,000
94,500
96,000
1680
In
solution
101,000
109,000
109,000
103,000
93,100
96,100
885
T4
Total
82,100
98,000
96,100
103,000
82,600
92,800
1570
In
solution
87,600
104,000
99,600
102,000
86,500
95,300
334
T8
Total
80,900
97,800
85,500
112,000
77,500
105,000
50
In
solution
79,200
94,200
82,800
109,000
77,200
91,600
10
T12
Total
67,300
76,800
213
101,000
62,400
88,200
57
In
solution
62,600
73,200
101
96,100
59,000
86,000
41
At the second test site, the sulfate concentrations were quite low (200 mg SO4271). Only after the addition
of extra sulfate (2000 mg SO42"/1) or of zero valent iron could the redox be reduced to below -200 mV.
The redox conditions are presented in Table 2. Table 3 shows the removal of Ni from the groundwater by
bioprecipitation. The above-mentioned conditions lead to complete Ni removal. Note that the conditions
without carbon source or with inhibition of the bacterial activity (addition of HgCl2) did not lead to metal
removal. Also Pb, Zn, Cr, and Cd could be removed.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Table 2: Redox Potential Under Different Conditions for Groundwater from Test Site 2
Test conditions
Rl: aquifer + GW
R2: aquifer + GW + HgCl2
R3: aquifer + GW + K-acetate
R4: aquifer + GW + K-acetate +
Dd8301
R5: aquifer + GW + Postgate C +
K-acetate + Dd8301
R6: Aquifer + GW + FeA4
R7: aquifer + GW + HgCl2 + FeA4
R8: aquifer + GW + K-acetate + FeA4
R9: aquifer + GW + K-acetate +
FeA4 + Dd8301
TO
197 mV
325 mV
175 mV
229 mV
88 mV
221 mV
303 mV
138 mV
106 mV
Tl
201 mV
316mV
173 mV
197 mV
44 mV
144 mV
278 mV
-129mV
-398 mV
T4
203 mV
341 mV
132 mV
290 mV
-308 mV
6mV
-212mV
-402 mV
-246 mV
T8
181 mV
309 mV
159 mV
250 mV
-322 mV
32 mV
-208 mV
-189 mV
-229 mV
T12
235 mV
315mV
198 mV
145 mV
-284 mV
143 mV
-168 mV
-460 mV
-241 mV
T19
247 mV
301 mV
143 mV
142 mV
-316mV
73 mV
-88 mV
-380mV
-198 mV
NOTES: 5 ml K-acetate (25%); Postgate C
TO: at time zero; Tl: after 1 week;
months.
10X concentrated; 10 g FeA4
T4: after 1 month; T8: after 2 months; T12: after 3 months; T19: after 5
Table 3: Ni Concentrations at Different Conditions from Groundwater from Test Site 2
Test conditions
Rl:aquifer+GW
R2: aquifer+GW+HgC!2
R3: aquifer+GW+K-
acetate
R4: aquifer+GW+
K-acetate+Dd8301
R5: aquifer+GW+
Postgate C+K-acetate+
Dd8301
R6: aquifer+GW+FeA4
R7: aquifer+GW+HgC!2
+FeA4
R8: aquifer+GW+K-
acetate+FeA4
R9: aquifer+GW+K-
acetate+FeA4+Dd8301
TO
Tot.
62
54
62
37
424
57
65
48
34
Sol.
54
45
52
34
82
51
51
33
24
Tl
Tot.
52
44
45
54
270
51
72
28
42
Sol.
45
42
51
60
103
34
63
<20
25
T4
Tot.
80
68
62
100
3.2
1.2
6.5
1.3
1.3
Sol.
81
70
66
86
0.65
1.2
1.0
1.9
7.7
T8
Tot.
56
93
33
65
3.4
6.7
16
4.6
9.2
Sol.
53
63
28
70
<2.5
2.8
2.8
<2.5
<2.5
T12
Tot.
65
69
73
78
22
3.1
7.5
3.9
28
Sol.
74
74
16
74
1.1
2.2
1.2
1.9
1.5
NOTES:
Total: metals are measured in the groundwater after acidification; Sol.: metals are measured in the
groundwater after filtration (metals bound to suspended solids are not measured).
5 ml K-acetate (25%); Postgate C 10X concentrated; 10 g FeA4; Concentrations below the remediation
standard (20 ug/1) are presented in bold.
TO at time zero; Tl after 1 week; T4 after 1 month; T8 after 2 months; T12 after 3 months.
Both projects will continue by the start of column experiments under the most optimal conditions. These
tests will allow the determination of the kinetics of the remediation system, which is necessary for the
optimal design of the pilot project in the field. The results will be presented in the next interim report.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
5. HEALTH AND SAFETY
For safety reasons, no methanol was used and all the tests were performed with acetate as the electron
donor. The study must now show that the use of acetate is an applicable alternative.
6. ENVIRONMENTAL IMPACTS
For environmental reasons, no molasses or compost extract was used. The product contained
undetermined impurities that contaminated the ground after infiltration in the aquifer.
7. CONCLUSIONS
The batch tests showed for both sites the feasibility of metals removal from groundwater by the induction
in situ bioprecipitation. However it took quite long times before the redox potential dropped to below -
220 mV. This indicates that a long lag period will be necessary and, at the moment, no information is
available about the kinetics. Therefore, both projects will continue by starting experiments under the most
optimal conditions. These tests will allow the determination of the kinetics of the remediation system,
which is necessary for the optimal design of the pilot project in the field. The results will be presented in
the next interim report.
8. REFERENCES
1. Corbisier, P. Thiry E., Masolijn A. and Diels L. (1994) Construction and development of metal ion
biosensors. In Campbell A.K., CrickaL.J., Stanley P.E. eds. Bioluminescence and
Chemoluminescence : Fundamentals and Applied Aspects. Chichester, New York, Brisbane, Toronto,
Singapore. John Wiley and Sons pp.150-155.
2. Corbisier, P., Thiry, E., Diels, L.(1996) Bacterial biosensors for the toxicity assessment of solid
wastes, Environmental Toxicology and Water Quality: an international journal, 11, 171-177.
3. Diels, L., Dong, Q., van der Lelie, D. Baeyens, W., Mergeay, M. (1995) The czc operon of
Alcaligenes eutrophus CH34: from resistance mechanism to the removal of heavy metal. J. Ind.
Microbiol. 14, 142-153.
4. Diels, L. (1997) Heavy metal bioremediation of soil in methods in Biotechnology, Vol. 2:
Bioremediation Protocols, edited by O. Sheehan Humana Press Inc. Totowa, NJ.
5. Diels, L. (1990) Accumulation and precipitation of Cd and Zn ions by Alcaligenes eutrophus CH34
strains, in Biohydrometallurgy (Salley, J., McCready, R.G.L., and Wichlacs, P.Z., eds.), CANMET
SP89-10, 369-377.
6. Mergeay, M. 1997. Microbial resources for bioremediation of sites polluted by heavy metals. In
perspectives in Bioremediation p. 65-73 Ed. J.R. Wildcet al. Kluwer Academic Publishers,
Nederlands.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 17
GERBER Site
Location
SERMAISE - Department of
ESSONNE - ILE DE
FRANCE Region
Technical Contact
Christian MILITON
ADEME
BP406
49004 ANGERS CEDEX 01 -
France
Project Status
New Project
Project Dates
06/1999
07/2002
Media
Soil and groundwater
Technology Type
Excavation and
treatment of waste
Contaminants
Complex contamination: solvents (BTEX and
chlorinated); PCBs; phenols, phthalates; Pb,
Zn
Project Size
Full-scale
1. INTRODUCTION
The GERBER site was operated since the beginning of the fifties until 1993 as a solvent regeneration
plant. Until 1972, one or two lagoons have been used to dumps residues of the activities. In 1972-1973,
an unknown but very significant quantity of drums was buried on the site. In 1983, the pollution of the
drinking water well of the village of SERMAISE by chlorinated organics was attributed to the GERBER
site located in the vicinity and a first preliminary investigation revealed buried drums with organic and
chlorinated material.
Nothing happened during the following years because the polluter didn't have the financial capability to
carry out significant depollution action. In 1992, in connection with the new legal and financial system
created to deal with « orphan » site, a first clean up project was carried out by ADEME. The project
consisted in the excavation of the main part of the buried drum area; 3,700 drums were excavated and
treated and approximative ly 14,000 tons of polluted soil was confined on the site. The treatment of this
polluted soil was carried out in 1998-1999; 10,650 tons of polluted soil were treated on site by solvent
washing and 5,850 tons that were less polluted were landfilled (hazardous waste landfill (classe 1)). The
total cost of these first phases of cleanup is about 10 millions euros.
2. THE PREVIOUS PROJECT IN 1999
In addition to the first phase rehabilitation works presented above, it was clear that the remaining part of
the site was still heavily polluted with not so much drums but with buried waste corresponding to the
ancient lagoons and associated polluted soil and groundwater. Therefore an impact and risk assessment
study was carried out in 1998 that characterized the remaining pollution:
• high concentrations of pollutants still cover 70% of the site
• highly contaminated soil was found to a depth of approximately 4-5 m
• total volume of polluted soil is estimated 50-75,000 m3.
The impact study and modeling showed that the migration of the pollutants in the groundwater seems to
be limited and that a two stages natural attenuation occurs: aerobic degradation of BTEX and then
reductive dechlorination of chlorinated solvents. Based on these first results it was decided to prepare a
new phase of evaluation and corrective action. The objectives of this new phase were to:
• improve the knowledge of the contamination source and to prepare the clean up of the remaining hot
spots
• complete the evaluation of the transfer of the pollution in the air and in the groundwater with a
detailed characterization of the mechanisms of the natural attenuation. Then, after this assessment of
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
the efficiency and limits of the process of natural attenuation an additional project of in situ source
reduction will be studied in order to have finally a restoration system able to reduce the risks to
acceptable levels.
3. THE SITUATION IN 2002
The results from complementary investigations and the evolution of the quality of groundwaters shown:
• the discovery of around 2,000 drums full of hazardous wastes, buried just near the area excavated in
1992, but not detected during the previous investigations
• a previously undetected plume with VOH in the chalk water table which flows eastward out of the
site, even though on the site and immediately downstream, the pollutants are the intermediate
products resulting from the degradation of the VOH. The main pollutants found in the plume are the
primary solvents which characterize the site (TCE, PCE, and CC14). It is possible that the natural
attenuation proved on the site is impossible in some areas out of the site
The new policy about remediation versus risk assessment conduct the French Ministry of Environment to
stop the remediation to the end of 2002, waiting for the results of a new risk assessment study and a
modeling, and asking for a better monitoring, because today the risks for human health and the
environment are not considered as proved.
4. REFERENCE
Definition of corrective actions taking into account natural attenuation and risk assessment approach,
former Etablissement Chimique du Hurepoix Site in SERMAISE -France - NATO CCMS meeting
ANGERS May 1999.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 18
SAFIRA
Location
Bitterfeld, Germany
Technical Contact
Dr. Holger Weiss
UFZ-Centre for Environmental
Research
Permoserstrasse 15
D-043 18 Leipzig
Germany
Project Status
New project
Project Dates
7/1999 - 6/2002
Costs Documented?
Yes
Contaminants
Complex
contamination,
chlorobenzene
Technology Type
9 different types of
biotic and abiotic
technologies
Media
Groundwater
Project Size
Pilot-scale
Results Available?
Not yet
1. INTRODUCTION
The aim of the SAFIRA project is the examination and further development of in situ groundwater
decontamination technologies. A site near Bitterfeld (Germany) was selected as a model location.
Different types of technologies (e.g., catalytic, microbial, sorption) have to prove their performance and
long term stability under the real-world conditions of an in situ pilot plant. It is a cooperation project
between UFZ Center for Environmental Research Leipzig-Halle, TNO (The Netherlands) and the
universities Dresden, Halle, Kiel, Leipzig, and Tuebingen.
2. BACKGROUND
The region of Bitterfeld was selected as the model location for investigations into developing powerful in
situ technologies for the remediation of complexly contaminated groundwater. The soil and water
environmental compartments in the Bitterfeld/Wolfen district have suffered sustained damage as a result
of over a century of lignite-mining and chemical industry. Whereas relevant soil pollution is mainly
confined to industrial locations (plant sites) and landfills, the persistent penetration of the groundwater by
pollutants has resulted in contamination attaining a regional scale. Consequently, an area of about 25 km2
with an estimated volume of some 200 million m3 is now partly highly polluted and must be regarded as
an independent source of contamination. This pollution is characterised by the extensive distribution of
halogenised hydrocarbons, especially chlorinated aliphatics and chlorinated aromatics.
3. TECHNICAL CONCEPT
Technology developed and tested in laboratories will be scaled up in two stages: a mobile test unit and an
in situ pilot plant. A mobile decontamination unit has been designed for this purpose as a "window in the
aquifer". Groundwater from a depth of about 20 m is pumped into a storage tank without coming into
contact with oxygen. This polluted water will then be used to charge five possible test columns with the
physico-chemical conditions of the aquifer being preserved.
The methods tested successfully in the laboratory and in the mobile decontamination unit have to prove
their chemical and hydrological long-term stability and will be optimised in a pilot plant. Five shafts with
a depth of about 22.5 m and an inner diameter of 3 m were constructed. Several experimental columns of
up to 1.4 m in diameter will be installed into these shafts and will be supplied with the contaminated
groundwater directly from the aquifer. The contaminated water will vertically flow through the reactors
and will be cleaned. Numerous sampling and process controlling facilities as well as a variable design of
the reaction columns will enable the analyses of relevant chemical and hydraulic processes during
operation and competitive development in technology under real-world conditions. The technologies
tested in the first phase of the pilot plant are:
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
• anaerobic microbial degradation of the contaminants
• aerobic microbial degradation
• electrocatalytical dehalogenation
• zeolith supported catalysts
• oxidizing catalysts
• sorption barriers
• redox reactors
• microbial degradation in combination of adsorption onto several high porosity media
• bioscreens
The assessment of the different techniques will follow chemical, ecotoxicological, economic and
environmental criteria.
4. ANALYTICAL APPROACH
A weekly sampling of the inflow and outflow of every reactor will occur. All samples will be analyzed in
the laboratory at the site. Regular analyses will include a GC analyses (TCE, DCE, dichlorobenzene,
chlorobenzene, benzene), ion-chromatography (chloride, sulfate, phosphate, nitrate), TOC, and AOX.
Additional samplings and analysis of water and solid material are optional.
5. RESULTS
First results of the experiments in the laboratory and in the mobile test unit are summarized in reports (see
references).
6. HEALTH AND SAFETY
The shafts will venthilated before the staff enter the shafts for sampling. The German regulations for
safety have to be followed. The shafts are equipped with warning systems for fire, gas, water, pressure in
the reactors, temperature, air quality and controlling the pumps. Most of this equipment is only be
necessary for research purpose.
7. ENVIRONMENTAL IMPACTS
The outflow water of the different reactors is cleaned additionally in a cleaning facility. This option was
necessary only for the pilot plant to demonstrate the technologies and to avoid environmental impact. The
hydrologic regime is not disturbed. Monitoring wells are installed around the shafts.
8. COSTS
Not yet available.
9. CONCLUSIONS
Not yet available.
10. REFERENCES
Not Applicable.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 19
Succesive Extraction-Decontamination of Leather Tanning Waste De
Location
University of Istanbul
Technical Contact
Dr. Erol Ercag
University of Istanbul
Faculty of Engineering,
Department of Chemistry
Avcilar, 34850
Istanbul, Turkey
Tel: 0212 593 84 7, Ext.
1191
Fax: 0212 591 1998
Ercaa^ijlstanbul. edu.tr
Project Dates
Accepted 1998
Final Report 2001
Costs Documented?
No
Report Status
Interim
Results Available
None
posited Soil
Contaminants
Organic and
inorganic
Project Size
Laboratory/field
Progress on this project is current as of January 2002.
1. INTRODUCTION
Since old leather tanning industries have been moved from a central region to the outskirts of Istanbul,
namely from Zeytinburnu to Tuzla of Istanbul, considerable land into which the tanning wastes were
dumped over years are now waiting to be reused. Now the Greater City Municipality of Istanbul is
considering this emptied region for recreational and housing purposes. This region now poses
considerable health hazard for the potential future users of this land.
2. AIM
This project was purported to perform the treatability study of the contaminated soil at Zeytinburnu.
3. METHOD
Sampling of soil over the abandoned tanning industrial area will be made, and the organic and inorganic
contaminants in the soil will be analysed. Volatile organic compounds (VOCs) will be analysed by a
photoionization dectector capable of detecting more than 250 chemicals.
According to the types of organic (e.g., additives and modification agents) and inorganic (e.g., chromium,
sulfide, etc.) constituents present as contaminants, a treatability study of soil consisting of organic
extraction with suitable solvent (e.g., methylene chloride) followed by acid leaching of toxic heavy metals
will be carried out. Both synthetic and real soil samples will be carried out to optimize solvent, acid,
leachant concentration, solids-to liquid ratio and so on.
Currently, points from which soil samples are to be taken have already been determined. Several samples
are to be taken from the same point according to the distance to the surface. The depth from which
samples are planned to be taken will be roughly 1 meter at maximum. At the same sampling positions,
VOC measurements will also be made.
4. RESULTS
Not available.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
5. COSTS, HEALTH, AND SAFETY
Not yet available.
6. CONCLUSIONS
Insufficient data to draw any meaningful conclusions.
7. REFERENCES
Not applicable.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 20
Innovative Treatment Technologies: A Summary of Work Completed on a DNAPL Site at
Cape Canaveral, Florida
Location
Cape Canaveral, Florida
Project Status
Ongoing/ Interim
Media
Groundwater
Technology Type
In situ chemical oxidation
In situ thermal remediation
with six phase heating
In situ thermal remediation
and steam injection
Technical Contact
Thomas O. Early
Oak Ridge National Laboratory
P.O. Box 2008, MS 6038
Oak Ridge, TN 37831-6038
Tel: (865) 576-2103 (Office)
Fax: (865) 574-7420
Project Dates
Contaminants
Chlorinated solvent DNAPLs
Costs Documented?
Spring 2002
Project Size
Field
treatability
gesting
Results Available?
Spring 2002
1. INTRODUCTION
Dense non-aqueous phase liquids (DNAPLs) pose a serious, long-term threat to groundwater
contamination due to their toxicity, limited solubility in ground water, and significant migration potential
in soil gas, groundwater, and/or as separate phase liquids. DNAPL chemicals, particularly chlorinated
solvents, are among the most common of environmental contamination problems in the United States as
well as for most industrialized countries. There are thousands of DNAPL-contaminated sites in the United
States, often at contaminant volumes that are difficult to detect, but in quantities that can represent
significant sources of groundwater contamination. Many federal, state, and local government agencies as
well as private-sector sites have DNAPL contamination. The Office of Management and Budget estimates
that the federal government alone will spend billions of dollars for environmental clean up of DNAPL
contamination problems.
There are many uncertainties associated with treatment of DNAPL sources in the subsurface. First, it is
difficult to define accurately the location and distribution of the DNAPL. Secondly, the aggressive,
innovative treatment technologies currently being marketed have not been subjected to rigorous
evaluation in order to determine their performance and cost of application under a variety of site
conditions. It is difficult, if not impossible, to make meaningful comparisons of either performance or cost
among these technologies because of the variable conditions present at the demonstration sites and
inconsistent objectives of the individual demonstrations.
2. TECHNICAL CONCEPT
In 1998, a multiagency consortium (Interagency DNAPL Consortium, or IDC) was organized to address
cost and performance issues related to DNAPL source treatment using innovative technologies. The U.S.
Department of Energy/Office of Environmental Management (DOE/EM), the U.S. Department of
Defense (DOD) through the Air Force Research Laboratory in cooperation with the 45th Space Wing, the
National Aeronautics and Space Administration (NASA) and the U.S. Environmental Protection Agency
(EPA) agreed to cooperate in demonstrating innovative DNAPL remediation and characterization
technologies at a NASA site on Cape Canaveral Air Station (Launch Complex 34), Cape Canaveral, FL.
The IDC was formed to:
address a serous, wide-spread and shared environmental problem adversely affecting many U.S.
federal agencies (e.g., DOE, EPA, DOD, NASA, Department of Interior, Department of Agriculture);
accelerate both the demonstration and deployment of DNAPL remediation, characterization and
monitoring technologies for the purpose of reducing the perceived technology risk associated with
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these technologies;
• increase regulatory and user acceptance of these technologies by providing documented, cost and
performance data; and
• provide increased opportunities to test new sensors designed to support in situ remediation of DNAPL
contamination problems.
In order to conduct the side-by-side demonstrations, a Management Team was organized consisting of
representatives from DOE, NASA, USAF, DOD, and EPA. The Team is a collaborative decision-making
body that draws upon the strengths of each agency to solve problems associated with the project. The
Team formed a Technical Advisory Group (TAG) whose members came from industry, academia and
federal agencies and are experts on DNAPLs and DNAPL treatment technologies. The TAG made
recommendations as to the treatment technologies to use and participated in review of work plans and
technical reports for each of the demonstrations. With the assistance of the TAG, the Management Team
selected three of the most promising remediation technologies for deployment and evaluation at Launch
Complex 34: in situ chemical oxidation with potassium permanganate, electrical resistance heating, and
thermal treatment using steam.
3. SITE CONDITIONS
Launch Complex 34 was selected as the test site following an intensive evaluation by a variety of DNAPL
characterization methods. A zone of DNAPL contamination was discovered in a region covering about
0.3 acres (0.12 ha) in front of a building in which TCE was used to clean rocket engine parts. It is
believed that TCE reached the subsurface through leaking floor drains and piping as well as by direct
discharge to the ground surface. DNAPL was found to extend to a depth of-45-ft. (13.7m) below ground
surface where a clay aquitard is encountered. Extensive contamination by DNAPL also was discovered
underlying the building, but the extent of this contamination was not determined. The site in front of the
building was subdivided into three treatment cells, each 50 x 75-ft (-15 x 23 m) in size.
The lithologies present at the test site include the following units in ascending order: the Lower Confining
Unit (LCU) that occurs at a depth of about 45-ft (13.7 m) and is believed to be a barrier to downward
DNAPL migration, the Lower Sand Unit (LSU), the Middle Fine-Grain Unit (MFGU), and the Upper
Sand Unit (USU). The MFGU is about a factor of 10 less permeable than either the USU or LSU. The
water table surface occurs at a depth of about 7-ft (~2 m), but is somewhat variable depending on the
amount of rainfall.
The mass of DNAPL in each cell was determined by collecting and analyzing continuous soil cores. An
unaligned systematic sampling design was used to select the location of 12 cores in each cell. Each 1.6-ft
(0.5 m) section of core was analyzed for its total TCE content. Consequently, nearly 300 samples were
collected from each cell and used to construct a 3-D model of the distribution of TCE. From these data the
mass of total TCE and TCE as DNAPL within each cell was computed and the results are presented in
Table 1. The soil analytical data can be evaluated by several different methods and the results for each are
provided in the table. First, the TCE concentrations were contoured using the Earth Vision software and
the mass of TCE and DNAPL was computed from the volume and concentration of the isoconcentration
shells within the cells. Alternatively, we used a kriging method that takes into account the spatial
variability and uncertainty of the TCE distribution to estimate masses throughout the cells. Kriging yields
a mass estimate and uncertainty in that mass for the desired confidence interval (80%).
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4. ANALYTICAL APPROACH
4.1 In Situ Chemical Oxidation (ISCO)
In situ oxidation using potassium permanganate is a potentially fast and low cost solution for the
destruction of chlorinated ethylenes, BTEX (benzene, toluene, ethylbenzene, and xylene) and simple
poly cyclic aromatic hydrocarbons. In particular, potassium permanganate reacts effectively with the
double bonds in chlorinated ethylenes such as trichloroethylene (TCE), perchloroethylene,
dichloroethylene isomers, and vinyl chloride. It is effective for the remediation of DNAPL, absorbed
phase and dissolved phase contaminants and produces innocuous breakdown products such as CO2,
chloride ions and MnO2(s). The permanganate solution typically is applied by injection at a concentration
of one to three percent. This solution is easily handled, mixed and injected and is non-toxic and non-
hazardous.
Bench-scale laboratory tests of potassium permanganate with TCE have resulted in up to a 90% reduction
of the contaminant in four hours of treatment. The effectiveness of the in situ injection of permanganate is
a function of the reaction kinetics, the transport and contact between potassium permanganate and the
contaminant, as well as competitive reactions with other oxidizable species (e.g., iron, natural organics).
The effective use of this remedial technology requires an engineered approach for maximizing the contact
between potassium permanganate and the target contaminant. As with many technologies, low
permeability and heterogeneity of soils present a challenge and require a carefully designed
application system.
At Cape Canaveral, the ISCO demonstration took place during between August, 1999 and May, 2000.
Permanganate injection occurred in three phases. In each phase, potassium permanganate solution was
pumped to a manifold and thereafter injected into the subsurface through a number of soil lances that
were advanced in 2-ft (0.6m) increments by direct push methods. Injection occurred to a total depth of
about 45 ft (13.7 m). The location of the injection points was determined in such a way that the zones of
influence for neighboring injections overlapped resulting in complete invasion of the DNAPL
contaminated zone.
4.2 In Situ Thermal Remediation with Six Phase Heating (SPH)
The Six Phase Heating (SPH) technology removes contaminants from soil and groundwater by resistively
heating the soil matrix, groundwater, and contaminants in the treated region. In SPH normal three-phase
electricity is split into six separate phases, which is delivered to the subsurface through metal electrodes
arranged in a hexagonal array. As the temperature of the subsurface increases, a point is reached when
boiling of the TCE-groundwater system occurs (~73°C). In principle, a combination of direct
volatilization and steam stripping drives contaminants to the vadose zone where it is captured by vapor
recovery wells for removal and treatment in an ex situ treatment system.
The SPH demonstration at Cape Canaveral began in August, 1999 and continued with several
interruptions until July, 2000. The system was shut down during October and November, 1999 due to the
impact of several hurricanes and tropical storms that caused equipment damage and unanticipated releases
of TCE to surface water. Another shutdown occurred during the spring of 2000 due to replacement of an
electrical generator.
4.3 In Situ Thermal Remediation with Steam Injection
Thermal remediation by steam injection and is another thermal treatment technology used at Cape
Canaveral to treat DNAPL contamination. We used a suite of technologies developed by the University of
California and Lawrence Livermore National Laboratory that includes Steam Enhanced Extraction (SEE),
Dynamic Underground Stripping and Hydrous Pyrolysis/Oxidation (DUS/HPO). The steam treatment
system uses boilers to generate steam, which is then pumped into centrally located injection wells. The
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steam front progresses outward from the center of the treatment cell to the periphery volatilizing and
mobilizing contaminants as it moves. A network of extraction wells is located near the outer boundary of
the cell and contaminants are vacuumed to the surface for treatment. The initial application of steam to
the subsurface at Launch Complex 34 was accompanied by co-injection of air. Air is a non-condensable
gas and is believed to help prevent formation of a condensation front of TCE DNAPL at the steam-
groundwater interface that might be mobilized downward.
At Launch Complex 34, a network of thermocouples is used to produce a 3-D image of temperature
throughout the treatment cell as well as in a ring surrounding the cell. Careful monitoring of temperatures
helps to evaluate the progression of the steam front and also helps confirm that the steam-TCE vapor
mixture is not migrating beyond the extraction wells at the edge of the cell.
HPO is a companion process to DUS in which at steam temperatures the oxidative breakdown of TCE
will occur rapidly and yield non-toxic byproducts such as CO2 and chloride ions. Therefore, with the
application of DUS/HPO it is anticipated that some TCE will be extracted as vapor and treated at the
surface while another component will be totally mineralized in situ.
The steam demonstration began in July 2001 and is expected to continue until early 2002.
5. RESULTS
5.1 ISCO
Table 1 gives the results of the pre- and post-demonstration sampling of the oxidation test cell and an
estimate of TCE removal from the cell. The contouring results indicate that the oxidation cell originally
contained in excess of 6000 kg of TCE (>5000 kg of DNAPL). Following the ISCO demonstration the
residual mass of TCE was 1100 kg (-800 kg DNAPL). This suggests a TCE removal efficiency of 82%
for TCE (84% for DNAPL). Kriging of the same soil core data yields somewhat different results. At the
80% confidence interval (CI) the ranges of values for the TCE mass both before and after the
demonstration are higher than for the contouring method.
The spatial distribution of TCE in the oxidation cell following the ISCO demonstration indicates that
sharp declines in the soil TCE content occurred for each of the lithologic units and that the only region
where treatment was not effective was on the southwestern corner of the cell which underlies the
building.
Table 2 gives the mass of KMnO4 and volume of solution injected for each phase. The cumulative volume
of fluid injected represents over three pore volumes of the test cell. Consequently, it is apparent that there
was significant displacement of contaminated groundwater within the cell to regions beyond the cell
boundary. During the period of peak permanganate injection (April 2000), a steep hydraulic gradient
centered on the cell was developed, especially in the LSU. We believe that the duration of the elevated
heads was short-lived owing to the high transmissivity of the lithologic units. We attempted to evaluate
the impact of groundwater displacement to see if DNAPL might have been mobilized outside of the cell.
However, the region around the cell has significant TCE contamination so it is not possible to determine
if there were any significant increases in DNAPL. We are still evaluating data to test this hypothesis.
5.2 SPH
Table 1 presents the before and after mass estimates for total TCE and TCE DNAPL in the SPH test cell.
The contoured data indicate that the mass of TCE prior to the SPH demonstration was ~11,300 kg
(-10,500 kg DNAPL). The post-demonstration mass of TCE was ~1100 kg (-340 kg DNAPL). These
data suggest a removal efficiency of TCE of 90% (97% for DNAPL). As for the oxidation cell, kriging of
the soil data are provided.
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The vapor recovery system affords an opportunity to measure the amount of TCE recovered from the cell.
During the period of operation, -1950 kg of TCE was recovered along with a small amount of TCE
degradation products. The recovered TCE accounts for approximately 17% of the TCE thought to have
been in the test cell. The amount of TCE left in the cell following the demonstration along with what was
recovered accounts for only -27% of the total. We believe that there are several possible explanations for
the "missing" mass of TCE:
• The mass estimates for TCE in the cell are grossly in error
• Some TCE extracted into the vapor treatment system escaped before being measured
• Some TCE vapor escaped into the atmosphere by fugitive emissions through the surface of the test
cell during the demonstration
• Some TCE migrated laterally in the subsurface beyond the boundaries of the test cell
• Some TCE was destroyed in situ by HPO or other types of reactions
The results of this demonstration are still being evaluated, but we believe that several of these possible
explanations are the most likely cause for the missing mass. Specifically, we believe that some unknown
quantity of TCE migrated beyond the cell boundary in the subsurface. Some of the thermocouple data
indicate that the MFGU may not permit an easy pathway for vertical migration of steam and TCE vapor
due to its lower permeability. Consequently, we believe that lateral migration of some vapor and
contaminated groundwater probably occurred to regions outside of the cell boundary near the LSU-
MFGU contact. There is evidence that shallow groundwater flow also occurred through the SPH cell due
to the heavy rains associated with tropical storms during September-October 1999. In addition,
displacement of contaminated groundwater in the ISCO cell due to KMnO4 injection may have
contributed to some lateral flow in the SPH cell. Together, these mechanisms are believed to have
resulted in lateral migration of contamination outside of the cell.
The great increase in chloride content in groundwater within the cell suggests that oxidation or other types
of degradation reactions mineralized a significant amount of TCE. However, boiling of groundwater may
account for some of the observed increase in chloride concentrations.
Our information on fugitive emissions is confined to a series of short-term measurements using vapor-
trapping chambers placed on the ground surface. The results are not definitive, but we cannot rule out this
process as contributing to the missing TCE mass.
5.3 Steam Treatment
The steam demonstration has only been in operation for several months and available performance
information is being collected. However, the steam and co-air injection process appears to be working
well and significant recovery of TCE by the extraction wells has been observed. Furthermore, information
obtained from an extensive thermocouple network suggests that the steam-air-TCE mixture is not
migrating laterally in an uncontrolled fashion and bypassing the extraction well network. The initial
amount of TCE in the steam cell prior to the demonstration is reported in Table 1.
6. HEALTH AND SAFETY
All of the technologies tested at Launch Complex 34 have been deployed at other sites over a period of at
least several years. Consequently, while certain precautions must be taken, most health and safety issues
were anticipated and addressed successfully.
For ISCO, KMnO4 is a stable oxidant and does not present unusual handling problems. However,
precautions must be taken to avoid skin contact with the KMnO4by wearing Tyvek suits and by
maintaining a solution of vinegar, hydrogen peroxide, and water to neutralize oxidant spills on the ground
or clothing.
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The SPH technology has several potential areas where health and safety considerations must be
addressed. Foremost among these is controlling the transport and distribution of high voltages (up to 500
V) used to power the electrodes. The vendor was successful in insulating the ground surface from the
current passing through the aquifer. Secondly, when the water in the aquifer is at the boiling point,
monitoring wells screened in the heated zone either must remain sealed or must be vented to the off gas
treatment system. Opening a well cap under these conditions leads to pressure release and flash boiling of
groundwater and presents a threat of serious burns to personnel.
For the steam technology the major health and safety issue is related to the handling of steam and the
potential for burns.
7. ENVIRONMENTAL IMPACTS
There are two major sources of environmental impact from the application of these technologies. First,
with ISCO an industrial grade of KMnO4 was used to make the oxidant solution with a concentration up
to -3% by weight. This grade of permanganate contains trace amounts of a number of constituents. At a
concentration of 1-2%, the solution exceeds the drinking water standard for several elements (e.g., Cr)
and approval was required from the State of Florida to permit injection. In addition, it is possible that the
permanganate solution can oxidize and mobilize indigenous metals associated with the geologic media.
These effects are believed to be short-lived.
The second type of environmental impact is related to the impact of the oxidant or thermal treatment
process on the microbiological community present in the subsurface. In order to evaluate this impact, we
sampled the soil in each cell prior and subsequent to treatment and evaluated changes in the microbial
population. We are in the process of collecting and evaluating these data, but it seems clear that
application of the technologies caused a net reduction in the overall numbers of microbes. However, we
do not know at this time how different types of bacteria were affected by the demonstration.
8. COSTS
Table 3 presents a summary of the cost of applying both the ISCO and SPH technologies at Cape
Canaveral. Results for the steam technology are not complete at this time and only estimates are provided
in Table 3. The cost is very sensitive to several factors. For ISCO, the cost is strongly related to the
amount of TCE that needs to be oxidized and to the oxidant demand from the media itself. The oxidation
test cell at Cape Canaveral contained ~6000kg of TCE, requiring a rather large amount of KMnO4 which
contributed significantly to the cost. In contrast, the major cost for SPH results from the electricity used to
heat the media and groundwater in the test cell and to produce steam. The incremental cost of vaporizing
the TCE is inconsequential. Therefore, the amount of TCE in the cell is not a significant cost driver.
The costs incurred to apply these technologies depend on the specific way it is deployed (e.g. delivery
system used, performance target to be achieved, etc.). What is shown in Table 3 is specific to the design
of the demonstrations we conducted.
9. CONCLUSIONS
Demonstrations of the three DNAPL source remediation technologies used at Cape Canaveral are
providing a rich source of data that will be evaluated during the next year. We have completed collecting
most of the monitoring data associated with the ISCO and SPH demonstrations; the steam demonstration
is still in progress and monitoring results are incomplete at this time.
In general, we can conclude that both the oxidation and SPH demonstrations were successful in removing
and/or destroying a significant fraction of the TCE from their respective test cells. Treatment efficiencies
equal to or exceeding 80% for SPH and from 62-84% for ISCO are indicated by the data. There is an
indication that for the SPH demonstration as much as -70% of the TCE cannot be accounted for. There is
evidence that some of the "missing" mass was destroyed in situ by oxidative reactions, although some
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may have migrated laterally outside of the cell. In addition, fugitive emission of TCE vapor through the
ground surface cannot be ruled out.
These demonstrations and the associated cost and performance data are only one step of a planned effort
to test innovative DNAPL source remediation technologies under a variety of site conditions. Based on
the Cape Canaveral and other related demonstrations, we recognize that a number of scientific and
engineering questions about the technologies remain to be resolved. Further testing and scientific inquiry
are the only way in which these questions can be answered.
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January 2002
Table 1: Estimated masses of total TCE, DNAPL, and cleanup efficiency from application of the ISCO,
SPH, and DUS/HPO technologies at Launch Complex 34
Pre-Demonstration
Mass of Total TCE (kg)
Contouring
Kriging (80% CI)
Mass of TCE DNAPL (kg)
Contouring
Post-Demonstration
Mass of Total TCE (kg)
Contouring
Kriging (80% CI)
Mass of TCE DNAPL (kg)
Contouring
CLEANUP EFFICIENCY FOR TOTAL
Contouring
Kriging (80% CI)
Cleanup Efficiency for TCE DNAPL(%)
Contouring
ISCO
6122
6217 to 9182
5039
1100
15 11 to 2345
810
82
62 to 84
84
SPH
11,313
7498 to
10,490
1101
1031 to 1535
338
90
80 to 93
97
Steam
11,797
NA
10,649
NA
NA
NA
NA
NA
NA
NA = Data not available
Table 2: Amount (Volume and Mass) of KMnO4 Injected
Injection
Phase
Phase 1
Phase 2
Phase 3
usu
Volume (m3) Mass of
KMnO4 (kg)
325 6059
249 4923
165 3372
MFGU
Volume (m3) Mass of
KMnO4 (kg)
353 8484
82 1348
225 4589
LSU
Volume (m3) Mass of
KMnO4 (kg)
476 13,904
1316 24,277
Table 3: Cost Summary of Technologies
Technology
ISCO
SPH
Steam
Cost ($US)
Per kg of TCE Removed or
Destroyed
$236
$63
Not available yet
Per m3 of Geologic Media
Treated
$236
$135
Not available yet
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January 2002
Project No. 21
Development and Use of a Permeable Adsorptive Reactive Barrier System for
Ground Water Cleanup at a Chromium-Contaminated Site
Location
Wood impregnation plant
Leisi, Willisau, canton
Luzern, Switzerland
Technical Contact
Prof. Rita Hermanns Stengele
Institute of Geotechnical
Engineering
Swiss Federal Institute of
Technology Zurich
CH-8093 Zurich, Switzerland
Tel: +41-1-6662524
Fax:+41-1-6331248
E-mail:
hcj]MMMMiM^^M^h?ijAi
Project Status
New
Project Dates
Accepted 2000
Costs Documented?
Yes (estimated)
Contaminants
Chromium (CrVI)
Technology Type
Permeable reactive
wall
Media
Ground water
Project Size
Full-scale
Results Available?
No
Information in this project summary is current as of January 2000.
1. INTRODUCTION
This on-site remediation project will be conducted at an ongoing wood impregnation plant in Willisau, a
small village in the canton of Luzern, Switzerland. The downstream plume of chromium (CrVI)
contaminated ground water will be treated by an innovative permeable adsorptive reactive barrier (PRB)
system. A full-scale field installation will be conducted to clean up the contaminated ground water.
Laboratory tests are running to evaluate the appropriate adsorptive filler material (no zero-valent iron).
Project objectives are to learn about the long-term efficiency of the wall system regarding the
geochemical/physical aspects, as well as the mechanical aspects.
2. BACKGROUND
The wood impregnation plant has existed since the beginning of the 20th century. It is located in the small
village of Willisau in the canton of Luzern, Switzerland. The area is about 20,000 m2. Site investigation
showed a main contamination with chromium in the soil and in the ground water due to the impregnation
work, the handling, and, in the main case, the dump of impregnated wood on the unpaved terrain without
any cover against rainfall.
Downstream from the plant area, the ground water is collected in a pumping station. The main
contaminant in the ground water is chromium (CrVI) with a concentration ten times more than allowed in
the Ordinance relating to the cleanup of contaminated sites (1998) in Switzerland.
The aquifer is about 10 m thick; the ground water level about 10m under the surface. That means a
permeable reactive barrier system of about 20 m depth has to be installed. The permeability of the aquifer
is about kf « 10-3 - 10-4 m/s.
The project is funded by the Swiss Agency for the Environment, Forests and Landscape (50%). The other
project partners are: Institute of Geotechnical Engineering, Swiss Federal Institute of Technology, Zurich;
Dr. Franz Schenker, Geological Consulting, Meggen; BATIGROUP AG, construction company, Zurich
and Ulrich Leisi, Willisau (owner of the plant), (all together 500/
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3. TECHNICAL CONCEPT
In the initial stage of the project, appropriate adsorptive filler (e.g., clay, bentonite, modified clay, or
bentonite, zeolite) will be evaluated in the laboratory. They will be characterised based on mineralogy
(e.g., x-ray, BET surface, exchange capacity). Following the selection of suitable materials, various mixes
of reactive and filler materials will be prepared. This mixture will be tested regarding its effectiveness to
reduce the contaminants, as well as regarding its mechanical behaviour and stability. Soil mechanical tests
(e.g., permeability tests, erosion tests, and compressive strength tests) will be carried out. Batch and
column tests will be used to measure parameters like adsorption capacity, time of reaction, and by-
products.
At the same time, field data from the plant, especially regarding geology and hydrogeology, will be
collected. Depending on the results, the ground water flow and contaminant transport will be modeled
using a simulation system. The design of the reactive wall or the funnel-and-gate system (e.g., length,
depth, and number of gates) also will be calculated using flow and transport modeling.
After finishing the laboratory tests, the PRB will be installed in the field. The construction of the PRB
with the chosen suitable material for underground conditions will be tested in situ. The field results
obtained will be compared with both the laboratory and numerical values. During the field installation
careful performance monitoring is required. Parameters requiring monitoring to assess performance
include: contaminant concentration and distribution, presence of possible by-products and reaction
intermediates, ground water conductivity and ground water levels, permeability of the PRB, and ground
water quality. Monitoring wells will be installed on both sides (upgradient and downgradient) of the wall
in order to obtain information about remediation of contaminants and of the long-term performance (long-
term monitoring).
4. ANALYTICAL APPROACH
Mineralogical composition will be determined using x-ray diffraction, BET surface area measurements
with nitrogen, exchange capacity, and porosity. Pore size distribution will be determined with mercury
pressure porosimetry and adsorption characteristics with water isotherms.
Chemical analysis depending on type of contaminant (e.g., atom adsorption spectometry or infrared
spectometry) will be conducted.
Soil mechanical parameters will be determined using Swiss Standard Tests (e.g., compressive strength by
unconfined compression strength tests, stress and deformation behaviour by oedometer tests, time-
settlement behaviour (consolidation) by oedometer tests, friction angle and cohesion by direct shear tests,
permeability tests with triaxial permeability cells).
5. RESULTS
The project started in summer 2000. Laboratory tests are running to evaluate appropriate adsorptive filler
materials. There are no final results available at the moment. The installation of the PRB will start in
autumn/winter 2001. The performance will be evaluated in the following months and years by monitoring
the ground water quality, the remaining adsorption capacity of the filler material, and the functioning of
the whole wall system.
The results of the project will be presented in half-year periods to the Swiss Agency for the Environment,
Forests and Landscape and to all persons involved.
6. HEALTH AND SAFETY
During the installation of the PRB, no volatile substances will be released because no volatile
contaminants were measured in the water or in the soil.
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To avoid direct contact with heavy metals during excavation of soil and installation of the PRB, suitable
coveralls, shoes, and gloves had to be worn by the manual workers.
7. ENVIRONMENTAL IMPACTS
An emission of volatile substances will not occur because of the above-mentioned types of contaminants.
To avoid an unacceptable noise level during the installation of the PRB, the Swiss Regulations will be
followed.
Pumped water will be analysed and, in the case of contamination, sent to a treatment plant.
8. COSTS
In the very early stages of this project, the cost was estimated about sfr. 1.3M (about U.S.$ 0.8M).
Specific costs will be reported at a later date.
9. CONCLUSIONS
The objective of this research project is the development of a novel adsorptive media to apply in PRBs for
ground water cleanup at a chromium-contaminated site. Geochemical and soil mechanical tests are
currently being conducted. Laboratory test results should be applied and verified by implementing field
tests.
As soon as suitable, the permeable adsorptive reactive barrier system should be verified in full-scale at the
chromium contaminated wood impregnation plant in Willisau. During and after installation of the PRB, a
monitoring concept has to be carried out to verify the long-term behaviour of the reactive wall, as well as
the ground water contamination.
10. REFERENCES
1. EPA United States Environmental Protection Agency: Field Applications of in situ Remediation
Technologies: Permeable Reactive Barriers. In EPA 542-R-99-002, 1999.
2. Gavaskar, A.R.; Gupta, N.; Sass, B.M.; Janosy, R.J. & O'Sullivan, D.: Permeable Barriers for
Groundwater Remediation. Design, Construction and Monitoring. Ohio: Batelle Press Columbus,
1998.
3. Kohler, S. and Hermanns Stengele, R.: Permeable Reactive Barrier Systems for Groundwater
Cleanup. GeoEng 2000. International Conference on Geotechnical & Geological Engineering,
Melbourne: (in print) 2000
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January 2002
Project No. 22
Thermal In-situ Remediation of the Unsaturated Zone by Steam Injection
Location
Former hazardous waste
disposal site,
Muhlacker, Germany
Project Status
New project
Contaminants
TCE, BTEX
Technology Type
Steam injection
Technical Contact
Dr.-Ing. H.-P. Koschitzky
Dipl.-Ing. T. Theurer
Research Facility for
Subsurface Remediation,
VEGAS,
University of Stuttgart,
Pfaffenwaldring 61
D-70569 Stuttgart, Germany
koschi@iws.uni-stuttgart.de
Project Dates
July 1999-
November2001
Media
Unsaturated zone
Costs Documented?
Not yet
Project Size
Pilot-scale
Results Available?
Preliminary
1. INTRODUCTION
Combined steam injection and soil vapour extraction can accelerate and improve the clean-up of
contaminated unsaturated soils due to significant changes in contaminant properties with increasing
temperature. The main effect is the dramatic increase in contaminant vapour pressures leading to high
removal rates in the vapour phase.
A pilot scale demonstration project using the technology is currently carried out at a former hazardous
waste disposal site near the town of Muhlacker in southwestern Germany.
2. BACKGROUND
In the late 1960s a disposal site for hazardous wastes containing chlorinated solvents and galvanic sludges
was opened in a forest near Muhlacker. The wastes were deposited within a layer of silty loam which was
considered to be impermeable enough to protect the subsurface underneath from being contaminated by
the leachate of the waste site. Nevertheless, by the late 1970s, contaminants had migrated through the
unsaturated zone below which consists of highly heterogeneous weathered sandy marl and were detected
in the underlying Keuper gypsum aquifer 30m below ground surface. Detailed site investigation lead to
the conclusion that separate phase contaminants (mainly TCE) were retained by a capillary barrier
intersecting the unsaturated zone at a depth of 15 m below ground surface.
Soon after that the site was included in the model site program ("Modellvorhaben") funded by the state of
Baden-Wurttemberg and remediation activities started. The site was encapsulated by sheet piles and an
asphalt cover was placed on the surface to reduce the leachate flux from the deposited waste.
Remediation of the deposited waste itself and the groundwater zone was conducted as well as conven-
tional soil vapour extraction in the unsaturated zone. Due to the complex nature of the subsurface, in-situ
remediation of the unsaturated zone by means of conventional methods was ineffective. To enhance
contaminant removal a thermally enhanced remediation scheme was installed in a section of the site
where steam can be injected in the highly contaminated zone between 7 and 15m below ground surface.
The total volume of soil to be treated in the target area is approximately 3000 m3.
The pilot plant is operated by the two companies Ziiblin Umwelttechnik GmbH and Preussag
Wassertechnik GmbH and VEGAS from the University of Stuttgart who conducts the scientific oversight.
The pilot study is funded by the "Kommunaler Altlastenfonds" and the city of Muhlacker, represented by
the consultant company Weber-Ingenieure GmbH.
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3. TECHNICAL CONCEPT
The egg-shaped test field with a diameter of about 20 m consists of one central steam injection well
surrounded by six extraction wells. The extraction wells can be used simultaneously for vapour and liquid
extraction. All wells reach to a depth of 16 m below ground surface and are screened from 7 m to 15 m.
Steam is generated using a gas-fired 110 kW steam generator. Extracted gases are passed through a
condenser. Incondensable gases flow through a catalytic combustion unit before being vented to the
surrounding atmosphere. Condensate flows in liquid separators where the contaminant is separated from
the water. Liquids are removed from the wells with surge pumps, passed through a cooler and flow in a
separator where the non-aqueous phase is separated from the water.
In order to measure temperatures in the subsurface up to a depth of 15 m, ten temperature monitoring
lances were installed with a total of 100 sensors spaced every 70 cm of depth. Detailed monitoring of gas
and liquid flow rates and temperatures is carried out during the pilot test.
4. ANALYTICAL APPROACH
Soil samples were taken and analyzed to determine the extend of subsurface contamination. For this
purpose contaminants were extracted from the soil by a solvent and analyzed using the HPLC method.
During operation, contaminant concentrations are measured regularly in the extracted vapours and liquids
using GC and HPLC methods and a flame ionization detector (FID).
5. RESULTS
After at least about ten months of steam injection, almost complete heating of the target zone has been
achieved. Since March 2001,the steam injection was finished and the test field is cooling down. Up to
now more than 2500 kg of TCE have been removed, about 95% were extracted in the gaseous phase, and
the remaining part as solute in condensed water. The cooling process is expected to be finished end of
2001.
6. HEALTH AND SAFETY
Safety equipment is used by the staff according to German safety regulations. The pilot plant is equipped
with warning systems to control vapour and liquid streams, temperatures and performance of the pumps.
7. ENVIRONMENTAL IMPACTS
Extracted vapours and liquids are cleaned on-site in a treatment facility consisting of a catalytic
combustion unit and stripping columns. Thus, emissions to the environment are avoided. Measures for
protection against noise are undertaken. Monitoring wells were installed to control contaminant
concentrations in the underlying aquifer.
8. COSTS
Not yet available
9. CONCLUSIONS
Despite the low permeability of the subsurface, steam injection could be applied successfully. The
problem of buoyancy of the heat front because of capillary water in the subsurface could be overcome by
using intermittent steam injection towards the end of the heating process. Conductive heat transport in
injection breaks warmed up regions of the soil, where convective heat transport was negligible.
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10. REFERENCES
1. Koschitzky, H.-P., Theurer, T., Schmidt, R., Winkler, A., Farber, A. (2000): Pilot-scale study of
steam injection for thermal in-situ remediation of the unsaturated zone below a hazardous waste site.
Proc. ConSoil2000, Leipzig
2. Koschitzky, H.-P., Theurer, T., Schmidt, R., Winkler, A., Farber, A. (2000b): In situ remediation of
unsaturated zone by steam injection: results of pilot studies. Proc. ..Implementation of in-situ
remediation techniques: Chlorinated solvents and heavy metals", Utrecht
3. Koschitzky, H.-P., Theurer, T., Farber, A. (2001): Einsatz des thermischen In-situ-
Sanierungsverfahrens TUBA unter schwierigen Bedingungen. Boden und Altlasten-Symposium,
Berlin 21.02.-22.02. 2001 (in German)
4. Schmidt, R., Koschitzky, H.-P. (1999): Pilothafte Sanierung eines BTEX Schadens an einem
ehemaligen Gaswerksstandort mit der thermisch unterstutzten Bodenluftabsaugung (TUBA) durch
Dampfinjektion, Wiss. Bericht WB 99/5 (HG 262), Institut fur Wasserbau, Universitat Stuttgart
(in German).
5. Theurer, T., Winkler, A., Koschitzky, H.-P. & Schmidt, R. (2000): Remediation of a landfill
contamination by steam injection. In: Groundwater 2000, Proc. of the Intl. Conference on
Groundwater Research, Copenhagen, Denmark, 6-8 June 2000, 371-372.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 23
Bioremediation of Pesticides
Location
Stauffer Management Company
Superfund Site, Tampa, FL
Technical Contact
Brad Jackson
U.S. EPA, Region 4
61 Forsyth Street, SW
Atlanta, GA 30303-8960
Tel: 404-562-8925
Fax: 404-562-8896
Neil C.C. Gray, Ph.D.
AstraZeneca Canada
2101HadwenRoad
Mississauga, Ontario
L5K 2L3
Tel: 905-403-2748
Fax: 905-823-0047
E-mail: neil.gray^astrazcncca.com
Project Status
Final Report
Project Dates
Accepted 2000
Final Report 2001
Costs Documented?
Yes, for both field
demonstration and
full-scale operations
Contaminants
Chlordane, DDT,
ODD, DDE,
dieldrin, molinate,
toxaphene
Media
Technology Type
Composting process
(Xenorem TM)
Soil and pond sediments
Project Size
Field Demonstration:
500 yd3
Full-scale: 8,000 yd3
Full-scale: 16,000 yd3
in 4,000 yd3 batches
Results Available?
Yes, for both field
demonstration and
full-scale operations
1. INTRODUCTION
The Stauffer Management Company (SMC) Tampa site is one among a small number of U.S.
contaminated waste sites implementing bioremediation at full-scale to cleanup soils with pesticide
contamination. A completed field demonstration (500 yd3) using soil contaminated with high levels of
DDT showed that the DDT could be biodegraded without the end accumulation of the major metabolites,
ODD and DDE. In comparison, DDT was readily degradable, so was the more recalcitrant metabolites; a
reduction of more than 90 percent for ODD occurred.
Beginning in May 2000, the project has been operating under full-scale conditions at the SMC Tampa
site, with 4,000 yd3 of contaminated soil being treated in each batch.
In addition to the operation at the SMC site, 8,000 yd3 of pesticide contaminated soil (with high levels of
toxaphene) from the Helena Chemical superfund site (Tampa, FL) was also excavated and successfully
treated using this technology; this project was finished in early 2001.
2. BACKGROUND
Located in Tampa, Florida, the SMC site formulated and distributed agricultural chemical products
(organochlorine, thiocarbamate and organophorphorus pesticides) from 1951 to 1986. Up to 1973, waste
materials from the facility were disposed of on site by two methods: burial or incineration. The
containerized wastes, packaging materials, and other pesticides buried led to pesticide contamination in
soil, surface water, and sediment in on site ponds and in groundwater underlying the site.
The site received final status under the Superfund program in 1996. Thermal desorption was initially
chosen as the remedial option. However, due to high sulfur and other compounds in the soil, the
implementation of thermal desorption was determined to be unsafe for the SMC site. Therefore,
bioremediation was identified as the selected remedy for the pesticide-contaminated surface soils and
sediments at the site.
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The objective of the laboratory research trials and the field demonstration was to determine if the
composting process could meet the specified cleanup levels or achieve 90 percent reduction in
contaminant concentration. These objectives were met, leading to the implementation of bioremediation
as the full-scale technology for the site.
3. TECHNICAL CONCEPT
AstraZeneca Canada, an affiliated company of SMC, developed a patented enhanced composting process
called XenoremTM for remediating soils contaminated with recalcitrant organics, such as chlorinated
pesticides, PAHs and explosives. XenoremTM uses anaerobic and aerobic cycles to bioremediate the
parent compound and daughter products of concern. Laboratory studies (e.g. radio-labeled biodegradation
studies, fate studies, microbial screening etc.), were followed by comparative lab and pilot studies (14, 60
and 100 yd3), and a field study (500 yd3), before moving to full-scale operations. A number of
engineering configurations were also comparatively evaluated in the field, including landfarming,
biopiles, and composting in order to evaluate the XenoremTM technology.
Organic amendments are added to the contaminated soil to enhance the temperature within the pile and to
aid in creating the anaerobic periods. Aerobic periods were created by mechanical mixing, using a SCAT
windrow turner. The indigenous microflora associated with the contaminated soil is manipulated by
changing the environment associated with the soil matrix. Based on a decision tree, created from the
results of microcosm and respirometry studies, the duration and degree of each of the anaerobic/aerobic
cycles is predetermined.
For the first 4,000 yd3 batch, the soil was excavated, screened, mixed and amended with dairy manure,
wood chips and chicken litter. The amended soil matrix was engineered into a compost windrow, built
inside a Big Top structure. Due to potential odor issues from some of the pesticides, and the high
groundwater table in the area, it was prudent to carry out the operation in an enclosure. An odor abatement
system, consisting of two blowers, four particulate prefilters and a 10 ton carbon charge to polish the air
stream was used.
4. ANALYTICAL APPROACH
To monitor the progress in the full-scale operation, eight composite samples were collected from the
windrow, on a regular basis (e.g. after an anaerobic/aerobic cycle); the seven chemicals of concern, as
listed in the Record of Decision for the site, were chlordane, ODD, DDE, DDT, dieldrin, molinate and
toxaphene. At time-zero (TO) and at the end of the run (Tf), 40 composite samples were taken. The soil
samples were analyzed using EPA Method 8081A. For toxaphene analysis, gel permeation
chromatography (SW846 Method 3640A) and sulfuric acid (based on SW846 Method 3 665A) clean-up
methods were performed on the soil samples prior to chemical analysis by EPA Method 8081 A.
The environmental parameters (temperature, redox, oxygen, and moisture levels) were monitored
continuously using a data acquisition/controller system, permitting real-time access to the data.
Measurement confirmation was also carried out using hand-held probes.
5. RESULTS
Tables 1 and 2 show the cleanup levels specified for selected constituents, the initial (TO) and end (Tf)
concentrations for the field trial and full-scale operation, and the percent reduction in concentration over
that period.
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January 2002
Table 1: Summary of End-Points Achieved for the 500 yd3 Field Trial
Pesticide
ROD Level
(ppm)
To Value
(ppm)
Tf Value
(ppm)
% Degraded
Comments
Chlordane
ODD
DDE
DDT
Dieldrin
Molinate
Toxaphene
2.3
12.6
8.91
8.91
0.19
0.74
2.75
47.5
242
11.3
88.4
3.1
10.2
469
5.2
23.1
6.8
1.2
90%
ROD
ROD
90%
Table 2: Summary of End-Points Achieved for the 4,000 yd3 Full-scale Operation
Pesticide
ROD Level
(ppm)
To Value
(ppm)
Tf Value
(ppm)
% Degraded
Comments
Chlordane
ODD
DDE
DDT
Dieldrin
Molinate
Toxaphene
2.3
12.6
8.91
8.91
0.19
0.74
2.75
3.8
26
6.6
82
2.4
0.2
129
94%
6. HEALTH AND SAFETY
A complete Work Plan, including a Site Specific Health and Safety Plan was followed for both the field
trial as well as for the full-scale operation. Air monitoring was carried out during all soil handling
operations, with no excursions over the action limits cited.
It should be noted that if the soil contains high levels of sulfur, the production of hydrogen sulfide could
occur.
7. ENVIRONMENTAL IMPACTS
No environmental impacts were found. Once the soil is treated, it is available to be used as fill at the site.
8. COSTS
For the full-scale operation (4,000 yd3 batch) the total project costs were estimated at $192/yd3, including
$132/yd3 for the treatment using XenoremTM; this cost can be significantly reduced if the work is carried
out by the owner of the site, if the amendments used are local and if the operation is greater in scale.
Regulatory requirements and/or the end point that has to be achieved also influences the costing.
9. CONCLUSIONS
Data collected in the field trial, the full-scale operation, and the previous laboratory and pilot-scale work
demonstrated that the ROD chemicals of concern are biodegradable. The XenoremTM technology, when
operating within the optimal environmental/process windows is effective in reducing the target pesticides
to the ROD levels and/or at least 90%, for the SMC Tampa site.
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It has been demonstrated that the field conditions can be manipulated/controlled to provide/create the
necessary conditions for the technology to work successfully. As additional data and "learning curve"
experiences are evaluated, the operational parameters for each new batch is being modified, to increase
the overall efficiency of the operation.
10. REFERENCES
1. Gray, N.C.C., P.R. Cline, A.L. Gray, L.E. Moser, G.P. Moser, H.A. Guiler, B. Boyd and D.J.
Gannon, 2001. Full-scale soil bioremediation of chlorinated pesticides. 6th In Situ and On-Site
Bioremediation International Symposium, San Diego, CA. June 4th-7th.
2. Gray, N.C.C., P.R. Cline, A.L. Gray, L.E. Moser, G.P. Moser, H.A. Guiler, B. Boyd and D.J.
Gannon, 2000. Bioremediation of DDT and toxaphene contaminated soils. 16th Annual International
Conference on Contaminated Soils, Sediments and Water, Amherst, MA, October 16th.
3. Gray, N.C.C., P.R. Cline, A.L. Gray, L.E. Moser, G.P. Moser, H.A. Guiler, B. Boyd, and D.J.
Gannon, 2000. Anaerobic/aerobic cycling to bioremediate pesticide contaminated soils. 6th
International Conference on Advanced Oxidation Technologies for Water and Air Remediation,
London, Ontario, June 25-30th.
4. Gray, N.C.C., P.R. Cline, G.P. Moser and D.J. Gannon, 2000. Bioremediation of toxaphene
contaminated soil. Second International Conference on Remediation of Chlorinated and Recalcitrant
Compounds. Monterey, CA. May 24th.
5.
Gray, N.C.C., 2000. Full-scale bioremediation of chlorinated pesticides, Biotech Mag, April edition
6. Moser, G.P., N.C.C. Gray and D.J. Gannon, 2000. Treatment of nitroaromatic contaminated soils
using the Xenorem technology. Second International Conference on Remediation of Chlorinated and
Recalcitrant Compounds, Monterey, CA. May 23rd.
7. U.S. Environmental Protection Agency, 2000. Cost and Performance Report: Bioremediation at the
Stauffer Management Company Superfund Site, Tampa, Florida.
8. Moser, G.P., N.C.C. Gray and D.J. Gannon. 2000. Compost Decontamination of Soil Contaminated
with Polychlorinated Biphenyls Using Aerobic and Anaerobic Microorganisms. U.S. Patent No.
6,083,738 (July 4th).
9. Moser, G.P. and N.C.C. Gray. 2000. Compost Decontamination of Soil Contaminated with
Pentachlorophenol Using Aerobic and Anaerobic Microorganisms. U.S. Patent No. 6,033,899 (March
7th).
10. Moser, G.P., N.C.C. Gray and D.J. Gannon, 2000. Compost Decontamination of Soil Contaminated
with Polychlorinated Biphenyls using Aerobic and Anaerobic Microorganisms. U.S. Patent No.
6,083,738 (July 13th).
11. Moser, G.P. and N.C.C. Gray, 1999. Compost Decontamination of Soil Contaminated with TNT,
HMX, and RDX with Aerobic and Anaerobic Microorganisms. U.S. Patent Number: 5,998,199
(December 7th).
12. Gray, N.C.C., G.P. Moser and L.E. Moser, 1999. Compost Decontamination of Soil Contaminated
with Chlorinated Toxicants. U.S. Patent Number 5,902,744 (May llth).
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13. Bernier, R.L., N.C.C. Gray and A.L. Gray, 1997. Anaerobic/aerobic Decontamination of DDT
Contaminated Soil by Repeated Anaerobic/Aerobic Treatments. U.S. Patent Number: 5,660,613
(August 26th).
14. Bernier, R.L., N.C.C. Gray and L.E. Moser, 1997. Compost Decontamination of DDT Contaminated
Soil. U.S. Patent Number: 5,660,612 (August 26th).
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Project No. 24
Surfactant-Enhanced Aquifer Remediation
Location
Site 88, Marine Corps Base,
Camp Lejeune, NC
Project Status
Completed Project
Contaminants
Tetrachloroethylene
(PCE)
Technology Type
Surfactant flushing
Technical Contacts
Laura Yeh
Naval Facilities Engineering
Service Center
1100 23rd Ave.
Port Hueneme, CA 93043
Tel: 805-982-1660
Fax: 805-982-1592
E-mail: ychsi@iifcsc.ij.ayy.niJI.
Leland M. Vane, Ph.D.
U.S. EPA
National Risk Management
Research Laboratory
26 W. Martin Luther King Dr.
Cincinnati, OH 45268
Tel: 519-569-7799
Fax: 513-569-7677
E-mail: vane.lelandi@epa.gov
Gary A. Pope, Ph.D.
The University of Texas
Austin, TX 78712
Tel: 512-471-3235
Fax: 512-471-3605
E-mail: ggojc@mail.utgxas.cdii
Frederick J. Holzmer
Duke Engineering & Services
4433 NW Seneca Ct.
Camas, WA 98607
Tel: 360-834-6352
Fax: 360-834-7003
E-mail:
Project Dates
Accepted 2000
Final Report 2001
Media
Groundwater
Costs Documented?
Yes
Project Size
Field Demonstration
(wellfield size of 20 feet
by 30 feet)
Results Available?
Yes
1. INTRODUCTION
Surfactant flushing offers the potential to address hazardous waste sites contaminated with non-aqueous
phase liquids (NAPL) in groundwater. A field demonstration of surfactant enhanced aquifer remediation
(SEAR) was conducted for dense-NAPL (DNAPL) remediation at the Marine Corps Base (MCB) Camp
Lejeune Superfund Site. The project was the first field demonstration to implement surfactant recycling
(i.e., surfactant recovery and reinjection) in the United States.
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2. BACKGROUND
A PCE-DNAPL zone was identified and delineated at the central dry cleaning facility, known as Site 88,
at the MCB Camp Lejeune, North Carolina. Discovered by extensive soil sampling in 1997, the site was
further characterized by a partitioning interwell tracer test (PITT) in 1998.
The DNAPL zone is located in a shallow aquifer beneath the dry cleaning facility at a depth of
approximately 17 to 20 feet below ground surface (bgs). A thick clay aquitard is present at about 20 feet
bgs, which has effectively prevented further downward DNAPL migration at this site. The shallow
aquifer is characterized as a relatively low-permeability formation composed of fine to very-fine sand,
with a fining downward sequence in the bottom two feet of the aquifer. The bottom, fine-grained zone,
referred to as the basal silt layer, grades to silt then clayey silt before contacting the aquitard. Permeability
decreases downward through the basal silt layer as a function of decreasing grain size with depth.
DNAPL was present in the test zone as free-phase and residual DNAPL in the fine sand and basal silt.
Recovery of free-phase DNAPL was undertaken before the PITT by conventional pumping and water
flooding. The pre-surfactant PITT measured approximately 74-88 gallons of PCE in the test zone. The
average DNAPL saturation estimated by the PITT was approximately 4 percent near the dry-cleaning
building and decreased to about 0.4 percent at a distance of about 15 to 20 feet from the building.
A field demonstration of surfactant-enhanced aquifer remediation (SEAR) was conducted at Site 88
during the spring of 1999. The objectives of the field demonstration were to: (1) validate in situ surfactant
flooding for DNAPL removal, (2) promote the effective use of surfactants for widespread DNAPL
removal, (3) demonstrate that surfactants can be recovered and reused, and (4) show that surfactant
recycle can significantly reduce the overall cost of applying surfactants for subsurface remediation.
3. TECHNICAL CONCEPT
The plan-view footprint of the SEAR demonstration well field was 20 feet by 30 feet. The SEAR
demonstration was conducted during April to August 1999, with a 58-day surfactant flood and followed
by a 74-day water flood. The demonstration utilized a custom surfactant, Alfoterra 145 4-PO sulfate™,
which was developed for the dual objectives of high PCE solubilization and desirable effluent treatment
properties (for surfactant recovery and reuse).
During the surfactant injection period, the extraction well effluent was treated using two membrane-based
processes to first remove the contaminant and then to reconcentrate the surfactant for reinjection.
Pervaporation was used to remove PCE from the extraction well effluent while micellar enhanced
ultrafiltration (MEUF) was employed to recover the surfactant. Regulations by the state of NC required
95 percent contaminant removal prior to surfactant reinjection. The pervaporation system removed 99.94
percent of the PCE from groundwater in the absence of surfactant and 95.8 percent PCE during periods of
peak surfactant concentrations. The MEUF system concentrated the surfactant from < 1 percent by weight
(wt %) in the extraction well effluent to 5 wt%, slightly above the reinjection concentration of 4 wt%.
Recovered surfactant was reinjected into the contaminated aquifer for the final 18 days of the surfactant
flood, thereby demonstrating the technical and regulatory feasibility of recovering and reusing surfactants
for aquifer remediation projects.
4. ANALYTICAL APPROACH
Monitoring included regular collection of samples for analysis in accordance with the sampling and
analysis plan. System operations also were continually monitored according to the work plan. Likewise,
the analytical methods used to monitor and assess the SEAR performance can be found in the sampling
and analysis plan.
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5. RESULTS
A total of 76 gallons of PCE was recovered during the surfactant flood and subsequent water flood, of
which approximately 32 gallons of PCE were recovered as solubilized DNAPL and 44 gallons were
recovered as mobilized free-phase DNAPL. Performance assessment of the demonstration is based upon
the analysis of 60 soil core samples that were collected at the completion of the SEAR demonstration.
Continuous soil cores were collected from approximately 17-20 ft bgs and field preserved with methanol.
Soil core data analysis estimated that a total of 29±7 gallons of DNAPL remains in the test zone following
the surfactant flood, distributed between the upper zone (fine sand sediments) and the lower zone (basal
silt layer).
Post-SEAR soil core data was further analyzed by subdividing the data into the upper and lower zones to
evaluate the effects of decreasing permeability upon the post-SEAR DNAPL distribution. The results
indicate that approximately 5 gallons of DNAPL remains in the upper zone, i.e., equivalent to about 92-96
percent removal from the upper zone, and approximately 24 gallons of the DNAPL is estimated to remain
in the lower zone, which was relatively unaffected by the surfactant flood. Effective DNAPL recovery
from the lower zone was limited by the permeability contrast between the upper fine sand zone and the
low-permeability basal silt layer. Hydraulic conductivity (K) in the upper zone is estimated to be on the
order of about 1 x 10-4 to 5 x 10-4 cm/sec (0.28 - 1.4 ft/day), whereas K in the basal silt is estimated to
be as low as about 1 x 10-5 to 1 x 10-4 cm/sec (0.028 - 0.28 ft/day), decreasing with depth to the aquitard.
Based on soil samples analyzed prior to the surfactant flood, the highest pre-SEAR DNAPL saturations
occurred in the upper, more permeable zone. The upper zone is the primary transmissivity zone for
transport of the dissolved-phase PCE plume at Camp Lejeune. Data analysis of post-SEAR DNAPL
conditions indicates that greater than 92 percent of the source was removed from the upper, transmissive
zone, and that the remaining DNAPL is relatively isolated in the basil silt layer (i.e., low-permeability
zone). The flux of dissolved PCE, from dissolution of DNAPL in the lower zone, to the upper zone will
be primarily limited to diffusion. Therefore, the source of the dissolved PCE plume is believed to be
substantially mitigated compared to pre-SEAR conditions. The overall effect of the surfactant flood is that
transport of the dissolved PCE plume from the SEAR treatment zone should be greatly reduced since the
primary mechanism for plume generation is now largely limited to diffusion of dissolved PCE from the
basal silt zone to the overlying transmissive zone. Details of this demonstration project can be found in
the Final Technical Report (Battelle and Duke Engineering & Services, 200la).
6. HEALTH AND SAFETY
No significant health and safety issues are associated with the implementation of SEAR, other than
potential exposure to DNAPL from handling the DNAPL-laden wastewater.
7. ENVIRONMENTAL IMPACTS
Environmental impact concerns for surfactant flushing include: hydraulic containment and recovery of
injected fluids, toxicity and biodegradability of the surfactant, and the potential risk associated with
mobilizing DNAPL. The demonstration at Site 88 maintained effective hydraulic control and recovery of
the injectate, with the exception of a minor loss of hydraulic control for a short period, followed by
reestablishment of hydraulic control. The surfactant used at Camp Lejeune exhibits low toxicity and was
biodegradable. DNAPL was mobilized, by design, during the demonstration. Downward migration by
mobilized DNAPL was addressed as result of the thick aquitard present at the site.
8. COSTS
An evaluation of the costs associated with the demonstration, as well as estimated costs for a full-scale
remediation at Camp Lejeune, can be found in the Cost and Performance Report for Surfactant Enhanced
Aquifer Remediation (SEAR) Demonstration, Site 88, MCB Camp Lejeune, NC (Battelle and Duke
Engineering & Services, 200 Ib). The report also includes a comparison of costs for full-scale SEAR at a
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high-permeability site, as well as cost comparisons to alternative remedial technologies. The alternative
technologies were compared only on a cost basis since there is no performance data for these technologies
at Site 88, MCB Camp Lejeune. Under the majority of scenarios studied, contaminant removal followed
by recovery and reuse of surfactant provided an overall cost savings. However, in all scenarios, the net
effect on remediation cost of recovering and reusing surfactants was marginal.
9. CONCLUSIONS
Results from the project indicate greater than 92 percent removal from the upper portion of the treatment
zone, which is the zone that contained the highest DNAPL saturations before conducting the
demonstration. The DNAPL in the basal silt layer (i.e., low-permeability zone) was relatively unaffected
by the surfactant flood. The SEAR demonstration targeted the removal of DNAPL from only
approximately 25 percent of the entire DNAPL zone for Site 88. Therefore, the amount of reduction in the
PCE plume as a result of the demonstration is difficult to confirm at this time unless the remainder of the
DNAPL zone is remediated to a similar degree as the demonstration area.
10. REFERENCES
1. Battelle and Duke Engineering & Services, 200la. "Final Technical Report for Surfactant-Enhanced
DNAPL Removal at Site 88, Marine Corps Base Camp Lejeune, North Carolina." Prepared for
NFESC by Battelle, Columbus, OH and Duke Engineering & Services, Austin, TX.
2. Battelle and Duke Engineering & Services, 200Ib. "Final Cost and Performance Report for Surfactant
Enhanced DNAPL Removal at Site 88, Marine Corps Base Camp Lejeune, North Carolina." Prepared
for Naval Facilities Engineering Service Center (NFESC) by Battelle, Columbus, OH and Duke
Engineering & Services, Austin, TX.
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January 2002
Project No. 25
Liquid Nitrogen Enhanced Remediation (LINER): A New Concept for the
Stimulation of the Biological Degradation of Chlorinated Solvents
Location
The Netherlands
Technical Contact
Chris Schuren,
Emile Marnette
Tauw bv
E-mail: chs@itauw.nl
Gijsbert-Jan Groenendijk
Hoek Loos bv
Project Status
New project
Project Dates
February 2000-
July 2003
Costs Documented?
Media
Soil and groundwater
Technology Type
Substrate injection
Contaminants
VOCls
Project Size
Field demonstration
Results Available?
Yes
1. INTRODUCTION
One of the major problems involved in soil remediation today is the treatment of deep groundwater
contaminated with chlorinated hydrocarbons. Biological degradation by microorganisms will often be the
best clean-up option. In practice, however, the addition of the substrate required to stimulate the
biological processes in-situ is a problem. Substrate infiltrated in liquid form mixes very slowly with the
contaminated groundwater and infiltration systems tend to clog easily. Furthermore, the limited radius of
influence of an infiltration well requires a dense network of wells.
In cooperation with gas company Hoek Loos, engineering consultancy Tauw has developed a new
remediation concept, overcoming most of the limitations inherent to the conventional in-situ biological
systems for degradation of CAH.
Remediation of soil contaminated with CAH. The Netherlands have numerous sites contaminated with
CAH. The most common remediation approach concerns pump and treat. However, authorities frequently
impose severe restrictions on groundwater extraction. In-situ air sparging based on the injection of
compressed air (possibly in combination with techniques such as steam injection, electro reclamation etc.)
may be an alternative for contaminants located in relatively shallow soil layers.
Over the past few years, methods to promote indigenous biological degradation of contaminations at
greater depths have been developed: the bacterial population present is stimulated to biotransform CAH
contamination. All methods involve introduction of a substrate (electron donor) into the subsurface.
Groundwater substrate transport. Substrate infiltrated in the subsurface as a liquid will mix very
slowly with the ambient groundwater. Degradation will mainly occur at the interface of the infiltrated
substrate and the contaminated groundwater. Infiltrated substrate flowing along with groundwater may be
degraded before reaching other contaminated areas downstream. Consequently, the network of infiltration
points required to effectively stimulate an existing natural attenuation processes will have to be very
dense. The cost of such networks makes them practically unfeasible, particularly for contaminations
located at large depths. Another potential problem involved in infiltration of substrates in liquid form is
clogging of the wells by biomass formation.
LINER - Gas/substrate injection. The injection of a substrate with gas as a means for distribution is a
concept which has not yet been tested as a remediation technique. This method combines two concepts:
stimulation of biodegradation of CAH by the addition of a substrate, and in-situ air sparging. Due to the
anaerobic nature of the targeted microbiological processes, nitrogen gas was used instead of compressed
air. The flow rate at which gas is distributed both horizontally and vertically within the soil is expected to
be much higher than that of water, which should make the injection of gas a much more effective
procedure than infiltration of an aqueous solution. Also, introducing substrate with a carrier gas is
expected to result in a much better mixing of the substrate with the groundwater than introducing the
substrate as a solution. Another advantage is the relatively low costs of injecting gas at great depths.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Earlier tests indicated that due to the stirring created in the soil by the injected gas (input of energy),
contaminants are more readily available for biological degradation or physical removal, which is a
favorable side-effect of the method (Tonnaer et al., 2001).
Objective. The objective of this research was to demonstrate in a field pilot test that injection of a
substrate with nitrogen carrier gas is a feasible alternative to the in-situ remediation methods commonly
applied to remediate CAH. The following aspects of gas injection were investigated:
• radius of influence and distribution pattern of the injected gas;
• effects of the injected substrate on the degradation rate of PCE, the original contamination.
2. MATERIALS AND METHODS
A pilot scale injection system consisting of a single injection well was installed at a depth of 43 m below
grade. Figure 1 gives a schematic representation of the pilot setup. A number of nested monitoring wells
was installed at a distance of 2, 4 and 6 m from the injection well at depths of 14-15 m, 24-25 m, 34-35 -
and 43-44 m below grade.
Figure 1: Schematic view of the pilot setup and spatial distribution of biodegradation
m
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Figure 2: LINER pilot test setup
Figure 2 shows the LINER pilot test setup. Liquid nitrogen is vaporized and the gas pressure is reduced to
the appropriate injection pressure. Methanol is nebulized into the nitrogen gas flow using nozzles.
Methanol was used because in several lab studies and field tests at other sites it proved to be a good
substrate to enhance biodegradation of CAH. During the first 12 weeks of the pilot study, methanol was
used as substrate. Nitrogen gas was injected daily for 4 minutes per day. About 10 m3 of nitrogen gas and
about 1 L methanol was added per injection.
After 12 weeks, the substrate was changed to a mixture of ethyl lactate and methanol (50/50 vol %). Each
month monitoring wells were sampled and analyzed for CAH, ethene, and ethane. In addition, methanol,
ethyl lactate and ethanol (ethyl lactate disintegrates into ethanol and lactate) were occasionally analyzed
at a selection of the monitoring wells.
Before the first substrate injection and after about 30 weeks, sulfate and methane were measured to see
whether substrate addition affected electron acceptor concentrations.
3. RESULTS AND DISCUSSION
Substrate distribution. At the injection location, methanol has been measured in high concentrations,
ranging from 130 mg/L at a depth of 34 m bgs to 570 mg/L at a depth of 14 m bgs. This vertical
distribution of methanol indicates the methanol vapor to be sufficiently stable to be distributed by the
nitrogen gas flow. Also ethyl lactate and ethanol were detected after injection at the location of injection
over this large range in depth.
No methanol, ethyl lactate, or ethanol, however, were detected in monitoring wells located laterally from
the injection well. Because of the high detection limit of methanol (2 mg/L), combined with biological
consumption, methanol may have reached the wells without being detected. Based on substrate
measurements, no clear distribution pattern of substrate could be observed.
Stimulated biodegradation of CAH. Since it became obvious that the distribution of substrate could not
directly be assessed by substrate analyses, analyses of CAH and degradation products were intensified. In
Figure 1 the extent to which CAH degradation was stimulated is shown qualitatively. The light color
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January 2002
represents the area where transformation of the CAH to the end product ethene was accomplished. The
dark color represents the area where dechlorination was incomplete and stopped at c/'s-dichloroethylene.
In Figures 3 and 4, results of two monitoring wells are shown that are representative for complete
degradation to ethane (Figure 4) and incomplete degradation to c/'s-dichloroethylene (Figure 3). During
the first 12 weeks no shift in the relative concentrations of the CAH or their degradation products was
observed in either well and therefore no significant biodegradation occurred. After 12 weeks, another
substrate was used (mixture of methanol and ethyllactate) and biodegradation clearly started. The total
concentration of degradation products increased compared to concentrations of PCE, the initial
compound. It is not clear whether the enhanced biodegradation is a result of switching substrates, or
whether the end of a lag in microbial growth was reached.
Figure 3: Absolute concentrations (a) and relative concentrations (b) of PCE and its degradation
products as a function of time at the location of Injection Well 901 at 14 m bgs.
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Figure 3a shows a significant decrease of the PCE concentrations in Monitoring Well 901 (14-15 m bgs).
The TCE concentration remained about constant, indicating that TCE rapidly was converted to cis-
dichloroethylene. The degradation seemed to stagnate at c/'s-dichloroethylene. A possible explanation is
that there was not enough biomass yet to convert c/s-dichloroethylene to vinyl chloride. Figure 3b shows
the relative contribution of the different compounds to the total molar concentration of ethenes. The
relative contribution of c-DCE increased significantly while PCE was almost been depleted.
Figure 4: Absolute concentrations (a) and relative concentrations (b) of PCE and its degradation
products as a function of time at 4 m distance from Injection Well (monitoring well 903 at 43 m bgs).
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In Monitoring Well 903 at 4 m distance from the injection well and 43 m bgs a significant decrease in
PCE and TCE concentrations was observed (Figure 4a). PCE was almost depleted and a complete
transformation to ethane occurred.
Electron acceptor processes. Before the start of the pilot test, sulfate concentrations ranged from 63 to
82 mg/L and did not change significantly during the test (30 weeks). Only in well 901 (at the location of
injection) did sulfate concentrations decrease to about 20 mg/L. Methane concentrations were < 1 mg/L
before the start of the test and concentrations did not increase. Methanogenesis apparently was not
stimulated by the addition of the substrates. Because the addition of the substrates resulted in
chloroethene transformation without significant sulfate reduction and methanogenesis, the lack of
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
substrate, not unfavorable electron acceptor processes, must be the cause of the absence of biological
degradation under natural circumstances.
Based on the results of the pilot test, LINER appears to be a promising technique for distribution of
substrates in the subsurface. At the site of the pilot test a full-scale remediation will be carried out using
LINER.
4. ACKNOWLEDGEMENTS
The Dutch Soil Research Program (8KB), Philips, the province of Gelderland and the Province of South
Holland are acknowledged for their financial support.
5. REFERENCE
Tonnaer, H., E.C.L. Marnette, P.A. Alphenaar, C.H.J.E. Schuren, K.M.J. van den Brink. 2001. LINER-
gasinjectie. Een nieuw concept voor de stimulering van de biologische CKW-afbraak. Report nr. SV-080,
CUR/SKB, Gouda, The Netherlands (in Dutch).
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January 2002
Project No. 26
SIREN: Site for Innovative Research on Monitored Natural Attenuation
Location
United Kingdom
Technical Contact
Theresa Kearney,
National Groundwater and
Contaminated Land Centre
Environment Agency
Olton Court, 10 Warwick Rd,
Olton, Solihull,
West Midlands B92 7HX
Project Status
Ongoing
Project Dates
September, 1999-
-2003
Costs Documented?
Yes
Contaminants
Organic solvents
Technology Type
Monitored natural
attenuation (MNA)
Media
Consolidated and non-consolidated aquifer
Project Size
>£1 million
Results Available?
Yes
1. INTRODUCTION
SIReN is the acronym for the Site for Innovative Research on Monitored Natural Attenuation (MNA).
This project aims to promote the application and understanding of MNA in the UK. The overall aims of
the project include 1) the identification of a site which could potentially allow the demonstration of
natural attenuation under UK conditions, and 2) the use of that site for the development of research
projects studying the fundamental aspects of natural attenuation processes. The SIReN site, once
characterized, will be open to any bona fide researcher to conduct research on natural attenuation funded
from other bodies. The project was developed by AEA Technology, Shell, the Environment Agency and
CL:AIRE (Contaminated Land: Applications in Real Environments). In Phase 1 of the programme the
project team selected a UK site suitable for research into MNA selection. The criteria used for site
selection included: long term site availability (3-5 years); a suitably complex mixture of contaminants; an
aquifer characteristic of UK conditions. In Phase 2 of the program a detailed site characterization was/is
being performed. In addition, three different guidelines for MNA were benchmarked (the UK
Environment Agency Guidelines (Environment Agency, 2000), the ASTM Standard Guidelines (ASTM,
1998) and the NICOLE -TNO draft MNA Protocol. Finally, Phase 3 of the project includes management
of research at the site and dissemination of information gained through said research. Herein, we present
the results of the site selection (Phase 1), up-to-date site characterization and the results of the
benchmarking exercise (Phase 2) and the status of the ongoing research at the SIReN site (Phase 3).
2. BACKGROUND
Many organic contaminants degrade naturally in the biosphere without the interference of man. The
biogeochemical processes that recycle organic and inorganic compounds occur naturally on many
contaminated sites and can be harnessed to mitigate risks to human health and the environment associated
with the contamination. Monitoring such transformations and modeling their long-term performance can
be a useful alternative remedial tool. Termed "monitored natural attenuation", this approach has been
shown to be effective over a range of sites, especially when compared with more engineered solutions
(Brady et al., 1997; Wickramanayake and Hinchee, 1998). Although MNA has been demonstrated at a
range of sites (Thornton et al., 1999; Brady et al., 1997; Begley et al. 1996), there is still a dearth of
research into MNA in minor sedimentary aquifers and in particular those situated on consolidated
formations. Such conditions are not uncommon in the UK.
Assessment of natural attenuation requires knowledge of the in situ contaminant mobility, and the
biological, chemical and physical decomposition processes of the contaminants. There is growing
awareness of MNA amongst regulators, problem owners, property developers, future property owners,
and consultants in the UK; however, a well-documented demonstration of MNA at a complex site will
have an important role in improving further understanding of this approach. It is for this reason that the
SIReN project has been established, with the results of the site selection (Phase 1), an initial site
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characterization and a MNA guideline benchmarking exercise (Phase 2) and the status of ongoing
research projects (Phase 3) presented herein.
3. TECHNICAL CONCEPT
Natural attenuation is the process by which organic contaminants degrade in the biosphere by natural
biogeochemical processes such as biodegradation, reduction, hydrolysis, sorption, dilution and dispersion
(ASTM, 1998). Monitored natural attenuation is the term used to describe the process of monitoring and
demonstrating such transformations, and modeling long term performance.
4. ANALYTICAL APPROACH
Presented below is the analytical approach taken in Phase 1 of project SIReN. To find a suitable
demonstration site for monitoring natural attenuation, a number of sites were reviewed. Criteria were
identified to assess the suitability of the sites for Project SIReN. The ideal site should:
1. Site available for 3-5 years
2. Biodegradable groundwater plumes
3. No ongoing remediation process
4. Good site data available.
5. Have contamination in a consolidated aquifer
A site chemical plant located in the North West of England was selected as the site for SIReN. During
Phase 2 of SIReN, verification of the subsurface conditions and the potential for natural attenuation was
needed before research could begin in earnest. The data from these analyses are included below. Also
included in Phase 2 was the benchmarking exercise of 3 MNA guidelines. Finally, research has been
ongoing at the site over the past 24 months and the research project titles and authors are detailed below.
5. RESULTS
Phase 1: Over 200 sites were considered. Of these a site was selected in the north west of England. This
site was a single owner chemical plant with mixed contaminants including BTEX, chlorinated solvents,
LNAPL, and DNAPL. The project team agreed that the contamination could be managed successfully by
monitored natural attenuation (MNA).
Phase 2: Having chosen the demonstration site for SIReN, verification of the subsurface conditions and
the potential for natural attenuation was needed before research trials could begin in earnest. Therefore,
Phase 2 of SIReN involved a detailed site characterization using readily available data. To supplement the
understanding of the groundwater regime mathematical modeling was also carried out. A report
summarizing the conceptual understanding of the geology, hydrogeology, and contaminant fate and
transport is now available (Environment Agency 200la).
The site typifies many of the industrially contaminated sites in the UK, in that manufacturing has taken
place for many years and it is close to major surface water courses. The main aquifer beneath the site is a
sandstone that is overlain by thick, low permeability glacial clay deposits. This is also typical of northern
industrial sites in the UK. Four distinct geological strata were identified (layers 1 to 4) during the site
characterization. There are two (and possibly 3) water bearing units at the site and these are separated by
a relatively impermeable layer or aquitard. The latter restricts the vertical migration of water and /or
contaminants to the aquifer below. The groundwater is not used locally for drinking but is a significant
source of water for irrigation and industrial use.
There are two contaminant source zones in the ground and evidence that some contamination has reached
the groundwater. The contaminants are mainly hydrocarbons (predominantly benzene, ethylbenzene,
toluene and xylene) with some naphthelene, styrene, and chlorinated aliphatic hydrocarbons). The current
understanding of the contaminant distribution is derived from soil analysis and groundwater samples from
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boreholes. The results suggest that dissolved phase contaminants are migrating within the groundwater
body in a north north-westerly direction. There is evidence that natural attenuation is occurring within the
contaminated zone.
Mathematical modeling was used to predict the fate and transport of the contaminants in the groundwater.
This shows that the contaminated groundwater plumes are unlikely to extend more than 250 m from the
source and that they would continue to migrate for approximately 15 years after the contamination
entered the ground and then stabilize. Eventually natural attenuation processes would cause shrinkage of
the plumes. Despite having characterized the site successfully a number of questions remain unanswered
about subsurface flow mechanisms and contaminant migration pathways. To address these a second phase
of investigation was initiated. This was designed to improve the data set by employing field testing
methods which include sampling and analysis of newly installed data points. This work is on-going and
will be reported on in 2002.
The MNA guideline benchmarking exercise was also carried out during SIReN Phase 2, the details of
which can be found in an Environment Agency report (Environment Agency, 200 Ib). Of the three
Guidelines/protocols included in the study the Agency guidelines were shown to compare well with the
ASTM and NICOLE-TNO protocols. In part due to the tiered system of lines of evidence, the ASTM
guidelines proved easiest to apply and were the most transparent. However, the Agency guidelines also
provided for transparent decision making, did not require application of a model if evidence of MNA was
considered decisive, and was more defensible than the ASTM system. Moreover, because of the
requirement for regular regulatory monitoring, the Agency guidelines had the least potential for accidental
delay and could therefore prove to be more cost effective than the other systems. It should be noted
however, that the potential for bottlenecks does exist when applying the Agency guidelines. In particular,
the requirement for regular regulatory involvement in decision making may potentially result in resource
implications for the regulatory bodies. To offset this, clear procedures should be established for the
submission of MNA 'case' information with clear systems also set up to data review once utilization of
MNA is agreed.
Phase 3: As a part of SIReN phase 3, 4 research projects have been ongoing. These are as follows:
• Predictive modelling of organic contaminant migration at a petrochemical site (Daniel Benitez
Galvez, MSc Thesis Imperial College London).
• Application of the Environment Agency MNA guidelines to data from the site (Angela Sheffield MSc
Thesis, Nottingham)
• Investigation into methods for speciating Iron in the Groundwater (supervised by Simon Bottrell
(Leeds);
• Microbial Ecology: Factors Influencing Natural Attenuation in a Contaminated Sandstone Aquifer
(Anne Tucker, PhD Thesis, Essex).
• Results from each of these will shortly be available on the SIReN website
(www.clairc.co.uk/sircii/indcx.htm).
6. HEALTH AND SAFETY
The site investigation work was carried out using the best available techniques to minimize the potential
impacts.
7. ENVIRONMENTAL IMPACTS
The project aims to confirm natural attenuation and therefore will provide evidence of improvements in
the groundwater quality with time. This will represent a reduction in the environmental impacts.
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8. COSTS
The overall costs of the project are as follows:
The total Environment Agency contribution is estimated to be -£150,000, with £ 25,000 provided for
Phase 1 and £124,729 in Phase 2. During phase 1, over £1 million worth of site investigation reports were
reviewed. During Phase 2, in kind contributions from the project team should total -£120,000. Through
phase 3, the project team in kind contributions should be - £143,000 and are looking to manage ~£1
million per year in research grants.
9. CONCLUSIONS
Phase 1: During the first phase of the project over 200 sites were considered as possible field locations.
From these sites, a single owner chemical plant was selected for the SIReN project.
Phase 2: The site owners have since granted permission for Phase 2 of project SIReN to go ahead, and
have agreed for the site to be used as a demonstration site for 3-5 years subject to certain conditions of
confidentiality and safety. Characterization of the SIReN site is underway and the current understanding
is that there is/are:
1. 4 different geological layers;
2. 2 possibly 3 water bearing zones;
3. 1 aquitard;
4. groundwater flows towards surface waters (i.e. north and north-west); and
5. evidence of contamination in the soil and migration into groundwater.
Phase 2 (MNA benchmarking): The Agency guidelines compared well with both the ASTM and
NICOLE-TNO protocols. These guidelines have since been applied to the SIReN data by Ms Angela
Sheffield in her MSc thesis entitled 'Application of the Environment Agency MNA guidelines to data
from the SIReN site'. Results of this application will be presented in 2002.
Phase 3: Four research projects have been, or are being, carried out at the site. Further applications for
research funding are in process. Preliminary groundwater modeling suggests that the contamination is
unlikely to migrate beyond 250 m from the source zone and will stabilize in approximately 15 years. This
site will therefore be available to the research community for at least the next 3-5 years.
10. REFERENCES
1. Environment Agency 2000 R&D publication 95: Guidance on the Assessment and Monitoring of
Natural Attenuation of Contaminants in groundwater.
2. ASTM Standard Guide for remediation of Groundwater by Natural Attenuation at Petroleum release
sites. American Society for Testing and Materials Annual Book of ASTM Standards, ASTM.
Philadelphia, PA.
3. Brady P.V., Brady M. and Borns D.J. (1997) Natural Attenuation: CERCLA, RBCAs and the Future
of Environmental Remediation. Lewis Publishers, USA
4. Wickramanayake G.B., and Hinchee R.E. (1998) Natural Attenuation of Chlorinated and Recalcitrant
Compounds. Battelle Press, USA.
5. Thornton S.F., Lerner D.N., and Banwart, S.A. (1999) Natural Attenuation of phenolic compounds in
a deep sandstone aquifer. In Proceedings of 1999 Bioremediation Conference. Volume 5: pp. 277-
282., Battelle Press, USA.
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6. Begley J., Croft B.C. and Swannell R.P.J. (1996) Current Research into the bioremediation of
Contaminated Land. Land Contamination & Reclamation 4: 199-208.
7. Environment Agency 200la Project SIREN: Phase 2a Conceptual Site Model & Groundwater Model
Technical report P2-208/TR/2 ISBN 1 85705 6027.
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January 2002
Project No. 27
Hydro-biological Controls on Transport and Remediation of
Organic Pollutants for Contaminated Land
Location
Former gas works site, United
Kingdom
Technical Contact
Prof. Howard Wheater
Department of Civil &
Environmental Engineering,
Imperial College of Science,
Technology & Medicine,
London, SW7 2BU
Project Status
New project
Project Dates
February 1998 -
February 2001
Costs Documented?
Yes
Contaminants
PAHs, phenols,
substituted benzenes
Technology Type
In situ
bioremediation
Media
Soil and groundwater
Project Size
Not available
Results Available?
No
Information in this project summary is current as of January 2000.
1. INTRODUCTION
The research will (a) investigate contaminated soil at a representative former gasworks site and quantify
the physical, hydrological and chemical characteristics and assess the transport of organic contaminants to
groundwater; (b) In situ microbial biodegradative activity will be evaluated using reverse transcriptase
polymerase chain reaction (RT-PCR) techniques and the potential for enhancement assessed and tested;
(c) The information on biodegradative activity will be incorporated within a modeling framework, in
order to predict the long-term impact of current and enhanced in situ bioremediation; and (d) The model
will be developed as a decision support system to provide guidance for bioremediation design for
groundwater protection.
The project objectives are to:
1. Investigate polynuclear aromatic hydrocarbon (PAH), phenol and aromatic hydrocarbon
contaminated soil and groundwater at a representative former gas works site and quantify the
physical, hydrological and chemical characteristics, including spatial and temporal variability.
2. Assess in situ biodegradative activity in the vadose/unsaturated zone and evaluate potential for
enhanced bioremediation.
3. Incorporate the information on biodegradation activity within a modeling framework incorporating
hydrological and geochemical controls on microbial activity and hence to predict long term impact of
current and enhanced on-site biodegradation on groundwater.
4. Develop the model as a decision support tool for assessing the potential for remedial design to reduce
the risk of groundwater pollution and thereby provide aquifer protection.
2. BACKGROUND
The research is focussed on a case study contaminated field site, belonging to BG Property Holdings Ltd.
The research is laboratory and field-based and directed towards developing field-scale relationships and
techniques over a period of 3 years. Extensive site characterisation is being undertaken to a research level
to define the spatial heterogeneity of the hydrological, geochemical and microbial conditions.
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3. TECHNICAL CONCEPT
The research programme focuses on the vadose zone and capillary fringe, and soil-groundwater
interactions, with respect to behaviour of PAH contaminants typically found on gasworks sites (coal tar
constituents). It seeks to evaluate transport of organic contaminants in the vadose zone in order to assess
their impact on groundwater pollution. The programme looks at identifying in situ biodegradation
processes that may be occurring in the subsurface. We seek to identify and quantify the natural processes
and rates. A new methodology is being applied to define in situ microbiological activity (see below).
Natural processes have been identified and the potential and limiting contaminant degradation rates of
these processes will be estimated and implications for clean up quantified.
An important aspect of the microbiological analysis is that the actual and potential level of activity can be
identified. The detailed analysis of site variability is indicating the likely factors limiting microbial
activity, and the potential for enhanced microbial activity is being investigated through manipulation
experiments in the laboratory and on site considering, for example, hydrological controls on redox status,
enhanced oxygen and nutrient supply, and effects of toxicity. Bioventing is being applied in situ.
To represent the interdependence of hydrological, chemical and biological controls on microbiological
degradation of contaminants, a numerical model of unsaturated zone flow and transport processes is being
developed at Imperial College. This provides a vehicle for data assimilation and analysis. The model will
be used to assess the effects on groundwater pollution through bioremediation. This will provide both a
decision support system for remediation options and a tool for presenting assessment options to
regulators.
4. ANALYTICAL APPROACH
To define the hydrological fluxes, in situ soil and groundwater conditions, and soil and groundwater
hydraulic properties, conventional borehole cone penetrometry techniques, piezometer and geophysical
techniques are being used (including EM39 borehole logging and electrical resistance tomography) in
conjunction with pumping tests. This is supplemented by specialist soil monitoring equipment
(tensiometers, neutron probe, in situ permeametry, air permeametry and O2/CO2 respirometry probes).
The spatial location and chemistry of contamination will be investigated in detail using conventional
methods of core analysis from boreholes and trial pits, with detailed analysis of soil water, groundwater,
non-aqueous phase contaminants and soil and aquifer geochemistry.
A major focus of the programme is to determine the intrinsic bioremediation. The majority of bioactivity
assessment methods employed to date have been based on the measurement of microbial metabolism
(e.g., dehydrogenase activity or adenylate concentration), which is not related to specific catabolic
functions, or 14C-mineralisation assays, which are conducted ex-situ and represent catabolic potential
rather than in situ activity. Recently, methods have been developed at King's College for monitoring
specific in situ catabolic gene expression using direct isolation of mRNA from contaminated soils. King's
College has also successfully developed the reserve transcriptase-polymerase chain reaction (RT-PCR)
technique for the quantification of specific mRNAs from environmental samples. Hence a novel bioassay
system will be applied to cores from the site.
Following initial site characterisation, appropriate locations and substrates will be defined for a series on
on-site manipulation experiments to investigate the potential for enhanced degradation. Previous work by
Smith and Bell (Pieltain 1995) has demonstrated complex effects of PAH mobility in the hydrological
environment which can affect redox status and bioavailability. Depending on site conditions, hydrological
and chemical controls will be investigated in addition to manipulation of oxygen and nutrient status.
Possible field trials will include addition of moisture and nutrients via an infiltration system, oxygenation
by passive venting (bioventing), or oxygen release compound systems, or more active means such as air-
sparging, or by addition of hydrogen peroxide. Effects of toxicity of co-contaminants will be considered.
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5. RESULTS
The effects of biodegradation will be incorporated in a modeling framework. An underlying deterministic
model will be developed, based on the SPW and SLT codes developed at Imperial College (Karavokyris,
Butler and Wheater, 1990, Butler and Wheater, 1990), which represent soil-plant water interactions. A
biochemical model component will be introduced to simulated effects of microbial degradation in
response to nutrient, moisture and oxygen availability, and coupled with soil water and gas flow models
to provide time-dependent degradation rates, and transport of soluble waste products. A framework for
the analysis of uncertainty in soil contaminant transport models has recently been developed at Imperial
College in collaboration with Prof.G.Dagan (Tel Aviv). This will be extended to include effects of
heterogeneity in microbial processes through 1-D stochastic simulations. The model will be applied to the
interpretation and generalisation of the site-specific data. The effects of quantified biodegradation rates on
in situ biodegradation will be examined in the context of climatological, hydrological and geochemical
controls and evaluated in comparison with site data. The results of the detailed modeling will be
incorporated in a simpler, rule-based procedure to provide a management tool to evaluate site
management options, and to produce long-term response within a framework of risk management.
6. HEALTH AND SAFETY
A health and safety programme has been developed for the fieldwork component of the project.
7. ENVIRONMENTAL IMPACTS
No significant environmental impacts of the project have been identified.
8. COSTS
The cost of the project is estimated to be $605,000 over three years.
9. CONCLUSIONS
The anticipated outcomes of the project are as follows:
• Assist in the development of an effective on site remedial treatment of typical gas works
contaminants.
• Develop a better understanding of the underlying processes of bioremediation at field scale and the
effects of the physical and chemical heterogeneity associated with disused industrial sites and made
ground.
• Design tools to translate the knowledge learnt into practical techniques for site characterisation and
application.
10. REFERENCES
1. Butler, A.P. and Wheater (1990) Model sensitivity studies of radionuclide uptake in cropped
lysimeters. Nirex Safety Series report NSS/R253, UKNirex Ltd.
2. Karavokyris, I., Butler, A.P., and Wheater, H.S. (1990) The development and validation of a coupled
soil-plant-water model (SPWI). Nirex Safety Series report NSS/R225, UKNirex Ltd.
3. Pieltain, F.J.M. (1995) The effect of different rainfall regimes and drainage conditions on the mobility
of PAHs from soil contaminated with coal tar. Ph.D. thesis, University of London.
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January 2002
Project No. 28
Demonstration of a Jet Washing System for Remediation of Contaminated Land
Location
Former refinery site, Southern
England
Technical Contact
Tony Wakefield
Wakefield House
Little Casterton Rd
Stamford
Lincolnshire
PE9 1BE
Project Status
New Project
Project Dates
August 2000 -
September 2000
Costs Documented?
Yes
Contaminants
Tars, petroleum
hydrocarbons.
Technology Type
Ex situ soil washing
Media
Soil and made ground
Project Size
Demonstration
Results Available?
No
Project 28 was completed in 2000.
1. INTRODUCTION
This project will demonstrate the application of an ex situ process-technology to the remediation of soil
and other solid wastes that are contaminated with organic residues at a former refinery site. The
demonstration will take place over a six-week period in August-September 2000 during which time over
500 tonnes of material will be processed. In addition to the refinery wastes, the project will also include
the processing of materials from gasworks reclamation and materials from other oil industry sources.
The project is supported by exSite, a registered environmental body that uses funding from the UK
landfill tax scheme to facilitate a research programme focusing on brownfield land regeneration. The
work is being carried out Eurotec Land Remediation Ltd.
2. BACKGROUND
This project aims to demonstrate the successful transfer of technology from the mining industry to the
remediation of land affected by contamination. Jet pump technology has been used by the mining industry
for a number of years as a means of high capacity materials handling over long distances. It is particularly
suitable for dealing with sand, gravel and soil, using water as the carrying medium. The heart of the
process is a self-priming pump with no moving parts. It can handle 120 tonnes of material per hour with
minimal operational maintenance. A feature of the jet pump, in its original application, is its relative
inefficiency in imparting ordered energy to the material that is pumped. This characteristic has been
exploited in the development of the jet pump scrubber that will be demonstrated by this project.
3. TECHNICAL CONCEPT
The heart of the scrubber is a jet pump. A jet pump accepts fluid energy rather than energy supplied via a
rotating shaft. It has no moving parts. It operates by a process of transfer of energy by shearing forces, a
turbulent process in which spinning cells of fluid interact between the incoming and the motive fluids.
The process is inefficient at pumping because the greater part of the energy input is lost to turbulent
dissipation. However, the reverse is true for a scrubber because of the cleaning action of the turbulence.
In addition to the turbulence the scrubber also cleans particles by:
Direct contact between solid particles. Where particles are small in comparison with the diameter of a
turbulence cell they are forcibly rubbed together.
Cavitation. By raising the driving pressure in the pump, the turbulence cells spin so fast that the
associated centrifugal force causes such a vacuum at the centre of the cell that the water boils. As these
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"Bubbles " collapse. A violent dissipation of energy occurs, helping to breakdown the binding between
contaminant and solid particle.
In operating the scrubber it is possible to create an intensity of energy dissipation of up to 20MW/m3. The
pressure and temperature of the scrubber can be carefully controlled to optimise performance. The
scrubber uses water as its carrier medium.
The scrubber has been used to separate surface contaminants from solid particles including the removal of
adherent clays and iron oxide from quarry product and the removal of crude oil from contaminated beach
sands. This demonstration will evaluate its effectiveness for separating contaminated tar and oils from
excavated soil and made ground.
4. ANALYTICAL APPROACH
No details are currently available.
5. RESULTS
No details are currently available.
6. HEALTH AND SAFETY
No details are currently available.
7. ENVIRONMENTAL IMPACTS
No significant environmental impacts of the project have been identified.
8. COSTS
The cost of the project is estimated to be £100,000 for the trial.
9. CONCLUSIONS
No details are currently available.
10. REFERENCES
None.
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January 2002
Project No. 29
Automatic Data Acquisition and Monitoring System for Management of Polluted Sites
Location
Italy
Project Status
In progress
Contaminants
TPH, BTEX
Technology Type
Remote monitoring
Technical Contact
Dr. Gilberto Latini
Dr. Claudio Mariotti
Dr. Armando Sechi
Dr. Leonardo ZAN
AQUATERS.P.A.
ViaMiralbello53
61047 S.Lorenzo in Campo
(PS)
Italy
Tel: (+39) 07217311
E-mail:
leonardo.zan@aquater.eni.it
armando.scchi@aquatcr.cni.it
Project Dates
Start: January 1998
End: February 2001
Media
Groundwater, soil, air
Costs Documented?
Not yet available
Project Size
Prototype
Results Available?
Yes
1. INTRODUCTION
This project deals with an automatic remote and on-site environmental monitoring system designed and
implemented to control remediation processes in sites contaminated by petroleum and its by-products
(other compounds can also be monitored). The monitoring system is PC based (such as a remote station),
and doesn't require any further PC running on site to control the remediation process and data acquisition,
but only sensors to acquire data on the parameter/process to be monitored. An AD converter with internal
processor coupled with modems (analogue, radio or GSM) monitors and automatically transmits data to
any number of remote stations, as required by the user.
The system is based on National Instruments hardware running Lab View software.
Process and monitoring data are stored on site and sent to the remote station on demand or at any desired
frequency.
On-site alarms (out-of-range values, failures etc.) are automatically activated by the system and the alarm
log can be received in the form of a SMS.
SMS can also be sent to the on-site station to activate any further instructions.
Data and process parameters can be automatically transmitted to an IP and published on a Web site,
which can be accessed only by providing the user's name and password.
This project represents the state-of-the-art of a remote monitoring system.
2. BACKGROUND
The project started as a preliminary monitoring network developed under RESCOPP (Remediation of Soil
Contaminated by Petroleum Products - P# EU-813), as a cooperation between Italian and French
companies under the EU EUREKA Funding program during the years 1993-1997. Since then the project
has been financed by the Research Funding Program of ENI (Italian Oil Company)
The project focused on developing innovative tools for monitoring remediation processes on sites
polluted by petroleum products.
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3. TECHNICAL CONCEPT
Control Process Parameters:
To monitor a remediation process it is essential to have knowledge on environmental media (components)
and their interactions with water and pollutants. This means that the process is first developed on a
theoretical basis, and then the monitoring system is implemented according to the results achieved.
Monitoring sensors are then placed where the process develops. Data bases linked to the system provide
logs of events and the history of the monitoring activity. The minimum set of parameters to be verified in
petroleum-polluted sites are:
Interstitial Gas
VOCs
CO2
02
CH4
Pressure
Soil in the Vadose Zone
Temperature
Humidity
Groundwater
Water level
Temperature
pH
Eh
Elec. Conductivity
Dissolved O2
TPH
BTEX
Total heterotrophs
It might also be necessary to monitor the meteorological parameters that affect data evolution during all
the processes involved in remediation.
These parameters are:
Temperature
Barometric pressure
Humidity
Solar radiation
Wind speed and direction
Rainfall
4. ANALYTICAL APPROACH
Measuring principles
The sensors connected to the monitoring system must assure that all data are measured with the same
accuracy and validity as those measured in the laboratory.
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System architecture
The system is composed of:
1. Sensors
2. AD converters with inner processor units
3. Software
4. HW (PC Pentium based)
5. Data transmission network (analogue, GSM or radio modem)
6. Monitoring wells
7. Measuring gauges
8. Analytical equipment for gas and water sampling
5. RESULTS
The system was installed in the Porto Marghera contaminated site (Venice, Italy) to test its effectiveness
in monitoring and automatically managing a biopile process.
As the system is still a prototype, it only collects data referring to:
1. Hydrocarbons
2. Temperature
3. Humidity
4. Dissolved oxygen
The system is on-line since February 2001 and all collected data can be seen on Aquater's Website
(www.aquater.eni.it/).
Another groundwater monitoring test has been carried out at Aquater's headquarters.
It consists in a groundwater source (monitoring well) activated by a local unit. The parameters of the
pumped water (T, pH, DO, EC, and Eh) are measured by sensors. If the local unit reads an out-of-range
parameter it activates a water sampler which collects and stores a sample or set of samples. The system
also transmits a warning message (SMS) reporting the out-of-range parameter to the designated operator.
This monitoring system prototype meets the expectations required at this date.
6. HEALTH AND SAFETY
The system is totally safe as it avoids any handling of polluted water or soil.
7. ENVIRONMENTAL IMPACT
The aim of the project is to reduce the number of laboratory analyses and water-soil samples to a
minimum, while increasing the capacity to monitor any type of remediation process from virtually
anywhere in the world (no matter where the local station is located).
8. COSTS
The total cost of the project can be forecasted in 1 Million Euro (approximately 1.2 Million US $), 50%
of which is required for the purchase of special sensors.
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9. CONCLUSIONS
Based on the amount of data collectable by this system and thanks to the drastic reduction of laboratory
analyses and site visits, it can be concluded that the system is very inexpensive and extremely cost-
effective.
The alarm system prevents any loss of data for the final user.
The system is ready for use and enables continuous monitoring on any contaminated site. The monitoring
activity can also be considered a long term validation test following site remediation.
10. REFERENCE
RESCOPP project report (EUREKA Eu-813)
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase I
January 2002
Project No. 30
Approved Biological Treatment Technologies for the Sustainable Cleanup of
TNT-Contaminated Soil
Location
Clausthal-Zellerfeld,
Germany
Technical Contact
Dr. Jochen Michels
DECHEMAe.V.
Theodor-Heuss-Allee 25
60486 Frankfurt/Main
Germany
Project Status
Interim
Project Dates
Costs Documented?
Yes
Contaminants
TNT
Technology Type
Three different soil
bioremediation
technologies
Media
Soil
Project Size
Field-scale
Results Available?
Soon
1. INTRODUCTION
The aim of the Joint Project "True to Scale Test of Biological Processes at the Former Ammunition Site
'Werk Tanne' with Assessment" is the evaluation and comparison of three on-site bioremediation
procedures for TNT contaminated soil under field conditions with regard to efficiency, ecology and
economy. The decontaminated soil material has been characterized by innovative analytical strategies to
assess the ability of repositioning decontaminated soil heaps. The Joint Project is part of the Joint
Research Group "Processes for the Bioremediation of Soil". This interdisciplinary group is developing
innovative processes for soil bioremediation. It is logically divided into three columns of research:
process development, backup research, and true to scale testing. The findings will be incorporated in the
Handbook "Processes for the Bioremediation of Soil", which will be released in Oct. 2001. It is intended
to assist the authorities and problem owners to find and select promising clean-up processes, thus
contributing to the reusability of economically attractive sites.
2. BACKGROUND
The former ammunition site "Werk Tanne" near the city Clausthal-Zellerfeld in the Harz Mountains was
one of the twenty former TNT production sites in Germany. With a monthly production capacity of
2,8501 TNT it was the fifth largest explosives production site of the third Reich. The site was built into a
forested area of 119 ha and had two TNT production lanes. In contrast to other sites in Germany like
"Stadtallendorf', "Hirschhagen" or "Krummel", after World War II the area was not converted to an
industrial site or a residential quarter. From 1992 the abandoned site was used for different approaches in
the biological remediation of TNT-contaminated soil. From 1998 the Joint Project "True to Scale Test of
Biological Processes at the former ammunition site 'Werk Tanne' with Assessment" has successfully
tested three different biological remediation technologies in field scale.
3. TECHNICAL CONCEPT
A test area was prepared on the site for the three different remediation installations, including two tents
and one building, safety areas regarding to safety of labor and safety of emission. The Industrieanlagen-
Betriebsgesellschaft (IABG) takes over the central project management for the tasks of the site
coordination, the scientific attendance and the planning for the required construction works. The site
coordination ensures comparable conditions with regard to the treatments and the success evaluation.
These conditions are (i) comparable soils and contamination; (ii) comparable analysis and documentation;
(iii) comparable control soils and site conditions.
At different areas on the site "Werk Tanne" soil are taken and sieved to 60 mm. The soil was mixed
frequently to ensure a homogeneous TNT contamination of 1,000 to 1,200 mg/kg soil (dm) throughout
the pile before it was given to the soil treatment companies. The involved companies and procedures are:
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Anaerobic/Aerobic Composting Process
The process by Umweltschutz Nord was originally developed by Bioremediation Inc. For the
anaerobic/aerobic composting process the contaminated soil material was mixed with easy utilizable
substrates to maintain anaerobic conditions and deposited into a pile. During the treatment term of about
12 weeks the soil pile was moved every 1 to 2 days in the beginning and only once a week afterwards.
While the substrate was depleted during the treatment the pile shifted continuously from anaerobic to
aerobic conditions. Transformation of the pollutants and immobilization of the transformation products
occurred simultaneously during the entire process term. During two years four different batches of about
80 metric tons were treated. The initial concentrations of approx. 1,000 mg nitroaromatics per kg soil
were rapidly reduced within 7 days. The concentration was durable below the detection limit of 0.5 mg/kg
within three weeks. The maturing process to degrade the organic aggregates was concluded after 12
weeks. In cooperation with the involved authorities the decontaminated soil could be released on site.
Dynamic Pile Process
The dynamic pile process by Plambeck ContraCon is an anaerobic/aerobic treatment process with two
distinct stages. The process was developed by the University of Marburg, Germany. During the anaerobic
stage, which was maintained by easy utilizable substrates, TNT was transformed to reduced metabolites.
The pile was static during the anaerobic stage, but after the switch to aerobic conditions the heap was
aerated and the soil material was treated mechanically for the remaining term of about 12 weeks. The
point of time to switch the conditions is dependent on the reduction stage of the nitroaromatics and occurs
usually after half of the task. During the aerobic phase the reduction products were irreversibly bound to
the soil organic matrix. During two years four different batches of about 32 metric tons were treated. The
nitroaromatics were rapidly reduced to the corresponding amino(nitro-)aromic compounds during the
anaerobic stage. After maintaining aerobic conditions the concentration of amino(nitro-)aromic
compounds felt into the range of the detection limit. The refilling of the material on site was also
permitted by the authorities.
White Rot Fungi Process
White rot fungi were cultivated in large amounts on straw and then were piled up in alternating layers
with the contaminated soil material. During the static and aerobic soil treatment process by AWIA
Umwelt the fungi proliferated through the soil matter and destructed the nitroaromatics with the aid of its
extracellular enzyme system. Four different white rot and litter decaying fungi have been tested with 30
metric tons of contaminated soil material each. The process term was about a year; after 12 weeks the soil
was mixed once and the straw/fungi substrate was renewed. A watering and aeration system was installed
for maintenance humidity, nutrient supplementation, and aeration of the soil material in order to help the
fungi to predominate over the soil-specific microflora for optimal detoxification. The aeration of the soil
was carried out by an exhauster, which removed surplus water as well. Exhausted air and effluent were
decontaminated afterwards. Especially in the final phase of decontamination, the concentration of harmful
substances in the soil was minimized by addition of fresh cultures of the fungus. The TNT initial
concentration of about 2.000 mg/kg (dm) could be reduced to 50 mg/kg soil material (dm). The refilling
of the material on site was also permitted by the authorities.
4. ANALYTICAL APPROACH
A special scientific concept has been developed by IABG in cooperation with the authorities for the
evaluation of the soil material and the processes. This includes the following test systems:
• Chemical analysis of nitroaromatics and known metabolites (incl. new described polar metabolites)
• Genotoxicological analysis (Ames-test)
• Ecotoxicological analysis (aquatic: Luminescent Bacteria (DIN); terrestric: Potential Nitrification
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(Swedish EPA), soil respiration (Swedish EPA), acute growth of higher plants (ISO), acute earth
worm test (ISO))
• Physico-chemical soil characterization (pH, Corg, Nutrients, Soil Constituents)
• Human toxicological analysis
• Air monitoring
The backup research of the Joint Research Group had developed extended test systems for the
ecotoxicological potential of the processed soil material using test batteries, humification process by
NMR-spectroscopy with [15N]TNT, and long-term stability using [14C]TNT under simulated climatic
worst case conditions.
5. RESULTS
The soil material could successfully been decontaminated by all three remediation processes and the
material could be refilled on site. This was the first time that biologically decontaminated TNT-soil could
be repositioned in Germany. The ecotoxicological tests showed no ecotoxicological hazard potential left
in the soil material and the finished tests to the long-term behavior could show no remobilization of toxic
metabolites. The results from the NMR-spectroscopy showed that TNT-metabolites are bound covalent to
the soil organic matter and that they were further destructed due to the humification process.
6. HEALTH AND SAFETY
Different test systems were conducted according to the safety rules of labor:
• Biological material
• Air-monitoring (mononitrotoluenes, Germ pollution)
• Human toxicological test (TNT metabolites in urine, hemoglobine adducts)
7. ENVIRONMENTAL IMPACTS
Not available yet
8. COSTS
The individual process costs were calculated and appeared to be comparable to standard biological
treatment costs of TPH-contaminated soil in Germany.
9. CONCLUSIONS
Biological remediation of TNT-contaminated soil is now an approved process in the meaning of
sustainability. TNT metabolites will be humificated in the soil and destructed further in a way that no
hidden hazardous potential will be left in the soil material.
10. REFERENCE
Michels, J, Track, T, Gehrke, U., and Sell, D. (Fachredaktion), Umweltbundesamt (Herausgeber). 2001.
Biologische Verfahren zur Bodensanierung. Griin-weiBe Reihe des BMBF (only available in German
language).
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January 2002
Project No. 31
Phytoremediation Evaluation of Petroleum Hydrocarbon in Surface Soil
Location
13 sites in US and Canada
Technical Contact
Steve Rock
National Risk Management
Research Laboratory
26 W. Martin Luther King Dr
Cincinnati, OH 45268
Tel: 5 13-569-7149
Fax: 513-569-7879
E-mail: rock.stcvcn(?/jcpa.gov
Project Status
Ongoing
Project Dates
Accepted 2000 2001
Costs Documented?
Installation and start-
up costs recorded
Contaminants
Petroleum, PAHs
Technology Type
Plant enhanced
bioremediation
Media
Soil
Project Size
3-4 year field-scale test
plots
Results Available?
Yes, preliminary
1. INTRODUCTION
The Remediation Technologies Development Forum (RTDF) cooperative trials are designed to test the
ability of plants to enhance degradation of petroleum hydrocarbons in surface soils. There are now
thirteen field trial locations with two new sites in Canada. Results in progress are now available for six
locations. As would be expected there is variation among the locations in the responses developing among
the vegetation treatments. Two locations have statistically significant responses that indicate enhanced
degradation in vegetated plots. One location is showing a promising trend. Treatment mean differences
are not apparent yet in two locations. The ability to detect treatment differences appears to be related to
the degree of prior weathering of the contaminants, the spatial variability of the contaminant at the sites,
and perhaps the time needed for treatment effects to become apparent. It appears for less weathered
contaminants, phytoremediation effects will become apparent within a couple growing seasons. It remains
to be determined how plants will affect remediation on highly weathered sites.
Several lines of evidence, including microbial data may be helpful for indicating the presence of
degrading organisms. The role of phytoremediation may ultimately be determined by a combination of
the degree of weathering, the time available for treatment, and the determination of acceptable endpoints
for remediation based on risk assessments and future site uses.
2. BACKGROUND
The TPH Subgroup of the RTDF, Phytoremediation Action Team initiated these trials to test the use of
vegetation to enhance treatment of surface soils contaminated with weathered petroleum hydrocarbons.
Collaborators include PERF (Petroleum Environmental Research Forum), USEPA, Environment Canada,
the U.S. Department of Defense, major petroleum and energy corporations, environmental consultants,
and university participants. The TPH Subgroup began meeting in March 1998 to develop a standard
protocol for conducting cooperative field trials. Features of the protocol specify common procedures for
each trial covering vegetation treatments, experimental design, analytical parameters, analytical
laboratories, and data analysis. The RTDF protocol, initial site descriptions, and annual reports are
available at http://www.rtdf.org.
3. TECHNICAL CONCEPT
The purpose of the project is to determine efficacy of agricultural and non-crop plants for degradation of
aged petroleum hydrocarbons in soil at multiple locations and under varied climatic conditions. The
standard plot size is 20' x 20' minimum, although the shape of the plots varies widely. There are four
replications of each treatment. The statistical design is a randomized complete block (place plots based on
presence of TPHs in site characterization. For soil and plant samples, take 8 random sample cores per plot
and make a composite sample. The three standard treatments are as follows:
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• Local optimized treatment: grass, mix of species, including trees
• Unplanted and unfertilized control (kept weed-free by post-emergent herbicide, hand-picking of
weeds, or tilling).
• Standard Mixture of rye 10-15% (annual or perennial), legume 20-25% (alfalfa, clover, birds-foot
trefoil), and fescue 60-70% (varieties chosen for local conditions).
Over the course of the trial, vegetated plots should be fertilized with nitrogen and phosphorus at the rate
corresponding to the carbon to nitrogen to phosphorus ratio of 50:2:1. Additional fertilizer can be added
to account for plant uptake requirements. All vegetated plots should be fertilized at the same rates. The
rate of fertilization should be divided into several applications to minimize adverse effects on plant
growth due to excess nitrogen. Accurate records should be maintained on rates of fertilization and how it
is applied. After considerable discussion it was decided that the unvegetated treatment should not be
fertilized so that the vegetation treatments are compared with a control that represents no treatment. This
trial will not attempt to separate the effects of plants from the effect of fertilizer. Participants are
encouraged to include an unvegetated and fertilized control treatment if space and resources permit.
Soil sampling: Eight random sub-samples per plot composited make one sample. Cores will be taken at 0
to 6" and 6" to 12". Take soil samples as described at the following times and soil depths sampling
location at the following times:
T=I: Initial site characterization (after tilling) samples taken in grid over whole site.
T=0: Before planting, after seedbed preparation.
T= 1: 6 months after planting, or end of first growing season.
T=2: 18 months after planting, or end of second growing season.
T=3: 30 months after planting, or end of third growing season.
4. ANALYTICAL APPROACH
• Agronomic conditions: pH, salinity, available nutrients, and soil analysis (texture, organic matter, EC,
CEC, soil type). The analyses should be tailored to the region.
• Contaminant concentrations: PAHs using EPA method with GC, TPH using DCM solvent, TPH
fractions using TPHCWG method.
• Microbial analysis (times 0 and 3 for plate counting and MPN, times 0, 1,2, and 3 for PLFA and
DGGE analysis).
5. RESULTS
Site A in California is located at an oil refinery. Data is available from samples taken at planting and the
end of the first and second growing seasons. The analysis of variance and inspection of treatment means
for Site A show no clear differences or trends among the treatments at either of the sampled soil depths.
Large differences among the four replications and high variability in the data may be obscuring most
treatment effects at this stage in the trial. The hydrocarbons at Site A are highly weathered. Our
hypothesis concerning this site is that given the weathered nature of the hydrocarbons in the surface soils,
it is going to be difficult to detect clear evidence of biodegradation.
Site B in Ohio is located on a former landfarm. The depth of soil sampling was changed between the
initial Time 0 sampling and what has been called a second Time Ob sampling. Based on a new starting
reference time, results are available after one growing season. The surface soil samples showed a general
decline in concentrations from TOb to Tl although treatment means were not significantly different. There
is an indication that all of the vegetated treatments declined in concentration more than the unvegetated
control plots. This may indicate that treatment effects are developing.
Site F in New York is a former manufactured gas plant site. Analytical results are available from samples
taken at planting and the end of the first and second growing seasons. The surface soil at Site F showed
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consistent declines in concentration of TPH and PAHs from Time 0 to Time 1 and from Time 1 to
Time 2. By Time 2, there were statistically significant differences between the control plots and the
willow/poplar plot for TPH and PAHs. All vegetated treatments had lower concentrations than the control
plots for TPH and PAHs. There are a number of positive trends at Site F that may show an advantage of
vegetation treatments given enough time. The less weathered surface soil may have more potential for
further degradation than the deeper soil.
Site G in Kansas is utilizing sediments excavated from a motor pool waste lagoon. Analytical data is
available from sampling at planting and at the end of the first growing season. After one year similar
patterns were observed at the two soil depths. TPH concentrations began the trial in the range of 11000 to
16000 mg/kg and decreased to 5000 to 7000 mg/kg after one year. Concentrations of TPH and PAHs in
the unvegetated control treatment decreased less than the vegetated treatments. Biomarker normalized
data showed better statistical separation of the treatment means than the original TPH concentrations.
Compared to the other RTDF sites, Site G showed the clearest response to the vegetation treatment after
one growing season.
Site J in Arkansas is located at an oil production site. Only characterization data from the time of planting
was available. Most of the contamination at this site is in the top 15 cm. PAH concentrations were lower
at this site than the other RTDF sites. TPH concentrations were in the range of 10000 to 13500 mg/kg in
the surface soil. The apparent low degree of weathering at this site may indicate a high potential for
biodegradation.
Site K in Indiana is located at a former manufactured gas plant site. The contaminants are coal tar
residues that extend from the soil surface to greater than 180 cm below ground. Hybrid poplars were
planted as the single vegetation treatment. Soil was sampled to greater depths than the other field sites.
Analytical results for priority pollutant PAHs are available from the time of planting and the end of the
first two growing seasons. Based on the data received, there is no clear trend showing that PAHs are
degrading in the vegetated treatments after two years.
Observable evidence of degradation is probably obscured by high variability among the plots with PAH
concentrations ranging over an order of magnitude. Based on the data normalized to a high molecular
weight PAH, there may be an indication that PAH levels are decreasing. Although trees have grown well
at the site, a longer period of time may be needed to establish an effect of vegetation treatments at this
location since treatment is desired in deeper soil than at the other field sites.
6. HEALTH AND SAFETY
No information available.
7. ENVIRONMENTAL IMPACTS
No information available.
8. COSTS
Phytoremediation-specific unit costs have been summarized for the first year at each of the field sites. The
total startup costs ranged from $16,854 to $62,174 for the six sites. The operation and maintenance costs
for the first year of the study ranged from $16,500 to $30,400. The total project costs for the first year
ranged from $38,392 to $86,278. The calculated unit costs for the first year of the study ranged from
$4.00to$10.37/ft3.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
9. CONCLUSIONS
Considered as a group, it appears some field sites will show significantly enhanced hydrocarbon
degradation with vegetation treatments while other field sites may not show enhanced treatment during
the time of the trials. Differences between field sites may be related to differences in hydrocarbon
composition and weathering.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase I
January 2002
Project No. 32
Remediation of Chlorinated Solvents in Groundwater by Chemical Reduction
Using Zero-Valent Iron, Pneumatic Fracturing, and Reagent Atomization
Location
Marshall Space Flight Center
Technical Contact
Amy Keith
Building 4200, Room 436
MSFC,AL35812
Tel: 256-544-7434
Fax: 256-544-8259
E-mail:
amv.keith(o),msfc.n.asa.gov
Project Status
Monitoring/Inject
Project Dates
Accepted 2001
Final Report
Costs Documented?
Yes
Contaminants
Trichloroethene
Technology Type
Chemical reduction
Media
Low permeability clayey residuum
Project Size
Results Available?
Yes
1. INTRODUCTION
The Marshall Space Flight Center (MSFC) is located in northern Alabama within Redstone Arsenal
(RSA). MSFC was listed with RSA on the National Priorities List on May 31, 1994. Past solvent
management practices during the 1960 era of rocket engine testing at MSFC resulted in groundwater
contaminated with chlorinated volatile organic compounds (CVOCs) beneath MSFC. Five major plumes
with fourteen main contaminant source areas (SAs) have been identified at the facility. Source areas are
those areas that have elevated concentrations of CVOCs in soil and groundwater that may act as the
continuing source of contamination in the downgradient groundwater. MSFC is pilot testing in-situ
technologies to identify the effective remedial technologies approaches for remediating the source areas.
SA-2 and SA-12 were chosen for testing in-situ chemical reduction technology using pneumatic
fracturing and the Liquid Atomized Injection® (LAI) injection process for delivery of a zero-valent iron
(ZVI) slurry (Ferox®) to subsurface target zones. The results from these and other on-going or planned
in-situ pilot tests (chemical oxidation, dynamic underground stripping, enhanced bioremediation, and
phytoremediation) will be used to complete a CERCLA feasibility study for the groundwater medium
at MSFC.
2. BACKGROUND
The subsurface beneath the area consists of a low-permeability clayey residuum overlaying karst bedrock.
The majority of the contaminants are believed to lie within the basal layer of the residuum, called the
rubble zone, that transitions into the underlying bedrock. The residuum groundwater, which is naturally
aerobic, moves mostly in a lateral manner through the rubble zone to wetlands and springs downgradient.
The degree of hydraulic connection between the rubble zone and the bedrock is variable throughout the
site. Due to the complex hydrogeology of the site, only a few remediation technologies are expected to be
effective at MSFC. After screening available technologies, in-situ chemical reduction was chosen for
pilot-scale tests to treat dissolved trichloroethene (TCE) conditions in groundwater. SA-2 and SA-12 were
identified for implementation of the in-situ chemical reduction treatability studies. The MSFC team
included CH2M HILL as the prime contractor and ARS Technologies, Inc. (ARS) as their specialty
technology subcontractor.
3. TECHNICAL CONCEPT
Chemical reduction using ZVI reduces TCE by reductive dechlorination where hydrogen ions are
liberated by the corrosion of iron in water. TCE uptakes the hydrogen ion and releases a chloride ion,
ultimately reducing TCE to dichloroethene, vinyl chloride, and ethene. The release of chloride ions can be
monitored to measure the progress of the reaction process. The low-permeability residuum severely limits
the amount and distribution of fluids that can be delivered. Pneumatically fracturing the residuum and
atomizing the chemical reagents to be injected delivers increased quantities of the ZVI slurry and more
evenly distributes the slurry within the matrix contamination. ARS uses nitrogen gas for fracturing and as
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
an inert carrier during Ferox® injections, and incorporates a Liquid Atomized Injection (LAI) process to
deliver fluids into the subsurface.
4. ANALYTICAL APPROACH
At SA-2, because of the presence of unexploded ordnance, the entire area with the highest levels of
groundwater contamination could not be treated with the ZVI injections. To address the inaccessible
areas, a downgradient treatment zone was created through overlapping injections, forming a permeable
reactive zone to treat migrating untreated groundwater.
At SA-12, a 10-foot by 50-foot treatment cell was demarcated within the area of highest groundwater
contamination. Subsurface intervals within the cell were pneumatically fractured and the ZVI slurry was
injected into the reactive treatment zones to treat the highest contaminant concentrations (subsurface and
groundwater media). The injection process allowed the ZVI placement to occur without damage to
numerous subsurface utilities and structures in the highly industrialized area. DNAPL-like concentrations
(about 500 mg/1) of TCE were unexpectedly encountered at a location within SA-12 after the field test
implementation had begun.
5. RESULTS
At SA-2, 11,000 Ibs of ZVI were injected achieving an iron-to-TCE weight ratio of 200:1. Follow-up
sampling showed iron impregnation of the subsurface matrix. Pressure readings and field measurements
for iron during Ferox® injection indicated that the radius of influence ranged from 20 to 60 feet.
Groundwater conditions were changed from an aerobic, non-reducing state to anaerobic, reducing
conditions. TCE concentrations were reduced from 72,800 ppb to 3,400 ppb (over 95% reduction) over
the initial fourteen months. Monitoring continues and further reductions are expected.
At SA-12, 4,500 Ibs of ZVI were injected achieving an iron-to-TCE weight ratio of 100:1. At SA-12
similar radii of influence and geochemical effects on groundwater conditions were observed as those at
SA-2. Some reduction in TCE groundwater concentrations were observed initially, but the concentrations
rebounded and remained fairly constant throughout most of the groundwater performance monitoring
period. The low iron-to-TCE weight ratio and the lack of TCE degradation is attributed to the post-
implementation discovery of the DNAPL-like TCE conditions. Supplemental bench-scale tests indicate
that these types of conditions could be treated using ZVI and the effectiveness of additional injections at
SA-12 is being considered.
6. HEALTH AND SAFETY
All field work is performed under a Health and Safety Plan to address all pilot study activities. All
workers review the HSP before work begins at the site and it is maintained on site during activities. Each
subcontractor must provide a HSP specific to the work they do. The plan includes project-specific
physical hazards, project-specific chemical hazards, and emergency procedures. All personnel were
HAZWOPER trained. The in-situ pilot tests have been implemented safely and without incidents, and the
field implementation phases passed all internal health and safety audits.
7. ENVIRONMENTAL IMPACTS
Injection of ZVI into groundwater may change the pH, the dissolved oxygen, and the oxidation reduction
potential (ORP) levels, and increase iron concentrations, within a localized area.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
8. COSTS
The total cost for completing the SA-2 tasks listed below was approximately $300,000, incurred between
1999 and 2001:
• Work planning
• Soil and groundwater sampling
• Bench-scale testing and report
• Utility surveys and video-logging
• Fracturing and ZVI injections (including mobilization and demobilization)
• Royalty fees (related to pneumatic fracturing, patented by the New Jersey Institute of Technology)
• Development of field documentation report
• Technical support and project management
The amount of ZVI injected into the subsurface beneath SA-2 was 11,000 pounds. Therefore, the cost to
implement the pilot test per pound of ZVI injected was $27.26, based on the total cost value. The actual
field implementation portion of the test was approximately 70 percent of the total cost which corresponds
to $19.06 per pound of ZVI injected.
9. CONCLUSIONS
In-situ chemical reduction using the Ferox® ZVI process is an effective method for treating dissolved
phase TCE in groundwater, where DNAPL-like concentrations are not present. The use of ZVI for
treating DNAPL or DNAPL-like conditions is a possibility, based on bench-scale results. The selective
injection method is useful for treating areas with limited accessibility and ARS' LAI process, combined
with pneumatic fracturing, is effective for delivering and distributing ZVI slurry in low-permeability
media. Results at SA-12 also show that ZVI can treat Freon contamination in groundwater.
10. REFERENCES
1. Marshall Space Flight Center. Summary (Draft): In-Situ Chemical Reduction Pilot Test Results for
Source Area 2. Prepared in consultation with CH2M HILL and ARS Technologies. September 2001.
2. Marshall Space Flight Center. Summary (Draft): In-Situ Chemical Reduction Pilot Test Results for
Source Area 12. Prepared in consultation with CH2M HILL and ARS Technologies. September 2001.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase I
January 2002
Project No. 33
Chemical Oxidation and Natural Attenuation at the Camden County Landfill
Location
Camden County, Georgia
Technical Contact
Clifton C. Casey
South DIV Naval Facilities
Engineering Command
Tel: 843-820-5561
Fax: 843-820-7465
E-mail:
cascvcc(?£cfdsouth.navfac .navv.mil
Project Status
First source area
complete.
Project Dates
Accepted 2001
Costs Documented?
Yes
Contaminants
Chlorinated ethenes
Technology Type
Chemical oxidation
and natural
attenuation
Media
Groundwater
Project Size
150ftx75ft
Results Available?
Yes
1. INTRODUCTION
In-situ Chemical Oxidation (ISCO) and natural attenuation was used to reduce the source of a plume of
chlorinated hydrocarbons and its residual concentrations in groundwater to meet regulatory cleanup goals.
The strategy for this remedial action was to incorporate an aggressive approach to reducing the mass of
contamination in the source area aquifer sediments followed by natural attenuation of the residual
contamination in groundwater. The cleanup objective was to protect a nearby residential community from
the plume of contamination that was moving offsite and meet state and federal regulatory cleanup goals
for groundwater.
2. BACKGROUND
The site is a 25-acre municipal landfill that was operated by the County during the mid 1970's to 1980. A
variety of wastes from the community and the Naval Base Kings Bay were disposed in the landfill.
Wastes were disposed by the trench method wherein trenches were dug, backfilled with waste, and
covered with fill. In the early 1990's, a RCRA Facility Investigation (RFI) identified groundwater
contamination at the perimeter of the landfill. A perchloroethene (PCE) plume was determined to be
migrating towards a subdivision located several hundred yards from the landfill. As an interim measure,
the Navy installed extraction wells to hydraulically contain the plume at the perimeter of the landfill
(Casey and Beregren, 1999).
Results of additional site investigations, determined that the PCE source was approximately 120 feet long
by 40 feet wide in the 30 to 40 foot horizon below ground surface. In addition, PCE degradation products
including trichloroethylene (TCE), cis-1,2 dichloroethene (DCE), and vinyl chloride (VC), were detected
in the groundwater. Total chlorinated aliphatic compounds (CACs), the sum of PCE and its degradation
products TCE, DCE, and VC, were detected at concentrations of more than 9000 micrograms per liter
(|ig/l) in the groundwater within the landfill source area. PCE concentrations were as much as 5 percent
of the pure phase solubility phase, therefore, the presence of a dense non-aqueous phase liquid (DNAPL)
was inferred.
An evaluation (Chapelle and Bradley, 1998) of the attenuation capacity of the aquifer determined that the
plume was readily degrading naturally as it moved away from the source area. The geochemistry of the
site indicated that the source area was sulfate reducing and the downgradient plume was an iron-reducing
environment. These environments allowed for the highly chlorinated compounds such as PCE and TCE to
be readily degraded to DCE and VC. The iron reducing environment downgradient was more ideally
suited for the lower chlorinated compounds that can be anaerobically oxidized under these environments
(Bradley and Chapelle, 1996, Bradley and Chapelle, 1998). Modeling results indicated that if the
concentrations of total CACs were reduced to 100 (ig/1, natural attenuation would address the residual
contamination, achieving compliance levels in the groundwater plume prior to reaching the
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
facilities boundaries.
The cleanup approach incorporated the use of aggressive source reduction using chemical oxidation,
followed by natural attenuation to degrade the residual concentrations in groundwater. Forty-four carbon
steel injection points were located in and around the source of contamination. Injection of Fentons
Reagent occurred in two zones starting on November 2, 1998. The primary treatment occurred in the
source area and a follow-up treatment took place within 25 feet downgradient. The injections were
completed on July 15, 1999.
3. TECHNICAL CONCEPT
In-Situ Chemical Oxidation using Fentons Reagent method was selected as the technology for source
reduction. The process involved injecting a 50% solution of hydrogen peroxide with ferrous sulfate as a
catalyst. Hydroxyl radicals formed by the reaction of the peroxide and catalyst are powerful, non-specific
oxidants. Complete mineralization of the contaminants is assumed to occur within a few minutes. The
final products of the reaction between the hydroxyl radicals and the contaminants are carbon dioxide,
water and chloride.
Natural biological attenuation at this site occurs by a process of reductive dechlorination. This occurs due
to naturally occurring microorganisms at the site that mediate an oxidation reduction reaction to obtain
energy and growth. In this reaction, the chlorinated solvent acts as an electron acceptor and a chlorine
atom on the molecule is replaced with a hydrogen atom. Dissolved organic matter (DOM) from the
landfill serves as the electron donor to drive the reaction. After chemical oxidation of the source area, the
dissolved organic matter is replenished by upgradient DOM that moves into the treated zone.
4. ANALYTICAL APPROACH
Pre and post-injection characterization of monitoring and injection wells included analyses for volatile
organic compounds. Carbon dioxide gas was analyzed during injection of the reagent to determine
completeness of the oxidation.
The natural attenuation evaluation included analyses of dissolved oxygen, ferrous iron, sulfate, hydrogen
sulfide, nitrate, nitrite, and molecular hydrogen as well as volatile organic compounds.
5. RESULTS
After two treatment phases of injections, the CACs in groundwater were reduced from approximately
9000 ppb to less than 100 ppb. These concentrations have remained below this value since completion of
injections. The state of Georgia Department of Natural Resources nominated the project for the State
Chamber of Commerce Environmental Excellence Award for which it won.
6. HEALTH AND SAFETY
During injection, the treatment area was secured such that only operation personnel were allowed onsite.
7. ENVIRONMENTAL IMPACTS
None
8. COSTS
The direct cost for ISCO was approximately $250,000. This costs does not include installation of
monitoring or injection points nor pre or post-injection monitoring. The natural attenuation evaluation
cost was $100,000.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
9. CONCLUSIONS
After two years of treatment in the initial source area, the ground-water concentrations have remained
below the 100 ppb total CAC target level. Downgradient the residual concentrations of the plume have
continued to drop due to natural attenuation and are expected to completely degrade within five years.
10. REFERENCES
1. Casey, C. and C. Beregen, C. 1999. Chemical Oxidation, Natural Attenuation drafted in Navy
Cleanup, Pollution Engineering, March 1999 Supplement.
2. Bradley, P. M. and F.H. Chapelle. 1996. Anaerobic mineralization of vinyl chloride in Fe (III)-
reducing, aquifer sediments. Environmental Science and Technology 30-2084-2086.
3. Bradley, P.M., and F.H. Chapelle. 1998. Microbial mineralization of VC and DCE under different
terminal electron accepting conditions. Anaerobe. 4:81-87.
4. Chapelle, F.H. and P.M. Bradley. 1998. Selecting remediation goals by assessing the natural
attenuation capacity of ground-water systems. Bioremediation Journal 2:227-238.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
COUNTRY TOUR DE TABLE PRESENTATIONS
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
ARMENIA
Information in this tour de table is current as of January 2001.
1. BACKGROUND
Twelve tail storages have been constructed in the Republic of Armenia at different years that accumulate
some 300 M cubic meters of wastes from mining industry. Waste composition is conditioned by mineral
combination of paragenetic minerals.
Existing economic situation in Armenia within the recent years prevents set-up of full control over the tail
storages. Being complex hydrotechnical facilities tail storages are representing a permanent hazard and
appear to be a reason for a calamity.
Due to the impact the natural and climatic conditions content of tail storages (mainly metals) is
weathered, transferred and spread to the adjacent areas by causing irreversible impact on human health,
environment, including fauna and flora and resulting in activation of desertification processes.
From this viewpoint conserved tail storages of Geghanush in the province of Syunik, and the tail storage
of Akhtala in the province of Lori are mostly hazardous. These tail storages are located on densely
populated and developed farming areas and cause huge damage to the environment and human vital
activity by simultaneously contributing to desertification of lands exclusion of them from the lands of
farming and other value.
The need to protect the tail storages proceeds from not only the fact, that it is necessary to minimize and
neutralize their harmful impact on the environment and human health, but also from rational use of
natural resources, since the latter contain big quantities of useful and rare metals that represent a material
value and their use might contribute to the country's development. However, these tail storages are not re-
processed due to a lack and high cost of adequate technologies. The tail storages (see Table 2) as objects
of hazardous hydrotechnical calamity by their impact on the environment and human health are classified
based on the following factors and effects:
Table 1: Classification of Tail Storages Based on Harmful Factors and Effects
#
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
Harmful factors and effects
Volume
Number of population in the affected zone
Lands located in the affected zone (quality, class)
Operated
Conserved
Facility construction form — ferro-concrete
Land dam
Content of hazardous substances, elements %lm2
Content of useful metals %lm2
Level of dispersion
Possibility to conduct measures to prevent hazardous impact
Grading unit (point)
1-3
1-5
1-5
1-2
1-4
1
2
1-5
1-5
1-2
1-5
According to the mentioned indicators classification of tail storages as the highest risk centres are referred
to in Table 3.
The storages of Geghanush in the province of Syunik and the storage of Akhtala in the province of
Tavush are selected as storages representing high risk and requiring primary preventive works to be
prepared and implemented.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Selection of these tail storages is conditioned by the following criteria:
1. The tail storages of Geghanush and Akhtala are located in densely populated areas. Towns of Kapan,
Shamlugh, Akhtala, a number of villages and settlements are located within its affected zone.
2. Desertification processes have been activated within the affected zone of the tail storages of
Geghanush and Akhtala, which has been resulted in total extinction of plants and continuation of land
alienation phenomenon.
3. Geological conditions of establishing and formation of the Kapan copper and Shamlugh copper multi-
metallic deposit, as well as content of harmful components in the Geghanush and Akhtala tail
storages caused by technological failure of ore material re-processing, which exceeds by 8-10 times
the indicators of the rest of the tail storages.
4. High percentage of useful metal content conditioned by the prerequisites mentioned in item 3, which
should protected for the economic development in the country.
5. The geographic location and natural-and-climatic conditions of the Geghanush and Akhtala tail
storages could contribute to the wash-up and dispersion of the tail storages, while in the case of a
collapse the animal kingdom of Vokhchi and Debed Rivers would be extinct.
6. Further operation of the Geghanush tail storage is prohibited given the fact, that drainage-system
facilities located in the tail storage to secure removal of stormwater are under high pressure and
additional accumulations on the currently conserved galleries would result in an accident by causing
great damage to the environment, to the residential houses in the town of Kapan and commercial
facilities.
7. Operation of the Akhtala tail storage is possible only in the case if the drainage-system canal is
reconstructed.
2. MEASURES AIMED AT MITIGATION AND NEUTRALIZATION OF HARMFUL IMPACT
OF THE TAIL STORAGES
In order to minimize hazardous impact of the tail storages generated due to the mining industry
production activity it is necessary to conduct recovery and reclamation of the storage surfaces.
A tail storage or slurry field of each and every non-ferrous metallurgy-concentrating mill are former
landscapes, which appeared to be under a layer of toxic substratum of chemical substances. Meanwhile,
production wastes are fully eliminating natural fertile lands and fruitful biocenosis and new neo-
landscapes of technological origin that lost their original economic and social values are spontaneously
generated that leads to desertification.
All the prerequisites generate a necessity to conduct land reclamation, which includes a number of
engineering, reclamation and biological measures to set-up fruitful land-and-plant landscapes.
In order to mitigate and neutralize harmful impact of the conserved tail storage of Geghanush in the
province of Lori and tail storage of Akhtala in the province of Tavush it is necessary:
1. To arrange and carry out a periodical wetting system for tail storage surfaces layers and sow perennial
plants.
2. For that purpose it is necessary to select a method for artificial raining of the whole tail storage area.
Water used for artificial raining could be procured both by gravity and pumping methods.
3. To cover (encircle) the whole surface of the tail storage by a liquid of polyacrylamide. The advantage
of this method is, that polyacrylamide is gradually being hydrolysed by generating polycrylacidic
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
ammoniac brine, which changes the structure of land surface layer by strengthening it and
simultaneously remaining transparent for air and water and creating favourable enough conditions for
regular growth of plants.
4. As a temporary measure to strengthen the tail storages surface land layer by means of special machine
equipment to prevent shift of surface land layer under wind impact.
5. To reconstruct and repair drainage-system facilities surrounding the tail storages in order to prevent
transportation of wastes from the Geghanush and Akhtala tail storages to other areas through river
waters and generation of new desertification centres.
6. To cover the tail storage surface by a 10-15 cm-thick land layer and sow perennial grass plants.
Financial-and-economic calculations and cost estimation for the implementation of mitigation and
neutralization measures of harmful impact of the tail storage of Geghanush in the province of Syunik and
tail storage of Akhtala in the province of Lori should be refined by a competent designing organization
taking into account peculiarities of local natural-and-climatic conditions, location of tail storages,
availability and quantity of surface waters, feasibility studies of invested measures, etc.
The measure of covering the tail storage by a 10-15 cm-thick land layer is not observed by the financial
and economic calculation, since it requires large-scale land works that would deteriorate the landscape
natural balance.
In order to prevent harmful impact of the tail storages on the environment it is considered reasonable to
input combined measures with the following essence.
The tail storages surface is preliminary processed by polyacrylamide. Then a wetting system for the
surface land layer is constructed and afterwards perennial plants are sown.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Table 2: Classification of Tail Storages Located on the RoA Territory
#
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Tail storage title and
location
Right-bank tributary to
Vokhchi River, Village of
Darazam
Right-bank tributary to
Vokhchi River, Village of
Pkhrut
On Vokhchi River
On Artsvanik River
On Geghanush River
On Davazam River
In gorge No. 1 of Agarak
In gorge No. 2 of Agarak
In gorge No. 3 of Agarak
On Nahatak River nearby
settlement of Akhtala
Nearby Village of Arazap
(Province of Ararat)
On the right-bank of a
tributary to the Nazik
River nearby Settlement
of Dastakert
Year of
putting
into
operation
1953
1958
1962
1978
1961
1957
1978
1979
1971
1982
1960
Year of
conservation
1961
1969
1977
Working
1989
1977
Working
Working
1988
Working
1968
Volume
Mm3
3
3.3
30
210
4.6
30
9
17
3.2
20
3.1
Particles
average
diameter
0.067
ii
-"-
-"-
0.084
0.087
II
II
0.082
0.085
Waste
content
Mo
Cu
Si02
A1203
MgO
CaO
Ti02
FeO
Na2+K2
O
P205
s
Zn
Pb
rare
metals
173
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
AUSTRIA
1. LEGAL AND ADMINISTRATIVE ISSUES
Austria has had a Federal Act for the Remediation of Contaminated Sites (ALSAG) since 1989. The main
focus of this act is to provide federal funds for the clean-up of the most dangerous contaminated sites in
the country. The fund is created through a tax on landfilling. The amount of waste tax depends on the
technical standard of the landfill. Hence, landfills with a low standard have to be either adapted to the
high standard defined in the Landfill Ordinance, or closed by 2004 the intake of waste tax will decrease.
At present, the Federal Ministry for Agriculture, Forestry, Environment and Water Management
(BMLFUW) is working on an amendment on ALSAG which will regulate the waste tax intake on a new
basis. Additionally, the current and future use of the site should play a more important role when
remediation goals are defined and the polluter-pays-principle will be strengthened in the amendment.
In order to support sound decision making, the Austrian Standards Institute has published a standard on
"Contaminated Sites - Risk Assessment Concerning the Pollution of Soil" in spring 2000 and has started
to work on a standard on "Contaminated Sites - Risk Assessment Concerning the Pollution of Soil-Air."
2. REGISTRATION OF CONTAMINATED SITES
The BMLFUW registered 2.499 suspected sites. So far, the major part relates to abandoned landfill sites
because their data and registration are easily available. Detailed risk assessments showed that 148 sites
pose a considerable risk to human health or the environment and therefore were classified as
contaminated sites.
Currently, the work of identification of potentially contaminated sites focuses on industrial sites in Upper
and Lower Austria.
Remediation projects for registered contaminated sites are funded via the Kommunalkredit Austria AG on
behalf of the Federal Ministry BMLFUW. So far, 110 remediation projects, with a total cost of EURO
340 mio. (approximately 200 mio. US$) were funded.
3. TECHNOLOGY DEVELOPMENT PROGRAM
In 2001, the BMLFUW issued a concept on research priorities to tackle contaminated land problems in
Austria. Currently, an initiation of a Center of Competence is under development which will guide and
co-ordinate future research activities. All these initiatives will stimulate technology development in
Austria.
4. REMEDIAL METHODS IN USE
"Safeguarding" Methods: Number
capping of landfill 29
extraction of landfill gas 11
enclosure 32
hydraulic measures 38
pump and treat 20
in-situ sorting of material 9
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Remediation Methods: Number:
excavation off site 24
groundwater remediation 11
soil vapor extraction/bioventing 18
bioremediation 2
soil washing 4
thermal treatment 4
biological treatment 4
immobilisation 4
5. RESEARCH AND DEVELOPMENT ACTIVITIES
The Austrian Environment Agency has been the coordinator of the EU Concerted Action CLARINET
(1998-2001). This project has been one of the main R&D initiatives on contaminated sites in Europe.
Further information can be obtained from the CLARINET website at httm//wwwaclarmetat.v
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BELGIUM
1. LEGAL AND ADMINISTRATIVE ISSUES
A. Background Information
The Belgian Constitution dividing the authority between the Federal State and the Regions confers the
responsibility of environment protection policy almost exclusively to the three Regions: Flanders,
Wallonia and the Brussels-Capital Region, with very limited exceptions.
This means that there cannot be such thing as a federal legislation on soil protection, nor any federal
strategy in this matter. As long as Europe does not enforce a common framework to all Members States,
the three Regions are free to legislate or not, in this issue, according to their own policy, the requirements
of their citizens, and the constraints of their economy.
However, concerted work has been recently initiated between the three Regions in order to see to what
extent the three respective soil policies (the Flemish one, already in use, and the two others, in
preparation) could be harmonized.
B. Summary of Legislation
Until now, only Flanders has adopted a full legislative framework for contaminated sites. The main
characteristics of the Flemish Decree on Soil Remediation, adopted in 1995 and brought into force in
different stages, were presented in previous NATO/CCMS Pilot Study meetings. Its guiding principles are
the registration of all polluted or suspected sites, the distinction between duty and liability, and the
distinction between historical and new soil contamination.
In the two others Regions, Brussels and Wallonia, the present legislations are based mainly on Waste
Decrees and on Town and Country Planning provisions.
Wallonia has the oldest legislation in Belgium - and one of the oldest in Europe - dealing specifically
with brownfield issues: the Act of 1978 on the restoration of disused economic sites now amended and
included in the Walloon Planning Code.
Since 1999, Brussels-Capital Region and Wallonia have also adopted special regulations for gas stations:
these include control measures (soil and groundwater) and remediation procedures, according to soil
standards and intervention values in relation with the land uses authorized in the surrounding area. Those
regulations apply to all kind of situations: closing establishment, new establishment, license renewal or
transfer, suspicion of pollution, etc. In addition, they impose a strict calendar for the control and eventual
renovation of all existing gas stations.
Subsequently, a principle agreement between the three Regions, the oil companies and the Federal
Government has been adopted, providing for the creation of a common Fund for the remediation of gas
stations. The Fund will be financed on an equal basis by the oil companies and the consumers, through a
special levy.
Last but not least, the Walloon Government has launched a Strategic Programme for Contaminated Soils
and Brownfield Sites, including the preparation of a comprehensive Soil Decree. This programme, which
started in 2000, should be implemented and presented to the Walloon Parliament for adoption next year,
after hearings involving all public and private stakeholders.
During the present transitory period, special measures will enhance the rhythm of brownfield sites
reclamation, provide new means for a thorough updating of existing inventories of derelict and
brownfield sites, and for preliminary investigations of these sites.
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C. Administrative Aspects
For institutional reasons (see § 1 .a), there is no Federal Agency for the Environment:
• In the Flemish Region, OVAM (Public Waste Agency of Flanders) is the responsible authority for
soil control and remediation.
• In Brussels-Capital Region, the responsible authority is the Brussels Institute for
• Environmental Management.
• In Wallonia, as long as no decree on soil remediation has been passed, responsibilities are shared
between various bodies: the Walloon Waste Office is the responsible authority for landfills and other
polluted sites, according to the Waste Decree; the Town and Country Planning Administration is
responsible for derelict land and brownfield sites.
The transitory measures adopted by the Walloon Government enhance the role of SPAQuE (the Public
Society for the Quality of Environment) in the whole procedure, from inventory to remediation and
aftercare; SPAQuE will also be in charge of the preliminary investigations of sites listed in the new
inventory.
"Clean" or very slightly polluted sites will then be redeveloped under the authority of the Town and
Country Planning Administration, while contaminated sites will be transferred to SPAQuE, for thorough
characterization and subsequent reclamation on the basis of the Waste Decree.
2. REGISTRATION OF CONTAMINATED SITES
Flanders:
According to the legislation, a soil register has been created by OVAM. The Flemish authorities proceed
with a systematic examination of potentially polluted areas mainly on three occasions:
• at the time of property transfer;
• at the closure of licensed installations; and
• whenever the license has to be renewed.
All information on soil pollution is compiled in the soil register, which serves as a data base for policy
decisions and also as an instrument to protect and inform potential land purchasers.
A "soil certificate" is requested for all sorts of property transfers. This system has increased the number of
voluntary investigations, and sometimes induces voluntary remediations, in order to avoid to be listed as
contaminated in the register.
Wallonia:
A registration system has existed since 1978, based on the special brownfield legislation and aiming at the
redevelopment of those sites. It takes into account more than 2.000 sites, covering 9.000 hectares of
derelict land. The transitory measures (see § l.b) have allowed not only to implement a general updating
of this registration procedure, but also to enlarge its scope and provide new means for the investigations.
These will rely on the hazard ranking system 'Auditsol', developed by SPAQuE.
For the sites polluted by waste, the Walloon Waste Office holds an additional list of sites for which a
remediation plan should be prepared, has been approved, or is into execution (more than 900 sites
registered today).
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Brussels Region:
No registration system is known at this moment. A first investigations/mapping strategy is in preparation.
3. REMEDIAL METHODS IN USE
Until recently, there have been no comprehensive statistics on remedial methods and technologies used
for clean-up in Belgium. The following soil and groundwater remediation techniques are available and
used:*
• Excavation and transport of contaminated material to a deposit site and/or processing of the
contaminated soil.
• Hydrodynamic methods, by means of drains, water remediation, processing of slurry, etc.
• Use of degassing systems.
• Use of isolation techniques (horizontal and vertical isolation by means of cement, clay, bentonite,
bitumen, etc.)
• Immobilization techniques by means of cement, lime, absorption methods for oil, etc.
• Remediation technologies: microbiological remediation, in-situ and ex-situ (landfarming, biopiles,
etc.), water and chemical extraction, flotation, thermal treatment, steam-stripping, a combination of
physico-chemical and biological remediation techniques, electro-reclamation, infiltration and
wash out.
*Data collected with the help of Ecorem n.v.
4. RESEARCH AND DEVELOPMENT ACTIVITIES
For soils contaminated with heavy metals and metalloids, the following remedial techniques are in
research and/or anticipated for use in the coming years:
1. In-situ immobilisation by means of soil additives.
2. Bio-extraction of heavy metals by means of micro-organisms in a slurry-reactor.
3. Phyto-extraction by means of plants with increased capacities of metal-accumulation.
4. In-situ bioprecipitation of heavy metals by sulfate reducing bacteria.
More generally, there is a great need and expectation for low-energy, cost-effective remedial
technologies. Research is progressing in the Universities and Public research Institutes, mainly in
microbiology and phytoremediation areas, although no comprehensive evaluation is yet available.
VITO (The Flemish Applied Research Institute) is currently engaged in the following R&D activities:
• inorganic reactive barriers (zero valent iron): treatability studies, material selection, circumventing
clogging, protocol development for deployment and monitoring;
• biological permeable reactive barriers and permeable barriers for mixed pollutions;
• circumventing bio-availability limitations for bioremediation of PAH and mineral oil;
• developing protocols for monitoring of natural attenuation, in-situ bioremediation and pump & treat
remediation as well as field monitoring for these technologies;
• phytoremediation;
• bioremediation of TNT.
5. CONCLUSIONS
Since the adoption of the Flemish Decree on the soil remediation, there has been recently a growing
recognition of soil and groundwater contamination issues in Belgium. In the Flemish Region, the
implementation of the Soil Decree has a highly positive influence on soil management and soil
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environmental quality. Forthcoming months will show new developments in Wallonia, and maybe in
Brussels.
However, the main problems will probably remain in the three Belgian Regions:
• the lack of resources of many liable parties, for the cleanup of historical pollution;
• need to improve the cost-efficiency and environmental merit of the remediation programs, whether
funded by public or private money; and
• difficulty to match stringent soil regulations with the necessity of redeveloping brownfield sites, in a
sustainable land use strategy.
This last point might become, in the near future, the most difficult issue to cope with.
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CANADA
Information in this tour de table is current as of January 2001.
1. LEGAL AND ADMINISTRATIVE ISSUES
Canada is a country of 9,970,610 square kilometers and a population of 30 million inhabitants. The
country's political structure is federalist, divided in 10 provinces and 3 territories with the recent creation,
in 1999, of Nunavut Territory. The Canadian constitution leaves authority of non-federal contaminated
sites with the provinces and territories for which they exist. Most provinces have established their own
regulations or guidelines. Federal lands, which represent about 41% of the Canadian lands, are not subject
to provincial/territorial legislation.
There are three federal Acts that are applicable to all Canadian lands:
The Canadian Environmental Protection Act, which states that if a person releases a regulated toxic
substance into the environment, this person must take all reasonable emergency measures to remedy any
dangerous condition or reduce/ mitigate any danger resulting from the release. There are a number of
regulations under the CEPA which may affect the management of contaminated sites. These include the
Polychlorinated Biphenyls (PCB) Regulations, the PCB Treatment and Destruction Regulations, Storage
of PCB Material Regulations and Contaminated Fuel Regulations;
The Fisheries Act, which stipulates that no work or undertaking shall be carried out that may result in
harmful alteration, disruption or destruction offish habitat, unless authorized by the Minister or by
regulation. Further, it is an offence to deposit or allow the deposit of any deleterious substances in waters
frequented by fish, unless authorized by regulation under the Fisheries Act or another Federal Act. The
Act also specifies that if anyone is to engage in any work which may result in the disruption or
destruction offish habitat, or to deposit a deleterious substance in water frequented by fish, then plans,
studies and specifications of the procedure must be provided to the Minister and;
The Canadian Environmental Assessment Act (CEAA) which requires an Environmental Assessment
(EA) if an activity falls within the definition of "project" on CEAA's Inclusion List. As of June 1999, the
remediation of contaminated sites has been added to this List and therefore requires an EA.
2. REGISTRATION OF CONTAMINATED SITES
The nature and number of contaminated sites which exist in Canada are not fully known, however, most
provinces hold some type of registry of the environmental condition of lands containing general
information on contaminated sites. These data banks are used primarily for statistical and report
production purposes and are updated regularly. In most cases, sites have already been investigated and
require minor remediation, or have already been cleaned up to government requirements.
In terms of federally owned sites, the Office of the Auditor General of Canada has estimated that there are
5000 federal contaminated sites, with an associated clean-up cost of $2 billion, although these numbers
have not been confirmed.
The Treasury Board Secretariat of Canada has recently released a Contaminated Sites Inventory Policy.
The Policy's objective is to provide Canadian Parliament, the public, and federal departmental managers
with complete, accurate and consistent information on federal contaminated sites and solid waste
landfills.
By April 2001, all federal departments are required to establish and maintain a database of their
contaminated sites and solid waste landfills. This information will then be incorporated into a central
Federal Contaminated Sites and Landfills Inventory.
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In addition to the inventory policy, a second Policy on Accounting for Costs and Liabilities Related to
Contaminated Sites was released in 2000 by the Treasury Board Secretariat. In the interest of improved
financial reporting and to comply with the evolving requirements of the accounting profession, the intent
is to capture and record federal liabilities for the remediation of contaminated sites. Significant
environmental liabilities exist and will impact both the fiscal framework and the accumulated deficit of
the government. In order to provide a fair and comprehensive statement of the government's financial
position, it is necessary to identify, quantify and record these liabilities.
In 1989, the Canadian Council of Ministers of the Environment initiated the five-year, $250 million (50%
federal) National Contaminated Sites Remediation Program. The program remediated 45 orphan sites—
sites for which the owner cannot be found, or is unable to pay for remediation—demonstrated over 50
technologies, and assessed 325 and remediated 18 federal sites. Scientific tools such as soil quality
guidelines and the National Classification System, which ranks sites based on health and environmental
risks, were also developed.
These tools are still used by many federal departments and by provincial and municipal governments.
Since the program ended in 1995, significant progress on the assessment and remediation of federal
contaminated sites has been made by federal government departments. Current spending on this issue
averages about $ 94 million per year.
Sydney Tar Ponds
In 1998, the federal government approved Can$41.5M over 3 years to address the Muggah Creek
Watershed in Nova Scotia, which rests within an urban area setting and is home to the worst hazardous
waste site in Canada. The watershed is 22.44 square kilometers (22,400 hectares) and encompasses the
Tar Ponds, the former Coke Ovens site and the Municipal Landfill site. The contamination includes
poly cyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, PCBs and heavy metals.
Selection of appropriate remediation technologies to remediation this site will involve bench and field
scale evaluations. This technology demonstration program is currently underway at an estimated cost of
Can$ 5 million.
3. REMEDIAL METHODS IN USE
Canadian contaminated sites are generally categorized as follows:
• Unregulated former disposal sites;
• Industrial properties - spills, leaks, open storage areas, fill areas;
• Electrical facilities - PCB leaks and spills;
• Fire-fighter training areas;
• Ports and waterways where past industrial discharges contaminated sediment;
• Lagoons used to store or "treat" industrial effluents;
• Mine tailings ponds;
• Municipal and industrial landfills;
• Military training areas; and
• Wood preserving sites.
In 1997, a general reference manual entitled: "Site Remediation Technologies" was published for federal
employees involved with site remediation work.
The following is a summary of the reference manual reflecting Canadian general remediation strategies
and related technologies.
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In-situ Remediation of Soil and Groundwater
Soil Vacuum Extraction
Bioremediation (bioventing, bioslurping, land treatment)
Soil Flushing
Thermal Treatment (volatilization, solidification)
Electrokinetics
Phytoremediation
Treatment Walls
Pump and Treatment of Groundwater
Air Stripping
Steam Stripping
Advanced Oxidation
Carbon Adsorption
Bioreactors
Membrane Separation
Oxidation/reduction
Ion Exchange
Precipitation
Coagulation/Flocculation
Filtration
In-situ Containment
• Slurry Walls
Grout Curtains
• Sheet Pile Walls
Surface Caps
Ex-situ Remediation of Excavated Materials
Soil Washing
Thermal
Biological
Chemical
Metal Extraction
Fixation/Stabilization
Disposal (industrial/municipal landfills, hazardous waste disposal, aquatic disposal, storage, re-
use/recycle)
4. RESEARCH AND DEVELOPMENT ACTIVITIES
Several universities and research institutes across country dedicate their work to groundwater
contamination, soil remediation technologies, sediments contamination and biotechnology.
Although federal funds are not currently committed specifically to contaminated sites technology
development, there are numerous federal initiatives which provide indirect funding for advancement and
promotion of remediation technology such as: Sydney Tar Ponds Clean-up, Technology Partnerships
Canada, Industry Canada's Environmental Solutions Database, etc.
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5. CONCLUSIONS
Contaminated sites remain an issue of concern for Canadian governments and private industry. Despite
the absence of a National approach, federal, provincial and territorial governments are have made
significant progress on the assessment and remediation of their contaminated sites. Advancement in
contaminated site technologies and site cleanups will continue to be addressed as an important
environmental challenge.
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CZECH REPUBLIC
1. INTRODUCTION
At the previous meetings of the Pilot Study, the legislation background and administrative procedure of
remediation of environmental damages caused by the former Soviet Army and remediation of the polluted
sites in the course of privatisation have been fully described.
From 1990-2000, the amount provided from the state budget for study and decontamination work on the
previous Soviet military bases, including risk analysis and supervision reports, equalled approximately 1
118 mil. CZK. It is expected that it will be necessary to expend a further 320 - 370 mil. CZK by the year
2008. In this year the clean-up continues on six sites and two tenders are intended to be called for the
supplier of the remedial action (chlorinated hydrocarbons in groundwater in area of previous military
laundry and site with free oil phase on groundwater level). Total expenses in 2001 should be 75 mil.
CZK.
In the course of privatization, some principles of reimbursement of environmental obligations by the
National Property Fund was modified by the Resolution of the Government of the Czech Republic No.
51/2001, On Principles of Settlements of Ecological Obligations Originated before Privatization, which
amends Resolutions No. 123/1993 and No. 810/1997. Important new principles are following:
• the order of remediated sites will reflect priorities assessed by Ministry of the Environment with
respect to their risk on health of human beings and/or ecosystems;
• consent of the Government for the National Property Fund to make an Ecological Liability
Agreement with new owner of the privatised property has effectiveness only two years;
• in the case of serious ecological threat due to pollution of groundwater or soil in privatised enterprises
the Ecological Liability Agreement can also be made in cases that the Project of Privatisation was
submitted before the 1 March 1992 in spite of an
absence of Eco-audit in the project. Obligatory conditions are the risk analysis to prove serious threat
and recommendation of the Ministry of the Environment;
• The National Property Fund is authorised to reimburse expenses of prospections, risk analysis and
their bringing up-to-date, making projects, remediation of polluted soil, groundwater and building
constructions, supervisions and pilot studies in the case of new unattested technologies;
• the Ecological Liability Agreement can be terminated after the remediation measures, imposed by the
Czech Environmental Inspection (CEI), was reached what must be confirmed by CEI.
In the period from 1991 to 31 December 2000, the Government of the Czech Republic confirmed 257
agreement guarantees of the National Property Fund, in an amount of 139.233 billion. CZK; of this
number 240 Environmental Liability Agreements were concluded. The expenses paid until now for
remedying historical burdens on the privatised property by the National Property Fund were as follows:
1993 - 9.1 mil. CZK, 1994 - 139.2 mil. CZK, 1995 - 817.7 mil. CZK, 1996 - 949.7 mil. CZK, 1997 - 1
375.3 mil. CZK, 1998 - 2 173.6 mil. CZK, 1999 - 1 758.9 CZK, 2000 - 2 129 mil. CZK. Remediation
activities were finished at 17 sites, 89 cases are continuing. Until now, the greatest remedy is former
coking plant Karolina in the centre of the town Ostrava where more than 500 000 tons of soils polluted by
coal tar is remediated by the technology of thermal desorption (supposed expenses over 1.7 billion CZK).
2. LEGAL AND ADMINISTRATIVE ISSUES
Meanwhile, the reimbursement of expenses of remedying historical environmental damages by the
National Property Fund is not subject of the process of approximation of the Czech Republic to the
European Union, the amendments of several Acts important in protection of the soil and groundwater
which were enacted during the last year are, at least in part, result of the harmonisation and
implementation of the environmental legislation of the European Communities to the Czech Republic.
The Water Act No. 254/2001 will come into force on 1 January 2002. The polluter-pays principle
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accepted in the previous version has been used here also. Obligation to remedy contaminated surface and
ground water respectively has been, however, imposed to the owners of the privatised property in spite of
the fact that they are not polluter if they were informed about these ecological damages or the price of the
property was reduced due to high probability of environmental damages at the site. For the purposes that
remedial measures cannot be imposed on polluter or on the owner of property, and there is a threat of
serious deterioration or pollution of surface or ground water, the water management authority shall
establish a special account within its budget which will be supplemented annually to maintain the balance
of CZK 50,000,000.
In the field of the waste management the clean-up and reclaiming of landfills that have been closed by law
is a serious financial problem. Since 1996 only technically secured landfills have been in operation in CR.
Landfilling of waste highly predominate, only about 2 % of waste were incinerated. A new Act No.
185/2001, on Wastes, which will come to force on 1 January 2002, is fully compatible with EU
regulations. All the necessary implementation regulations are close to completion.
Act No.66/2000 on Geological Works has included determination and elimination of anthropogenic
pollution in the geological environment (rocks, soils and groundwater) as part of geological works.
Consequently, the planning, carrying out and assessment of clean-up works may be carried out only by
legal and natural persons who fulfil the conditions laid down by the legal regulations ("an organisation")
and in which there is a person with certificate of professional qualification to plan, carry out and evaluate
remedial actions who is responsible for the management and evaluation of such work.
The requirements of the EC Air Protection legislation will be covered by the new Clean Air Act and its
implementing Decrees. This legislation will come into force in November 2001.
The most important with respect to the topic of this meeting is preparation of the draft of new Act on
identification of chemical environmental burdens in groundwater, soil, rocks, and building constructions
and their remediation. Previous legislative background was concentrated on remediation of historical
contamination in process of privatization of the state enterprises. This new law will implement risk based
contaminated land remediation and management duty on broad range of land owners who use or used
pollutant listed in the appendix of the law. The law proposal should be submitted to the Government and
Parliament next year and is expected to be in force in 2003.
Following regulations for the remediation of contaminated sites are a substantial part of the draft:
1. each owner of property in which harmful chemicals listed in appendix of the Act are used and each
owner of land with landfill owe the duty to make prospection of the site for these chemicals in
groundwater, soil, and building constructions;
2. ascertained concentrations of the chemicals are compared with control standards (control standards: A
level - background; B level - approximately the average between A and C levels; C level -
concentration which may be harmful if this control standard is exceeded, different C levels for soil are
given according to type of land use);
3. owner of the property in which control standard A are exceeded and risk analysis prove an
unacceptable risk for individual humans or ecosystems owe the duty made remediation of the site to
the target concentration levels assessed by regional authorities or by Czech Environmental Inspection;
4. in the case that duty of remediation is assessed the owner owe the duty to effect insurance against loss
and damage due to environmental burdens. If the insurance is not effected the owner owe the duty to
build up financial reserve;
5. if remediation cannot be realised to the target limits due to the lack of proper technology of if
expenses are too high and inadequate to the health risk decrease, compensatory measure can be
assessed by CEI. Compensatory measures have form of financial dues.
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3. BROWNFIELDS
The Ministry of the Environment, as the highest body of the environmental state administration, bears
responsibility in preparing and implementing state policy in the sector of Brownfields. In The State
Environmental Policy ofCR, 2001, the necessity to prevent further investments in "green-field"
construction. There is not, however, any unified approach to the brownfields despite the fact that the
statistics continue to show an ongoing delpetion of greenfields in the Czech Republic in recent years.
Many of polluted sites remediated in the frame of the privatisation process or as historical burdens after
the former Soviet Army is possible to consider as Brownfields. The first attempt at recovery of unused
territory is being implemented in the historical centre of the coal mining and iron works - in the region of
town Ostrava with the support of US EPA. The Welsh Development Agency has elaborated study "A
strategy for industrial land reclamation in the Czech Republic".
The MoE (Department of Environmental damages) provides support for 2 projects: 1) Integration of
information on landfills and contaminated sites from the past and their risk assesment, and 2) Analysis of
toxic intermediates of polyaromatic hydrocarbons biodegradation. These projects are payed from the
research and development fund.
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FINLAND
1. LEGAL AND ADMINISTRATIVE ISSUES
A. Soil Protection
The new Environmental Protection Act (86/2000) - which entered into force 1.3.2000 - implemented the
IPPC directive (96/6I/EC). Environmental Protection Act (EPA) is a general act on the prevention of
pollution. In section 7 of the act is the soil pollution prohibition. The use of Best Available Technology
(BAT) is written as a legal principle in section 4 of EPA, and it applies to all activities within the scope of
the act. The regulation of contaminated soil was removed from the Waste Act (1072/1993) to the new
Environmental Protection Act, in which chapter 12 is titled "Treatment of polluted soil and groundwater."
A decree on the assessment of the decree of pollution and the need for restoration of the soil is currently
being prepared in the ministry of the environment.
B. Waste Legislation
The Waste Act (1072/1993) and Waste Decree (1390/1993) implemented the provisions of Council
Directive (75/442/EEC) on waste and Council Directive (91/689/EEC) on hazardous waste. The other
European Community provisions on waste and waste management have been implemented through
general regulations issued by the Government or the Ministry of the Environment, such as the decree on
the incineration of hazardous waste ( 842/1997)etc.
The definitions of waste and hazardous waste in the Finnish Waste Act is similar to the definitions in the
Waste Framework Directive 875/442/EEC and Council Directive (91/689/EEC) on hazardous waste.
Therefore polluted soil material is always classified as waste. Whether polluted soil is hazardous waste, is
decided on case by case basis. The decree on landfills implements the Council Directive on Landfills
(99/3 I/EC). Polluted soil is within the scope of the decree. So, even special landfills for polluted soil have
to meet all the legal demands of the landfill decree.
The Waste Tax Act (495/1996 changed by 1157/1998) lays a tax on all waste disposed on municipal
landfills. However, polluted soil is excluded from the scope of the tax.
C. EIA-Legislation
There is a special act (468/1994) and a decree (268/1999) on Environmental Impact Assessment.
2. PERMITS FOR SOIL TREATMENT INSTALLATIONS
A. Procedure for "On Site" Soil Restoration
According to the special rule in the Environmental Protection Act section 78 an environmental permit is
required for the treatment of polluted extractable land resources. Action may, however, be initiated to
restore soil or to remove polluted soil material for treatment elsewhere by making the relevant notification
to the regional environment center if;
• the extent of the polluted soil and the degree of pollution have been adequately established
• treatment observes an approved treatment method in general use; and
• the activity does not result in any other pollution of the environment
The second criterion mentioned above refers to the technique or a method used in the restoration. Apart
from removing the soil, restoration methods can be divided into soil washing, stabilization, biopiling,
incineration and different soil venting methods. Whatever kind the method is, it has to be familiar in
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Finland to be subject to notification procedure only. Some prior practice of the method in Finland should
be required. Therefore new methods may at first be subject to permit procedure.
The notification is a cheaper and less time consuming procedure compared to permit procedure. In
practice a notification is always given first and it is then up to the permit authority to award whether it is
sufficient or whether a permit procedure should take place. The permit procedure is according to the
legislation a primary rule, and it can be replaced by the notification procedure only if the criteria in the
section 78.2 are met. However, in practice more than 90% of the restoration activities since 1.3.2000 have
been subject to the notification procedure only.
B. Liability to Apply for a Permit for "Off Site" Treatment of Soil
An environmental permit is required for "institutional or commercial recovery or disposal of waste"
(section 28.3). Polluted soil material which has been removed from the soil is considered as waste and
therefore falls within the scope of Waste Act and other regulation concerning waste. An "off site"
treatment of soil material is considered as recovery or disposal of waste and therefore subject to
environmental permit procedure.
There are some derogations concerning the permit requirement in section 28 of the Environmental
Protection Act. Small scale recovery or disposal activities neither institutional nor commercial) can be
excused from the permit requirement. In addition, permit is not required for "short-term activities
undertaken on a trial basis when the purpose is to test a raw material for fuel, manufacturing or
incineration method or treatment equipment, or to investigate the impact, usefulness or other
corresponding feature of such activities." In these cases a notification according to section 61 of
Environmental Protection Act shall be made to the competent permit authority, at least 30 days before
starting the activity.
C. Permit Authorities
The regional environment centers (13) issue permits for soil restoration. However, this power can be
transferred to a local authority if "special causes" exist (section 80). In practice the transfer of power is
possible only to big municipalities which can offer the expertise needed. The application of transferring
the power is handled by the ministry of the environment. So far only Helsinki municipality environment
centre has been transferred the power of handling notifications (not issuing permits) according to section
78 in Environmental Protection Act. No other municipality has applied for transfer of powers.
Following rules according to the Environmental Protection Decree sections 6-7 apply when polluted soil
material is restored "off site" (waste disposal or recovery): The regional environment centers (13) issue
permits for restoration in which the minimum capacity is 5000 tons of waste per year. The municipality
issues permits for smaller activities.
D. Summary of the Permit Procedures Concerning Soil Restoration
Soil restoration activities are in the first place permitted according to the special procedures stated in
section 78 (permit or notification). In most cases only a notification to the regional environment centre (in
Helsinki the municipal environment centre) is required. According to section 28, a permit is required for
the "off site" treatment as well (recovery or disposal of waste). However, if the soil material is restored or
treated "on site", only the procedure in section 78 applies.
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Table 1: Summary of possible procedures concerning restoration of polluted soil.
Legal
basis
EPA 78 §
(permit or
notification)
EPA 28.2 §
(permit)
When?
always for restoration
(on site)
when the soil material is
removed and taken "off
site" for treatment
Derogations?
No
short-term testing of method,
equipment or impact (EPA 30
§) -> notification
Competent authority
regional environment
centre (In Helsinki
municipal env. centre)
regional environment
centre or municipal
authority
In general the new procedure according to section 78 in the Environmental Protection Act is considered to
be fluent. Testing of new clean-up techniques is possible by using the notification procedure according to
sections 30 and 61 in the Environmental Protection Act. Presentation of new techniques in factual
restoration projects, however, should at first be subject to the permit procedure according to section 78.
For mobile establishments (which have recently been introduced in soil restoration) some problems may
arise, when the restoration of the soil material (waste) has to be done "off site" - this might be because of
the technique exceeds the emission limits for a certain area. "Off site" treatment of the soil is subject to
permit procedure according to section 28 in the Environmental Protection Act and cab not be done inside
the procedure according to section 78 in the act.
Location of the activity is one of the legal considerations for granting the permit. So, mobile activities as
such can not be permitted since the exact location of the activity can not be defined. Instead, small mobile
technologies/plants are treated the same as large capacity immovable soil treatment plants; a separate
environmental permit is needed for every site where the treatment activity takes place.
3. ENVIRONMENTAL IMPACT ASSESSSMENT (EIA)
A. Restoration of Soil
According to the general rule in the Act on Environmental Impact Assessment (468/1994) section 4, EIA
applies to all activities which "may cause significant impacts to the environment." Most of such activities
are listed in the decree on EIA (268/1999). However, if the activity is not listed in the decree, the general
rule mentioned above may still apply. The restoration of soil may become subject to EIA if it "may cause
significant impacts to the environment." However, the ruling interpretation in Finland is that soil
restoration is not subject to EIA since restoration as such endeavors on cleaning the environment, not
polluting. EIA could only become relevant in severe restoration projects in which there would be a
potential danger of harmful impacts to soil or groundwater.
B. Recovery or Disposal of Soil Material (Waste)
"Institutional or commercial recovery or disposal of waste" (section 28.3) may become subject to EIA on
the basis of criteria set out in the EIA-decree section 6. An "off site" disposal or recovery of polluted soil
material can become subject to EIA. In considering whether or not EIA applies, relevance is given to the
amount of waste, the classification of the waste and the technology at issue.
In case of physical or chemical purification or incineration of the soil material, the minimum capacity of
5000 tons per year is the limit for EIA if the soil material is classified as hazardous waste. If the soil
material is classified as (ordinary) waste, the minimum capacity of activities/establishments subject to
EIA is 100 tons per day. Biological treatment of waste is subject to EIA if the capacity of the
plant/establishment is 20 000 tons per year at the minimum. In case of disposal, more than 50 000 tons of
waste per year is always subject to EIA.
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C. Summary of Applying EIA in Soil Restoration
A soil restoration project is, according to the ruling interpretation of the law among authorities, not
subject to EIA. However, soil cleaning plants in cases where the soil is removed from the soil, can be
subject to EIA if the conditions in the EIA-decree section 6 are met. If the soil is classified as hazardous
waste, EIA is required for relatively small capacity plants/establishments. Biopiling is considered as a
biological treatment of waste and therefore subject to EIA if the capacity of the establishment is 20 00
tons per year or more.
For mobile soil treatment plants/technologies, a similar problem in relation to EIA exist as in relation to
environmental permit: EIA is by definition a location based instrument and therefore the EIA requirement
should be assessed case by case on all different "off site" treatment/restoration locations.
4. SUBSTANTIVE LAW CONCERNING SOIL RESTORATION
Recognition of a polluted soil is found in EPA section 7: "...deterioration of soil quality as may endanger
or harm health or environment, may substantially impair the amenity of the site or cause comparable
violation of the public or private good." The definition is broad and no consistent practice has bee
developed, although some unofficial guidance (a memorandum of the ministry of the environment 1994)
has been available about target-values and limit-values of different harmful substances in the soil.
However, a new decree on assessment of the decree of pollution and the need for restoration. The new
decree will introduce the criteria for soil pollution (target-values, limit-values) and the need for
restoration.
5. USE OF TREATED SOIL MATERIALS
There is no special legislation or other criteria concerning the use of contaminated soil in earthworks.
Guidelines (non-legal) on reuse have been prepared in Finnish Environment Institute. Until now treated
soil waste has been reused for construction of landfills and earthworks of industrial and storage areas as
other wastes also.
6. CLASSIFICATION OF THE SOIL AND ITS LEGAL EFFECTS
Classification of polluted soil as waste or hazardous waste has been a controversial issue and
interpretations in different regional authorities have been inconsistent. In many cases the classification has
been based on the proposed interim limit values of contaminated soil. Due to this, a major part of the
removed soil material has been classified as hazardous waste. According to new criteria most of the soil
removed from contaminated sites shall not be classified as hazardous waste.
Despite the renewed criteria, some of the removed soil will still be classified as hazardous waste. The
classification of the soil as hazardous waste has at least the following relevant legal effects:
1. EIA applies for all plants/establishments with a capacity of at least 5000 tons per year.
2. In the case of incineration techniques, the decree on hazardous waste incineration (842/1997) is
applied. This decree regulates the technical standards and especially the emissions to air. In practice,
hazardous waste incineration is not allowed on delicate areas, such as housing or recreation areas.
3. For removing the soil "off site", a certain transport document is issued.
4. If a permit is required for recovery or disposal of waste (section 28 in EPA), a financial guarantee is
required to cover the possible malfunctions in the activity.
5. The disposal or recovery on hazardous waste can not be released from permit requirement. (For a non
hazardous waste treatment plant a derogation from the permit requirement is possible according to the
EPA section 30. This possibility is originally based on the Waste Framework Directive art. 11)
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7. SUMMARY
In general, the material regulation in Finland concerning environmental technology, emissions to soil,
water and air does not hamper the implementation of new remediation technologies. On the contrary, the
principle of Best Available Technology is a general principle in the Environmental Protection Act
(section 4), and it applies to all activities. The waste legislation at present in most cases allows the
treatment of polluted soil without applying the regulation concerning hazardous waste - this should
encourage the presentation of new methods and technologies.
The procedural regulation of restoring contaminated sites is also considered to be quite fluent by all. In
most cases, only a notification to the competent authority is needed. However, the environmental permit
system may in some cases hamper the use or introduction of new technologies. Especially removable soil
treatment plants, which in most cases are both environmentally and economically feasible, may become
subject to a double permit procedure. This is however only in cases, where the removed soil material has
to be taken "off site" for treatment; permit may be required for both the restoration project and the
treatment of the soil material.
The economic burden on the disposal of polluted soil does not in every possible way support the
treatment of polluted soil. Even though polluted soil is subject to landfill regulation and the indirect
economic burden there off, the disposal of polluted soil is still excluded from the scope of waste tax.
8. THE SOIL TREATMENT MARKET IN FINLAND
In recent years about 200 polluted sites have been restored per year. A sum of approx. 30-35 million euros
is used every year in restoring. During the next 10-15 years, at the minimum 3000 sites should be
restored, at the cost of approx. 0,4-0,8 billion euros. Closed mines or the treatment of removed water
sediments is not included in these calculations. In total 20 000 sites in Finland have been classified as
"potentially contaminated." About 10 companies which the Finnish market on soil remediation. Also
some new companies are intending to enter the market - both from Finland and other countries. Some
new technologies have even been introduced, such as bioremediation techniques, reactive barrier
solutions, electrokinetic methods and phytoremediation.
In addition there are 54 (1998) permitted locations where it is possible to compost soils contaminated by
oil based compounds and case by case also other substances which are verified to be compostable.
There are 5-7 consultant enterprises which offer case by case services to manage contaminated sites
combining different technologies.
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FRANCE
1. LEGAL AND ADMINISTRATIVE ISSUES
A. Background information on legal and legislative action
It may be considered that the French policy in matter of polluted land has been defined in its general
features and objectives by the December 3, 1996, circular letter of the Minister of the Environment. This
policy can be characterized by a will of efficiency and realism. The circular letter includes a paragraph
entitled: "The principles of a realistic policy for the treatment of polluted sites and soils", in which it is
written that "...it is a long term action, to the scale of the century and half of industrial history of our
country. The development of this policy can only be progressive and according to the public and private
means that will be possible to mobilize..."
Another aspect of this policy is the principle of dialogue, also mentioned in the circular letter of
December 1993. This principle is put in practice between the Ministry of the Environment and the
different actors that take part in the management of polluted sites: governmental agencies (ADEME,
Water Agencies), industrial operators of potentially polluting installations, associations for the protection
of the environment, experts, consultants and enterprises specialized in evaluation and treatment of
polluted land and, in the case of pollution related to domestic waste, Municipalities and Territorial
Institutions. This dialogue occurs in many occasions, especially in the national working groups that
discuss the projects of methodological guides prepared by the Ministry of the Environment, before these
guides are issued as references for technical regulations.
B. Summary of legislation
In the case of polluted sites, the basic legal reference is the law of July 19th 1976 on the Installations
Registered for the Purpose of Environmental Protection (Installations Classees pour la Protection de
I'Environnement: 1C Law) which covers all environmental aspects of industrial activities (including waste
management and treatment or disposal). According to this law industrial installations have to be either
authorized (if they have potentially a strong environmental impact) or declared (if they have potentially a
little environmental impact). Another basic reference which may be applied in the case of pollution of
land is the law of July 15th 1975 on elimination of waste and recovery materials (Elimination des Dechets
et Recuperation des Materiaux: Waste Law). Additional laws, improving the management of the
environment, complete the I.C. and waste laws:
Law of July 13th 1992 created a new policy for the management of domestic wastes including:
• the progressive banishment of direct landfilling of waste within a time limit often years,
• the institution of a tax on the direct landfilling of domestic waste,
• a specific section on the selling of industrial land, where installations regulated by the 1C Law have
been operated, that oblige the vendor to inform the purchaser of the possibility of the pollution of the
considered land. In this situation the purchaser has the possibility to cancel or to renegotiate the sale.
Law of February 2nd 1995 regulated the procedures in the case of "orphan" polluted sites and finance this
action by the extension of the waste tax (law of July 1992) to special (polluting) industrial waste treated
or disposed in collective installations.
Law of Dec. 31 1998 (finance law) that creates a new general tax on polluting activities (TGAP). This tax
replaces different previously existing taxes and is applied on air pollution, noise, used oils, treatment /
disposal of domestic and industrial waste.
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In connection to these laws, additional legislative decrees and circular letters (directives) have been
issued, mainly:
• decree of September 21, 1977, that defines the obligations of the operator of an industrial installation
in the case of cessation of activity
• circular letter of December 3, 1993, defining the policy for polluted sites
• circular letters of April. 3 and 18, 1996, requiring the realization of preliminary diagnostic and
simplified risk assessment for active industrial sites
• circular letter of June 7, 1996, describing the procedure to be carried out to apply the polluter pays
principle.
• circular letter of Sept. 1, 1997, indicating the possibilities to imply the owner of the polluted site.
• circular letter of March 11, 1999, specifying administrative and legal procedures applicable to
polluted sites remediation
• circular letter of December 10, 1999, listing the principals to fix the remedial objectives
C. The concept of polluted sites
At the origin in 1978 and during the eighties, problems of polluted sites and soils were systematically
related with problems of wastes.
A wider concept of pollution of land designated by "polluted sites and soils" was introduced at the
beginning of the nineties. Accordingly, on December 3, 1993, the circular letter dealing with the "policy
of rehabilitation and treatment of polluted sites and soils" was issued by the Minister of the Environment
and gathered the main elements of a new policy for the subject encompassing:
• a systematic registration of potentially polluted sites
• a concerted definition of priorities
• the treatment of every polluted site according to its impact and the use of the land.
At the present time, the definition of a polluted site is: site generating a risk, either actual or potential, for
human health or the environment related to the pollution of one of the medias, resulting of past or present
activities.
Practically, polluted sites are industrial sites, active or inactive, waste sites, and accidental pollution sites.
D. Administrative aspects
Although there is a recent tendency towards some regionalization, France remains a centralized country.
For the environment, like for other subjects, laws are discussed and voted by the parliament and
regulations are enacted by the Government and have a national validity. At the central level, the Ministry
of the Environment is responsible for the management of the environmental policy. More precisely, inside
the Ministry of the Environment, the Department in charge of industrial pollution and waste management,
including the problem of polluted sites is the Direction of Prevention of Pollution and Risks (Direction de
la Prevention des Pollutions et des Risques: DPPR). At the local level the basic geographical
administrative unit is the department (there are 99 departments in the country), and in every department,
the Prefect, who is the representative of the government, is responsible for the implementation of the
regulations. In the particular case of polluted sites, for which, the basic framework law is the Law on
Registered Installations (1C Law, mentioned above in b). The Prefect is assisted by the Inspectors of the
Registered Installations who control industrial activities (including waste management and disposal) and
who are in almost all cases members of the Regional Direction of Industry, Research and Environment
(Direction Regionale de I'lndustrie, de la Recherche et de I'Environnement: DRIRE).
Basically the legal and administrative action is based on the polluter pays principle, the polluter being,
according to the 1C Law, the operator of the installation at the origin of the pollution.
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The circular letter of the Minister of the Environment dated June 7, 1996, gives a detailed definition of the
procedure to be carried out by the authorities to manage the suspected or proven contaminated sites
according to the polluter pays principle and, in case of unsuccess, to deal with the orphan sites. This
procedure may be explained as follows: in the case a registered installation is suspected to be responsible
of land pollution, the Prefect may require the operator, according to the 1C Law (section 23), to carry out
the actions (investigations or clean up) requested by the Inspectorate of Registered Installations
(Inspection des Installations Classees}. If the operator doesn't comply with the order, the Inspector of the
Registered Installations writes to the Prefect a report assessing this non execution. In this situation, the
Prefect may require the operator to deposit to a public accountant a sum representing the estimated cost of
the requested work. If this procedure does not succeed, most of time because of insolvency of the
operator, the public accountant states the insolvency of the responsible party to the Prefect who will then
send the file of the considered case to the Ministry of the Environment, requiring the site to be considered
as "orphan". If the Ministry agrees, the case is presented to the specific National Commission of the
Agency of the Environment and Energy Management (ADEME) to be financed by public funding
(TGAP). Then, if the case is accepted by the Committee, the Prefect is allowed to issue an order asking
ADEME to carry out the requested investigations or clean up. After the requested actions have been
carried out ADEME has to initiate lawsuits against potential responsible parties in order to try to get the
reimbursement of the public money spent for the case.
The position of the authorities concerning the owner of a polluted site is a subject of active discussion.
Some years ago, the position of the Ministry of the environment was rather to consider the owner as a
responsible of second row and generally no action was initiated against him. Now this position has
changed and the Ministry may require the prefect (circular letter of sept 1. 1997), in the case of unsexes of
the action against the operator of the installation, to engage administrative action against the owner.
However the existing jurisprudence is rather controversial and the legal validity new position of the
Ministry is not proven.
E. Summary of policy developments
As it has been explained above the French approach to deal with polluted sites is basically connected with
the legislation on the environmental management of industrial installations (1C Law) and to a more
limited degree to the management of waste (waste law).
This means that there is no specific legislation relative to soil protection or polluted sites. Although the
development of such legislation has been already considered, it seems that it will probably not happen in
the short or middle term and that the existing approach will continue.
In this view the existing laws (1C Law) will be applied and completed by technical directives (circular
letters) issued by the Ministry of the Environment to organise the management of polluted sites. These
technical directives are related to technical guides developed at the present time.
A First Technical Guide has been issued in 1996 (draft 0) and 2000 (draft 2) to organise the preliminary
evaluation and priority ranking of suspected polluted sites. The proposed preliminary evaluation includes
two steps:
Step A. which is a documentary study (a historical review and a vulnerability study) based on available
and accessible data, and is completed with a site visit. The historical review includes a description
of the sequences of activities that have taken place in the course of time, their precise locations
and any associated environmental practices that may have been carried out. The vulnerability
study includes an investigation of the parameters (geology, etc.) that could have relevance for the
fate and transport of the contaminants and the potential targets (housing, drinking water supply
etc.) likely to be affected.
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During the site visit the data deriving from the documentation study should be verified and
additional data acquired. An evaluation and identification of existing and potential impacts takes
place and a further investigation programme is prepared.
Step B, initial diagnosis (and the simplified risk assessment (SRA) includes the collection of data that
have not been available within the previous study but are conditional for the simplified risk
assessment. The SRA demands an understanding of the contamination's spatial distribution and
transport mechanisms, the identification of possible hazards and the description of possible
rehabilitation methods. At this stage it is necessary to develop some field investigation in order to
acquire the data that make this understanding possible.
Simplified Risk Assessment (SRA); based on the results of the preliminary evaluation, a simplified risk
assessment is conducted according to a scoring system: the site in question is classified in one of 3
groups:
• sites needing further investigation and detailed risk assessment
• sites for which monitoring systems should be applied
• sites that can be used for specific purposes without further investigations or implementation
of measures
The decision making process within the SRA is supported by defined guideline values.
For the sites where the preliminary diagnostic concludes that the pollution and risks are serious, the
realization of the impact study and risk assessment will give the basis to determine the rehabilitation
objectives and to select the remedial options.
A second methodological guide, under the responsibility of the Ministry of the Environment, in
cooperation with a national working group, has been issued in 2000 (draft 0). This guide defines the
objectives and contents of the impact study (detailed investigations) and detailed risk assessment. The risk
assessment takes into account the present and future uses of the site and its surrounding, especially for the
water and air dispersion routes. Targets taken into account are human health, water resources, ecosystems
and buildings. The maximum tolerable excess lifetime cancer risk to be used for defining remedial
objectives is 10 ~5.
The proposed detailed evaluation includes two steps (B Sauvale, D.Darmandrail in Risk Assessment for
Contaminated Sites in Europe-Policy Framework, CARACAS 1999:
Step A: in-depth diagnosis. The main objectives are:
1. to verify or refute hypotheses made following the initial diagnosis, and, in particular, to identify and
characterise all sources of pollution and to establish the actual condition of the site.
2. to estimate the extent of pollution in the transfer media (this should be done for all media concerned
3. to understand the transfer mechanisms of pollutants in these media
4. to evaluate (if necessary) the impacts, whether direct, indirect or cumulative
5. to collect all the informations needed to implement the detailed risk assessment
Step B: detailed risk assessment which should enable:
• the identification of significant unacceptable risks to human health and other receptors, and which
therefore require treatment to reduce or eliminate these risks
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• the definition of remedial objectives on the basis of current scientific knowledge, consistent with the
defined land use of a site and its surroundings. These objectives or tolerable risks levels should be
both technically and economically realistic
• the determination of a remedial strategy adapted to the site, indicating actions which will enable risks
to be reduce
2. REGISTRATION OF CONTAMINATED SITES
Although France was probably one of the first countries to carry out some kind of inventory of polluted
sites in 1978, limited attention has been given to the problems of land pollution until the beginning of the
nineties.
National register
At the national level, since 1993, a national register is managed by the Ministry of the Environment
(DPPR). In this register are gathered the sites that are known by the local authorities and can be
considered as polluted.
These sites are listed in a computerized databank and reports are periodically issued by the Ministry to
inform the public of the situation. A publication of this register was issued in Dec. 1994, gathering 669
sites; another one based on the situation of Dec. 1996 was issued in Dec. 1997, with 896 polluted sites
plus 125 sites already restored without any limitation of use. In June 2001, 3058 polluted sites are
inventoried including:
• 219 treated sites without use restriction
• 1014 treated sites with use restriction
• 537 industrial sites still working with a programmed simplified risk assessment
• 1288 sites at the present time in evaluation or in remedial operation
Inventories
In addition to this registration system are actions of inventory carried out through two specific ways:
a. The historical inventories, initiated at the regional level, based of the consideration of local industrial
history in order to discover, in connection with the existence of past polluting industrial activities, the
places where pollution can be suspected. These inventories are mainly based on the consideration of the
archives and indicate suspected sites (or potentially polluted sites). At the present time (middle of 2001)
such inventories are finished in 26/99 departments. It is expected that about 200 000 to 300 000 suspected
locations will be collected at the end of these studies (2005) for the whole national territory among which
some thousands will require corrective action.
b. The evaluation of the pollution of active industrial sites (including industrial waste treatment and
disposal sites). In April 1996, the Ministry of the Environment instructed the Prefects of departments to
order the owners of registered installations to carry out preliminary investigations and simplified risk
assessment of their sites. A preliminary classification of priority activities to consider in the orders is
given in the annexe of the circular letter. Within 5 years (end 2002) it is previewed that some 2000 sites
assigned with priority 1 will be evaluated.
Estimation of the number of polluted sites
The two previously mentioned actions, historical inventories and evaluation of active industrial sites, are
not enough developed to allow a significant evaluation. The only very approximative estimation possible
at the present time is 200,000 to 300,000 suspected sites and some thousands of cases requiring corrective
actions.
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3. REMEDIAL METHODS
A. Summary data on remedial technologies used in the country
According to a 2001 study (BIPE, Polluted sites market in France, Confidential), the techniques used for
the polluted soils in 400 sites where a rehabilitation project has been carried out can be listed as follows:
• Landfilling: 5-10%
• On site isolation: 10-15%
• In/on site treatment: 20-30%
• Biotreatment (biopiles): 25-30%
• Incineration: 5-10%
• Thermal desorption: 8-10%
• Other: 5-10%
In more than on third of these cases, combination of techniques has been used.
B. Policy initiative and other factors influencing the use of remedial methods
For the first cases of rehabilitation during the eighties and in the beginning of the nineties, most of the
techniques used were isolation and treatment or disposal in the installations of the waste system.
It appeared soon that waste treatment plants (incineration) were often technically inappropriate and very
expensive and, because of recent regulations, inducing restrictions of use and technical constraints,
landfilling has become more and more difficult and costly.
These circumstances create a positive evolution for the use of specific soil treatment techniques.
C. Methods used for remediation
The techniques that have been and are still the most frequently used to clean soils are microbiological
degradation and soil venting, but in cases where no treatment technique can be technically or
economically applied, isolation remains one of the most frequently used technique,.
Biodegradation is most of the time carried out on site by the mean of composting or bio-piles (11 biopiles
in 2001). Contaminants degraded are petroleum compounds, light and heavy oils and even polyaromatic
hydrocarbons. Soil venting addresses volatiles hydrocarbons and chlorinated solvents in the unsaturated
zone. It is sometimes associated with in situ biodegradation (bio-venting). To depolute the satured levels
(groundwater) venting is combined with air sparging.
More recently, new treatment capabilities have been made available either by specific own development
or by technology transfer. The techniques concerned are soil washing (solvent washing: 1 plant in 2001)
and thermal desorption.
At the present time six thermal treatment installations, with various level of performance (quantity and
complexity of pollution that can be treated) have been made available in France.
4. RESEARCH DEVELOPMENT AND DEMONSTRATION
A. Summery of government supported R&D
The support of R&D by the Government is mainly provided by the Ministry of the Environment and the
Ministry of Research and Education through three different ways:
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• Ministry of the Environment, Section in charge of Research and Economic Affair (SRAE) that
develops research programs focusing on behaviour of contaminants in regard of risks and possibilities
of treatment
• Ministry of the Environment, Section in charge of Industrial Environment (SEI) that develops the
methodological guidance documents to be used in connection with regulations
• Agency of the Environment and Energy Management (ADEME) in charge of evaluation and
rehabilitation of orphans polluted sites that develops specific research programs to improve the basis
of decision making procedures and to optimise the choice of remedial techniques and the control of
their efficiency.
The total amount of funds made available through these three actions is about 20 Millions FF/year (40
Millions FF/year in 2002 = 6.1 Millions €)
Concerning the development of rehabilitation techniques, some public money is supplied by the
Ministries of Research an of Industry through funds to help technical innovation (RITEAU projects) and
international cooperation (EUREKA projects).
In addition to governmental funding, some support to R&D projects are also provided by Regions most of
the time in connection with the economical redevelopment of brownfields (North or Lorraine Regions).
B. Private R&D programs
In addition to research programs financed by public funds, some enterprises develop specific R&D
activities. These enterprises can be gathered into two categories:
• Enterprises responsible of polluted sites that are looking for optimisation (technical and economical)
of the management of these sites: atypical example of such enterprises is Gaz de France that is in
charge of about 467 gaswork sites
• Enterprises that are active in evaluation and/or clean up of polluted sites and that try to improve their
know-how.
C. Perspectives
According the present time it may be estimated that the R&D programs will be mainly oriented in two
directions:
• increase the efficiency of the management of the suspected and proven polluted sites by the
preparation of technical guidance documents associated with the development of specific tools to
improve the decision making procedures
• develop more economical and efficient equipments and processes to characterise and to treat the
pollution.
• Considering the treatment techniques, two possibilities are simultaneously developed:
• improvement of existing techniques: a typical example is bioremediation with many projects trying to
extend its application to recalcitrant pollutants (PAH, PCB...)
• development of new treatment techniques: reactive walls, supercritical extraction, electro migration
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January 2002
GERMANY
1. LEGAL AND ADMINISTRATIVE ISSUES
Soil protection and the management of contaminated sites in Germany have been regulated on the federal
level since 1999. The Federal Soil Protection Act was enacted on March 1st, the accompanying Soil
Protection Ordinance on July 19th.
The act and the ordinance cover most of the items connected with the management of contaminated sites
with two major exceptions, where the Laender may provide legal regulations:
• Identification (Article 11):
The Lander may issue provisions regarding identification of contaminated sites and of sites
suspected of being contaminated.
• Experts and Investigating Bodies (Article 18):
Experts and investigating bodies that carry out tasks pursuant to this Act shall possess the necessary
expert knowledge and reliability for such tasks and shall have the appropriate required equipment.
The Lander may set forth the details of the requirements pertaining to experts and investigating
agencies pursuant to the first sentence of this paragraph, as well as to the nature and extent of their
tasks, submission of the results of their activities and the official naming of experts that fulfil the
requirements pursuant to the first sentence of this paragraph.
Identification and Registration
The Laender identify and register the sites, which are contaminated, and the sites, which are suspected to
be contaminated, according to their own criteria.
The Federal Soil Protection Ordinance gives some hints to be considered:
(Sites) ... where pollutants were handled ... over an extended period of time or in significant amounts
and where operation, management ... or disturbances of proper operation suggest the existence of
significant inputs of such substances into the soil. At abandoned waste deposits, such evidence shall
in particular be deemed to exist in cases in which the type of operation or the time of closure suggest
that the waste was not properly treated, stored or deposited.
The actual inventory shows more than 360.000 registered sites.
Federal States For
Waste Dis
[1] [
Baden- Wtirttemberg J6.229
Bavaria J10.034
Berlin J763
Bran^nburg |8.189
Bremen |l73
Hamburg J491
Hesse J6.630
Mecklenburg W.-Pomerania J4.078
Lower Saxony J8.957
North Rhine-Westphalia J18.116
Number of (Suspected)
mer Former
posal Sites Industrial Sites
2] [3]
|11.567 |17
3.295 |13
796
329
Sites
[4]
J6.220 J67983
|14.447 J25
|18.154 |18
313
327
*
|l.638 J2.129
J63.539 fj^O
J7.264 |ll
|50.000 |58
|17.147 |35
169
342
957
263
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase in) January 2002
Rhineland-Palatinate
Saarland
10.578 |No Data
1.686 3.530
Saxony J8.590 |l9.115
Saxony-Anhalt J6.296 J14.692
Schleswig-Holstein J3.181 J16.451
Thuringia
Germany Total
6.138 12.824
100.129 259.883
10.578
5.216
|27.705
J20.988
J19.632
18.962
J362.689
Remarks:
• Rhineland-Palatinate will update the inventory in 2001.
• The difference between [4] and the sum of [2] and [3] is due to regional classification.
The Laender are aware of the problem that different criteria will cause different and not comparable data.
A first step has now been made to compile the regional criteria for the registration such as:
• Are sites with different reasons for suspicion (for example: former industrial site plus uncontrolled
waste disposal) are counted once or twice?
• Are overlapping sites counted once or more than once?
• Will information be deleted about sites which are not anymore suspected to be contaminated?
• Are the inventories based on individual hints or on general estimations?
• Is the process of identification seen as finished?
• Are sites, which have been remediated according to the present use of the site, removed from
the registers?
2. REQUIREMENTS PERTAINING TO EXPERTS AND INVESTIGATING AGENCIES
On the behalf of the Committee "Contaminated Sites" (part of the working group of the Federal
Government and the Federal States on "soil protection") a group of experts worked out regulations
concerning the investigation of (suspected) contaminated sites; Title: Guidelines for quality assurance in
the field of contaminated sites (Arbeitshilfen zur Qualitatssicherung in der Altlastenbehandlung).
Chapters:
• Investigation strategy
• Sampling of soil, air (in the ground) and groundwater
• Treatment of the samples
• Field analysis
• Chemical and biological analysis
• Interpretation and assessment of the results
• Simulation of groundwater flow and transport processes
The Committee has recommended publishing these guidelines for using and testing. The guidelines (until
now only German version available) can be downloaded at http://www.lua.nnv.de/altlast/altqs.htm.
3. RESEARCH AND DEVELOPMENT
A. Stars
A Database on about 1,100 relevant environmental substances has been set up by the Federal
Environmental Agency with:
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1. physical and chemical characteristics of the substances,
2. behavior in the environment (stability, degradation etc.),
3. ecological toxicology (human, mammal, acceptable daily intake),
4. substance specific regulations,industrial health and safety requirements,
6. regulations according of the German soil protection act,
7. regulations of the Federal States.
B. Joint Research Projects
The technology development program is mainly funded by the Federal Ministry for Education and
Research (BMBF). There are currently three major projects:
• Treatment Walls for the Remediation of Contaminated Sites
• reliable data for planning and construction
• demonstration of rue environmental impacts
• technological aspects of installation and operation
• (Enhanced) Natural Attenuation
• Prognosis of Leachate from Contaminated Materials
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GREECE
1. LEGAL AND ADMINISTRATIVE ISSUES
In Greece the Environmental Law 1650/86 was enacted in 1986 and was designed to cover all aspects of
environmental protection. In that law specific provisions were included regarding soil protection from the
disposal of municipal and industrial wastes, and from excessive use of fertilisers and pesticides. Although
no specific legislation, guidelines or standards exist for soil quality, there are several components in
Greek law which refer directly or indirectly to control of soil and groundwater contamination.
Apart from Law 1650/86, the basic elements of Greek legislation related to contaminated sites are two
Joint Ministerial Decisions (JMD) dealing with the management of municipal and hazardous wastes
respectively. The Municipal Waste Management Act (J.M.D 69728/824/96) was enacted in May 1996 and
imposes obligations on local authorities for developing waste management plans. One important issue is
the registration of old waste dumps and their gradual elimination through reclamation and rehabilitation.
The Hazardous Waste Management Act (JMD 19396/1546/1997) was enacted in July 1997. This Act
defines hazardous wastes and refers amongst others, to the duties of the producer or holder of hazardous
wastes to avoid contamination of land from hazardous wastes disposal.
In the "National Plan and the Framework of technical specifications, regarding hazardous waste
management", which are being prepared today, a more specific approach to the investigation and
management of sites, contaminated by hazardous waste dumping, will be included.
2. CONTAMINATED SITES
The paucity of heavy industry and other production activities that give rise to hazardous wastes has
restricted the number of contaminated sites in Greece. Such sites are more likely to be related to improper
dumping of household and industrial wastes, to mining spoil and tailings ponds, to petroleum refining and
storage sites. So far there has been no specific survey for the identification and registration of
contaminated sites in Greece. According to the first inventory of household waste disposal sites in 1988,
some 3500 sites were operating without any environmental protection measures, and about 1500 sites
with limited measures.
Research carried out by universities and research institutes has identified a number of industrially
contaminated sites, including the Lavreotiki Peninsula, the large mining area of Northern Eubea, the
Thriassion pedion area in the Attica prefecture, the industrial zones of Thessaloniki and Athens
(Schimatari-Inofyta) etc. Today a study is being planned by the Ministry of the Environment for the
registration of sites suspected of dumping hazardous wastes.
3. REHABILITATION ACTIVITIES - REMEDIAL METHODS
In recent years, there has been considerable interest in rehabilitation activities, mainly concerning
municipal waste disposal sites, but also on sites contaminated from industrial and mining activities. Three
major rehabilitation projects concerning municipal wastes disposal sites are currently in progress:
1. The site of Schistos, which stopped operating in 1992
2. The landfill site of Ano Liossia (Attica)
3. The landfill site of Tagarades (Thessaloniki)
Regarding full scale projects for the remediation of contaminated soils, available information is very
limited. There is however a number of cases, where industrially polluted soils have been remediated,
using the following techniques:
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1. Excavation and of site landfilling
2. Ex-situ and in-situ bioventing applied for soils contaminated with organic volatile and semi-volatile
compounds
3. Soil vapour extraction applied for volatile contaminants
4. Soil washing applied for the case of soils contaminated with acids
5. Soil flushing applied for soils contaminated with acids, metals and organics.
4. RESEARCH DEVELOPMENT AND DEMONSTRATION
There is no specific National R&D programme in the field of Contaminated Land. However, several
Greek Universities and Research Organisations are actively involved in the development of innovative
soil remediation technologies, such as:
• In situ chemical stabilisation of heavy metal polluted soils
• Removal of heavy metals from contaminated soils by chemical extraction techniques
• Bioremediation of soils contaminated by heavy metals and metalloids
• Remediation of polluted ground waters using permeable reactive barriers
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ITALY
1. LEGAL AND ADMINISTRATIVE ISSUES
After the Ministry Decree (DM) of 1989, which started the collection of regional data on contaminated
sites, a more comprehensive national legislation relevant to contaminated sites has been enforced at the
beginning of 1997 by the adoption of the Waste Act (D. Lg.vo 22/97); this law provides the institutional
framework for contaminated sites assessment and management, and establishes the requirements for the
development of the technical and administrative procedures relevant to contaminated sites inventory,
characterization and assessment, clean-up, safety measures and monitoring (Art. 17). These procedures
have been set out in technical and more specific administrative guidelines adopted with the Environment
Ministry Decree (DM) 471 of October 25th 1999 which is actually the 'implementation decree' of Art. 17
of D.Lg.vo 22/97.
Law 426 of December 9th 1998 establishes a first list of 15 sites of national interest within the National
Plan for the Clean-up of Contaminated Sites. The Plan is relevant to sites, which, because of their size,
complexity and extent of environmental and health risks, are object of direct involvement and funding
from the government. These sites altogether cover an inland and off-shore potentially affected area of
over 330,000 hectares, more than 1% of the state territory. The Ministry of the Environment together with
the ANPA (National Agency for the Protection of the Environment) and with the other competent
national and local agencies and institutions, are responsible for approving and issuing permits relevant to
site investigation, assessment and remediation projects.
More recently the National Plan has updated the list that includes now 41 sites and a public investment of
approximately 500M euros for the years 2001-2003. The budget will be mostly dedicated to cover costs
of investigations and emergency safety projects. By a preliminary estimate the overall area potentially
affected by the sites of national interest, should cover around 2% of the state territory. The list includes
major poles of the oil, chemical, steel works, asbestos and mining industry, partly or entirely dismissed,
together with some large areas affected by illegal waste dumping. In some cases projects are carried out
according to formal agreements between stakeholders and control bodies.
The sites of national interest add to the regional inventories of contaminated sites which accounts now for
approximately 10,000 sites plus 6,000 gas stations. So far though only four out of 20 regions have
completed their inventory and formally approved the remediation plan, with priorities and costs, by
regional laws.
The total estimated cost, for long term remediation of national and regional sites amounts to
approximately 30,000-35,OOOM euros.
2. REGISTRATION OF CONTAMINATED SITES
Three different procedures are envisaged by DM 471/99 to register and to initiate actions at contaminated
sites:
• a notice that is communicated to local authorities from the polluter;
• an ordinance that is issued by controlling authorities; and
• voluntary registration and actions, on behalf of site owners, especially for historic
contamination episodes.
Obligations and schedules for contaminated site notice communication, under procedure 1, to
Municipality and Regional authority are established. Tasks and powers of local authorities and competent
institutions in issuing ordinances to parties responsible of pollution are defined under procedure 2.
Ordinances are issued by competent Municipality. For procedure 3, that also requires a formal registration
of the site to local authorities, the deadline has been established within current year 2001. Public sites and
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sites lacking of an identified responsible party, are also collected in the register. Regions define priorities
of actions on registered sites.
The sequence of actions implemented at contaminated sites is the following:
• definition of site boundaries and owners
• description of main features and prevailing pollution problems
• definition and implementation of emergency actions when needed
• definition and implementation of site characterization plan
• definition of remediation and environmental restoration plan
• planning of safety actions in order to protect site workers and residents
• implementation of health monitoring programs, when needed, in order to track the extent and trend of
past exposures
• plan of technical, professional, institutional and occupational requirements
• plan of financial requirements
All projects for investigation and remediation must be approved by the competent local or national
authority.
3. REMEDIAL METHODS IN USE
In situ and on site methods are in principle encouraged together with the reuse of off-site treated soils.
Solutions that reduce long term control and monitoring needs are privileged.
As a general comment, one and a-half experience with the new legislation has proved a positive
stimulation in remediation initiatives; nevertheless, some limitation in the ability to force present site
owners to take care of pollution generated by past activities at the same site, is recorded. Furthermore
restrictive quality criteria for soil, especially for the case of materials excavated and exported from the
polluted site, limit the number of cleanup and reuse options. As a consequence of the new national
legislation, regions in the north industrial areas of the country, if on one side are experiencing an increase
in actions aimed at restoring contaminated sites, on the other side are recording some percentage increase
of containment and soil dumping solutions with respect to practices used under former regional laws.
Several demonstrated and emerging technologies are being applied for cleanup of soil and groundwater.
On the basis of a preliminary screening within major engineering companies and most active regions,
static and hydraulic containment account for more than 70% of remedial techniques applied. Soil vapor
extraction and soil venting, for cleanup of volatiles in the unsaturated zone, play a major role with
approximately 40% of techniques sometimes applied jointly with hydraulic containment of contaminated
aquifers. Consolidated or innovative on site techniques are also experienced in some cases. Off site
technologies are quite limited because of legal restrictions on the exportation, transportation, processing
and reuse of polluted soil.
4. RESEARCH AND TECHNOLOGY DEVELOPMENT PROGRAMS
There is no specific national program for technology development. Nevertheless research activities are
being carried out by academic and research institutions under sponsorship of the Ministry for Scientific
and Technological Research, the Ministry for the Environment, the National Agency for the
Environmental Protection, the EU Commission and the national oil industry.
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A research and development laboratory has been recently (2001) established at the ACNA industrial
contaminated 'site of national interest' as part of its rehabilitation program. The laboratory, mostly funded
by the government and under agreement with local authorities, will be managed by an academic
consortium for environmental chemistry. Remediation projects with biological and chemical technologies
will be carried out by several research units. Following the starting period, the laboratory will become a
national "Center of Excellence" for further research and development of remediation technologies and a
national reference in this field.
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JAPAN
1. SITUATION OF THE TACKLING TO SOIL CONTAMINATION IN JAPAN
In August 1991, the soil environmental quality standards were set for 10 substances, such as cadmium,
from the viewpoint that secures the functions of soils that produce food and purify the water quality and
also can form groundwater and hold it as desirable standards to be maintained in protecting human health
and the living environment.
The Environment Agency set "Survey and Countermeasure Guidelines for Soil and Groundwater
Contamination" that showed the technical method of the survey/countermeasure regarding soil and
groundwater contamination in January 1999.
In July 1999, "the dioxin and the like measure special measure law" was established. On the basis of this
law, local governors determine the area that needs the measure and also the countermeasure plan. Local
governments can carry out the clean-up measures on the basis of the countermeasure plan. The
environmental quality standards that are related to the dioxin-contaminated soil do not include not the
exposure route that passes groundwater but the exposure route of the direct skin contact and ingestion of
contaminated soil for the first time.
Also, in June 1996, the Clean Water Law was revised regarding groundwater pollution control. The local
governors are able to assign the clean-up measure to the polluters when necessary to protect human health
from adverse effects caused by contaminated groundwater.
2. SUBJECTS OF THE PRESENT CONTOL MEASURE AGAINST SOIL POLLUTION
Previously, the tackling regarding the soil pollution control has mainly consisted of the establishment of
environmental quality standard for soils and the promotion of the voluntary clean-up by operators and
owners for the compliance of soil environmental quality standards. The following subjects are pointed out
regarding the present soil antipollution measure.
The exposure pathways of direct ingestion and skin contact of contaminated soil have not yet been
considered to protect human health, except for dioxin. In other words, the control and management of the
appropriate environmental risk that is related to the direct ingestion of contaminated soil is not done.
The need that takes the control measure with regard to soil contamination itself is very high from the
viewpoint of a preventive for groundwater contamination. However, operators and owners entrust the
present control measure to the voluntary clean up. In other words, the actual condition of the soil
contamination is not grasped accurately because of having no law system. As a result, the enforcement of
appropriate and quick measure is not able to expect.
Residents think anxiously about the soil antipollution measure, because there is not the legal rule
regarding soil contamination. Also, being connected to the trouble in case of the land transaction, the flow
of the land transaction might be hindered.
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3. PROPOSED RISK-BASED SOIL MANAGEMENT FOR CONTAMINATED SOIL
Exposure Pathway from
Dioxin-contaminated Soil
vaporization
s
o
1
L
blown-up
absorption '
adheren
run-off
seepage
filtration
;e
inhalation ^_
direct ingestion ^_
deposition
surface
water
ground
water
dermal absorption
milk, meal
vegetable
bioconcentration via foo
i
fish
drinking
water
*|
>
Exposure Scenario in Residential Area
• Direct Ingestion
• Dermal Absorption
• Inhalation of Soil Particle (Dust)
• Inhalation of Vaporized Dioxin
When the subjects regarding the present soil pollution control measure are considered, preventing the
adverse effects on human health and the living environments caused by soil contamination and the safety
and relief of the nations with regard to soil contamination need to be secured. By 1) understanding the
actual condition of soil contamination, 2) reduction of environmental risk derived from soil
contamination, and 3) prevention of the occurrence of new environment risk associated with the change of
land use, the new system that is able to manage the environment risk caused by soil contamination
appropriately is necessary.
It is conceivable in the following manner for the scheme of the soil risk management system:
3.1 Investigation of Soil Contamination
The landowners should perform soil investigation at potentially contaminated sites, such as chemical
factory in case of changing land-use, in order to understand the actual condition of soil contamination
accurately.
3.2 Management of Information on Contaminated Soils
As for the land, which contamination became clear by the survey of soil contamination, local government
does the registration, announcement to the cadastre as a necessary land to control the environment risk by
soil contamination.
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3.3 Risk Reduction Action for Contaminated Soil
The landowners, operators, or polluters should select a control measure that reduces environmental risk
from soil contamination through covering, containment, and clean-up, such as removal and destruction,
and carry it out in order to protect human health and the living environment by the soil contamination of
the land that contamination became clear.
3.4 Control of Off-Site Movement of Contaminated Soil
So that new environmental risk does not occur along with the change of the land-use, the landowners,
operators or polluters who intend to do the carrying out of contamination soil carries out a regular
measure.
3.5 Groundwater Pollution
Unlike soil, groundwater has the characteristics of flowing and of being related closely to surface water
and drinking water. Because of this, at present, the clean-up action command system for contaminated
groundwater is established as the measure of case that there is possibility that exerts the influence on
human health, for instance, the proper groundwater is used as drinking water in the Clean Water Law.
Therefore, the facing needs to try hard to the proper application of the clean-up action command system.
However, from the viewpoint that secures groundwater comprehensively, it should be examined from
now on about the groundwater security measure.
4. CASE OF DIOXIN-CONTAMINATED SOIL-THE TSURUMI RIVER YOKOHAMA
In the Tsurumi River watershed where the urbanization goes on sharply as the suburb of Yokohama city,
a flood-control basin is being established to prevent the flood damage of the downstream area. This flood-
control basin secures the capacity that accumulates floodwater by enclosing the periphery in the
embankment and then digging the inside. Floodwater is introduced into flood control basin from dam that
made a part of the embankment that faced to the river of low. When the water level in the river goes
down, floodwater is returned into the river through the drainage gate.
The waste materials that contain PCB in a deeper place than 2 m from the ground surface in the
construction work place of discharge gate were confirmed in 2000. The excavated waste materials consist
of soil, vinyl fragment, and piece of wood etc. containing PCB. Bowling core investigation showed that
the quantity of the contamination soil is expected as about 80,000 m3. The Ministry of Construction
established "Treatment technology examination committee for PCB-contaminated soil in a Tsurumi River
multipurpose flood-control basin" which is composed of each specialist in January, 2000, to set the proper
measure of the dispersion prevention of PCB. Furthermore, on basis of dioxin analysis this committee
announced that the PCB-contaminated soil exceeds environment standard value lOOOpg-TEQ/g of dioxin.
It was judged as difficulty that the treatment of PCB- or dioxin-contaminated soil would be completed
until the final of the world soccer that is held in the International Stadium Yokohama in June, 2002.
This committee came to the following conclusions:
• The contaminated soil dug is transferred to the temporary storage place for a while inside flood-
control basin.
• The temporary storage facility is isolated with the periphery foundation by a vertical
impermeable wall.
• On the upper part of the temporary storage facility is capped in order to prevent intrusion of rainfalls.
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• Soil A (soil with PCB concentration of 10 mg/kg or greater, or dioxin concentration of 1000 pg-
TEQ/g or greater) is isolated by soil B (soil with PCB concentration of less than 10 mg/kg or dioxin
concentration of less than 1000 pg-TEQ/g).
• The following three methods were selected as demonstration technologies, which can be applied to
the PCB- or dioxin-contaminated soil after the world soccer game.
Table 1: Selected Demonstration Technologies
Method
Principle
In Situ Vitrification
(GeoMelt Method)
An electrode is placed in a container in the ground, which holds
contaminated soil. Electricity is passed through the electrode, generating
heat (1600 - 2000 D) that brings the soil to a molten state and thermally
cracks organic compounds such as dioxins into safer substances such as
carbon dioxide. Gases such as carbon dioxide produced by thermal
cracking of organic compounds are collected in a cover and decomposed
by a thermal oxidizer at more than 850 D.
Base Catalyzed
Decomposition Method
Safe alkali reagents (sodium bicarbonate) are added to and mixed with
contaminated soil. Soil is detoxified by dechlorination of dioxins in the
soil by heating at 350 to 400 D in a soil reactor like rotary kiln. The small
amounts of gaseous dioxins, which are not dechlorinated in a soil reactor
are collected in a condensation unit. The liquid containing dioxins is then
rendered harmless by adding alkaline reagents and heating at over 300Din
a liquid BCD reactor.
Anaerobic Thermal Processor (ATP)
The ATP technology uses a physical separation process to thermally
desorb organics such as polychlorinated biphenyls (PCBs) from soils,
sediments, and sludge. The ATP system mixes and heats contaminated
soils, sediment, and sludge in the processing unit. The processor consists
of four separate thermal zones: the preheat (204 - 343 D), retort (482 -
621D), combustion (649 - 788D), and cooling zones (260 - 427D). In the
preheat zone, water and volatile organic compounds (VOC) vaporize. At
the same time, the reagents dehalogenate or chemically break down
chlorinated compounds (including PCBs).
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LATVIA
The Republic of Latvia has a huge amount of old contaminated sites inherited from the former Soviet
System. The largest portion of these sites consists of former Soviet military sites, many of which need
remediation activities. This makes the situation very specific as it is impossible to use the principle
"polluter pays," which step by step starts to be the main principle in a solution of current environmental
problems in Latvia. There the polluter is well known but it will never pay, especially if it is former Soviet
Army. It means that it is necessary to look for specific ways to solve this problem. This creates huge
economical and juridical difficulties. From one side, the State does not have resources to pay for clean up
activities. From other side, most landowners, which received their properties in the processes of
denationalization and privatization, also do not have enough resources. They also ask for rules for dealing
with pollution on their lands, which is polluted by others in previous times; but such rules are still not
defined. A similar situation exists with international investors who are interested to run their business in
some former military sites, such as naval bases, airfields, different reparation plans etc. This means that at
present moment, the polluted former military sites are not only an environmental problem, but a
hindrance to the growth of economics as it creates difficulties for investments. This is also a huge
problem for the Latvian Armed Forces as our military units mainly are stationed in former Russian
military bases.
The goals of the ongoing and past activities in an area of polluted sites are to:
• create economic and juridical mechanisms for solution of the historical pollution problem;
• implement the principle "polluter pays" for current activities; and
• form economic and juridical mechanisms for pollution prevention and pollution control.
Site remediation predominantly will take place as part of the normal commercial redevelopment of land
with funding considered at the level of individual site and not as part of specific overall national
environmental improvement program. An inception could be the sites with a very high level of risk to
human health and environment. Therefore the most urgent task is to set up a legislative base for
contaminated sites and pollution prevention. Currently, the "Law on Pollution" is adopted by the Cabinet
of Ministers of the Republic of Latvia and has been in force since July 2001.
The purpose of this law is to prevent and reduce damage on human health, property, and the environment
caused by pollution, to counteract consequences of such damage and to:
• prevent pollution or, where that is not possible, to reduce emissions to air, water and soil arising from
polluting activities;
• prevent or, where that is not possible, to reduce the use of non-renewable natural resources and
energy at polluting activities;
• prevent or, where that is not possible, to minimise the generation of waste;
• provide for inventory and registration of contaminated and potentially contaminated areas lying
within the national territory;
• determine the measures for investigation of contaminated and potentially contaminated areas and for
remediation of contaminated areas;
• identify the persons, who shall cover the investigation costs of contaminated and potentially
contaminated areas and the remediation costs of contaminated areas.
This law determines the requirements on the operator concerning pollution prevention and control and a
procedure for pollution prevention and control, including, inter alia:
• requirements for start-up, operation and cessation of polluting activities;
• permitting conditions for polluting activities and water use, and a notification procedure for those
polluting activities, which are not subject to authorisation;
• a procedure for laying down environmental quality standards;
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• a procedure for laying down emission limit values for certain substances, conditions on polluting
activities and other restrictions on the operation of polluting activities;
• a procedure for inventory, registration, investigation, and remediation of contaminated areas;
• conditions on supervision, control and monitoring of polluting activities and a public
information procedure.
This law applies also to certain mobile sources, identified by the Cabinet of Ministers. Activities
involving radioactive substances, nuclear waste, sources of ionising radiation, and genetically modified
organisms are regulated by other legislation. The Regional Environmental Boards (under the MEPRD)
carry out the monitoring and control of polluted territories except the military territories that are under the
response of Ministry of Defence.
Unfortunately, at present moment we have little time to see how the law "works". About the effectiveness
of the Law of Pollution and obtained experience and results the first presentation could be given at the
beginning of the next year.
But now I would like to return to contaminated sites by the Soviet Army. First of all, it is necessary to
mention that currently the ecological assessment of former military sites has been done using a single set
of methods. This has been done into the framework of Latvian-Norwegian cooperation project. The
experts of the Latvian and Norwegian Geological Surveys assessed and investigated more then 600
former Soviet military sites, 255 of which were incorporated in a special computerized database. The
database contains all information collected during the studies of former military sites.
The Latvian and Norwegian specialists developed criteria, based on which all sites have been subdivided
into four groups:
1st group - it is evident that site is polluted with hazardous substances and poisons that spread into the
environment or the site is contaminated with explosives that all together could cause essential threat to
human life and to the environment, detailed investigations and clean-up activities are urgent;
2nd group - there is only some information about pollution of the site with hazardous substances that
could cause threat to human life and to the environment. Further site investigations are required.
3rd group - pollution of site is insignificant and the possibility of migration of hazardous substances also
is insignificant. Site investigations are required only in case of change of land use;
4th group - no evidence of pollution and hazardous materials. Further site investigations are not required.
According to the mentioned criteria 255 main former military sites were assessed and result was
following:
1st group - 14 sites:
2nd group - 17 sites;
3rd group - 62 sites;
4th group - 171 sites.
The most dangerous for human health and the environment is 1st group that consists of 7 former rocket
bases, 2 big fuel stations, 1 very large bombing range, 1 ammunition storage site, 1 airfield, 1 tank
reparation plant, and 1 submarine base in former Liepaja Naval Base.
Petroleum pollution of the soil was found to be the most widespread of all the problems resulting from the
Soviet Army's activities. The most polluted petroleum areas were found in places where fuel and
lubricants were pumped, stored, and transported as well as in the sites where transport and combat
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materials were washed (especially after accidental spills). Almost in all detailed investigated fuel storage
sites free phase oil has been found.
Unexploded ordnance in former bombing ranges and ammunition storage sites (especially if explosives
are deep in soil) is another very serious problem.
Detailed pollution investigations are carried out only at some of military sites, and have mainly been done
with assistance of our donor countries (Denmark, Norway, Germany, and Canada as well as the USA and
Sweden).
Up until now, clean-up activities have been carried out only in some of the most harmful sites. Mainly,
those are pilot projects with the purpose of finding the best clean-up technologies and preventing the
spread of hazardous substances to drinking water reservoirs and ambient surface water bodies.
The Latvian Ministry of Defense and the Ministry of Environmental Protection and Regional
development have incorporated environmentally sound approaches in practice of military training. In
these undertakings, very important support is being received on a USA and Swedish initiated project - so
named the Environmental security project. The main purpose of this project is to:
• strengthen the cooperation and coordination between military and civilian organizations; and
• train military personnel in environmental management to prevent further degradation.
In the framework of this project, the Latvian, U.S., and Swedish military and environment officials agreed
to cooperate to develop the Environmental Base management Plan for Adazi Military Training Base. The
management plan served as a pilot project, and during the project period they:
• established objectives and developed procedures to achieve sound environmental management;
• determined the level of environmental training necessary for personnel at various stages of command;
• set priorities and monitored clean-up activities that must take place in order to ensure the continued
operations of the base; and
• initiated activities aimed at preventing further environmental damage or pollution, wastewater
treatment, hazardous waste management, land management for control of erosion and protection of
rare and endangered species.
Also I would like to mention Liepaja Naval Base Project. Liepaja was the biggest Soviet Navy Base in the
Baltic Sea. Now this former base is being transformed into a commercial port. The Special Economic
Zone is established in the territory of former base.
From the beginning, the Liepaja project was a part of Phase 2 of the NATO/CCMS Pilot Study on
Environmental aspects of Reusing Former Military Lands. Recently, the project was transformed into
partnership project between Canadian public-private sector consortium, the City Council of Liepaja,
Liepaja Special Economic Zone and the Latvian Government to share information on managing the
redevelopment of large former military sites. The Canadian side the project was financed by the Canadian
International Development agency.
The main objective of this project is was to work out the comprehensive strategy for the long-term
cleanup and marketing of the Navy Base District. The main approaches used in the Republic of Latvia for
solution of the problem of contaminated sites are to:
• use a co-financing approach for funding necessary investigation and clean-up activities (state,
municipality, international donor, and private means);
• make assessment of pollution (common and in some cases also very detailed) of former military sites;
• organize training for Latvian specialists (including military personnel);
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• get as much assistance as possible from international organizations and from bilateral cooperation
with main donor countries,
• carry out some clean-up pilot projects at the most significant harmful sites; and
• negotiate with landowners, investors etc. in every concrete case about terms of clean-up activities
(clean-up standards, budgeting, land tax reductions etc.
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LITHUANIA
Information in this tour de table is current as of January 2001.
1. INTRODUCTION
The Republic of Lithuania is a small country on the Baltic Sea. It occupies an area of 65.600 km, with a
population of 3.7 million, or 56 people per sq. km. The five largest Lithuanian cities are:
Vilnius (600,000 people),
Kaunas (400,000 people),
Klaipeda (200,000 people),
Siauliai( 150,000 people)
Panevezys (130,000 people).
These cities are the largest industrial centres and, at the same time, the main polluters of soil and
groundwater. Along with these industrial centres, Mazeikiai Oil Refinery, Akmene Cement Plant, Jonava
and Kedainiai Fertiliser Plants, as well as road and railway transport and agricultural enterprises are
among most significant polluters. Many contaminated sites were left in former Soviet military bases. In
rural settlements, there are territories contaminated with agrochemicals, oil products, or simply waste.
2. SOIL CONTAMINATION AND ECONOMY
It should be noted that the extent of pollution caused by industry and agriculture has decreased
considerably since 1990, because after the fall of the Soviet Empire, unilateral economic links orientated
towards the East were disrupted. This exerted a negative effect upon the development of Lithuanian
economy. Today the government of the Republic of Lithuania, businessmen, and industrialists attempt to
develop economic links in all directions, with Western countries in particular. However, this process is
difficult, and it will take much time until Lithuanian economy has recovered. The volume of production
has decreased several times. Therefore current soil, water, and air pollution levels are considerably lower.
The current poor economic condition of Lithuanian industry and agriculture is clearly good for reducing
the risk of soil pollution. Decreased level of diffuse soil pollution from agriculture is a good example of
the current situation. The amount of fertilisers and pesticides used in agriculture is now about 10 times
less as compared with the figures of 1986-1989 (see Figure 1 and 2). Farmers and communities are still
buying some mineral fertilisers, but the majority are limiting use to minimum application rates.
Figure 1: Total Usage of Nitrogen, Phosphorus and Potassium Fertilisers in Lithuania (1986-1996)
fl
60
300
250
200
150
100
50
0
• Nitrogen fertilisers
D Potassium fertilisers
• Phosphorus fertilisers
1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996
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Following the re-establishment of independence in Lithuania and the collapse of the collective farm
system, levels of production and the use of pesticides decreased significantly. Currently only the most
profitable farms are making extensive use of pesticides since these are the only enterprises that can afford
both the spray products and good (often reconditioned) spraying equipment. Nonetheless the rates of
pesticide application remain limited by high price so there is a tendency towards economic and rational
use. This is particularly so with herbicides since manual labour is very cheap and hand-weeding of crops
is very common.
Average pesticide use is less than 2 kg active ingredient per hectare which is very low compared to some
EU Member States (e.g., The Netherlands) and much lower than levels of use during the Soviet period.
However, the use of pesticides is now gradually increasing again, notably herbicides (Figure 2).
Figure 2: Total Usage of Various Pesticides in Lithuania
VI
O
H
10000
8000
6000
4000
2000
0
• Insekticides
D Fungicides
• Herbicides
D Retardants
• Defoliants
1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996
Current situation: More rationale application, more effective storage, handling, spraying etc., mainly due
to rather high prices of agrochemicals, resulted not only in decreased diffuse soil pollution, but also
reduced the probability of cases when soils are contaminated heavily. Earlier quite often it was resulted
by poor storage and handling of unused agrochemicals (especially pesticides) much of which was stored
in leaking containers or else discarded in the forest or village dump.
Of course the improving economic situation will result in increase of mineral fertiliser and pesticide
application. The same tendency could be traced in industry.
3. INFORMATION ABOUT CONTAMINATED SITES
Information about contaminated sites in Lithuania is not very exhaustive. The best situation concerns
contaminated sites in former Soviet military bases. A detailed investigation was carried according to the
project "Inventory of Damage and Cost Estimate of the Remediation of Former Military Sites in
Lithuania" financed by the PHARE Programme of the European Community. The Project was completed
at the beginning of 1995. The results achieved are useful for the Ministry of Environmental Protection
when planning future remediation activities. During the investigation, 275 Military bases of the former
Soviet Union were registered. They occupied more than 1% of the country's territory. As the survey
shows, the number of military units located in Lithuania totaled 421. The size of Military bases greatly
varies - from less than 100 m2 (a workshop) to almost 14 000 ha (forestry). Judging by the number of
pollution and environmental damage cases registered in the military bases (see Table 1), pollution with oil
products (21% of military bases) and wastes (17% of military bases) prevail, alongside with the damage
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to landscape and soil (16% and 29%, respectively). Soil pollution with heavy metals, rocket propellant,
cases of radioactivity also were stated.
Table 1: Number of Pollution and Environmental Damage Cases Registered in the Territories of Former
Military Bases
Type of the environmental damage
Oil products
Mechanical soil damage
Damage to landscape
Wastes
Damage to forest
Bacteriological/biological pollution
Hazardous chemicals
Radioactivity
Rocket propellant
Explosives
Number of cases
566
778
438
478
249
137
56
9
20
12
Total territory
(ha)
399
11137
7140
1288
3293
14
p/p*
p/p
p/p
p/p
Distribution according
to the damage type
(%)
20
29
16
17
9
5
2
0,2
1
1
*p/p - point-source pollution
Having analysed the results of the inventory performed at military areas, 10 bases were selected for a
detailed investigation. Geological-hydrological and environment pollution investigations were conducted
on a broad scale. The results of the investigations were submitted in 25 volumes in Lithuanian and
English. It was also calculated that cleaning of the contaminated military sites to the permitted
contamination levels requires huge funds-about 730 million USD.
Many contaminated sites connected with transport and transport accidents - including roadsides polluted
by road and railway transport, bus/railway station, petrol pump territories, etc. Many polluted territories
are situated near Klaipeda (the Lithuanian port), through which up to 10 million tons of oil and oil
products are carried every year. The territory of Oil Terminal Company in Klaipeda is considerably
polluted. There are more than 110,000 cubic meters of soil and ground with oil levels reaching
10 000 ppm.
Another dangerous source-storage places, dumps of old pesticides and other agrochemicals. In the 954
storages of the country, about 2,200 tons of pesticides that are unsuitable and prohibited from using are
accumulated. These pesticides must be immediately utilised because cases of fire are frequent in such
storages. There are large quantities of contaminated ground in the territories of these storages.
Investigation and cleaning of these territories also requires considerable investment.
An inventory of Lithuanian landfills and other waste territories was also carried out in 1994. No
comprehensive information still concerning industrial contaminated sites
Cleaning of contaminated ground to a larger extent has been started in Lithuania just in 1995. The largest
soil bioremediation site is located near the city of Klaipeda. Costs for remediation of 1 m3 of
contaminated soil is about 60-70 USD. Potential polluters (plants, enterprises, agrocompanies, etc.) are
forced to carry out investigations of pollution parameters (composition, concentration, total area,
migration to groundwater) and, if necessary, to plan soil remediation and utilisation activities. Mainly ex
situ bioremediation or civil engineering based methods (excavation/disposal, dilution) are used.
Phytoremediation is also being applied. Practically no innovative chemical or physical process based
techniques are being used in Lithuania, mainly because of high treatment costs.
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4. STRATEGY AND POLICIES
Although the main environmental priorities in Lithuania have been assigned to water and atmosphere
protection, at present more and more attention is given to soil protection issues. One of the priorities
included into Lithuanian Environmental Strategy (approved in the Parliament on 25 September 1996) is
soil quality improvement and sufficient formation of land use structure.
In Environmental Status Review of the Strategy, it has been stated that soil and upper ground layer is
most heavily contaminated in cities, especially in industrial areas, near highways, fly-overs and also in
former military areas. The main goals for soil protection from pollution are as follows:
• reduction of soil pollution rising from use of manure, artificial fertilisers and other agricultural
chemicals (plant protection products);
• reduction of soil pollution with oil products;
• reduction of soil pollution with heavy metals (especially in cities and industrial areas)
Besides, soil protection issues have been included in such environmental protection sector as reduction of
ground water pollution.
In the Action Programme of the Strategy, the following activities concerning soil pollution have been
indicated:
• preparation of Draft Soil Protection Law;
• preparation of soil quality and monitoring standards and norms;
• implementation of environmental sound means of fertilising and use of plant protection products;
• preparation of Draft Law on Liability for Past Environmental Damage (legislation for management of
contaminated sites renaturalisation);
• compilation of inventory of polluted areas, including the former Soviet military sites, and
development of cleanup and renaturalisation programmes;
• creation of polluted sites data base and monitoring plans.
The main activity concerning soil protection included in Action Program of the Strategy is the Draft Soil
Protection Law. This draft was prepared and presented to Government in July 1998. Following
obligations for land (soil) users has been stated in the draft law:
• to take care of soil fertility;
• to take care of fertile layer of the soil while carrying-out earthworks (such as construction, building,
exploitation of mineral resources quarries, etc.) and use this layer for damaged soil recultivation;
• to implement preservative measures for soil erosion prevention;
• to use manure, artificial fertilisers and plant protection products strictly according established
requirements;
• to prevent pollution of soil with waste, waste waters, radioactive, biological, poisoning and other
substances harmful for human health and environment;
• to present all obligatory information on soil quality and use conditions for control institutions;
• to inform control institutions in case of soil pollution (accidental spills) and to take measures for
cleanup of soil and stop migration of pollutants to other environmental components (ground and
surface water, etc.).
Draft Soil Protection Law is prepared like framework, and corresponding regulations, rules and
recommendations are necessary for its implementation (some of them are already in force or under
preparation). The Parliament of Lithuania decided to include provisions of Draft Soil Protection Law into
the Law on Land but until now such decision is not implemented.
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Another important document concerning contaminated sites is Lithuanian Waste Management Law (has
come into force since 1 July, 1998). A new Lithuanian Waste Management Strategy is also being
discussed.
Other normative documents concerning soil and ground quality are:
1. Hazardous Substances: Maximum Permitted and Temporary Permitted Concentrations in Soil.
Hygiene Norm - HN 60-1996.
2. Recommendations for Evaluation of Soil Chemical Contamination, 1997.
3. The Maximum Permitted Level of Oil Products in the Upper Lithosphere (Ground) Layer - LAND
(Lithuanian Environmental Normative Document) 12-1996.
4. The Regulations of Sewage Sludge Application, LAND 20-1996.
Standards, defining soil quality, sampling procedures, sewage sludge application on land (on the basis of
LAND 20-1996) are in the nearest future plans. All the above-mentioned Lithuanian environmental
documents are expected to be fully harmonised with EU regulations, directives and standards.
5. CONCLUSIONS
There is lack of comprehensive information about contaminated industrial sites. Inventory studies also
should be done of such potential sources of soil pollution as oil tanks, pesticide, fertiliser storages, sewage
sludge filtration fields, territories of previous accidents related with hazardous substances, etc. As a rule
soil and even ground water around such territories is heavily contaminated. The Lithuanian Geological
Survey prepared a database and started an inventory of contaminated areas and potential point sources of
contamination. Because of Lithuania's poor economy, soil remediation activities are not financed on state
scale. No innovative process based techniques are being applied in Lithuania, mainly because of high
treatment costs.
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THE NETHERLANDS
1. LEGAL AND ADMINISTRATIVE ISSUES
The Netherlands policy on contaminated land has been focused on the restoration to multifunctionality up
to 1998. The application of the multifunctionality approach to the estimated 110,000 seriously
contaminated sites would have incurred costs of around € 50 billion. The Netherlands is now spending
about € 0.5 billion per annum, which equals the sum that was initially thought to be sufficient to resolve
the entire problem. But at this speed it would take about 100 years to end the operation.
In the meantime soil contamination would hamper construction and redevelopment essential to economic
and social development, and dispersal of contaminants in the groundwater keeps on making the problem
even bigger. For this reason another policy has been introduced. This policy development is known by its
acronym BEVER.
The new approach abandons the strict requirement for contamination to be removed to the maximum
extent, and instead permits clean-up on the basis of suitability for use. At the same time government
proposed other changes to soil protection legislation, including greater devolution of responsibility for
clean-up to local authorities and the creation of more stimulating instruments.
Basically the policy has switched from a sectoral to an integrated approach. This means that the market
has to play a more prominent role and take more of the financial burden.
Soil contamination should not only be treated as an environmental problem. The soil contamination
policy should also be geared to other social activities such as spatial planning and social and economic
development and vice versa.
The strategy is:
• to protect clean soil
• to optimise use of contaminated soil
• to improve the quality of contaminated soil where necessary
• to monitor soil quality
This new approach will be paired to stimulation of the development and application of new technology
and to a more cost-effective organisation of the actual clean-up. These measures taken together are
expected to cut costs by 30-50%.
In this approach remediation is part of a comprehensive policy regarding soil contamination. Prevention,
land use, treatment of excavated soil, reuse of excavated soil (for example as building material),
monitoring of soil quality and remediation have to be geared to each other in a more sophisticated
manner. This "internal" integration is being promoted under the concept of "active" soil management.
To stimulate market investment a different approach to government funding is announced. The taxpayers'
money will be used in such a way that it evokes private investment. This will be done by improving the
existing financial instruments and by the creation of a private sector contaminated land fund. The legal
instruments will be made more effective.
The discretion of provinces and municipalities will be further enlarged to create the flexibility which is
needed to initiate and stimulate the measures that are best suited to the local situation (tailor made
solutions).
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With these measures Dutch government wants to achieve ambitious objects:
• Within 25 years all sites should be made suitable for use and further dispersal stopped. That means
that each year almost four times as much sites will have to be remediated as is the case now.
• Presuming that the costs will be reduced with 30-50%, this requires a duplication of the total annual
expenditure on soil remediation.
• In order to monitor the results of these efforts and to make information on soil quality accessible to
the general public (for example potential buyers) and to authorities (for example planning authorities)
we want to have a system of soil quality maps covering the whole country in 2005.
In 1999 a lot of attention is paid to the introduction and implementation of the new approach.
2. REGISTRATION OF CONTAMINATED SITES
Based on the Soil Protection Act there are two driving forces to investigate soil quality:
• Anyone intending to excavate and to move soil for building activities, has to report the quality of the
soil to provincial authorities;
• Companies who don't want to investigate the soil quality on a voluntary basis might be obliged to
do so.
Based on these activities a lot of seriously contaminated sites have been identified. These numbers have
increased enormously since the first case at Lekkerkerk.
Table 1: Inventory of sites
11980 j 350 j 0.5 billion |
["1986 | T~600i 3 billion |
fl999 | UO^O] 15-25 billion* j
* based on new policy
3. REMEDIAL METHODS
In the new policy the remediation goal is "Function-oriented and cost-effective remediation". The Cabinet
chose this new remediation goal in its standpoint on the renewal of the soil remediation policy of June
1997. The new remediation goal has been worked out in the report, "From funnel to sieve". Here the
summary of this report is mentioned.
Delineation
The new remediation goal applies to serious soil contamination caused before 1987.
The new goal does not affect the need for remediation and the time at which it must take place. For the
decision-making on 'need' and 'time' the intervention values and the urgency system remain unaltered in
effect. Finally, the new remediation goal only applies to contaminated terrestrial soils, not to aquatic
sediments.
Strategy
The starting-point in the new Consideration Process for the remediation goal is an integral approach to
the whole case of soil contamination. The approach differs for the top soil and the subsoil. In the approach
to the top soil, a difference is made according to the type of soil use. The prevention of contact with the
contamination is all-important. In the approach to the subsoil it is a question of removing contaminating
substances. In this connection, the costs also determine the result to be achieved. The end result must lead
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to as limited as possible care about residual contamination. At calibration times the remediator checks
whether the desired remediation result is being obtained.
Routes
There are three routes for obtaining an approved remediation plan:
• via a standard approach per case or cluster of cases. By this means the decision-making may be
simpler;
• via custom-made work per case or cluster of cases. This is obvious if the standard approach offers no
solutions.
• via custom-made work per area. This variant is possible in exceptional cases. The remediation goal is
tailed to special features of an area.
The motto here is: 'standard approach if possible, custom work if necessary'.
The Top Soil
In the standard approach for the top soil one produces a living layer. The thickness and the quality of this
are dependent on the type of soil use. For two types of soil use soil cultivation values are determined for
substances which occur in quantity. These apply as a back remediation value when removing soil and as a
quality requirement for soil to be applied. The standard approach results in a limited care scope. In special
situations custom work per case is possible with good motives. Determining the remediation goal for the
type of soil use, agriculture and nature, is always custom work per case. The authorised authority
exceptionally determines a special area result for specific areas. This may be lower or higher than the soil
cultivation values. Custom work per area will come about through a democratic procedure.
The Subsoil
The standard approach for the subsoil is aimed at removing contaminating substances to the level of the
so-called 'stable end situation'. This level is dependent on the soil structure and the substances present.
One must reach the stable end situation per case in 30 years maximum. The starting-point is as complete
as removal as possible of the source of contamination, cost-effective removal of the 'plume' and the
combating of further spread. In the remediation period one may - under certain circumstances use the soil
as a reactor vessel, without source and plume too. Calibration times are built in in order to be able to
investigate the extent to which one is on the road towards the stable end situation and to be able to adjust
if necessary.
Here too, custom work per case or cluster of cases is possible and - in exceptional cases - custom work
per area.
Care
In function-oriented and cost-effective remediation, residual contamination remains in the soil in many
cases. Therefore, 'care' is required. This care may consist of:
• registration (establishment)
• monitoring (measuring);
• after-care (active measures).
The burden of the care increases as less far-reaching remediation measures are taken. A firm component
of the remediation plan is a care plan. This contains the care measures the remediator takes.
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Responsibility
The causer of the pollution or the owner of the location is responsible for the remediation measures and
the associated costs.
After the remediation the remediator or the owner remains responsible for carrying out the care measures.
If at a location a change to a more sensitive type of soil use takes place whereby extra remediation is
necessary, the costs of this are charged to the person initiating the change in the soil use.
Reduction in Costs
The previous Cabinet accepted that with a new consideration method for a remediation goal a savings in
costs of 35-50 per cent can be made. We have examined the possible savings in more detail. From this it
appears that this assumption was correct. We presume that the cost reduction can be attained as follows:
• approximately 30 per cent by the new standard approach;
• approximately 10 per cent by cleaning and draining off less contaminated groundwater;
• approximately 5 per cent by custom work per area.
Monitoring will show the extent to which the cost reduction will be achieved.
Decision-Taking
The Consideration Process for the new remediation goal is a good opportunity for the proper authority to
streamline the assessment of the plans and the execution.
The Law on Environmental Control provides for various methods of granting licences 'in a sly way'. In
analogy to this, we suggest surveying the following possibilities:
The proper authority and interested parties will make agreements on the approach to more or less
remediation cases. Testing of individual cases on main lines alone thereby becomes possible more easily;
making more use of a differentiated system of arrangements whereby types of standard approach and
cases of custom work can be assessed in a proper manner.
The effectiveness and the efficiency of the soil remediation operation should thereby be assisted.
Quality
The proper authority must check on quality more so than formerly in all stages of execution. The
guarantee of this will therefore become even more important for all the parties involved. The proper
authority must also check the quality in the field.
4. RESEARCH, DEVELOPMENT AND DEMONSTRATION
Knowledge is essential for the implementation of policy. In conjunction with the introduction
of new policy R&D has been started. R&D on sustainable land management is managed by
the Centre for soil quality management and knowledge transfer, 8KB. The 8KB is dedicated
to the quality of the soil from the point of view of controlled risks for man and the
environment, without losing track of the financial aspect. In other words, the 8KB wants to
contribute to more efficient methods for soil remediation and to the development of soil
protection and soil management as instruments for preventing (further) soil contamination.
The 8KB is a co-operative body involving all parties interested in soil management, i.e. trade
and industry as well as the authorities. Initially, the activities will be set up for a period of four
years (1999-2002), with a possible continuation until 2009.
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The mission of 8KB is: "To develop and to disseminate knowledge about the functional and
cost-effective realisation of a soil quality appropriate to the desired use". The mission
perfectly matches the new Dutch government policy on soil remediation, i.e. functional
remediation and cost-effective contaminant removal. (BEVER).
A. R&D Themes
The 8KB anticipates initiatives in the following areas of attention:
Urban Development and Restructuring
Integration of the new development and the restructuring of urban centres in combination with
the remediation of contaminated locations, such as former (gas) works sites.
Restructuring Natural Areas
Nature development and re-designation of agricultural areas in combination with the
remediation of former dump sites and contaminated dredging sludge.
Water Systems Management
Integrating the management of surface water and deep groundwater with the quality of the
soil, which consists of earth and groundwater.
Remediation of Existing Contaminated Locations
Developing cost effective remediation strategies and methods for contaminated locations, in
which risk assessment, environmental merit, weighing alternatives and in situ methods are
important issues.
Maintenance and Soil Management
Risk assessment, management and monitoring of residual (mobile) contaminants will receive
increasing attention because it will often be impossible to fully remove the contamination.
Moreover, measures will have to be taken to prevent new contamination.
B. Duration of 8KB
Initially, the activities will be set up for a period of four years (1999-2002), with a possible
continuation until 2009.
C. Budget of 8KB
A demand-driven programme also implies the joint financing of the activities by all interested
parties. The annual costs of the 8KB, estimated at € 6.6 million are therefore borne by the
government via an ICES contribution (€ 4.5 million) and by public/private market parties (€ 2
million)]. ICES is an instrument if the government to strengthen the knowledge infrastructure.
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5. CONCLUSIONS
The Netherlands policy has been changed drastically in 1997. The introduction and implementation of the
new approach is on full swing. In 1999 the new remediation goal, "Function-oriented and cost-effective
remediation" has been defined. The basic approach is that the quality of the topsoil should fit in the
function of the soil, the subsoil is only remediated if there is a risk by mobile contaminants.
The 8KB, a centre for knowledge development and transfer is stimulating the introduction of the new
approach and the knowledge development. The 8KB started in 1999 and there are now (September 2001)
about 80 ongoing projects.
Addresses:
Policy
Ministry of Housing, Spatial Planning and the Environment
Site: www,,vrojll..,nl
R&D
Centre for Soil Quality Management and Knowledge Transfer
E-mail: skb@cur.nl
Site: www.bodembrecd.nl
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NORWAY
Information in this tour de table is current as of January 2001
1. LEGAL AND ADMINISTRATIVE ISSUES
The Pollution Control Act from 1981 is the main law regulating clean up of contaminated land in
Norway. The polluter pays principle forms an important basis of the Pollution Control Act. If the original
polluter can no longer be identified or held responsible, the current land owner may be held liable for
investigations and remedial actions.
The Pollution Control Act gives the authorities a very strong legislative tool for clean up of contaminated
land. Consequently, industrial companies may be held responsible for historic contamination which
occured before they took over the site or on their property before contaminated soil was regulated (i.e.,
before Pollution Control Act).
Norway has developed a system for risk assessment of contaminated land which is reported in SFT report
99:06 "Guidelines on risk assessment of contaminated sites." Generic criteria related to sensitive land use
have been calculated and the model for this is documented in the report. The system involves a step by
step approach where alternative and site spesific acceptance criteria can be generated and also allows
qualitative methods.
Two simple computer applications are available as excel spread sheet and on the internet at the following
addresses: http://www.risiko-foairensetgmnn.ffi.no and http://www.miljoringen.no. This will also be
available on SFTs home page
Registration of Contaminated Sites
Contaminated land in Norway is considered as a significant source for contamination of rivers, lakes and
fjords. The potential impact from industry, contaminated sediments and landfills on the marine
environment is of greatest concern. In some fjords reduced intake of seafood is recommended, due to
pollutants such as heavy metals, PCBs, PAHs or dioxins.
The actual status shows that more than 3500 contaminated sites are now registered in Norway. About
2100 of these sites are considered to have a potential for causing environmental problems. About 100 of
these have been given high priority and investigations and remediation have been started. Additionally ca.
500 sites need to be investigated. The remaining 1500 sites are considered not to represent environmental
problems as long as they remain undisturbed (recent land use). Changed land use or construction work
will lead to new assessments for these sites.
The Norwegian government established new national goals for the clean up of contaminated land in
October 1999:
• The most seriously contaminated sites shall be cleaned by end of 2005 (about 100 sites).
• Decisions on investigation and clean up on the secondly most contaminated sites by end of 2005 (500
sites).
Investigations and clean up will be carried out and paid for by privat and state owned companies as
polluters and responsible parties according to the law.
A GIS database was developed to keep track of all registered sites and any investigation or remedial
action carried out at the different sites. This database is now being changed and designed for public use
and will be available on internet by the end of next year.
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ROMANIA
In the last time period, the main tendency into the Romanian environmental strategy has been a strong
option for fulfilling the requirements for accession to European Union.
Some important political documents, containing strategic approaches of environmental protection in
Romania have been issued. It can be mentioned Medium-term Development Strategy of Romanian
Economy, The Government Program 2000-2004 and National Program for Accession to EU.
According to the previsions of these political documents, Ministry of Waters and Environmental
Protection developed specific strategy and policies in the field. The assessment of the state of
environment in Romania made on an annual basis reveals the main areas that need special consideration
for improvement.
In this respect, Romanian Government and Ministry of Waters and Environmental Protection have
decided to focus the efforts towards some main directions:
1. harmonization of environmental legislation
2. restoring the natural capital in damaged areas
3. implementation of national program for the management of industrial and urban waste and recycling
of materials
4. development of long-lasting management of waters resources
5. integrated pollution prevention and control
Environmental policy shifts from recovery actions towards prevention ones and following issues are to be
tackled:
1. The development of an integrated environmental monitoring system
2. Promotion of Environmental Management Systems ISO 14000 and EMAS
3. Encouragement of the environmentally-friendly products and of durable consumption
4. Public awareness
5. Resorting to economic, rather than command and control instruments in environmental policy
In order to create a unitary and coherent perspective regarding environmental priorities,
Ministry of Waters and Environmental Protection has drafted, in May 2000, "Romanian Short and
Medium-term Environmental Protection Strategy" and also, identifies the most important environmental
projects that have been included into National Environmental Action Plan, National Plan for ISPA
implementation and LIFE III Program.
The Romanian Government has adopted the draft Law for the ratification of the Agreement between
European Community and Romania as part of European Environmental Agency and to the European
Network for Information and Observation (EIONET).
1. LEGAL AND ADMINISTRATIVE ISSUES
In 2001 the institutional environmental framework changes by Government Decision no. 17, amended by
Government Decision no.353, that set up the structure and functioning of central environmental authority,
Ministry of Waters and Environmental Protection. The permitting procedures, monitoring and
enforcement of the legislation at local level are the responsibilities of the County Environmental
Protection Inspectorates that have similar structure to the central environmental authority.
During 2000-2001, the environmental legislative framework has been developed and oriented to address
the main issues in the field.
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The following legislative acts have been adopted in this period:
• The Environmental Protection Law no. 137/1995, amended in 2000, has created a self-financing
system that insures financial support for strengthening of the institutional capacity of the local
Environmental Protection Inspectorates.
• Emergency Ordinance no. 93/2001 amending the Law no. 73/2000 regarding Environmental Fund.
• Law No 22/2001 regarding the ratification of the Espoo Convention on environmental impact
assessment in trans-boundary context (OJ 105/01.03.2001) that transposes some of the provisions of
the Council Directive 85/337/EEC on the assessment of the effects of certain public and private
projects on the environment
• Law No 86/2000 regarding to the ratification of the Aarhus Convention on the access to information,
public participation to the decision making process and justice access for environmental issues (OJ
No 244/22.05.2000)
• Order of the Minister of Waters and Environment Protection No 1325/2000 regarding public
participation through representatives to the preparation of the environmental plans, programs, policies
and legislation (OJ No 580/20.11.2000).
• Governmental Decision No 173/2000 regarding the regulation of the special regime for the
management and control of PCB's and other similar compounds transposing Council Directive
96/59/EEC on the disposal of PCB/PCT (OJ No 131/28.03.2000)
• Emergency Ordinance No.78/2000 regarding waste regime, for the transposition of Council Directive
75/442/EEC on waste, (OJ 283/22.06.2000)
• Law no. 426/2001 for the approval and completion of the Emergency Ordinance No.78/2000
regarding waste regime
• Emergency Ordinance no. 243/2000 regarding the protection of atmosphere
• Emergency Ordinance no. 244/2000 regarding the safety of dams
• Emergency Ordinance no. 200/2000 regarding classification, labeling and packaging hazardous
substances and chemical products
• Law no. 451/2001 for the approval of the Emergency Ordinance no. 200/2000 regarding
classification, labeling and packaging hazardous substances and chemical products
• Governmental Decision No 964/2000 regarding the National Plan on water protection against the
pollution caused by nitrates from agriculture (OJ No 526/25.10.2000) for the transposition of Council
Directive 91/676/EEC
• Governmental Decision no. 662/2001 regarding the management of used oils
• Emergency Ordinance no. 16/2001 regarding the management of recyclable industrial waste
• Law no. 465/2001 for approval of Emergency Ordinance no. 16/2001 regarding the management of
recyclable industrial waste
• Government Ordinance no. 2/2001 regarding the juridical regime of fines
• Agreement between Ministry of Defense and Ministry of Waters and Environmental Protection
regarding the environmental permitting procedure for the military facilities and activities, 2000
2. REGISTRATION OF CONTAMINATED SITES
The Ministry of Waters and Environmental Protection carries out the main activity of registration of
contaminated sites.
Research and Development National Institute for Environmental Protection Bucharest (RDNIEP) is in
charge to draw up yearly report on the management of wastes in Romania. The local Environmental
Protection Inspectorates, based on questionnaires that are completed by companies that are generating
wastes, collect the data needed.
In 2001, the Research and Development National Institute for Environmental Protection Bucharest has
already issued Preliminary Report on the Management of Solid Waste in Romania for 2000. The data
have been collected from 4300 companies.
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According to the Preliminary Report, in 2000, in Romania were been generated 55 millions tons of solid
wastes out of which 47 millions tons industrial waste and 8.15 millions tons municipal solid waste. Only
10 millions tons (22%) of waste have been reused. The mining industry has generated the biggest amount
of waste, 22.7 millions tons representing 48% of the total.
In 1999, only 30% of industrial waste deposits had environmental permit and at least 50 deposits miss
minimal technical environmental protection measures.
Table 1: Waste generated by economic activities in 2000 (thousands of tons)
Mining industry
Energy production
Coal extraction and preparation
Agriculture
Constructions
Timber industry
Metallurgy
Other activities
Total
Generated waste
8247.781
5588.444
4192.223
3677.855
3033.077
2915.471
2480.455
16868.807
47.004.113
Recycled waste
762.062
408.235
19.665
264.616
829.649
305.215
1108.421
6639.537
10.337.400
Eliminated waste
7485.719
5180.209
4172.558
3413.239
2203.428
2610.256
1372.034
10229.27
26.447.699
Waste generated by economic activities in 2000
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14000-
12000-
10000-
8000-
6000-
4000-
2000-
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By category, mining solid sterile was generated in a biggest amount. 900,000 tons of hazardous waste was
produced in 2000, and only 24% of it has been reused. In four counties Bacau, Alba, Sibiu and Brasov the
amount of hazardous waste produced during 2000 represents 55% from total.
In The State of Environment 2000 paper, Ministry of Waters and Environmental Protection reports that
the industrial waste deposits are covering a surface of 11986 ha. A number of 83 hazardous waste
deposits have been recorded in 1999, in 30 counties, on a surface of 450 ha.
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The pollution of soil with chemical substances is extended over 0.9 millions ha out of which 0.2 millions
ha are excessively polluted. A serious pollution with heavy metals (Cu, Pb, Cd, and Zn) has been
recorded in Baia Mare, Copsa Mica and Zlatna areas.
Table 2: Categories of waste (thousands of tons)
Ashes
Chemical waste
Ferrous waste
Timber waste
Metallurgical slag
Other waste
Mining sterile
Generated waste
5965.099
2755.867
3014.415
1129.378
1843.591
2369.815
22697.408
Recycled waste
5.559
127.75
2991.311
1055.613
638.629
836.563
731.961
Eliminated waste
5959.54
2628.117
23.104
73.765
1204.962
1533.253
21965.447
Categories of waste
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4000-
3000-
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1000-
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^
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• Recycled waste
The Ministry of Waters and Environmental Protection monitors the quality of groundwater using the local
hydrological station capabilities. In this respect, some categories of hydrological drillings are in place:
1. Category I, located along the main rivers
2. Category II, placed in plains
3. Established in the area of main aquifers
4. Experimental, for special purposes as research
5. Around the main pollution sources
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The high depth drillings are included into the National Hydro-geological Network and are used mainly for
research.
The monitoring of groundwater shows some important deterioration of the quality of waters in certain
areas:
• Pollution of groundwater with nitrates, phosphates and organic materials because of inappropriate and
excessive use of fertilizers. The same contamination is recorded close to the main fertilizer plants like
Azomures Tg. Mures, Archim Arad, Doljchim Craiova, etc.
• Pollution with petroleum products and phenols in Prahova-Teleajan watershed, on an area of 70 km2
because of oil refineries
• Pollution with different type of industrial substances in the location of the large industrial plants as
Codlea Brasov, Victoria Fagaras, Isalnita Craiova, etc.
Figure 1: Some of the major polluted areas in Romania
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In 1999, 30% of the total environmental protection costs have used for the mitigation of effects of
pollution due to wastes.
3. TECHNOLOGY DEVELOPMENT PROGRAM
With a view to ensuring a unitary approach and a coherent action plan in the environment protection
sector, a Governmental Decision is being drafted in order to extend the competencies of the Inter-
ministerial Committee for the promotion and updating of the National Environmental Action Plan.
Consequently this Committee will have the competence to approve all the sectoral policies and strategies
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referring to activities with environmental impact. There is a step for a future national co-ordination of
technology and research programs in environmental field.
Ministries involved are supporting TDP taken into consideration the rehabilitation technologies of the
environment affected by certain activities.
4. REMEDIAL METHODS IN USE
No special new methods have been used in the last time. The most frequently used methods are:
1. Excavation and soil removal
2. On site insulation
3. Pump and treat methods
4. Natural attenuation
These methods are used on the small scale because of the high costs.
More and more actions are taken to prevent soil and groundwater pollution mainly by building safe waste
deposits and recycling by-products and materials.
5. RESEARCH AND DEVELOPMENT ACTIVITIES
Some important research institutes that are partially supported by the state carry out R&D activities in
environmental field. It can be mentioned: the Research and Development National Institute for
Environmental Protection Bucharest (ICIM), National Institute for Industrial Ecology Bucharest others
that are supported by certain ministries.
Ministry of National Education is financing R&D projects for universities. It can be count a lot of co-
operation activities between Romanian and foreign institutes and universities in Europe and North
America.
6. CONCLUSIONS
A large-scale decontamination action of polluted soil and groundwater is not still used in practice. A
significant effort is oriented to pollution prevention measures. The environmental legislation is
developing according to the EU requirements. The National Plan for Waste Management that will be
developed starting from the next year will ensure a more effective control of the waste.
7. BIBLIOGRAPHY
1. Official Journal of Romania, Part I, 2000-2001, collection of legislative documents
2. Projects portfolio submitted by the Ministry of Waters, Forests and Environmental Protection to be
included in " The National Action Plan for Regional Reconstruction and Economic Development in
South-Eastern Europe", 2000
3. The State of Environment in Romania 2000, Ministry of Waters, Forest and Environmental
Protection, Bucharest
4. The Medium-term Development Strategy of Romanian Economy, Chapter VI, Environmental
Protection, Territorial Planning and Regional Development, Government of Romania, March 2000
5. The Government Program 2000-2004, Government of Romania, 2000
6. Romanian Short and Medium-term Environmental Protection Strategy (2000-2004), Ministry of
Waters, Forests and Environmental Protection, May 2000
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7. National Program for Accession to EU- edition June 2001, Chapter 17, Environmental Protection
8. Report on the progresses for accession to EU Sept. 2000-June 2001, Chapter 2.3.22, edition
June 2001
9. National Environmental Action Plan, Ministry of Waters and Environmental Protection, 2000
10. National Plan for ISPA implementation, Ministry of Waters and Environmental Protection, 2001
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SLOVENIA
1. INTRODUCTION
Since it gained independence on 26 June 1991, the Republic of Slovenia has been striving to become a
full member of the EU. Slovenia signed the Europe Agreement on 10 June 1996, and it was ratified by the
Slovenian National Assembly on 15 July 1997.
On 16 July 1997, the EU Commission issued its opinion on Slovenia's application for EU membership.
The first session of the EU Subcommittee and Slovenia in the area of the environment, energy
management and regional development was held on 9 and 10 October 1997 in Ljubljana.
On 26 March 1998, the Government of the Republic of Slovenia discussed and adopted the document
entitled Environmental Accession Strategy (1) as part of the National Programme for the Adoption of the
Acquis.
The Strategy encompasses:
• the accession processes to the adoption of the acquis in the area of the environment;
• an action plan for the environmental accession activity;
• priority tasks.
The goals of the specified strategy are to draw up a document dealing with Slovenia's accession to the EU
in the area of the environment. The strategy takes into account the strategic documents of Slovenia and
the legislation and documents in the area of the environment. The drawing up of the environmental
legislation should compare, in accordance with the specified strategy, the requirements of the EU with the
existing Slovenian legislation.
2. ENVIRONMENTAL ACCESSION STRATEGY
The basis for the drawing up of the strategy is an environmental policy with a built-in principle of
harmonised development. At the same time, all environmental legislation must be altered following the
example of EU directives and gradually drawing closer to Western European environmental standards,
norms and other requirements. To this end the EU Commission has established many forms of technical
assistance. First, the Commission set up the Technical Assistance Exchange and Information Office
(TAIEX). This Office was set up to coordinate, assist, and inform the regulator (the Ministry of the
Environment and Spatial Planning) in drawing up any documents required to make Slovenia's full
membership of the EU easier.
Activities within the Environmental Accession Strategy
The activities were divided into three work stages:
THE INITIAL STAGE, ENCOMPASSING:
1. founding the Office for European Affairs at the Ministry of the Environment and Spatial Planning;
this was founded in January 1997 and coordinates all the activities of the ministry relating to EU
accession;
2. drawing up programme methodologies and assessments;
3. determining the approach in the formation of the strategy;
4. establishing links between the departments within the ministry of the environment, and establishing
links between the ministry of the environment and other ministries and programmes relating to the
EU;
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5. collecting documents and data relating to pre-accession processes;
6. drawing up time schedules with determination of priorities.
The initial stage was carried out in full and completed in April 1997.
The Strategic and Planning Stage, Encompassing:
1. drawing up the National Environmental Action Programme in accordance with accession activities;
2. determining priorities in the EU accession process;
3. appointing responsible persons for the drawing up and implementation of the strategy and accession
4. of the environmental strategy to the environmental acquis;
5. drawing up a time schedule for individual stages of harmonisation of legislation;
6. screening with the EU Commission for Environmental Acquis;
7. review of acquis already in force and acquis still to be dealt with;
8. assessment of harmonisation of Slovenian legislation with the acquis;
9. application of technical assistance EU programmes (TAIEX etc.);
10. action plan for the transposition of environmental acquis into Slovenian legislation.
This stage had been largely realised by the beginning of September 1997.
Implementation Stage, Encompassing:
1. drawing up the environmental strategy as a legally binding implementation document. The strategy
must be coordinated with other relevant national documents necessary for approximation to the EU;
2. a time schedule for the transposition of the environmental acquis;
3. drawing up cost estimates for the implementation and establishing of the time schedule of the
transposition of the environmental acquis;
4. drawing up scenarios of entry into force of the environmental acquis by priority tasks;
5. carrying out the activities for gradually achieving harmonised development and environmental goals.
3. THE REAL ENVIRONMENTAL SITUATION AND CHANGES IN RECENT YEARS
The Environmental Accession Strategy has established that the environment situation in Slovenia is
worrying.
This document deals with the environment situation in seven segments:
3.1. Quality of air
3.2. Waste management
3.3. Quality of water
3.4. Nature protection
3.5. Chemicals and genetically modified organisms
3.6. Noise from vehicles and machinery
3.7. Nuclear safety and protection against radiation.
3.1 Quality of Air
The quality of air in Slovenia has changed in the last ten years, with the concentration of SO2 decreasing
and the concentrations of O3, NOX and VOCs increasing. As regards CO2, it is not clear how Slovenia is
going to comply with the Kyoto Protocol, although after the Berlin conference (July 2001) it seems that
Protocol obligations will be easier to fulfil than appeared to be the case when the Protocol was signed.
The national programme of maintaining or improving the quality of air is based on the international
obligations of Slovenia, such as:
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1. The Convention on Long-range Transboundary Air Pollution;
2. The Vienna Convention for the Protection of the Ozone Layer;
3. The United Nations Convention on Climate Change;
4. The Montreal Protocol;
5. The London Amendments;
6. The Copenhagen Amendments.
Slovenia has already harmonised its legislation with the obligations deriving from the protocols on:
• reduction of SO2 emissions;
• reduction of NOX, VOCs, and POPs emissions (volatile organic compounds, persistent
organic pollutants).
The system of monitoring 24-hour concentrations of SO2 and smoke encompasses 49 stations in Slovenia.
According to the protocol, Slovenia must reduce sulphur emissions by 70 percent by 2010 (with respect to
1980 levels).
Industry is also making efforts to remove or replace the chemical substances that destroy the ozone from
all products and production processes. These efforts mainly involve the replacement of CFCs with
isobutane and cyclopentane.
NOX, ozone, VOC, CO2 and CO emissions are mainly caused by traffic. Over 30 percent of CO2
emissions and over 90 percent of CO emissions are caused by traffic. Traffic also causes some 70 percent
of NOX emissions; the government will therefore have to take suitable steps to reduce the emissions of
these gases from other sources since it will have little scope to do so from traffic.
Air quality is not a problem throughout the country. The air is generally of relatively good quality.
Problems occur in specific locations with temperature inversion, mostly around coal-fired power plants.
Slovenia annually emits some 7.1 tons of CO2 per capita (data from 1995). In accordance with the
Climate Convention, Slovenia should reduce CO2 emissions by 13 percent. In 1997 the government
started activities in this area by adopting a tax on CO2 emissions, which should force producers to reduce
greenhouse gas emissions and the use of non-renewable sources of energy. The funds obtained by the new
tax will be used for funding projects for improving the production of cleaner fuels.
Generally, it could be said that the air quality situation in Slovenia has improved in recent years, except
for traffic emissions.
3.2 Waste Management
In the area of municipal waste, the situation has been unchanged for some years. Some 77 percent of all
households are encompassed in the regular network of collecting and removing municipal waste. There
are some 850,000 tons of municipal waste collected in this way annually. Unfortunately the waste is not
classified and is unusable. Municipal waste is disposed at 54 local waste disposal sites. Some industrial
waste also ends up at these waste disposal sites. Silt from treatment plants of urban waste and industrial
waters is mainly deposited at these sites as well. According to the latest data there are over 600 such
treatment plants.
The capacity of all waste disposal sites is approximately 13 x 106m3. Some of these 54 sites are already
full, and by the latest calculations all will be full by 2010. There are 6,000 illegal waste disposal sites
whose location is known and which are used for illegal disposal of municipal and industrial waste. In
addition, karst caves were used for disposal of waste in the past. Figures 1 and 2 show all registered karst
caves in Slovenia and those used for disposal of waste. Some 600 caves have been used for disposal of all
kinds of waste; some are still so used.
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Another parallel problem occurring at the specified waste disposal sites (54 legal, 6,000 illegal and 600
karst caves) is leachate leaking into subsoil, thus endangering groundwater since some waste disposal
sites are located in areas with underground capture of drinking water.
Slovenian industry annually produces some 2 million tons of industrial waste. There are only 13 disposal
sites in Slovenia designated only for industrial waste. Industry has only two incineration plants for
hazardous waste; one has the capacity to annually process 7,000 tons of pharmaceutical waste, the other
1,000 tons of plant protection waste. Slovenian industry produces a total of 15,000m3 and 18,000 tons of
hazardous industrial waste, which amounts to some 40,000 tons annually. Approximately 10 percent of
the annual amount of hazardous waste is exported to neighbouring countries.
Annually there are some 2.3 million tons of demolition waste.
Agriculture, forestry and the food industry annually produce some 3.5 million tons of waste (these are
animal tissue waste (0.05 million tons annually), plant waste (0.08 million tons annually), animal
excrement, including destroyed straw (1.57 million tons annually), and forestry waste (1.1 million tons
annually)).
According to Government documents, i.e., the Strategic Waste Management Policy of the Republic of
Slovenia (EPA 1595, Porocevalec of the National Assembly, No. 36, 1996) the production of industrial
waste is to be reduced by some 45 percent by 2005. This will not be realised, however, under normal
conditions of industrial production.
Figure 1: All registered caves in the Land register of Slovenia
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Figure 2: Polluted or damaged caves in Slovenia
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3.3 Quality of Water
The quality of water courses and groundwater is monitored by permanent monitoring. Groundwater is of
relatively high quality in the western part of Slovenia, which includes the Slovenian Alps. In the southern
and eastern parts groundwater is polluted with pesticides and nitrates; around major industrial plants it is
polluted with heavy metals and solvents.
Monitoring of surface waters is carried out under the terms of the programme at 100 measurement points
in different rivers, streams and lakes. Monitoring is carried out six times a year at each point. Water is
classified into four quality classes. The first class encompasses the cleanest water, suitable for drinking
without any treatment. Surface water courses are polluted with large quantities of nitrogen and phosphor
compounds in intensive farming areas. Industrial wastewaters, which are discharged into water courses
untreated, mainly contain heavy metals and some organic compounds such as solvents.
Monitoring of technological and urban wastewaters has been taking place for more than ten years.
Polluters pay tax with respect to the content of individual measured parameters in wastewater.
Larger cities (e.g., Ljubljana and Maribor) still do not have treatment plants despite the urban sewage
situation already being relatively critical years ago.
3.4 Nature Protection
Slovenia's biological diversity is extremely large given the country's size. This diversity is a result of the
convergence of climate types, geological structures and differences in altitude. Forests make up some 53
percent of the country. Twenty-two marsh areas are protected as natural parks because of the endangered
animal and plant species. Industry and intensive farming exert considerable ecological pressure.
Agriculture contributes to up to 50 percent of the eutrophication process and 15 percent of pollution with
hazardous substances affecting ecosystems. The development of motorway infrastructure also endangers
certain species.
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Slovenia ratified the Convention on Biological Diversity (Official Gazette of the Republic of Slovenia,
No. 30/1996) in 1996. Together with the new Nature Conservation Act (Official Gazette of the Republic
of Slovenia, No. 56/99) and the Biological Diversity Act (in preparation) this document shall constitute
the legal framework for the regulation of this area.
3.5 Chemicals and Genetically Modified Organisms
Slovenia produces approximately 75 percent of the chemicals it requires for industry and the majority of
its consumer chemicals. Pesticides and oil derivatives are imported from other countries. Soil pollution,
industrial wastewater and local air pollution with chemical substances is becoming a bigger issue every
day; and it is being dealt with in a partial and dispersed manner, with most aspects left to local
communities. An integral approach to these issues at the national level does not exist, and the ministry
concerned is not capable of establishing one. The reason for this is that the legislation remains
uncoordinated with the acquis. Different regulations adopted practically on a daily basis show, however,
that the situation has been improving slightly. The ratification of the Convention on the Prohibition of the
Development, Production, Stockpiling and Use of Chemical Weapons and on their Destruction (Official
Gazette of the Republic of Slovenia, No. 34/1997) and the ratification of the Basel Convention (Official
Gazette of the Republic of Slovenia, No. 48/1993) shows that Slovenia desires to be among those
countries that control toxic and hazardous chemicals and waste, and thus the chemical industry.
The Chemicals Bureau founded in 2000 keeps records of chemicals that are banned or whose use is
restricted. The health inspectorate is responsible for supervising the effects of chemicals on employees'
health.
The area of gene technology is not yet regulated although, according to the government, a gene
technology act has already been drawn up. Researchers take into account the norms applicable in the EU.
Legislation governing this area is in preparation; although industrial production does not yet exist, some
medicaments made by this technology may be acquired. The Industrial Property Act is the basic act
encompassing the legal area of gene technology. The act provides for the protection of inventions in this
area as well as the protection of final products which are or which contain genetically modified
organisms.
3.6 Noise from Vehicles and Machinery
Noise pollution has never been systematically monitored in Slovenia. Within the Environment Protection
Act (Official Gazette of the Republic of Slovenia, No. 32/1993) implementing regulation has been adopted
prescribing noise protection in design and supervision of the construction of traffic facilities, and in
permits for the design of industrial and residential construction. Two acts govern this, the Decree on the
Noise in the Living and Natural Environment (Official Gazette of the Republic of Slovenia, Nos. 45/96
and 66/96) and the Regulations on Initial Measurement of Noise and Operational Noise Monitoring for
Sources of Noise and on Conditions for Their Execution (Official Gazette of the Republic of Slovenia, No.
70/96).
3.7 Nuclear Safety and Protection against Radiation
The Nuclear Safety Administration of the Republic of Slovenia (Slovenia has one nuclear power plant)
conducts the most important tasks for Slovenia's EU accession strategy in the area of nuclear safety,
protection against radiation and control of radioactive materials. The ratified conventions, such as the
Convention on Nuclear Safety (Official Gazette of the Republic of Slovenia, No. 61/1996), the
Convention on Early Notification of a Nuclear Accident (Official Gazette of the Republic of Slovenia, No.
15/1989) and legal acts assumed from Yugoslavian legislation in force in Slovenia constitute a basis for
the implementation of nuclear safety. The Nuclear Safety Administration of the Republic of Slovenia has
been drawing up new regulations in accordance with EU regulations.
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According to the IAEA experts the Krsko nuclear power plant is entirely safe. The ensuring of operational
safety of the nuclear power plant takes into account all Slovenian and international safety assessments and
studies. The issue of nuclear waste is being dealt with by the government: the Nuclear Waste Agency,
which is to draw up the strategy for the handling and storage of nuclear waste, has been founded for this
purpose.
4. HARMONISATION OF LEGISLATION IN THE AREA OF THE ENVIRONMENT WITH
THE ACQUIS
The Ministry of the Environment and Spatial Planning has drawn up the assessment of harmonisation of
legislation in the area of the environment with the environmental acquis. The initial screening was carried
out six years ago. The comparison of the requirements of the environmental acquis and the existing
Slovenian legislation showed some fairly large discrepancies which Slovenian legislation must remove or
adjust. The initial assessment was made within a Phare project. The first general analysis was made in the
form of a table. The initial assessment paid special attention to the differences in water protection, waste
management and biological diversity legislation.
In recent years five acts have been drawn up and adopted in the area of environment protection:
• The Nature Conservation Act (Official Gazette of the Republic of Slovenia, No. 56/1999);
• The National Environmental Action Programme (Official Gazette of the Republic of Slovenia,
No. 83/1999);
• The Land Survey Activity Act (Official Gazette of the Republic of Slovenia, No. 8/2000);
• The Construction Products Act (Official Gazette of the Republic of Slovenia, No. 52/2000);
• The Waters Act (Official Gazette of the Republic of Slovenia, No. 52/2000 and 2/2001).
The Government has drawn up 25 implementing regulations, although it should have drawn up 47. The
Ministry of the Environment and Spatial Planning has drawn up 14 implementing regulations, although it
has planned to draw up 31. According to the assurances of the Government and the Ministry other
regulations have already been drawn up and will be adopted by the end of 2001. Some activities in the
adoption of legislation harmonised with the acquis have been delayed, but these delays are not critical.
In order to speed up the work in this area, change and update the work in environmental protection, and
draw closer to other countries from the technical, technological and organisational points of view, the
government has established the Environmental Agency.
The Agency now encompasses some former services of the Ministry, such as the Hydrometeorological
Institute, the Administration for the Protection of Nature and the Administration for Geophysics. The
professional tasks carried out by the Agency are related to:
• integrated protection of the environment and natural resources (e.g., water, air and soil);
• assessment of environmental impact;
• public environmental protection services;
• protection from noise and other environmental risks;
• nature protection;
• water management and management of facilities and devices in water management;
• public water regulation services, and granting concessions for use of water;
• promotion and implementation of programmes for the efficient use of energy;
• monitoring and inventory of meteorological, hydrological, agrological and ecological conditions;
• meteorological, hydrological and ecological analysis and reports
• forecast of meteorological and hydrological processes and alerting of any irregular phenomena;
• monitoring and inventory of geological, seismological and other geographic phenomena;
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• determining the location and categorisation of geological, seismological and other geographic
phenomena;
• securing of facilities and devices against earthquakes;
• protection from and security against earthquakes, and early warning of earthquakes;
• waste management (other than radioactive waste);
• alleviating the consequences of natural and other disasters;
• fullfilment of international obligations in these areas and international data exchange.
5. ACTIVITIES TO BE COMPLETED BY THE END OF 2001
The government has prepared a plan of activities to be carried out by the Ministry of the Environment and
Spatial Planning in individual time periods.
The following main prescribed tasks had to be carried out due to differences between Slovene legislation
and the environmental acquis:
• development of comprehensive legislation on waste management (a parallel implementation
programme of the Slovenian strategy of waste management was created);
• harmonisation of Slovenian legislation in the area of water protection;
• preparation of a law regulating the area of biological diversity.
These tasks were successfully completed before 2000.
In 1997 and 1998 the following projects carried out within Phare-DISAE (Development Implementation
Strategies for the Approximation in Environment) were carried out due to the differences between
Slovenian legislation and the acquis:
• a costs estimate of harmonisation with the environmental acquis;
• legislation on waste management;
• public economic services in the area of environmental protection;
• funds reserved for long-term investments in environmental protection;
• noise legislation;
• implementation of legislation on wastewater management.
These projects have also been largely successfully carried out, while some are currently still being
realized.
6. CONCLUSION
By the end of 2000 Slovenia had successfully realised most of the priority tasks and projects and prepared
legislative acts. Negotiations with the relevant EU Commissions have shown that all activities for full
membership of the EU are being carried out in accordance with the time schedules.
In the most recent negotiations between Slovenian government officials and members of the EU
Commission for Environmental Acquis, which took place in April 2001, the environmental chapter could
therefore be closed.
All of these activities indicate that Slovenia has for some time been KNOCKING ON THE EU's DOOR.
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7. RESOURCES
1. Environmental Accession Strategy for accession to the EU - part of the National Programme for the
Adoption of the Acquis Communautaire.
2. Porocevalec of the Slovenian National Assembly, Year XXVII, No. 6, Ljubljana, 31 January 2001
3. Act Amending the Organisation and Competence of Ministries Act, Official Gazette of the Republic
of Slovenia, No. 30/2001.
4. United Nations, Economic Commission for Europe, Review of the effectiveness of environmental
policy - Slovenia, Geneva, 26 May 1997
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SPAIN
1. NATIONAL FRAMEWORK TO MANAGE CONTAMINATED SOILS IN SPAIN
LEY 10/1998, De Residues (Waste Act)
Boe 22-April 1998
Title V: Polluted Soils
Art.27. Contaminated soils declaration
Art. 28. Mending of environmental hazards due to soil pollution.
Functions of the Administrations
• Ministry of Environment:
-Legislation
-Coordination of Regional Governments
• Regional Governments (17)
-Executive Activities:
Investigation
Inventory
Register
Priorisation of Sites
Projections
Remediation
• Municipalities
-only urban wastes landfields
Waste Act
Art. 27. Contaminated Soil Declaration.
• Regional Governments are responsible for the elaboration of an inventory of those soils/sites with
high risk of threat for human health and environment.
• Criteria and standard to declare a soil as contaminated are setting up by the Central Government.
based in reuse of soils.
• The declaration of one area as a contaminated soil will force to carry out the necessary actions to its
cleaning and recovery, previous request of the Regional Authorities.
• The owner of the pollutant activity has always the liability to clean up the soils.
• When the site is public property its remediation is financed with public funds.
• National Plan for Remediation of Contaminated Soils (1995-2005)
• National Government is responsible for the elaboration of a list with all those economical/ industrial
activities which potentially can produce soil pollution.
• The declaration of one area as a contaminated land would be included as a marginal note in the
Property Register.
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Potentially Pollutant Activities
• Compulsory Declaration by the owner
• Included in the property register
• Situation report every year
• Ministry is making a decree
-list of "a Priori" Pollutant activities
-hazardous substances landfields
-low pollutants activities are excluded
Criteria and Standard to Declare a Soil as Contaminated
• Three classes of soils
-not contaminated
-contaminated
-potentially contaminated
• Due to concentration of some substances and heavy metals
• Risk
• Soil reuse after cleaning up
Table 1: Guideline Levels
Substance
1,1-Dicloroetileno
1,1,2,2-
retracloroetileno
1 , 1 ,2-Tricloroetano
1,2-Dicloroetano
1 ,2-Diclorobenceno
1 ,2-Dicloropropano
1 ,3-Dicloropropeno
CASRN
75-34-3
79-34-5
79-00-5
107-06-2
95-50-1
78-87-5
42-75-6
2-Clorofenol J95-57-8
^STricbrofenol^
2,4,6-Triclorofenol
2,4-Diclorofenol
1 ,2,4-Triclorobenceno
1 ,4-Diclorobenceno
1,4-dioxano
Acenafteno
88-06-2
120-83-2
120-82-1
106-46-7
123-91-1
83-32-9
Acetona (67-64-1
Aldrin
Antraceno
309-00-2
120-12-7
Benceno 71-43-2
Benzo(a) antraceno (56-55-3
I3enzo(a)pireno (50-32-8
clordano
Clorobenceno
57-74-9
108-90-7
Cloroformo (67-66-3
Dieldrm J60-57- 1
Endrin (72-20-8
Etilbenceno
Fenol
100-41-4
108-95-2
Industrial
use
100***
2**
10**
5**
100***
4
7**
100***
100***
90**
10**
90**
40**
100***
100***
1**
100***
10**
20**
2**
1**
35
25
j**
1**
100***
100***
Residential
Use
(mg/Kg soii
70**
0,3**
1**
0,5**
70***
0,5**
0,7**
10**
100***
9**
1**
9**
4**
60**
10**
0,1**
100***
j**
2**
0,2**
0,1**
10**
5**
0,1**
0,1**
20**
100***
Without Restrictions on
use
Soil
Organism
)
JX01[*J_
0,014
0.11
0,35
0.021
4,24
0,01(*)
0,02
0.15
1.5
0.05
0.096
29
0,05
Organismos
acuaticos
0,034
0,01(*)
0.37
0,05
0.1
0,06
0,01(*)
0,01(*)
0,05
0,01(*)
0,06
0.12
0.10
0.27
0,01(*)
0,01(*)!
JiPJjZL. 0,05
0.1
3.8
0.15
0.024
1
0.13
0.01(*)
0.05
1,4
0.17
0.23
15
0.01(*)
0.1
0,08
0.15
0.01(*)
0,01(*)
0.01(*)
Vertebrados
terrestres
0,44
3.3
1.5
0.11
0.5
0.2
0.40
14.7
0.35
#i 16.60
0.09
100***
2.54
22
0.4
0.01(*)
0.01(*)
2.7
1.65
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Table 2: Guideline Levels of Soil Use
EXPOSURE CENARIOS
Soil vapours inhalation
Soil Particles inhalation
Accidental ingestion of polluted soil
Ingestion of contaminated food
Skin contact with polluted soil
Residential
•
•
•
•
•
Industrial
•
•
Without Restrictions
•
•
•
•
National Plan for remediation of polluted soils
50%
50%
1. 1995-2005
2. ministry of environment
3. regional governments
4. R.G. lead the activities
5. Public Property sites
6. Inventory 2 steps: 4.900 sites
Waste Act
Art. 28. Mending of environmental hazards due to soil pollution
Cleaning and recovery could be carried out through voluntary agreements between the pollution
responsible or through collaboration agreements with the competent authority.
Remediation of Polluted Soils
• Polluter pays
• Subsidies to prevention
-NPHW
-Minimization
-End of line treatment of hazardous wastes
-Clean up technologies
• Ministry of environment + regional governments can loan to private for remediation
• Agreements mimam-regional governments
• Return normally with profit in 10-15 years:
-In cash
-In lands
-Housing
Table 3: Total from 1995-2000
YEAR
1995
1996
1997
1998
1999
2000
ESTATE
2,909
1,593
5,103
6,497
4,021
6,269
AACC
2,548
2,753
5,415
6,136
5,547
5,920
UE FOUNDS.
1,202
10,361
11,636
5,505
TOTAL YEAR
5,457
5,547
20,879
24,275
15,073
12,189
TOTAL 26,392 28,319 28,704
TOTAL PLAN
83,420
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25.000
ESTATE
AACC
UE FOUNDS. TOTAL YEAR
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SWITZERLAND
The information in this tour de table is current as of January 2001.
1. NEW ORDINANCE RELATING TO CHARGES FOR THE REMEDIATION OF POLLUTED
SITES
The cost of remediation for about 3,000 contaminated sites in Switzerland over the next 20 to 25 years is
estimated at about 3 billion Euro. The costs of decontamination are to be borne according to the "polluter
pays" principle. However, since in many cases the polluter can no longer be traced or may be unable to
pay, part of the cost has to be met by public funding. It is estimated that this requirement for public
funding will amount to about 1.3 billion Euro.
To contribute to public funding of the remediation of polluted sites, on 5 April 2000, the Federal Council
voted for the new ordinance relating to charges for the remediation of polluted sites, and this will come
into force on 1 January 2001. A tax will be levied on landfill, and on the export of waste for landfill
abroad, and this should bring in about 17 million Euro per year. The rates of taxation vary between 10 and
30 Euro per tonne of deposited waste. In principle, the federal government will refund to the cantons 40%
of the decontamination costs that are to be met by public funding.
The main points covered by the ordinance are:
• the procedure for taxing landfilling with waste in Switzerland, and the export of waste for landfill
abroad;
• the rates of taxation to provide about 17 million Euro per year to contribute to the decontamination of
polluted sites where costs accrue to the community;
• the prerequisites and procedures for subsidising the cantons, in particular the level of subsidy and the
costs of decontamination that can be taken into account.
Tax collected by virtue of this ordinance is to make a considerable contribution to the decontamination of
polluted sites in a way that is acceptable from the environmental point of view, makes economic sense,
and uses up-to-date technology, whilst being carried out rapidly and in a way appropriate to the degree of
ecological urgency.
2. SUSTAINABLE REMEDIATION OF CONTAMINIATED SITES
Over the past few months, the topic of contaminated sites has come to the fore, and one case has led to
discussions at the ministerial level throughout Switzerland and abroad (Bonfol chemical waste landfill
site in the Canton of Jura). Investigations on polluted sites and their decontamination are not only carried
out in the context of construction plans, but also increasingly in places where there is an urgent need from
the ecological point of view (i.e. without any relation to construction projects).
According to the Contaminated Sites Ordinance, which has been in force since 1998 the main goal of
remediating polluted sites is the long-term prevention of unlawful emissions at source. This can be
achieved either by decontamination or by securing/containment measures. At a first glance it may often
appear less expensive to make the site safe by containment measures, rather than carrying out
decontamination.
However, especially for contaminated sites with persistent pollutants (e.g., chlorinated solvents), making
the site safe can be much more expensive overall in the long term, as construction systems may need to be
supervised and maintained for hundreds of years. Measures to ensure safety make sense if it can be
guaranteed that after one or two generations the site can be left alone, without the need for further
measures to be taken. This should be the case for readily degradable pollutants that can be absorbed, for
instance mineral oils and for landfill sites containing municipal waste.
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I should now like to describe briefly two important current examples of polluted sites that need to be
decontaminated, each of which can be classified as a "persistent pollutants site" or PEPSI. The sites in
question are the hazardous landfill sites of Bonfol and Kolliken.
3. CURRENT EXAMPLES OF WORK ON CONTAMINATED SITES
Bonfol Landfill Site
This landfill site is located in the Jura mountains near to the border with France. It represents a threat to
groundwater and surface water on both sides of the border. This landfill site was used by the chemical
industry of the Basle area from 1961 to 1975, and contains about 114,000 tonnes of special chemical
waste, in particular residues of the production of agrochemicals, dyes and pharmaceuticals. After the
landfill site had been closed in 1975, it was sealed over, and a drainage system and waste water treatment
facility were installed. These safety measures cost 15 million Euro, with about 1 million Euro additional
annual maintenance costs.
Based on the presence of persistent organic pollutants and heavy metals, it is predicted that it would take
between 700 and 1,500 years until the site could be left to itself. Thus Bonfol represents a classical
"persistent pollutants site" or PEPSI.
Based on legislation, the Swiss Agency and the Canton of Jura demanded a feasibility study, and it
showed that it would be technically possible to carry out total decontamination of this site (i.e. excavation
and thermal treatment of the wastes), and to deal with the waste in an environmentally-compatible way.
According to initial estimates, the cost of decontamination would be about 100 million Euro. From the
economic point of view, decontamination should be less expensive in the long term than maintaining
safety systems for several centuries. It should also be mentioned that it is only possible to ensure
environmental protection for contaminated sites as long as the safety system remains in working order.
The chemical industry, which was the source of this environmental problem (=polluter), has declared that
it is prepared to take on the decontamination of this site within a reasonable period of time.
Kolliken Landfill Site
Kolliken landfill site is in the densely-populated Swiss central plateau area, and it is one of the largest
contaminated sites of Switzerland. It is the largest known PEPSI in Switzerland, and is located in
hydrogeologically highly-complicated surroundings. This landfill site was used from 1978 to 1985, and
contains about 400,000 tonnes of hazardous waste from all regions of Switzerland.
To protect the valuable groundwater supply, about 100 million Euro have already been invested in safety
measures, and the costs of operating the system are about 3 million Euro per year. Based on the quantity
of persistent pollutants present and the current leaching and degradation processes, it is to be assumed that
for this site too the safety system will need to be maintained for several centuries to a thousand years. The
cost of this will be enormous.
In the meantime it has been decided, on a political and rational basis, that Kolliken landfill site has to be
decontaminated/excavated. An original way was chosen to find the optimum solution for decontaminating
the Kolliken site, namely a competition for ideas was opened. An international jury, including two
representatives of the NATO/CCMS group selected three of the ideas for decontamination that had been
submitted, and these are now to be developed in greater detail.
The information available shows that differentiated excavation and treatment of hazardous material are
possible, at a cost of about 200 to 300 million Euro. These costs are considerably less than estimates
made about fifteen years ago, when (faced with an estimate of 700 Euro for decontamination) safety
measures were taken instead.
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Finally: A Swiss Speciality
Within the domain of contaminated sites there has been increasing discussion about 300m-long shooting
ranges and their logical contamination with spent ammunition over the past two to three years. There are
more than 2,100 such ranges in Switzerland, as there is an obligation for active members of the army to
do shooting practice till the age of 40 (actually more than 340,000 persons are concerned). Until a few
years ago about 9 grams of lead ended up in the ground per shot, and nowadays the figure is about 4
grams. Civil and military shooting put about 500 tonnes of lead underground or into the soil each year. It
is to be envisaged that, in the future, especially with the re-sizing of the army that is on the agenda, some
of the lead-polluted shooting ranges will be decommissioned. Many communities would like to clear
shooting ranges from any remnants of the shooting activities, and to treat the lead-contaminated material
in an environmentally appropriate way. However, at present there are few acceptable, satisfactory
solutions for treatment of such materials. The main options are soil washing and thermal treatment
(recycling of lead), and landfill for material that is only slightly contaminated with lead.
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TURKEY
1. LEGAL AND ADMINISTRATIVE ISSUES
There is a growing recognition of soil and groundwater pollution problems in Turkey since the
enforcement of the regulations of the Control of Solid Wastes (C ofSW) in March 1991 and the Control of
Hazardous Wastes (C ofHW) in August 1995. The main purpose of these regulations is to provide a legal
framework for the management of municipal solid wastes and hazardous wastes throughout the nation.
They basically regulate the collection, transportation, and disposal of wastes that can be harmful to human
health and the environment and provide technical and administrative standards for construction and
operation of disposal sites and related legal and punitive responsibilities.
C ofSWand C ofHW regulations have been recently subjected to some modifications in 1998 and 1999,
respectively. However, these changes are mostly related to some management and technical aspects of
waste collection, reuse, and disposal activities and have no implications related to contaminated sites.
There are a couple of new legislative proposals, which will most likely have same impact on
contaminated sites. The first of these proposals is about local governments and municipalities, and the
second one is about preparation of a regional "Environmental Emergency Response Plans" With the first
legislative proposal, local governments and municipalities will have explicit authority and responsibility
for planning, building and operating the new solid waste disposal sites and rehabilitating the old ones.
Considering that a large number of contaminated sites are in fact the old waste dumpsites, it is expected
that the new legislative proposal will have a positive impact on rehabilitation of contaminated dumpsites.
This new proposal also provides new financial tools for generating funds to fulfill the assumed
responsibilities. The second proposal will make the industrial facilities responsible for preparing their
own emergency response plans and get these plans approved by the local authorities. Thus, this new
legislative proposal will provide a framework for systematic approach for identification, registration and
rehabilitation of contaminated sites on regional basis. Another recent development has been related to a
proposal for amending the Environmental Law. This amendment proposes specific articles related to
issues of soil contamination and clean up of contaminated land.
2. REGISTRATION OF CONTAMINATED SITES
Existing regulations do not explicitly define the concept of contaminated sites. For example, the Control
of Hazardous Wastes defines what a hazardous waste is and provides lists categorizing hazardous wastes
based on their sources, chemical compositions and accepted disposal techniques. Thus, any site
contaminated with or subjected to any of these categorized hazardous wastes can implicitly be defined as
a contaminated site. However, difficulties arise from the lack of information for most of chemicals in
these lists regarding specific maximum concentration levels (MCLs) or remedial action levels.
Currently, identification of any contaminated site is not based on a certain systematic approach. These
sites are mostly identified after some potential environmental problems become obvious and public as a
result of the efforts of local authorities or concerned citizens. However, some current policy developments
by the Ministry of Environment can make the identification of contaminated sites somewhat more
systematic. In this new policy development, the waste management commission, an administrative body
proposed by the Control of Hazardous Wastes regulation, initiates preparation of industrial waste
inventory on a regional basis. Waste inventory is planned to be achieved by requiring all the industry to
fill out annual waste declaration forms revealing the type, amount, composition and the current disposal
practice of their wastes. This way, it is expected that waste generation activities and pollution potentials
of industries can be monitored; regionally effective waste reutilization and recycling programs can be
implemented; and finally regional needs for the type and capacity of waste disposal facilities can be
identified. In response to such efforts, an integrated waste management facility, including a landfill and
incineration unit for disposal of industrial wastes, is becoming operational at full scale in heavily
industrialized Marmara region.
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Another policy development related to identification of contaminated sites is the work progressing
towards the preparation of a "Soil Pollution Control" regulation. It is expected that this regulation will
clarify the existing confusion over the remedial action and cleanup levels and set a guideline for the
selection of appropriate cleanup technologies for various different types of contaminated soil sites.
3. REMEDIAL METHODS IN USE
Currently, there are no reliable and comprehensive case study based statistics or data on remedial methods
and technologies used for cleanup of soil and groundwater in Turkey. Regulatory aspects of acceptable
remedial methods and technologies are provided by the Control of Hazardous Wastes regulation, which
specifies acceptable remedial and/or disposal methods for a given type of contaminant group. In the
Control of Hazardous Wastes regulation, acceptable methods for a large number of contaminant group is
given as physical, chemical and biological treatment without stating the specific name of the method.
However, it clearly states that use of remedial technologies is a must for wastes containing a large group
of contaminants. Currently, there is no official knowledge regarding the widespread past use of particular
technologies for soil and groundwater cleanup in Turkey. However, it is known that land farming and at
few chemical spill site pump-and-treat type technologies are being used for waste treatment and
groundwater cleanup. Most probably these sites will set precedence, in terms of both cost and
performance, for cleanup in other similar sites.
4. RESEARCH AND DEVELOPMENT ACTIVITIES
There is a pressing need for research and development of soil and groundwater cleanup technologies in
Turkey. Some research is being conducted by private sector to develop equipment for field applications of
air sparging and soil vapor extraction systems at gas stations.
5. CONCLUSIONS
There is a growing recognition of soil and groundwater degradation problems in Turkey. Because the
enforcement of hazardous waste regulations is relatively new, some difficulties in the identification of soil
and groundwater contamination sites remain unresolved. Recent regulatory efforts are helpful for
identification of these sites contaminated as a result of past activities. In the near future a considerable
increase in the number of registered contaminated sites is expected.
Turkey presently relies heavily on surface water resources to satisfy water supply demands mainly
because of relative abundance of surface waters resources. Groundwater constitutes a relatively small
component of total available resources (17 percent) but it represents a significant portion (27 percent) of
total water withdrawal. However, due to growing water demand parallel to rapid population and industrial
growth, an increasing demand for food production, urban expansion and accelerated degradation of
surface water quality, protection of clean groundwater resources as well as remediation of contaminated
soil and groundwater sites are becoming environmental issues of high priority. The sustainable
development of groundwater resources requires proper waste treatment for communities and industrial
plants. Groundwater is the major source of drinking water supply and as such needs to be fully protected
and allocated only for high quality uses. Although legislation on groundwater exists, their protection
appears to be neglected at least in certain areas. With the spread of irrigation practices, the pollution threat
to groundwater is also increasing. To date, unsatisfactory efforts have been made to protect groundwater
from the increasing variety of potential pollution sources, such as agricultural chemicals, septic tanks, and
waste dumps. The control of soil and groundwater contamination is essential to Turkey's on-going
reliance on groundwater resources for potable water.
The management of municipal and hazardous wastes in Turkey is inadequate to ensure proper handling
and treatment. Industrial waste, particularly hazardous waste, has grown proportionately with industrial
production. Treatment facilities are minimal and their disposal is usually haphazard. They pose serious
dangers for soil and groundwater and in some cases for public health. The legal gap has to a certain extent
been filled with the regulation of the Control of Hazardous Wastes. Minimization of the generation and
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availability of facilities for proper storage and disposal of hazardous wastes has been embodied in this
Turkish regulation. The policies are being strengthened by the application of such mechanisms of
industrial waste management as the full implementation of environmental impact assessment for new
proposals, the requirement that waste management programs be prepared and implemented by existing
industries, and the encouragement of waste reuse.
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UNITED KINGDOM
This is an update to the Tour de Table papers presented at the Vienna Meeting (February 1998), the
Angers Meeting (May 1999) and Wiesbaden meeting (June 2000) of the Pilot Study.
1. LEGAL AND ADMINISTRATIVE ISSUES
Background to UK policy on land affected by contamination and the role of the "contaminated land
provisions" of Part IIA of the Environmental Protection Act 1990 ("the 1990 Act") have been described
in the previous Tour de Table papers. On 1 April 2000, the 1990 Act came into force in England. The
Secretary of State for the Environment, Transport, and the Regions also made the Contaminated Land
(England) Regulations 2000 under provisions of specific parts of the 1990 Act. Detailed information on
the implementation of the 1990 Act in England can be found in Department of Environment, Transport,
and the Regions (DETR) Circular 02/2000 [1]. The Circular aims to:
• Promulgate guidance to regulatory authorities on how specific parts of the 1990 Act should be
interpreted and the scope of any assessment that they must make. The guidance covers the definition
and identification of contaminated land, the remediation of contaminated land, and the apportionment
of liability and issues of cost recovery. It is an essential part of the new regime.
• Set out the way in which the new regime is expected to work, by providing a summary of
Government policy in this field, a description of the new regime, and a guide to the Regulations.
The responsibility for implementing the 1990 Act in Scotland and Wales rests with the Scottish Executive
and the National Assembly for Wales, respectively. In Scotland, this Act was implemented in July 2000,
whilst in Wales, it was implemented more recently.
After implementation of Part IIA in April 2000, Local Authorities were required to prepare and publish a
written strategy for inspecting their areas as a means of identifying contaminated land. The Environment
Agency has supported this task by providing relevant information that it holds already. To date, 85% of
the Local Authorities in England are reported to be either consulting formally on their inspection strategy
or have published it. It is expected that most of the remaining draft strategies will be published by the end
of September 2001.
After an inspection strategy has been published, the Local Authority is required to inspect its area from
time to time, in line with its written strategy in order to identify any land that meets the statutory
definition of contaminated land. The Environment Agency is currently aware of 19 contaminated land
determinations in England of which 4 are special sites (i.e. sites where it is likely that the Agency will be
the regulator). In addition, the Agency is currently involved in inspecting a further 19 potential special
sites.
2. TECHNOLOGY DEVELOPMENT PROGRAMMES
Technology development programmes that support the development of innovative methods for dealing
with land remediation are summarised below in table 1.
3. REMEDIAL METHODS IN USE
At the last Pilot Study meeting in Wiesbaden, Germany, it was reported that the Environment Agency had
commissioned a survey of remedial techniques that had been used in England and Wales for remediation
during the period January 1996 to December 1999. This survey has now been published [3].
254
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
4. RESEARCH AND DEVELOPMENT ACTIVITIES
Table 2 lists a number of completed, on-going, and proposed R&D projects related to the remediation of
land affected by contamination funded by the environmental agencies and the research councils.
Table 2: UK R&D Projects on remediation of land affected by contamination (not intended to be
inclusive)
PROJECT
STATUS
RESEARCH COUNCILS (BBSRC - Biotechnology and Biological Sciences Research Council;
EPSRC - Engineering and Physical Sciences Research Centre; NERC - Natural Environment
Research Council)
Bioremediation: a studv of stakeholders attitudes
Dual anaerobic svstem for bioremediation of
metal/organic wastes
Bioremediation and microbial population
dynamics
Cvanide biodegradation: a model for the
development of molecular probes for
optimisation of bioremediation
Phvtoremediation: an integrated biological
approach to decontamination of polluted soils
An integrated, multifunctional svstem for
bioremediation of waters containing xenobiotics
and toxic metals
Processes controlling the natural attenuation of
fuel hydrocarbons and MTBE in chalk
Non-invasive characterisation of NAPL-
contaminated land bv spectral induced
polarisation (SIP) tomographv
New sensor svstem for monitoring solvent
migration from contaminated sites
Studies into metal speciation and bioavailabilitv
to assist risk assessment and remediation of
brownfield sites in urban areas
In situ sensing of the effect of remediation on
available metal fluxes in contaminated land
Bacterial biosensors to screen in situ
bioavailabilitv, toxicitv. and biodegradation
potential of xenobiotic pollutants in soil
BBSRC
Dr Kate Millar, University of Nottingham
BBSRC
Professor Macaskie, University of Birmingham
BBSRC
Dr Head, University of Newcastle
BBSRC
Professor Knowles, University of Oxford
BBSRC
Professor Thompson, Centre of Ecology and
Hydrology (CEH)
BBSRC
Professor Livingston, Imperial College of
Science, Technology, and Medicine
EPSRC
Professor David Lerner, University of Sheffield
EPSRC /NERC
Dr Ogilvy, British Geological Survey
EPSRC/NERC
Professor Williams, University of Central
London
EPSRC/NERC
Professor Thornton, Imperial College of Science,
Technology, and Medicine
EPSRC/NERC
Professor Davison, University of Lancaster
NERC
Professor Killham, University of Aberdeen
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January 2002
ENVIRONMENT AGENCY
Environment Agency reports can be obtained from the R&D Dissemination Centre, WRC pic, Frankland Road, Blagrove,
Swindon, Wiltshire, SN5 8YF, United Kingdom.
Cost-Benefit Analysis for Remediation of
Land Contamination
To provide advice on assessing the costs
and benefits of different remedial
techniques when evaluating and
selecting the most appropriate
remedial strategy for a site.
Published in December 1999.
R&D Technical Report P316.
Costs and Benefits Associated with
Remediation of Contaminated
Groundwater: A Review of the
Issues.
To review and provide guidance on the
issues associated with the costs and
benefits of remediating
contaminated groundwater.
Published in December 1999.
R&D Technical Report P278 (Review)
R&D Technical Report P279 (Guidance)
Guidance on the Use of Digital
Environmental Data
To provide guidance on the nature and use
of digital environmental data in GIS
for improved land quality data
management.
Published in March 2000.
R&D Technical Report NC/06/32.
Prepared in collaboration with the British
Geological Survey.
Guidance for the Safe Development of
Housing on Land Affected by
Contamination
To provide good practice advice in respect of
remediation of land contamination and its return
to beneficial use for the purposes of housing.
Published in June 2000.
R&D Publication 66.
Prepared in collaboration with the National
House Building Council.
Risks of Contaminated Land to Buildings,
Building Materials and Services. A
Literature Review.
To provide a literature review of
information on the assessment and
management of risks from land
contamination to buildings.
Published in 2000.
R&D Technical Report P331.
Survey of Remedial Techniques for
Contamination in England and Wales.
Land
Published in 2000.
R&D Technical report P301
Assessing the Wider Environmental Value
of Remediating Land
Contamination: A Review.
To review the international approach to assessing
the wider environmental effect of different
remedial strategies as part of a selection process
Published in 2000.
R&D Technical Report P238.
Guidance on the Assessment and
Published in 2000.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Monitoring of Natural Attenuation
of Contaminants in Groundwater
To provide guidance on the assessment and
monitoring of natural attenuation of
contaminants in groundwater.
R&D Publication 95.
Development of Appropriate Soil
Sampling Strategies for Land
Contamination
To develop guidance to assist the design of a site
investigation strategy in accordance with the site
conceptual model and the data requirements for
risk estimation and evaluation.
Published in 2000.
R&D Publication
Technical guidance for dealing with
Special Sites
Published in 2001
R&D Publication
Bioremediation of contaminated soils with
biomass fuel crops
A review of remedial options for DNAPL
source treatment
To review the international experience of
source treatment of DNAPL
contaminants to evaluate
information transfer and
prioritisation of research into the
UK.
Project completed (available shortly)
R&D Technical Report P
Site for Innovative Research on Natural
Attenuation (SIREN)
To study the application of natural
attenuation at a specific site and to
encourage and disseminate the
outcome of projects to benefit our
wider understanding of the
applicability and implementation of
natural attenuation.
On-going project.
R&D Publication
Guidance on monitoring and verification of
remedial treatments for land
contamination
To provide guidance on the monitoring
requirements and the verification of
different remedial techniques to
enable performance to be established
during remediation and after works
have been completed.
On-going project.
Case Study CBA
Ongoing
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January 2002
Development of Remedial Treatment
Action Data Sheets
Ongoing
First 5 data sheets on biological treatments will
be available through the Agency's web site:
www .cnvironmcnt-ascncv. eov .uk
Technical Training on inspection and
remediation of contaminated land
To produce a training package for those
undertaking site inspections and/or
remediation of contaminated soils
and groundwater.
Ongoing
Landfill remediation technologies -
potential use in the context of the
landfill directive
New start in 2001/02
Guidance on Permeable Reactive Barriers
New start in 2001/02
Field study of the performance of cover
systems for land remediation
To provide baseline field evidence for the
long term performance of cover
systems to improve regulatory
confidence in their appropriate
application.
New start in 2001/02
SCOTLAND AND NORTHERN IRELAND FORUM FOR ENVIRONMENTAL RESEARCH
(SNIFFER)
Reports are available from the Foundation for Water Research, Allen House, The Listens, Listen
Road, Marlow, Bucks SL7 1FD, UK.
Protocol and Guidance Manual for
Assessing Potential Adverse Effects
of Substances on Designated
Terrestrial Ecosystems
To provide guidance on deriving site-
specific assessment criteria for
unacceptable risk to ecosystems.
Published in December 1999.
Framework for Deriving Numeric Targets
to Minimise the Adverse Human
Health Effects of Long-term
Exposure to Contaminants in Soil
To provide guidance on deriving site-
specific assessment criteria for
unacceptable chronic risk to human
health.
Published in January 2000.
Report No. SR99(02)F
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January 2002
CONSTRUCTION INDUSTRY RESEARCH AND INFORMATION ASSOCIATION (CIRIA)
Remedial Engineering for Closed Landfill
Sites.
To provide guidance on the range of
options for restoring closed landfill
sites to a range of different end uses.
Funders Report CP/61.
For information contact CIRIA at 6 Storey's
Gate, Westminster, London, SW1P 3AU.
Remedial Processes for Contaminated
Land: Principles and Practice.
To provide good practice guidance on the
selection and implementation of
certain categories of process-based
technologies.
Funders Report ROOO.
For information contact CIRIA at 6 Storey's
Gate, Westminster, London, SW1P 3AU.
Contaminated Land: Financial Control of
Risk.
To provide guidance to those involved in
the redevelopment of brownfield
sites on how to manage and limit the
Financial risk posed.
Funders Report.
For information contact CIRIA at 6 Storey's
Gate, Westminster, London, SW1P 3AU.
Contaminated land: in-house training
material
To produce training package aimed at the
construction industry to raise
awareness of the application of a
range of remedial techniques and
approaches to risk assessment.
On-going project.
Biological treatment for contaminated
land: case studies.
To develop good practice guidance when
using biological treatments for
remediating land contaminated in
the UK.
On-going project.
Client's guide for building on brownfield
sites.
To provide guidance to the construction
industry on adopting a sustainable
approach to building on
contaminated sites.
On-going project.
Safe working practice on contaminated
land - training material.
To provide training for those responsible
for site safety and construction staff
working on redevelopment of land
affected by contamination.
New start in 2000/2001.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
5. REFERENCES
1. Department of the Environment, Transport, and the Regions (2000) Environmental Protection Act
1990: Part IIA. Contaminated Land. Circular 02/2000. Available from the Stationery Office, PO Box
29, Norwich, NR3 1GN, United Kingdom: ISBN 0-11-753544-3 (Available on the web at
ww_w_.__ciiyironTO
2. Urban Task Force (1999) Towards an Urban Renaissance. Available from E & FN Spon Customer
Service, International Thomson Publishing Services Ltd, Cheriton House, North Way, Andover,
Hampshire, SP10 5BE, United Kingdom: ISBN 1-85112-165-X (An execu-tive summary is available
on the web at
3 . Environment Agency (2000)
4. DETR publication on research - check reference
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
UNITED STATES OF AMERICA
1. LEGAL AND ADMINISTRATIVE ISSUES
Three different federal programs provide the authority to respond to releases of hazardous substances that
endanger public health or the environment: (1) In response to a growing concern about contaminated
sites, Congress passed the Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA) in 1980. Commonly known as Superfund, the program under this law is the central focus of
federal efforts to clean up releases of hazardous substances at abandoned or uncontrolled hazardous waste
sites. The program is funded, in part, by a trust fund based on taxes on the manufacture of petroleum and
other basic organic and inorganic chemicals. (2) The second program is directed at corrective action at
currently operating hazardous waste management facilities. This program is authorized by the Resource
Conservation and Recovery Act of 1980 (RCRA) and its subsequent amendments. RCRA corrective
action sites tend to have the same general types of waste as Superfund sites. Environmental problems are
generally less severe than at Superfund sites although numerous RCRA facilities have corrective action
problems that could equal or exceed those of many Superfund sites. (3) The third program, also
authorized by RCRA, is a comprehensive regulatory program for underground storage tanks (USTs)
storing petroleum or certain hazardous substances. This law requires owners and operators of new tanks
and tanks already in the ground to prevent, detect, and cleanup releases. As of March 2001, over 417,000
confirmed releases had been reported, over 375,000 cleanups initiated, and over 258,000 cleanups
completed.
A. Implementation of Hazardous Waste Cleanup Legislation
Each program has a formal process for identifying, characterizing, and remediating contaminated sites.
These processes generally involve joint implementation with state agencies and the involvement of
various groups, such as local government agencies, local residents, businesses, and environmental public
interest groups. Superfund is administered by EPA and the states under the authority of the CERCLA.
Although the terminology may differ from one program to another, each follows a process more-or-less
similar to this one. Thus, in addition to comprising a defined single program, activities in the Superfund
program substantially influence the implementation of the other remediation programs.
RCRA assigns the responsibility for corrective action to facility owners and operators and authorizes EPA
to oversee corrective action. Unlike Superfund, RCRA responsibility is delegated to states. As of May
2000, EPA has authorized 34 states and territories to implement the RCRA Corrective Action program.
The UST program is primarily implemented by states, whose UST requirements may be more stringent
than federal regulations. The federal UST regulations require tank owners to monitor the status of their
facilities and immediately report leaks or spills to the implementing agency. The federal regulations
require UST owners and operators to respond to a release by: reporting the release; removing its source;
mitigating fire and safety hazards; investigating the extent of contamination; and cleaning up soil and
ground water as needed to protect human health and the environment.
B. Anticipated Policy Developments
The ongoing cleanup programs are focusing on the productive reuse of properties and "Brownfields"
initiatives have also become prominent at federal and state levels. Brownfields are abandoned, idled, or
under-used industrial and commercial facilities where expansion or redevelopment is complicated by real
or perceived environmental contamination. Estimates range from 450,000 to 600,000 such sites in the
United States. A growing realization of their great potential has heightened interest in their cleanup and
redevelopment. EPA has funded nearly 400 Brownfield Assessment Pilots and 28 Showcase
Communities projects to stimulate work in this area. The Assessment Pilots are funded at up to $200,000
to local communities to chart their own course toward revitalization. The pilots are seen as catalysts for
change in local communities, and often spur community involvement in local land use decision-making.
EPA has provided more than 100 Brownfields Cleanup Revolving Loan Fund grants for up to $1,000,000.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
In addition, EPA has provided brownfields job training and development grants to 46 communities to
provide environmental training for residents near brownfield sites. These programs have generated more
than 15,000 jobs and returned about $2.50 of private investment for every public dollar spent.
EPA's Brownfields program currently lacks independent legislation and operates under existing
Superfund and RCRA laws. Legislation is needed to better define program authorities and appropriate
levels of funding. Thirty Brownfields bills were introduced in the last Congress covering authorization,
funding, tax incentives, liability, State/Federal roles and other Federal agency programs. Although none
of these bills was enacted, there is optimism that legislation will emerge from this Congressional session.
A bill has already passed the Senate with an overwhelming majority and received support from the
Administration.
The reuse of contaminated sites is a priority in the Superfund program. Areas that were once dangerous
are now being cleaned up and turned into office parks, playing fields, industrial centers, shopping centers,
residential areas, tourist centers, and wetlands. Reuse has been incorporated as a cleanup objective at 200
Superfund sites and 15,000 jobs can now be identified as the direct result of these efforts.
EPA has also announced a grant initiative to clean up and reuse sites with abandoned underground
petroleum tanks. The program places special emphasis on environmental problems caused by the fuel
additive MTBE (methyl tertiary butyl ether). The program entails competitively awarded grants of
$100,000 to states for community pilot projects to plan cleanups, stop contamination of ground water,
protect public health, and allow for future economic development of the sites. Ten grants were included in
the original announcement and EPA recently stated its intention to expand the program with up to 40
additional grants.
2. IDENTIFICATION OF CONTAMINATED SITES
Almost half a million sites with potential contamination have been reported to state or federal authorities,
based on a 1996 assessment. Regulatory authorities have identified most of the contaminated sites.
Nevertheless, new ones continue to be reported each year, but at a declining rate. It is estimated that the
cost of remediating sites from the 1996 assessment will be about $187 billion (in 1996 dollars), and that it
will take at least several decades to completely cleanup all the identified sites.
3. REMEDIATION TECHNOLOGIES
A. Historical Remedial Technology Use in the U.S.
The most comprehensive information on technology use at waste sites is available for the Superfund
program. Although they represent a small percentage of all contaminated sites, technology selection is
representative of other hazardous waste sites. After reauthorization in 1986, most remedies involved some
treatment of contaminated soil, as opposed to containment or off-site disposal.
When treatment is selected, there is a trend toward greater use of in situ processes. In recent years, in situ
technologies have comprised approximately one half of the source control technologies selected in the
Superfund program. Because there is no excavation, these technologies pose a reduced risk from exposure
and can result in considerable cost savings, especially for large sites.
The most frequently selected treatment technologies for source control have been soil vapor extraction
(SVE), solidification/stabilization and incineration. These technologies are followed by bioremediation
and thermal desorption. Three-quarters of these remedial projects address only organics, while the
remainder address either metals alone or in combination with organics.
Ground water is contaminated at 70 percent of Superfund sites. Despite recent advances, 71 percent of
remedies selected for controlling groundwater plumes rely solely on conventional pump-and-treat
technologies; 2 percent use solely in situ treatment; 12% solely monitored natural attenuation (MNA); and
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the remaining 15% employ various combinations of these remedies. The most frequently selected in situ
treatment processes include air sparging, bioremediation, dual-phase extraction and permeable reactive
barriers (PRBs). Early applications of PRBs involved zero-valent iron to treat chlorinated solvents.
Research and demonstration is focusing on materials to treat other contaminants such as chromium,
polynuclear aromatic hydrocarbons (PAHs), and radionuclides. Control of groundwater plumes alone may
frequently not meet desired cleanup goals because of the presence of NAPLs (non-aqueous phase liquids).
B. Trends and Anticipated Remedial Technology Use
As part of the quest for more efficient and cost-effective site remediation technologies, a few subject
areas are particularly worthy of note at this time. These represent some of the focus areas in greatest need
of new technology.
The presence of DNAPLs (dense non-aqueous phase liquids) is probably the single most important factor
affecting our ability to attain clean-up levels in ground water. Studies have shown that pumping and
treating will often not achieve cleanup goals in a reasonable time frame. In addition, the total costs to
complete a groundwater cleanup are frequently not recognized either because of a 30 year planning
horizon or as a result of discounting when considering the time value of money. Although relatively little
data are available for projects employing DNAPL treatment technologies, very important results were
reported using steam extraction at a wood treating site in Visalia, California. In addition to steam
extraction, there is interest in the potential for using other in situ processes such as six-phase thermal
heating, oxidation, surfactant-cosolvent flushing and even biological processes. Oxidation is frequently
used by a limited number of vendors at full-scale, primarily for petroleum contamination. Otherwise, with
a few notable exceptions, there is relatively little field demonstration activity for either surfactant and co-
solvent flushing or thermal vaporization and mobilization processes. This is an important shortcoming
because DNAPLs are believed to be present at many sites. Future work is necessary to evaluate the
capability of these treatment processes and to determine the result of partial source term removal on the
resulting groundwater quality.
The trend toward greater use of in situ treatment processes has contributed to a need for improved site
characterization technologies. In the past, site characterization primarily involved production of
contaminant concentration profiles for the purpose of risk assessment. Now, however, with greater
interest in situ processes, it is necessary to better understand subsurface conditions to assess the feasibility
of in situ remediation options; to design these processes; to operate the in situ technologies with optimum
feedback and process control; and to know when treatment may be stopped because acceptable residual
levels have been achieved. There is a particular need to improve our ability to reliably locate DNAPL
through direct or indirect methods.
There is a growing awareness that belter site data can improve decision-making at hazardous waste sites.
These improvements can be achieved through use of an integrated approach that combines systematic
planning, dynamic work plans, and real-time measurement technologies to plan and implement data
collection. By carefully identifying and managing the potential causes of error (i.e., the sources of
uncertainty) the capabilities of new field-based characterization and monitoring technologies can be
realized. This has particular significance for Brownfields and voluntary cleanup programs where time and
cost are a primary concern for the redevelopment and reuse of properties.
There is a strong interest in bringing more efficiency to remediation efforts through use of optimization
techniques. The EPA, Corps of Engineers, Air Force, and other federal agencies have been working to
identify and evaluate tools for optimizing pump-and-treat systems. These agencies are also developing
programs to identify opportunities for realizing cost savings while maintaining acceptable levels of risk.
Tools including mathematical optimization algorithms, geostatistical models, and comprehensive system
audits have shown promising results for significantly improving performance and reducing operation and
maintenance costs. EPA has developed a procedure for screening sites to determine if more detailed
application of optimization techniques is warranted. The agency recently identified two sites in each of its
10 regional offices to apply the optimization techniques which have been formalized in a Remedial Site
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
Evaluation protocol. With 16 site evaluations completed, significant potential to improve effectiveness
was identified at 12 sites along with potential cost savings of $3.8 million per year.
Monitored natural attenuation continues to receive attention as an alternative to pump-and-treat
systems and as a final polishing step for various in situ remedies. Although natural attenuation offers
significant advantages, there are some important uncertainties about attenuation rates and endpoints. EPA
has issued a final guideline on this process that emphasizes the need for source control and rigorous long-
term monitoring. Successful monitoring programs need to be demonstrated, perhaps using new sensor
technology.
MTBE is a contaminant which is being found with alarming frequency in groundwater supplies. MTBE
is much more soluble and resistant to natural biodegradation than other gasoline constituents, such as
benzene, toluene, ethylbenzene, and xylenes (BTEX). MTBE plumes are usually larger, leading to more
drinking water wells being affected and more difficult and expensive cleanups. This constituent is more
expensive to treat at both the wellhead and in situ because it is harder to strip and biodegrade. EPA has
prepared 38 case studies of drinking water and remediation sites that treat soil and ground water
contaminated with MTBE. These studies are accessible through a web site
(http://www.epa.gov/swerustl/mtbe/mtberem.htm) which has been established to help site managers
assess technologies.
4. RESEARCH, DEVELOPMENT, AND DEMONSTRATION
Federal agencies currently are coordinating several technology development and commercialization
programs. The Department of Energy (DOE) continues to lead in funding for the development new
environmental cleanup technologies. These technologies are focused on improving the clean up at DOE
sites and include processes such as bioremediation, electrokinetics, and biosorption of uranium.
The Department of Defense (DOD) has several technology research and development programs targeted
at helping commercialize remediation technologies. The Environmental Security Technology
Certification Program (ESTCP) is designed to promote the demonstration and validation of the most
promising innovative technologies that target DOD's most urgent environmental needs. It is funded at $15
million per year. The Strategic Environmental Research and Development Program (SERDP) is a joint
program with DOD, DOE, and EPA—funded at $69.4 million per year—which devotes 17 percent of its
resources to remediation and site characterization technologies. DOD's high priority cleanup technology
needs include: unexploded ordinance (new sensors, signal processing and risk assessment); compliance
(source determination, fate and transport, and aircraft noise); cleanup (remediation technologies for
explosives in soil and ground water); pollution prevention (green munitions and green energetics); and
conservation (range sustainability issues).
EPA's program for the evaluation of new cleanup technologies is the Superfund Innovative Technology
Evaluation or SITE program. The SITE Demonstration Program encourages the development of
innovative treatment technologies and new technologies for monitoring and measuring. In the
Demonstration Program, technologies are field-tested on hazardous waste materials. Engineering and cost
data are gathered so that potential users can assess applicability to a particular site. A similar program
which seeks to provide independent third-party verification of promising environmental technologies, is
the Environmental Technology Verification (ETV) Program. The program operates 12 pilots covering a
broad range of environmental areas. EPA partners with various public and private organizations in the
different pilot areas to establish means for conducting the performance testing. Information for these
programs is available from their web sites at www.cpa.gov/ORD/SITE and www.epa.gov/ctv. The
publication source for EPA documents is www.epa.gov/ncepihom.
Cooperative public-private initiatives are particularly important because they focus on processes that
private "problem holders" view as most promising for the future. The involvement of technology users
helps to assure that the processes selected for development reflect actual needs and have a high potential
for future application. Led by EPA, the Remediation Technologies Development Forum (RTDF) is a
265
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
consortium of partners from industry, government, and academia, who share the common goal of
developing more effective, less costly hazardous waste characterization and treatment technologies.
RTDF achieves this goal by identifying high priority needs for remediation technology development.
EPA helps to develop partnerships between federal agencies (such as DOD and DOE) and private site
owners (responsible parties, owners/operators) for the joint evaluation of remediation technologies. The
program is organized around six action teams, which are co-chaired by a government and industry
representative. Information is available from the RTDF home page at www.frtr.org.
Agencies of the Federal Remediation Technologies Roundtable (including DOE, DOD and EPA) are
involved in an ongoing effort to collect and distribute cleanup case studies of cost and performance data.
The studies aid the selection and use of more cost-effective remedies by documenting experience from
actual field applications. Recently, the Roundtable announced publication of 56 new studies of full-scale
remediation and demonstration projects. This brings the total to 274 case studies which are now available
on the Roundtable's web site (http://www.frtr.gov) with a user-friendly search capability. The federal
agencies coordinated their individual documentation efforts by using standardized procedures to capture
their cleanup experience. These procedures are contained in an Interagency Guide which provides a
recommended format for documenting cost, performance, and matrix and operational parameters for 29
specific technologies. By adopting a common reporting format, the federal agencies hope to increase the
utility of data by making it easier to compare. Cost data, for example, are often reported without
documentation of the specific elements that are included.
Cost data, primarily from the Roundtable, were recently used to conduct a cost assessment for six
remediation technologies. (Complete report entitled Remediation Technology Cost Compendium — Year
2000 is available at www.cluin.org.) For four processes (bioventing, soil vapor extraction, thermal
desorption and groundwater pump and treat) curves were developed showing the relationship between the
unit cost for remediation and the quantity of material treated. Figure 1 shows the relationship of unit cost
to the volume of soil treated for bioventing. Economies of scale are evident where unit costs decrease as
larger quantities are treated. These data come from a comprehensive study conducted by the Air Force.
The higher unit costs which occur for lower quantities are attributed to the effect of fixed costs (the
baseline costs of constructing and installing the technology).
5. CONCLUSIONS
Legislative, regulatory and programmatic changes may alter the nature and sequence of cleanup work at
Superfund, RCRA, DOD, and DOE sites. Other than focused Brownfields legislation, no major
reauthorization of either the Superfund or RCRA programs is anticipated this year.
New technologies offer the potential to be more cost-effective than conventional approaches. In situ
technologies, in particular, are in large demand because they are usually less expensive and more
acceptable than above-ground options. Federal agencies and the private sector are actively involved in
developing and demonstrating new treatment and site characterization technologies. Various forms of
partnering are instrumental in increasing the efficiency and effectiveness of these efforts.
266
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Figure 1: Unit Cost/ Volume Curve Bioventing
267
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
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268
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
COUNTRY REPRESENTATIVES
Directors
Stephen C. James (Co-Director)
National Risk Management Research Laboratory
U.S. Environmental Protection Agency
26 Martin Luther King Dr.
Cincinnati, OH 45268
United States
tel: 513-569-7877
fax:513-569-7680
e-mail:
Walter W. Kovalick, Jr. (Co-Director)
Technology Innovation Office
U.S. Environmental Protection Agency
1200 Pennsylvania Ave, NW (5102G)
Washington, DC 20460
United States
tel: 703-603-9910
fax: 703-603-9135
e-mail: k
Co-Pilot Directors
Volker Franzius
Umweltbunde samt
Bismarckplatz 1
D-14193 Berlin
Germany
tel: 49/30-8903-2496
fax: 49/30-8903-2285 or-2103
e-mail: volker.franzius@uba.de
Anahit Aleksandryan
Ministry of Nature Protection
35, Moskovyan Strasse
375002 Yerevan
Armenia
tel: +37/42-538-838
fax: +3 7/42- 15 1-938
e-mail: gogafilamjnc^^
H. Johan van Veen
TNO/MEP
P.O. Box 342
7800 AN Apeldoorn
The Netherlands
tel: 31/555-493922
fax: 31/555-493921
e-mail: h.j.vanveen@mep.tno.nl
Country Representatives
Harald Kasamas
Bundesministerium fur Landwirtschaft und
Forstwirtschaft, Umwelt und
Wasserwirtschaft (BMLFUW)
Abteilung VI/3 - Abfallwirtschaft und
Altlastenmanagement
Stubenbastei 5
A-1010 Wien, Osterreich
Austria
tel: +43-1-5 1522-3449
email: haralcifa|samj^^
Jacqueline Miller
Brussels University
Avenue Jeanne 44
1050 Brussels
Belgium
tel: 32/2-650-3 183
fax: 32/2-650-3 189
e-mail: j millcr@ulb . ac . be
Lisa Keller
Environmental Technology Advancement
Directorate
Environment Canda - EPS
12th Floor, Place Vincent Massey
Hull, Quebec K1A OH3
Canada
tel: 819/953-9370
fax: 819/953-0509
e-mail:
Jan Krohovsky
Ministry of the Environment
Department of Environmental Damages
Vrsovicka 65
100 10 Prague
Czech Republic
tel: +420/2-6712-2729
fax: +420/2-673 1-03 05
e-mail: tajiOTfi7lgny.cz
269
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Hana Kroova
Czech Ministry of the Environment
Vrsovicka 65
100 10 Prague 10
Czech Republic
tel: 420/2-6712-1111
fax: 420/2-6731-0305
Kim Dahlstr* m
Danish Environmental Protection Agency
Strandgade 29
DK-1401 Copenhagen K
Denmark
tel: +45/3266-0388
fax: 45/3296-1656
e-mail: kda@rnst.dk
Ari Seppanen
Ministry of Environment
P.O. Box 399
00121 Helsinki
Finland
tel: +358/9-199-197-15
fax: +358/9-199-196-30
e-mail: ari.seppanen@vyh.fi
Christian Militon
Environmental Impact and Contaminated Sites
Department
French Agency for Environment and Energy
Management (ADEME)
2, square La Fayette
BP406
49004 ANGERS cedex 01
France
tel:(33)-2-41-91-40-51
fax: (33)-2-41-91-40-03
e-mail: dmstian.rniliton{g}adcmcIfr
Andreas Bieber
Federal Ministry for the Environment
Ahrstrasse 20
53175 Bonn
Germany
tel: 49/228-305-305-3431
fax: 49/228-305-305-2396
e-mail: MsbCT,andreas@bniu,de.
Anthimos Xenidis
National Technical University Athens
52 Themidos Street
15124 Athens
Greece
tel: 30/1-772-2043
fax: 30/1-772-2168
e-mail: axen@cen.tral .ntua.gr
Pal Varga
National Authority for the Environment
F6 u.44
H-10 11 Budapest
Hungary
tel: 36/1-346-83 10
fax: 36/1-3 15-08 12
e-mail:
Matthew Crowe
Environmental Management and Planning
Division
Environmental Protection Agency
P.O. Box 3000
Johnstown Castle Estate
County Wexford
Ireland
tel: +353 53 60600
fax: +353 53 60699
e-mail:
Francesca Quercia
ANPA - Agenzia Nazionale per la Protezione
deH'Ambiente
Via V. Brancati 48
I -00 144 Rome
Italy
tel. 39/6-5007-2510
fax 3 9/6-5 007-25 31
e-mail: gugiaa@an|MJt
Masaaki Hosomi
Tokyo University of Agriculture and
Technology
2-24-16 Nakamachi
Tokyo 184-8588
Japan
tel: +8 1-42-388-7070
fax:+81-42-381-4201
e-mail: hosomi@_gcjuat.acjrj
Oskars Kupcis
Ministry of Environmental Protection and
Regional Development
Peldu Str. 25
LV-1494 Riga
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Latvia
tel: +371/7-026-412
fax: +37 1/7-228-751
e-mail: oskars@varam .gov.lv
Kestutis Kadunas
Hydrogeological Division, Geological Survey
Konarskio 35
2600 Vilnius
Lithuania
tel 370/2-236-272
fax: 370/2-336-156
e-mail: teMutisJiadajnas^^
Bj0rn Bj0rnstad
Norwegian Pollution Control Authority
P.O. Box 8100 Dep
N-0032 Oslo
Norway
tel: 47/22-257-3664
fax: 47/22-267-6706
e-mail: bjom.bjomstad@sft.tclcmax.no
Marco Estrela
Institute de Soldadura e Qualidade
Centra de Tecnologias Ambientais
Tagus Park
EC Oeiras - 2781-951 Oeiras
Portugal
tel: +35 1/21-422 90 05
fax: +35 1/21-422 8 104
e-mail:
loan Gherhes
EPA Baia Mare
I/A Iza Street
4800 Baia Mare
Romania
tel: 40/4-62-276-304
fax: 40/4-62-275-222
e-mail: epa@multinet.ro
Branko Druzina
Institute of Public Health
Trubarjeva 2-Post Box 260
6 100 Ljubljana
Slovenia
tel: 386/61-3 13-276
fax: 386/61-323-955
e-mail: branko.druzinaffigov.si
Pablo Higueras
University of Castilla-La Mancha
Almaden School of Mines
Plaza Manuel Meca, 1
13400 Almaden (Ciudad Real)
Spain
tel: +34 926441898 (work in Puertollano)
fax:+34 926421984
e-mail: phigueras@igem-al.uclm.es
Ingrid Hasselsten
Swedish Environmental Protection Agency
Blekholmsterrassen 36
S-106 48 Stockholm
Sweden
tel: 46/8-698-1179
fax: 46/8-698-1222
e-mail: inhj@gjwironj>e
Bernard Hammer
BUWAL
3003 Bern
Switzerland
tel: 41/31-322-9307
fax: 41/31-382-1456
e-mail: bernard.hammer@buwal.admin.ch
Kahraman Unlii
Depratment of Environmental Engineering
Middle East Technical University
Inonii Bulvari
06531 Ankara
Turkey
tel: 90-312-210-1000
fax:90-312-210-1260
e-mail: kiinlu@mctu.cdu.tr
Theresa Kearney
Environment Agency
National Groundwater and Contaminated Land
Centre
Olton Court 10 Warwick Road, Olton
Solihul, West Midlands B92 7HX
United Kingdom
tel:+44/121—711-2324
fax:+44/121—711-5925
e-mail: ftejiija^teajTie^^
aecncv.sov.uk
271
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
ATTENDEES LIST
Michael Altenbockum
Altenbockum & Partner, Geologen
Lathringersrtasse 61
52070 Aachen
Germany
tel: +49/241-4017-462
fax: +49/241-4017-465
e-mail: info@altenbockum.de
Anahit Aleksandryan (c.r.)
Ministry of Nature Protection
35 Moskovyan str.
375002 Yerevan
Republic of Armenia
tel: 37/42-538-838
fax: 37/42151-938
e-mail: goga@arminico.com
Paul M. Beam
U.S. Department of Energy
19901 Germantown Road
Germantown, MD 20874-1290
United States
tel: 301-903-8133
fax: 301-903-3877
e-mail: |)aui.bcam_@cm.dgc.gov
Andreas Bieber (c.r.)
Federal Ministry for the Environment
Ahrstrasse 20
53175 Bonn
Germany
tel: 49/228-305-305-3431
fax: 49/228-305-305-2396
e-mail: b_icbcr.andrcas(^bma.dc
Harald Burmeier
Fachhochschule North-East Lower Saxony
Department of Civil Engineering
Herbert Meyer Strasse 7
29556 Suderburg
Germany
tel: 49/5103-2000
fax: 49/5103-7863
e-mail: h.burmeier@it-online.de
Jiirgen Busing
European Commission
Rue de la Loi/Wetsraat 200
B-1049 Brussels
Belgium
tel: +32/2-295-5625
fax: +32/2-296-3024
e-mail: Jiiergen.Buesing@cec.eu.int
Adrian Butler
Imperial College
London SW7 2BU
United Kingdom
tel: +44/207-594-6122
fax: +44/207-594-6124
e-mail: a.bytler@ic.ac.uk
Nadim Copty
Bogazici University
Institute of Environmental Sciences
80815Bebek
Turkey
tel: +90/212-358-1500
fax: +90/212-257-5033
e-mail: ncopty@boun.edu.tr
Maria da Conceicao Cunha
ISEC
Quinta da Nora
3030 Coimbra
Portugal
tel:+351239722694
e-mail: m«^inha@isec.j)t
Pierre Dengis
ISSeP
Rue Olu Leroi 200
B-4000 Liege
Belgium
tel:+32/4—229-8311
fax: +32/4-252-4665
e-mail: p.dengis@inep.be
Ludo Diels
VITO (Flemish Institute for Technological
Research)
Boeretang 200
2400 - Mol
Belgium
tel:32/14-33.51.OO
fax: 32/14-58.05.23
e-mail: leen.bastlaeiisffljyito.be
272
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Victor Dries
OVAM
Kan. De Deckerstraat 22-26
B-2800 Mechelen
Belgium
tel: +32/015-284-490
fax: +32/015-284-407
e-mail:
Branko Druzina (c.r.)
Institute of Public Health
Trubarjeva 2-Post Box 260
6 100 Ljubljana
Slovenia
tel: 386/1-432-3245
fax: 386/1-232-3955
e-mail: branko.druzina@ivz-rs.si
Vitor Ap. Martins dos Santos
German Research Centre for Biotechnology
Mascheroder Weg 1
D-3 8 124 Braunschweig
Germany
tel: +49/5 3 1-6 18 1-422
fax: +49/53 1-61 8 1-4 11
e-mail: vdsigigbf.de
Thomas Early
Oak Ridge National Laboratory
Bethel Valley Road 1
P.O. Box 2008
Oak Ridge, TN 37831-6038
United States
tel: 865-574-7726
fax: 865-576-8646
Marco Antonio Medina Estrela
ISQ - Institute de Solidadura E Qualidade
EN 249 - Km 3, Cabanas - Leiao (Tagus Park)
Apartado 119
278 lOeiras- Codex
Portugal
tel: +35 1/1-422-8 100
fax: +35 1/1-422-8129
e-mail: mag_strc|a@isq_.pt
Michel Foret
Minister for the Environment and Town &
Country Panning
Government Wallon
Place des Celestines 1
B-5000 Namur
Belgium
tel:+32/081-234-111
fax:+32/081-234-122
e-mail: foret@gov.wallonie.be
Volker Franzius
Umweltbunde samt
Bismarckplatz 1
D-14193 Berlin
Germany
tel: 49/30-8903-2496
fax: 49/30-8903-2285 or-2103
e-mail: volkcr.£ranzius@uba.dc
Arun Gavaskar
Battelle
505 King Avenue
Columbus, Ohio 43201
United States
tel: 614-424-3403
fax: 614-424-3667
loan Gherhes (c.r.)
Mayor's Office
Municipality of Baia Mare
37, Gh. Sincai Street
4800 Baia Mare
Romania
tel: 40/94-206-500
fax: 40/62-212-961
e-mail: ighcrhcsMbajamarccityjo
Philippe Goffin
Member of the Cabinet
Place des Celestines, 1
5000 - Namur
Belgium
tel: 32/81-234.111
fax: 32/81-234.122
e-mail: foretffigov .wallonie.be
273
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Neil C.C. Gray
AstraZeneca Canada Inc.
2101HadwenRoad
Mississauga, Ontario
L5K 2L3
Canada
tel: (905) 403-2748
fax: (905) 823-0047
e-mail: Neil.Gray@astrazeneca.com
Henri Halen
SPAQuE (Public Society for the Quality of
Environment) - Wallonia
Boulevard d'Avroy, 38/6
4000 Liege
Belgium
tel: 32/4-220.94.82
fax: 32/4-221.40.43
e-mail: h.halcn@spaquc.bc
Pablo Higueras (c.r.)
University of Castilla-La Mancha
Almaden School of Mines
Plaza Manuel Meca, 1
13400 Almaden (Ciudad Real)
Spain
tel: +34 926441898 (work in Puertollano)
fax:+34 926421984
e-mail: phigueras@igem-al.iiclm.es
Masaaki Hosomi (c.r.)
Tokyo University of Agriculture and
Technology
2-24-16 Nakamachi, Koganei
Tokyo 184
Japan
tel: 81/3-423-887-070
fax: 81/3-423-814-201
e-mail: hosomi@cc.tuat.ac.jp
Stephen C. James (Co-Director)
U.S. Environmental Protection Agency
26 Martin Luther King Dr.
Cincinnati, OH 45268
United States
tel: 513-569-7877
fax:513-569-7680
e-mail: iamcs.stcvc@cpa.gov
Kestutis Kadunas (c.r.)
Hydrogeological Division, Geological Survey
Konarskio 35
2600 Vilnius
Lithuania
tel 370/2-236-272
fax: 370/2-336-156
e-mail:
Harald Kasamas (c.r.)
Bundesministerium fur Landwirtschaft und
Forstwirtschaft, Umwelt und
Wasserwirtschaft (BMLFUW)
Abteilung VI/3 - Abfallwirtschaft und
Altlastenmanagement
Stubenbastei 5
A-1010 Wien, Osterreich
Austria
tel: +43-1-5 1522-3449
email: liarMd,kasamas,@bmu,g_v,at
Theresa Kearney (c.r.)
Environment Agency
National Groundwater and Contaminated Land
Centre
Olton Court 10 Warwick Road, Olton
Solihul, West Midlands B92 7HX
United Kingdom
tel: +44/121— 711-2324
fax: +44/121— 711-5925
e-mail: tlicrcsa.kcamcv@cnvironmcnt-
agency,gQv,iik
Oliver Kraft
Altenbockum & Partner, Geologen
Lathringersrtasse 61
52070 Aachen
Germany
tel: +49/241-4017-462
fax: +49/241-4017-465
e-mail: info@altenbockum.de
Hans-Peter Koschitzky
VEGAS, Research Facility
Chair for Hydraulics and Groundwater,
University of Stuttgart
Pfaffenwaldring 61
D - 70550 Stuttgart
Germany
tel: 49/71 1-685 -4717
fax: 49/71 1-685-7020
e-mail: hansj3eJgjjggjjcj]itA
stutteart.de
274
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Walter W. Kovalick, Jr. (Co-Director)
Technology Innovation Office
U.S. Environmental Protection Agency
1200 Pennsylvania Avenue, N.W. (5102G)
Washington, DC 20460
United States
tel: 703-603-9910
fax: 703-603-9135
e-mail: kovalick.walter@epa.gov
Jan Krohovsky (c.r.)
Ministry of the Environment
Department of Environmental Damages
Vrsovicka 65
100 10 Prague
Czech Republic
tel: +420/2-6712-2729
fax:+420/2-6731-03 05
e-mail: krhov@cnv.cz
Oskars Kupcis (c.r.)
Ministry of Environmental Protection and
Regional Development
Peldu Str. 25
LV-1494 Riga
Latvia
tel: +371/7-026-412
fax:+371/7-228-751
e-mail: oskarsfglvaram.gov.lv
Louis Maraite
Government Wallon
Place des Celestines 1
B-5000 Namur
Belgium
tel:+32/081-234-111
fax:+32/081-234-122
e-mail: foret@gov.wallonie.be
Peter Merkel
SAFIRA
Lehrstuhl fur Angewandte Geologie
Sigwartstr. 10
D-72076 Tubingen
Germany
tel: +49/7071-297-5041
fax: +49/7071-5059
e-mail: peter.mcrkcl@uni-tucgingcii.dc
Jochen Michels
DECHEMA
Theodor-Heuss-Allee 25
60486 Frankfurt am Main
Germany
tel: 49-69-75 64-157
fax: 49-69-75 64-388
e-mail:
Jacqueline Miller (c.r.)
Brussels University
Avenue Jeanne 44
1050 Brussels
Belgium
tel: 32/2-650-3 183
fax: 32/2-650-3 189
e-mail: j millcr@ulb . ac . be
Christian Militon (c.r.)
Environmental Impact and Contaminated Sites
Department
French Agency for Environment and Energy
Management (ADEME)
2, square La Fayette
BP406
49004 ANGERS cedex 01 FRANCE
tel:(33)-2-41-91-40-51
fax: (33)-2-41-91-40-03
e-mail: Christian .mil iton@ademe .fr
Marylene Moutier
SPAQUE
Boulevard d'Avroy, 38
4000 Liege
Belgium
Tel: +32/4-220-94 11
Fax: +32/4-221-4043
e-mail: m .moutie r@spaque .be
Francesca Quercia (c.r.)
ANPA - Agenzia Nazionale per la Protezione
dell'Ambiente
Via V. Brancati 48
I -00 144 Rome
Italy
tel. 39/6-5007-2510
fax 3 9/6-5 007-25 31
e-mail qucrcia@aiipa.it
275
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
Dominique Ranson
AIG Europe
Kortenberglaan 170
1000 Brussels
Belgium
tel: +32.2.739.92.20
fax: +32.2.740.05.36
e-mail:
AIG Europe Netherlands
K.P. Van der Mandelelaan 50
NL 3062 MB Rotterdam
The Netherlands
tel: +31. 10.453.54.96
fax: +31. 10.453.54.01
Hubertus M.C. Satijn
8KB
Buchnerweg 1
P.O. Box420
2800 AK Gouda
Netherlands
tel: +3 1/1 82-540-690
fax: +3 1/1 82-540-691
e-mail:
Phillippe Scauflaire
SPAQUE
Boulevard d'Avroy, 38
4000 Liege
Belgium
tel: +32/4-220-94 11
fax: +32/4-221-4043
e-mail: p .scauflairc@spaquc . be
Chris Schuren
TAUW
Handelskade 11
7400 AC Deventer
The Netherlands
tel: +3 1/570-699-591
fax: +3 1/570-699-666
e-mail: chs@tauw.nl
Dott. Armando Sechi
Aquater
C.P. 20
61047 San Lorenzo in Campo (PS)
Italy
tel: +39/721-73 1-345
fax: +39/721-73 1-376
e-mail:
Ari Seppanen (c.r.)
Ministry of Environment
P.O. Box 399
00121 Helsinki
Finland
tel: 358/9-199-197-15
fax: 358/9-199-196-30
e-mail: AjiJfepjiaiMaifg^
Robert Siegrist
Colorado School of Mines
Environmental Science and Engineering
Division
112CoolbaughHall
Golden, Colorado 80401-1887
United States
tel: 303-273-3490
fax: 303-273-3413
e-mail: rsicgris@mincs.edu
Phillip Sinclair
Coffey Geosciences Pty Ltd
ACN 056 335 5 16
ABN 57 056 335 5 16
16 Church Street
POBox40, KEWVIC3101
Hawthorn, Victoria 3 122
Australia
tel: +61/3-9853-3396
fax: +6 1/3- 9853-0 189
e-mail: phil ....... sinclair@coffcy .com .au
Kai Steffens
PROBIOTEC GmbH
SchillingsstraBe 333
D 52355 Duren-Giirzenich
Germany
tel: 49/2421-69090
fax: 49/2421-690961
e-mail: stcffans(^grob_iotoc.dc
Jan Svoma
Aquatest a.s.
Geologicka 4
152 00 Prague 5
Czech Republic
tel: 420/2-58 1-83-80
fax: 420/2-5 8 1-77-5 8
e-mail: aguatest@agitatgst,cz
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January 2002
Kahraman Unlii (c.r.)
Department of Environmental Engineering
Middle East Technical University
Inonii Bulvari
06531 Ankara
Turkey
tel: 90/312-210-5869
fax: 90/312-210-1260
e-mail: kunlu@metu.edu.tr
Katrien Van Den Bruel
IBGE-BIM (Brussels Institute for
Environmental Management)
Gulledelle 100
1200 Brussels
Belgium
tel: 32/2-775.75.17
e-mail: hdeu|ybgej)imj)e_
Monique Van Den Bulcke
Governement Wallon
Place des Celestines 1
B-5000 Namur
Belgium
tel:+32/081-234-111
fax:+32/081-234-122
e-mail: foret@gov.wallonie.be
Eddy Van Dyck
OVAM (Public Waste Agency of Flanders)
Kan. De Deckerstraat 22-26
2800 Mechelen
Belgium
tel: 32/15-284.284
fax: 32/15-20.32.75
e-mail: cvdyclc@ovam.be
Leland Vane
U.S. Environmental Protection Agency
26 Martin Luther King Drive
Cincinnati, Ohio 45268
United States
tel: 513-569-7799
fax:513-569-7677
e-mail: yancjcland@cga.gov
H. Job an Van Veen (c.r.)
TNO/MEP
P.O. Box 342
7800 AH Apeldoorn
The Netherlands
tel: 31/555-49-3922
fax: 31/555-49-3231
e-mail: hj^yjjnvaai@mcj)Jna,nl
John Vijgen
Consultant
Elmevej 14
DK-2840 Holte
Denmark
tel: 45 /45 41 03 21
fax: 45/45 41 0904
e-mail:
Frank Volkering
TAUW
Handelskade 11
7400 AC Deventer
The Netherlands
tel: +3 1/570-699-795
fax: +3 1/570-699-666
e-mail: fvo@tauw.nl
Tony Wakefield
Consulting Engineer
Wakefield House, Little Casterton Road,
Stamford
Lincolnshire PE9 1BE
United Kingdom
tel: +44/1780-757-307
fax: +44/1780-766-3 13
Terry Walden
BP Oil Europe
Chertsey Road
Sunbury-on-Thame s
Middlesex TW167LN
United Kingdom
tel: (44) 1932-764794
fax: (44) 1932-764860
e-mail: waldcnj t@bg . com
Anthimos Xenidis (c.r.)
National Technical University Athens
52 Themidos Street
15 124 Athens
Greece
tel: 30/1-772-2043
fax: 30/1-772-2168
e-mail: axcn@gcnfraLntua.gr
Mehmet AH Yukselen
Marmara University
Environmental Engineering Department
Goztepe 81040 Istanbul
Turkey
tel: 90/216-348-1369
fax: 90/216-348 -0293
e-mail: Yukclscn@inutck.org^fr
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
PILOT STUDY MISSION
PHASE III - Continuation of NATO/CCMS Pilot Study:
Evaluation of Demonstrated and Emerging Technologies for the Treatment
of Contaminated Land and Groundwater
1. BACKGROUND TO PROPOSED STUDY
The problems of contamination resulting from inappropriate handling of wastes, including accidental
releases, are faced to some extent by all countries. The need for cost-effective technologies to apply to
these problems has resulted in the application of new/innovative technologies and/or new applications of
existing technologies. In many countries, there is increasingly a need to justify specific projects and
explain their broad benefits given the priorities for limited environmental budgets. Thus, the
environmental merit and associated cost-effectiveness of the proposed solution will be important in the
technology selection decision.
Building a knowledge base so that innovative and emerging technologies are identified is the impetus for
the NATO/CCMS Pilot Study on "Evaluation of Demonstrated and Emerging Technologies for the
Treatment of Contaminated Land and Groundwater." Under this current study, new technologies being
developed, demonstrated, and evaluated in the field are discussed. This allows each of the participating
countries to have access to an inventory of applications of individual technologies, which allows each
country to target scarce internal resources at unmet needs for technology development. The technologies
include biological, chemical, physical, containment, solidification/stabilization, and thermal technologies
for both soil and groundwater. This current pilot study draws from an extremely broad representation and
the follow up would work to expand this.
The current study has examined over fifty environmental projects. There were nine fellowships awarded
to the study. A team of pilot study country representatives and fellows is currently preparing an extensive
report of the pilot study activities. Numerous presentations and publications reported about the pilot study
activities over the five-year period. In addition to participation from NATO countries, NACC and other
European and Asian-Pacific countries participated. This diverse group promoted an excellent atmosphere
for technology exchange. An extension of the pilot study will provide a platform for continued
discussions in this environmentally challenging arena.
2. PURPOSE AND OBJECTIVES
The United States proposes a follow-up (Phase III) study to the existing NATO/CCMS study titled
"Evaluation of Demonstrated and Emerging Technologies for the Treatment of Contaminated Land and
Groundwater." The focus of Phase III would be the technical approaches for addressing the treatment of
contaminated land and groundwater. This phase would draw on the information presented under the prior
studies and the expertise of the participants from all countries. The output would be summary documents
addressing cleanup problems and the array of currently available and newly emerging technical solutions.
The Phase III study would be technologically orientated and would continue to address technologies.
Issues of sustainability, environmental merit, and cost-effectiveness would be enthusiastically addressed.
Principles of sustainability address the use of our natural resources. Site remediation addresses the
management of our land and water resources. Sustainable development addresses the re-use of
contaminated land instead of the utilization of new land. This appeals to a wide range of interests because
it combines economic development and environmental protection into a single system. The objectives of
the study are to critically evaluate technologies, promote the appropriate use of technologies, use
information technology systems to disseminate the products, and to foster innovative thinking in the area
of contaminated land. International technology verification is another issue that will enable technology
users to be assured of minimal technology performance. This is another important issue concerning use of
innovative technologies. This Phase III study would have the following goals:
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2002
a) In-depth discussions about specific types of contaminated land problems (successes and failures)
and the suggested technical solutions from each country's perspective,
b) Examination of selection criteria for treatment and cleanup technologies for individual projects,
c) Expand mechanisms and channels for technology information transfer, such as the NATO/CCMS
Environmental Clearinghouse System,
d) Examination/identification of innovative technologies,
e) Examining the sustainable use of remedial technologies—looking at the broad environmental
significance of the project, thus the environmental merit and appropriateness of the individual
project.
3. ESTIMATED DURATION
November 1997 to November 2002 for meetings.
Completion of final report: June 2003.
4. SCOPE OF WORK
First, the Phase III study would enable participating countries to continue to present and exchange
technical information on demonstrated technologies for the cleanup of contaminated land and
groundwater. During the Phase II study, these technical information exchanges benefited both the
countries themselves and technology developers from various countries. This technology information
exchange and assistance to technology developers would therefore continue. Emphasis would be on
making the pilot study information available. Use of existing environmental data systems such as the
NATO/CCMS Environmental Clearinghouse System will be pursued. The study would also pursue the
development of linkages to other international initiatives on contaminated land remediation.
As in the Phase II study, projects would be presented for consideration and, if accepted by other countries,
they would be discussed at the meetings and later documented. Currently, various countries support
development of hazardous waste treatment/cleanup technologies by governmental assistance and private
funds. This part of the study would report on and exchange information of ongoing work in the
development of new technologies in this area. As with the current study, projects would be presented for
consideration and if accepted, fully discussed at the meetings. Individual countries can bring experts to
report on projects that they are conducting. A final report would be prepared on each project or category
of projects (such as thermal, biological, containment, etc.) and compiled as the final study report.
Third, the Phase III study would identify specific contaminated land problems and examine these
problems in depth. The pilot study members would put forth specific problems, which would be
addressed in depth by the pilot study members at the meetings. Thus, a country could present a specific
problem such as contamination at an electronics manufacturing facility, agricultural production, organic
chemical facility, manufactured gas plant, etc. Solutions and technology selection criteria to address these
problems would be developed based on the collaboration of international experts. These discussions
would be extremely beneficial for the newly industrializing countries facing cleanup issues related to
privatization as well as developing countries. Discussions should also focus on the implementation of
incorrect solutions for specific projects. The documentation of these failures and the technical
understanding of why the project failed will be beneficial for those with similar problems. Sustainability,
environmental merit, and cost-benefit aspects would equally be addressed.
Finally, specific area themes for each meeting could be developed. These topics could be addressed in
one-day workshops as part of the CCMS meeting. These topic areas would be selected and developed by
the pilot study participants prior to the meetings. These areas would be excellent venues for expert
speakers and would encourage excellent interchange of ideas.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase
January 2002
5. NON-NATO PARTICIPATION
It is proposed that non-NATO countries be invited to participate or be observers at this NATO/CCMS
Pilot Study. Proposed countries may be Brazil, Japan, and those from Central and Eastern Europe. It is
proposed that the non-NATO countries (Austria, Australia, Sweden, Switzerland, New Zealand, Hungary,
Slovenia, Russian Federation, etc.) participating in Phase II be extended for participation in Phase III of
the pilot study. Continued involvement of Cooperation Partner countries will be pursued.
6. REQUEST FOR PILOT STUDY ESTABLISHMENT
It is requested of the Committee on the Challenges of Modern Society that they approve the establishment
of the Phase III Continuation of the Pilot Study on the Demonstration of Remedial Action Technologies
for Contaminated Land and Groundwater.
Pilot Country:
Lead Organization:
U.S. Directors:
United States of America
U.S. Environmental Protection Agency
Stephen C. James
U.S. Environmental Protection Agency
Office of Research and Development
26 W. Martin Luther King Dr.
Cincinnati, OH 45268
tel: 513-569-7877
fax:513-569-7680
e-mail: jamcs.stoyc@cpa.gov
Walter W. Kovalick, Jr., Ph.D.
U.S. Environmental Protection Agency
Technology Innovation Office (5102G)
1200 Pennsylvania Ave, NW
Washington, DC 20460
tel: 703-603-9910
fax: 703-603-9135
e-mail: koyajigk.waltcr@gp_a.goy
Co-Partner Countries:
Scheduled Meetings:
Australia, Austria, Belgium, Canada, Czech Republic, Denmark, Finland,
France, Germany, Greece, Hungary, Ireland, Japan, New Zealand, Norway,
Poland, Portugal, Slovenia, Sweden, Switzerland, The Netherlands, Turkey,
United Kingdom, United States
February 23-27, 1998, in Vienna, Austria
May 9-14, 1999, in Angers, France
June 26-30, 2000, in Wiesbaden, Germany
September 9-14, 2001, in Liege, Belgium
May 5-10, 2002, Rome, Italy
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