0°v/t\ COMMITTEE ON EPA 542-R-01-001
THE CHALLENGES OF January 2001
MODERN SOCIETY 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
2000
ANNUAL REPORT
Number 244
NORTH ATLANTIC TREATY ORGANIZATION
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2000
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)
Wiesbaden
June 26-30, 2000
January 2001
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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
Projects: Permeable Treatment Beds 20
Project 4 : Rehabilitation of Land Contaminated by Heavy Metals 24
Project 5: Application of Bioscreens and Bioreactive Zones 30
Proj ect 6: Rehabilitation of a Site Contaminated by PAH Using Bio-Slurry Technique 35
Project 7: Risk Assessment for a Diesel-Fuel Contaminated Aquifer Based on Mass Flow
Analysis During Site Remediation 37
Proj ect 8: Obstruction of Expansion of a Heavy Metal/Radionuclide Plume Around a
Contaminated Site by Means of Natural Barriers Composed of Sorbent Layers 42
Project 9: Solidification/Stabilization of Hazardous wastes 47
Project 10: Metal-Biofilm Interactions in Sulphate-Reducing Bacterial Systems 54
Project 11: Predicting the Potential for Natural Attenuation of Organic Contaminants in
Groundwater 60
Project 12: Treatability Test for Enhanced In Situ Anaerobic Dechlorination 65
Project 13: Permeable Reactive Barriers for In Situ Treatment of Chlorinated Solvents 71
Project 14: Thermal Cleanup Using Dynamic Underground Stripping and Hydrous Pyrolysis/
Oxidation 75
Project 15: Phytoremediation of Chlorinated Solvents 83
Project 16: In-Situ Heavy Metal Bioprecipitation 94
Project 17: GERBER Site 99
Project 18: SAFIRA 101
Project 19: Succesive Extraction-Decontamination of Leather Tanning Waste Deposited Soil 104
Project 20: Interagency DNAPL Consortium Side-by-Side Technology Demonstrations at Cape
Canaveral, Florida 106
Project 21: Development and Use of a Permeable Adsorptive Reactive Barrier System for
Ground Water Clean-up at a Chromium Contaminated Site 110
Project 22: Thermal In-Situ Using Steam Injection 113
Project 23: Bioremediation of Pesticides 116
Project 24: Surfactant-Enhanced Aquifer Remediation 119
Project 25: Liquid Nitrogen Enhanced Remediation (LINER): A New Concept for the
Stimulation of the Biological Degradation of Chlorinated Solvents 123
Project 26: SIREN: Site for Innovative Research on Monitored Natural Attenuation 126
Project 27: Hydro-Biological Controls on Transport and Remediation of Organic Pollutants for
Contaminated Land 130
Project 28: Demonstration of a Jet Washing System for Remediation of Contaminated Land 133
Project 29: Automatic Data Acquisition and Monitoring System for Management of Polluted Sites .135
Country Tour De Table Presentations 138
Armenia 139
Austria 144
Belgium 146
Canada 150
Czech Republic 153
Finland 158
France 159
Germany 161
Greece 166
Italy 168
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Japan 173
Lithuania 179
The Netherlands 184
Norway 190
Slovenia 191
Switzerland 217
Turkey 220
United Kingdom 223
United States of America 230
Country Representatives 235
Attendees List 238
Pilot Study Mission 246
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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 second meeting of the Phase III Pilot Study on the Evaluation of Demonstrated and Emerging Tech-
nologies 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.
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 2001
THIS PAGE IS INTENTIONALLY BLANK
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
PROJECTS INCLUDED IN NATO/CCMS PHASE III PILOT STUDY
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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
11. 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
1
/
/
/
/
/
/
/
Groundwater
/
/
/
/
/
/
/
/
/
/
CONTAMINANT
in
CJ
O
/
/
/
/
/
/
in
CJ
O
£
/
/
/
/
/
/
/
/
Pesticides/PCBs
/
/
/
in
CJ
Q.
/
/
/
/
/
in
o
'c
cc
E5
o
_c
/
/
/
/
/
/
/
/
/
NOTES
PAHs, munitions
chemicals
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, 90Sr,
238U
PCBs, AOX, metals
Metals (Cu, Zn, Cd),
radionuclides (Lab-
scale)
Coal tars, phenols,
creosol, xylenols,
BTEX, NH4*
TCE, DCE, VC, PCE
PCE, TCE, DCE
PAHs, fuels, gasoline,
chlorinated solvents,
pentachlorophenol
COMPLETE
/
/
/
/
/
/
/
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
PROJECT
15. Phytoremediation of Chlorinated
Solvents
16. In-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
1
/
/
/
/
/
/
/
Groundwater
/
/
/
/
/
/
/
/
/
/
/
CONTAMINANT
in
CJ
O
/
/
/
/
/
/
/
/
/
/
in
CJ
O
£
/
/
Pesticides/PCBs
/
/
in
CJ
Q.
/
in
o
'c
co
E5
o
_c
/
/
/
/
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, Zn
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 III) January 2001
KEY:
AOX = adsorptive organic halogens PHCs = petroleum hydrocarbons
BTEX = benzene, toluene, ethylbenzene, SVOCs = semivolatile organic compounds
and xylenes TMB = trimethylbenzene
DCE = dichloroethene TCA = trichloroethane
HCH = hexachlorocyclohexane TCE = trichloroethene
PAHs = polycyclic aromatic hydrocarbons VC = vinyl chloride
PCBs = polychlorinated biphenyls VOCs = volatile organic compounds
PCE = tetrachloroethene
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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: Ecoremiffiglo.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)
Please note that this project summary was not updated since the 1999 report. An update will be provided
in the 2001 report.
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 reconnoitoring soil
examination, at 3.500 m3. Proceeding with these data, selective excavation of the contaminated zones was
a first option to be considered.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
In order to draw up a detailed proposal for decontamination, Ecorem proposed an elaborated analysis
campaign based on a sample grid.
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
10,997 m3
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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
0.5m 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;
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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 bio remediation 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
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Figure 1
ssiasS? ••-:.**"--.~tsas
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Figure 3
Bteremediaton
ixcavatton zora
-70-
0 10 20 30 40 SO
80
ao so 100
1600ppm
1400ppm
1200ppm
lOOOppm
800ppin
400ppn»
Oppm
OF 2 OF
(concentration of in mg/kg DM)
Figure 4
Excavation
10 20 30 40 50 80 TO 80 80 100
-
1600ppm
1400poro
.iOOppm
.
-400ppm
.Oppm
FIG-4: OF 5 OF
(concentration of hydrocarbons in in DM)
13
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Figure 5
aiowmediaUon z0n« Kxeavttisn zone
0-
-10-
•20-
-30-
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•50-
-60-
-70-
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70 80 90 100
FIG.8:DISPERTATIONOFHYDROCARiONSAFTCR10yONTHSOF
of in DM)
^»«^^-^^jgm^|||^5aig5y
Figure 6
FIG.6: OF TESTING LINE-UP
Ecorem
14
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Figure 7
- -
t
OF THE SOIL
15
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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.
Troj ska 92
171 00 Prague 7
Czech Republic
www.kap.cz
Tel: (00-420-2) 83 09 06 14
Fax: (00-420-2) 83 09 06 58
E-mail:
m.stanzcl(fl}prg .kap.cz
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
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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;
• 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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 3
Permeable Treatment Beds
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: cxbciti0(ajwcc.com
Media:
Groundwater
Costs Documented?
No. Cost estimation is available.
Location:
Former solvent blending plant,
Essen, Germany
Technology Type:
Permeable reactive barrier as in-
situ ground-water remediation
technology
Contaminants:
Chlorinated and nonchlorinated
solvents, BTEX-aromates, TCE,
PCE
Project Status:
Interim Report,
Field tests finalized
Project Dates:
Accepted 1997
Project Size:
Full-scale
Results available?
No. Field test results available.
Please note that this project summary was not updated since the 1999 report. An update will be provided
in the 2001 report.
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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 • 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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 humin.
• 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
6. REFERENCES
1. Eberhard Beitinger, and Eckart Biitow. Machbarkeitsstudie zum Einsatz einer Adsorberwand -
"Schonebecker Schlucht" in Essen, Internal Report, WCI, Wennigsen, 1997 (not published)
2. Eberhard Beitinger, and Eckard Biitow. Abschlussbericht zur Durchfiihrung von Pilotversuchenfur
eine geplante Adsorberwand - "Schonebecker Schlucht" in Essen, Internal Report, WCI,
Wennigsen, 1998 (not published)
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 4
Rehabilitation of Land Contaminated by Heavy Metals
Location
Lavrion, Kassandra (Greece)
Sardinia (Italy)
Estarreja (Portugal)
Technical Contact
Prof. loannis Paspaliaris
National Technical University
of Athens
9, Iroon Polytechneiou str.
15780Zografu
Greece
Tel: +3 0/1 -772-2 176
Fax: +30/1-772-2168
Project Status
2nd Progress Report
Project Dates
Accepted 1997
Final Report 2001
Costs Documented?
No
Media
Mining tailings and
waste rock,
pyrite cinders,
soil
Technology type
Alkaline additives
Surface barriers
Chemical fixation-
immobilisation
Soil leaching
Contaminants
Lead, zinc, cadmium, arsenic, acidity, sulfates
Project Size
Laboratory,
Demonstration-scale
Results Available?
Yes
1. INTRODUCTION
Polymetallic sulphide mining and processing operations result in the generation of millions of tons of
mining, milling, and metallurgical wastes, most of them characterised as toxic and 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 that 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 sulphide 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
• Application of alkaline additives to prevent acid generation from sulphidic wastes.
• Formation of surface barriers with bentonite, zeolite, or other additives to prevent pollutant
migration from the pyrite cinders and calamina residues.
• Chemical stabilisation 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 150,000 t/2,500 ha sulphidic tailings dam in Lavrion.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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:
Site
Lavrion, GR
Description
Redundant polymetallic sulphide mine
(argentiferous, galena, sphalerite, pyrite)
Material tested
Sulphidic and oxidic
tailings, soils
Stratoni, GR
Active polymetallic sulphide mines (galena-
sphalerite-pyrite) with a mining history of
more than 2.500 years.
Waste rock
Montevecchio,
Monteponi, Sardinia, IT
Extensive Pb-Zn historic mining area.
Currently, there is one operating and many
redundant mines.
Sulphidic tailings,
calamina red mud,
soils
Estarreja, PT
Chemical industrial site. Production of
sulphuric acid by roasting of pyrites in the
period 1952-1991.
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 sulphidic wastes
The technical objective is the development of a process for the inhibition of acid generation from
sulphidic wastes by making beneficial use of the oxidation-dissolution-neutralisation-precipitation
reactions so as to achieve: on the microscale, precipitation of reaction products around the pyrite grains,
inhibiting further oxidation and/or on the 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 test work 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 characterisation of the solid residues was performed.
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 includes: a) selection of the stabilising 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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
parameters including mode of application and addition rates of the stabilising agents, and c) lysimeter
kinetic tests.
c) Chemical stabilisation of metals in oxidic wastes and soils
The technical objective is to develop a process for the in-situ immobilisation 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 stabilising 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. Stabilisation was examined by chemical extraction tests and verified by actual biological
tests. Chemical extraction tests included toxicity characterisation 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 a 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.
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., and 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
SULPHIDIC 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. Referring to the Stratoni waste rock, the separation
of the sulphide rich -4 mm size fraction and its placement after mixing with 14% limestone on top of the
coarse was proven effective in preventing acid generation even under acidic conditions. Field tests are
currently in progress to assess the performance of above techniques under actual conditions.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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 stabilised 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 STABILISATION 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 stabilisers 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 stabilised with 5% gypsum was proven to
be a successful stabilising agent for Montevecchio soils.
Given that inorganic materials (e.g., phosphates, fly ash, and 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.
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 the 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 1.6m3 per ton soil.
5. COSTS
Cost estimates of rehabilitation technologies examined will be available upon evaluation of field-scale
test results.
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 1995 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.
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.
27
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
4. Hassling, 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
characterisation of the sulphidic 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 characterisation and development studies,
III 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 polumetallic 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
characterisation 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
stabilisation 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: Stabilisation 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: Stabilisation 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.
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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. /. 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: Stabilisation of highly polluted soils,
Contaminated Soil 1998, Edinburg
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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)
Project Status
Final report
Contaminants
Oil, BTEX, chlorinated
solvents, chlorinated
pesticides, and benzenes
Technology Type
In Situ
Bioremediation
Technical Contact
Huub Rijnaarts/Sjef Staps/
Herco van Liere
TNO Institute of
Environmental Sciences,
Energy Research and Process
Innovation
Laan van Westenenk 501
7334 DT Apeldoorn
The Netherlands
Tel:+31 555493380
Fax:+31 555493523
E-mail:
H.H.M.Rijnaarts@mep.tno.nl
Project Dates
Accepted 1998
Media
Groundwater
Costs Documented?
Yes
Project Size
Pilot to full-scale
S.Staps@mep.tno.nl
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. The source area contains high concentrations of PCE
and needs to be treated to prevent subsequent delivery to the plume area. Source remediation and plume
interception were therefore required. Analyses have shown insufficient natural biodegradation capacity
due to a shortage of intrinsic electron donor. Therefore a 50 m semi full-scale reactive zone has been
installed in the source zone. Results after 7 months have shown complete biodegradation of PCE to
ethene and ethane.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Oil refinery site. At this site in the Rotterdam Harbour area, it is required to manage a plume (>200 m up
to a depth of 4 m) of the dissolved fraction of a mineral oil/gasoline contamination (80% of the
compounds belong to the C6 - C12 fraction). The redox conditions are anaerobic and the natural
biodegradation capacity is unknown, but probably insignificant. To protect further spreading into the
harbour 3 types of bioscreens, pilot-scale sparging applications, were installed. The dimensions of each
pilot is 40 m by 0.4 m by 4 m deep. One bioscreen has been trenched and backfilled with gravel. The
other two bioscreens are vertical and horizontal air sparging fences. Results after one year is a total
biodegradation up to 70%. From 2001 the airsparging will be intensified and monitored.
Aromatic hydrocarbon (BTEX) sites. At three sites (> 250 m length and 10-80 m depth) in the northern
part of the Netherlands, deep anaerobic aquifers contaminated with Benzene, Toluene, Ethylbenzene or
Xylenes (BTEX) have been investigated. Under the existing sulphate-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, probably due to absence of adapted micro-organisms. Managing the
benzene plumes, i.e., by enhanced in-situ bioprocesses, is therefore required. Infiltration of electron
acceptors was investigated, for example minimal amounts of oxygen combined with nitrate. Push-pull
experiments at the site have shown complete biodegradation of BTEX. From 2001 pilot-scale application
and monitoring is planned.
Chlorinated pesticides site. Hexachlorocyclohexane (HCH) isomers are important pollutants introduced
by the production of lindane (gamma HCH). The redox conditions are mixed: sulphate reducing to iron
reducing. Natural degradation of all HCH-isomers was demonstrated at the site of investigation and in the
laboratories of TNO. To minimise all risks interception of the HCH/Chlorobenzene/benzene plume (>250
m length, up to a depth of 18 m) was needed to protect the canal located at the boundary of the industrial
site. The in situ bioremediation concept investigated at this site is integrated into new infrastructural plans
of a large transhipment facility. The semi full-scale design was constructed in 2000 and contains of 2
sequential bioscreens upstream. Here electron donor will be infiltrated and extracted and biological
biodegradation of HCH into monochlorobenzene and benzene will be monitored with monitoring filters.
Downstream an above ground (bio)reactor system is set up. Here the groundwater is extracted and
monochlorobenzene and benzene is mineralised. From 2001 testing of the complete system starts.
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. Microcoms 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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 complete
evaluations of technology performance are to be expected at the end of 2001.
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
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.
Brunia, A., Van Aalst-van Leeuwen, M.A., Bosnia, 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.
De Kreuk, H., Bosnia, 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
Gerritse, J., Alphenaar, A., & Gottschal, J.C. (1998) Ecophysiology and application of dechlorination
anaerobes. ASCE Conference on Environmental Engineering, 6-10 June, Chicago.
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.
Gerritse, J., Schraa, G., & Stams, F. (1999). Dechlorination by anaerobic microorganisms. 9th European
Congress of Biotechnology (ECB9), July 11-15, Brussels.
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)
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.
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
Rijnaarts, H. H. M. (1997). Data requirements for in-situ remediation. NICOLE-workshop "Site
assessment & characterisation", TNO-MEP, Apeldoorn, 22-23 January.
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.
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.
Rijnaarts, H. H. M., De Best, J.H., Van Liere, H.C., & Bosnia, 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
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., Bosnia, 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.
Rijnaarts, H.H.M. (1998) Application of biowalls/bioscreens. NATO-CCMS Pilot Project on Contam-
inated Land and Groundwater (Phase III), annual report no. 228, EPA/542/R-98/002, p. 19 - 20.
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.
Schippers, B. P. A., Bosnia, 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
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
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.
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.
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 III) January 2001
Van Liere, H. C., Van Aalst-van Leeuwen, M.A., & Rijnaarts, H.H.M. (1998b). In situ biodegradation of
hexachlorocyclohexane (HCH). EGS meeting, 20-24 April, Nice, France.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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:
crik. backlund(o),cbox.tninct. sc
Project Status
Interim
Project Dates
Accepted 1996
Final Report 2001
Costs Documented?
No
Media
Soil
Technology Type
Ex situ
bioremediation
Contaminants
coal tars, phenols, cyanides, metals,
ammonium compounds
Project Size
Full-scale (3,000 tons)
Results Available?
Yes
Please note that this project summary was not updated since the 1998 Annual Report.
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
35
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
36
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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
matliiasiffiscliluep.ch
Christoph Munz
BMG Engineering Ltd
Ifangstrasse 11
8057 Schlieren
Switzerland
tel: +41-1-732-9277
fax: +41-1-730-6622
E-mail: chnstophjnunz@bjnggng^ch
Josef Zeyer
Soil Biology
Inst. of Terrestrial Ecology ETHZ
Grabenstrasse 3
8952 Schlieren
Switzerland
tel: +41-1-633-6044
fax:+41-1-633-1122
E-Mail : zcver;® ito . um w . cthz . ch
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
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 III)
January 2001
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 8): dissolution of PHCs
into the aqueous phase (section A), anaerobic (section B) and aerobic biodegradation (section C) of the
dissolved compounds.
section A
section B
flow/through
reactor
denitrifying column
section C
aerobic column
Figure 8: Experimental setup of the laboratory
study on dissolution ofdieselfuel compounds
into sterile ground-water (section A) and
biodegradation in two laboratory aquifer
columns under denitrifying (section B) and
aerobic (section C) conditions
4. RESULTS AND EVALUATION
Dissolution ofNAPL 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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
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.
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.
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 8, 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 9. 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 8) and
39
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
compared with the depletion of the electron acceptor. Results indicate that the fate of lexicologically
relevant compounds is predictable by measuring inorganic compounds.
The development of risk with time was calculated after each section of the experiment (Figure 8) using
the corresponding concentrations of the relevant compounds as well as their toxicological properties. The
non-cancerogenic risk (Figure 10) as well as the cancerogenic 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.
400
concentration of the dissolved
compound (section A)
concentration after anaerobic
degradation (section B)
concentration after aerobic
degradation (section C)
ethyl benzene
7
6
£ 5
* 4
jfl 3
.
x co
0-C
0
risk after dissolution
(section A)
risk after anaerobic
degradation (section B)
risk after aerobic
degradation (section C)
_accerjtable-rjsk_
0
80
100
20 40 60
water flow through [I]
Figure 10: 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.
80
100
20 40 60
water flow through [I]
Figure 9: 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.
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:
1. 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).
2. 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
40
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
years. This indicates that biological processes enhance the depletion of PHC, and hence shorten the
time for PHC removal from the subsurface.
3. 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.
4. 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.
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.
5. 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 contaminaetd aquifer: Assessment of mineralization based on alkalinity,
inorganic carbon and stable isotope balances. / 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, Scerpella D. 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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
Resat Apak
Istanbul University
Avcilar Campus, Avcilar
34850 Istanbul, Turkey
Tel: 90/212-591-1996
Fax: 90/212-591-1997
E-mail:
Project Dates
Accepted 1998
Interim Report
1999
Final Report 2001
Media
Soil and groundwater (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
Please note that this project summary was not updated since the 1999 report. An update will be provided
in the 2001 report.
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
42
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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
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/de sorption 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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
lOO-SSOmgPb.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 were 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 solidifed
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 2001
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 2001
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,"/. Environ. Sci. and Health, Pi. A-Environ. Sci. and Engg., 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)," /. 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," /. 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," /. 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 Ground-water', 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. A. 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 III)
January 2001
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
Department
06531 Ankara
Turkey
Tel: 90-3 12-210-5869
Fax:90-312-210-1260
E-mail: kunlu(fl}mctu. edu.tr
Project Status
Near completion
Project Dates
Accepted 1998
Final Report 2001
Costs Documented?
No
Media
Soil, mining waste, and
wastewater and sludge
from pulp and paper
industry
Technology Type
Solidification/
stabilization
Contaminants
PCBs, AOX (adsorbable organic halides),
heavy metals
Project Size
Bench-scale
Results Available?
Partially
1. INTRODUCTION
Solidification and stabilization are treatment processes designed to either improve waste handling and
physical characteristics, decrease the surface area across which pollutants can transfer or leach, or limit
the solubility or 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 regulation of the Control of Hazardous Wastes (C of HW) 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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
future, but also concerns existing hazardous wastes and their safe disposal in compliance with the current
regulation. The Solidification/Stabilization (S/S) technology is recognized by the Turkish regulation of
the C of HW 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 unconfined compressive strength tests on, and measuring microstructural
characteristics of, 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 residue material from gold mining has relatively high heavy metal content,
in order to observe the performance of S/S technology effectively, much more concentrated waste in
terms of heavy metal concentration was considered to be useful. Concentrated mine waste was obtained
by the addition of the salts of some heavy metals.
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.
Mixing ratios for different waste groups are given in Table 1.
Table 1: Waste material and portland cement mixing ratios.
Waste Material
Residue material from gold mining (fine and coarse)
PCBs contaminated soil
Wastewater (ww) from pulp and paper industry
Sludge from treatment of pulp and paper industry
wastewater
Cement Percentage
10 and 20%
20 and 35%
1:6 and 1:8 (ww: cement)
30 and 50%
4. ANALYTICAL APPROACH
Before solidification, physical and rheological characteristics of all wastes, except wastewater, were
determined through Atterberg limits, maximum dry density, optimum moisture content, specific gravity,
and particle size distribution determinations. After these measurements, the samples were prepared for the
28 day-cure for solidification by compacting the desired waste:cement mixture—at its optimum moisture
content corresponding to its maximum dry density—in cylindrical molds having a height of 71 mm and a
diameter of 36 mm.
Physical tests and measurements were performed on these solidified samples. The unconfined
compressive strength tests were performed using triaxial shear apparatus and saturated hydraulic
conductivities of solidified duplicate samples were measured using a flexible wall permeameter. At the
end of the cure period—prior to the performance of leaching tests—samples were crushed and then
passed through sieves for fractionation to sizes greater than 2 mm and between 1-2 mm. The U.S. EPA's
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Toxicity Characteristic Leaching Procedure (TCLP) and distilled water leaching procedure were applied
using 2 and 3 grams of waste sample from each size fraction. On the leachate obtained by two different
leaching procedures, pH and concentrations of the following contaminants were measured: Cd, Cr, Cu,
Fe, Pb, Zn, Al, Ca, Mg, Na, K, Cl, SO4, CO3 and PO4. Heavy metals were analyzed by flame atomic
absorption spectrophotometer, chloride and carbonate ions by titrimetric methods and sulfate and
phosphate by spectrophotometric methods. Based on the results of the physical tests and the leachate
compositions obtained from solidified samples, for each waste type, the effectiveness of the S/S
technology in terms of contaminant encapsulation was assessed. For all chemical analyses, U.S. EPA
SW-846 standard methods were used.
5. RESULTS
Initial total metal analyses of gold mining residue material showed that heavy metal (Cd, Cr, Cu, Pb, and
Zn) concentrations were relatively high except for cadmium. However, in order to observe the
performance of S/S technology effectively, much higher heavy metal concentrations were required.
Therefore, nitrate or sulfate salts of these heavy metals were added to the gold mining residue. By the
additions of metal salts, original metal concentrations in the waste were increased approximately 1000
mg/kg for each metal. Because cement, as a binding agent, was mixed with waste material, metal
composition of cement was also determined to see any contribution to metal content of waste. The results
of total metal analyses for cement are given in Table 2. As seen from the table, Cd, Cr, Cu, and Pb are not
present in cement.
Table 2: Initial metal composition of mining waste and portland cement
Metals
Cd
Cu
Cr
Pb
Zn
Fe
Al
Ca
Mg
Waste (mg/g)
0.04
2.41
0.35
3.48
2.38
29.70
37.89
0.44
1.15
Cement (mg/g)
0
0.03
0.50
0
0.04
15.63
29.07
276.31
8.24
Before the 28 day-cure period, additional tests also were performed to determine some physical and the
rheological characteristics of the waste:cement mixture. By these tests, Atterberg limits, maximum dry
density, optimum moisture content, specific gravity, particle size distribution of each case were
determined. Results are given in Table 3.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Table 3: Physical and rheological characteristics of fine and
coarse gold mining waste and cement mixtures
Characteristics
Dry density (g/ml)
Opt. Moisture (%)
Liquid limit (%)
Plastic limit (%)
Plasticity index (%)
Soil classification
Specific gravity
Particle size
Distribution
10% cement
(fine)
1.77
15
27.8
18.05
9.75
ML (silt-low
plasticity)
2.72
18% clay
55% silt
27% sand
20% cement
(fine)
1.78
17
27.9
20.55
7.35
ML(silt-low
plasticity)
2.73
22% clay
52% silt
26% sand
10% cement,
(coarse)
2
10
21.75
17.05
4.7
SM (silty sands)
2.67
12% clay
29% silt
59% sand
20% cement,
(coarse)
2
11
22.1
16.05
6.05
SM(silty sands)
2.745
13% clay
29% silt
58% sand
The metal composition of the waste samples also was determined by the acid digestion method. Results
are given in Table 4.
Table 4: Chemical composition of fine and coarse mine waste and cement mixtures
Metals & Ions
Cd (mg/g)
Cu (mg/g)
Cr(mg/g)
Pb (mg/g)
Zn (mg/g)
Fe (mg/g)
Al (mg/g)
Ca (mg/g)
Mg (mg/g)
K (mg/g)
Na (mg/g)
S04-2 (mg/1)
P04-J (mg/1)
Cr (mg/1)
C03~2 (mg/1)
10% cement, fine
1.25
3.33
3.06
3.09
1.90
13.50
26.13
7.83
1.71
21.55
7.78
575.3
5.93
494.95
5232
10% cement, coarse
0.85
1.69
1.92
1.42
1.35
10.47
11.17
15.54
3.1
9.95
5.15
257.5
10.87
849.7
5475
20% cement, fine
1.00
2.55
2.14
2.32
1.99
13.31
24.36
17.72
2.49
12.95
2.0
520.3
20.1
1174.6
7320
20% cement, coarse
0.75
1.25
1.77
1.21
1.05
8.78
8.25
19.4
1.56
9
8.9
158.3
12.15
699.8
9660
Note that metal concentrations of coarse waste samples were diluted due to the addition of sand, which
shifted the texture of waste from silt (fine) to sand (coarse). Due to high concentrations of Fe, Al,
Ca, and Mg in the portland cement, waste samples also have very high concentrations of these
metals.
At the end of the cure period, TCLP and distilled water leaching procedure were applied and leachate
obtained for each waste group was analyzed for heavy metals and some ions. Results of these analyses are
given in Table 5.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Table 5: The chemical compositions of leachates obtained from
mining waste using TCLP and distilled water leaching procedures
Ions
(mg/1)
Cd
Cu
Cr
Pb
Zn
Fe
Al
Ca
Mg
K
Na
so42-
po43-
cr
co32-
10% cement, fine
1-2 mm
TCLP
1.85
0.31
0.37
0.39
0.71
ND
ND
94.6
17
58
152.2
149.9
0.31
150
1854
Water
0.23
ND
ND
ND
0.24
ND
ND
83.39
6.31
19
36
76.5
25.02
274.9
4320
>2mm
TCLP
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
Water
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
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
Water
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
>2mm
TCLP
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
Water
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
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
Water
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
>2mm
TCLP
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
Water
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
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
Water
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
>2mm
TCLP
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
Water
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 belowthe 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)
In general, the following observations can be made from Table 5. Metal concentrations in TCLP leachate
are significantly higher than the metal concentrations in distilled water leachate. At the same cement ratio,
fine waste samples produce leachate having lower metal concentrations than coarse waste samples.
Increasing cement ratio does not have any considerable effect on metal concentrations in the leachate.
Comparisons with EPA toxicity characteristic limits, which are given as 1 mg/1 for Cd, 5 mg/1 for Cr and
Zn, and 130 mg/1 for Cu, indicate that only Cd concentrations in the leachate from waste samples of 10%
cement ratio exceed the regulated level. All the other metal concentrations in the leachate do not exceed
the regulated levels. With regard to crashing effect on metal concentrations in the leachate, results show
that solidified samples crashed to form particle sizes >2mm produce lower metal concentrations in
distilled water leachate compared to solidified samples crashed to form particle sizes between 1-2 mm. In
the case of TCLP leachate, the same situation was observed only for coarse waste sample with 20 %
cement ratio. For other samples, crashing the solidified samples into different particle sizes did not affect
the metal concentrations in the TCLP leachate.
Besides leaching tests, unconfined compressive strength and hydraulic conductivity tests were performed
on duplicate cylindrical solidified samples of each treatment. The results of unconfined compressive
strength and hydraulic conductivity measurements are given in Table 6.
Table 6: Unconfined compressive strength and hydraulic conductivity results for
mine waste samples with different cement ratios
Property
Uncon. Comp. Strength, kPa
Hydraulic Conductivity, m/s
10% cement
(fine)
1153.46
2.1*l(r9
20% cement
(fine)
2520.4
1.09*l(r9
10% cement
(coarse)
1019
1.84*10-9
20% cement
(coarse)
3250
1.04*10-9
Results show that as cement ratio and the coarse fraction in the waste increase, unconfined compressive
strength also increase. At the same cement ratio, solidified fine and coarse waste materials have similar
hydraulic conductivity values. However, as the cement ratio increases, hydraulic conductivity values
decrease significantly both for fine and coarse samples.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
At this point, both physical and chemical analyses concerning the solidification/stabilization of metals in
the mining waste were completed. The other aspects of the project (the study on PCB-contaminated soil
and adsorbable organic halides, and AOX-containing wastewater and sludge) are currently under way.
Completed parts are explained below.
Concentration of AOX in wastewater and sludge obtained from the pulp and paper industry were
measured. AOX concentrations were 39 mg/1 in wastewater and 0.4 mg/g in sludge. Wastewater was
mixed with cement at two different ratios (1:6 and 1:8), which bound the optimum moisture content of
cement yielding maximum dry density. Samples were prepared for the 28 day-S/S cure by compacting the
wastewater:cement mixtures in cylindrical molds having a height of 71 mm and a diameter of 36 mm. At
the end of cure period, unconfmed compressive strength measurements were done on duplicate solidified
samples. The results are 5800 kPa and 5350 kPa for 1:6 and 1:8 wastewater:cement ratios, respectively,
which indicate that 1:6 wastewater to cement ratio yields stronger solid blocs. After the strength
measurements were taken, the TCLP was applied using solidified samples that were crushed to form
particle sizes >2mm and between 1-2 mm. The results of AOX measurements in TCLP leachate are given
in Table 7. Results show that the cement-mixing ratio and the crushing of the solidified samples into
different particle sizes did not affect the AOX concentration in the TCLP leachate. After solidification
with portland cement, nearly 90 % reduction in AOX concentration of wastewater is achieved. Similar
leaching tests have currently been conducted using distilled water as well.
Table 7: AOX concentrations in TCLP leachate obtained from solidified wastewater samples
of two different cement ratios and crashed particle sizes
Treatment
1:6 ww:cement
1:8 ww:cement
AOX Concentration (mg/L)
1-2 mm
3.24
3.20
> 2mm
3.33
3.35
Analysis involving PCB contaminated soil and pulp and paper sludge are currently underway. Sludge
samples were mixed with portland cement at the ratios of 30% and 50%. Both soil and sludge samples are
currently going through a 28 day-S/S curing period.
6. HEALTH AND SAFETY
Not applicable.
7. ENVIRONMENTAL IMPACTS
Not applicable.
8. COSTS
Not available.
9. CONCLUSIONS
When the results of leaching procedures are compared with the limiting values specified by the Turkish
regulation of the Control of Hazardous Wastes (C of HW), metal concentrations in the leachate are within
the acceptable range. Therefore, wastes with metal concentration levels similar to the mining waste
considered in this study can be disposed of in landfills. According to the U.S. EPA regulations, the
concentrations of heavy metals in TCLP leachate are below the specified toxicity limits, except for
cadmium. When the crushed size of solidified samples is taken into consideration, in general the crushed
samples with finer size (1-2 mm) yield higher metal concentrations in the leachate. This is probably due
to the increase in the surface area of crushed samples that contact the leachant.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
As performance criteria, besides leachate concentrations, the results of physical tests are also important.
According to the U.S. EPA standards, minimum value of unconfmed compressive strength is 350 kPa for
the disposal of solidified hazardous wastes in landfills. Unconfmed compressive strength values measured
for all treatments considered in this study are well above this limiting value. Therefore, these solidified
samples easily can be disposed of in landfills. Hydraulic conductivity values measured for all treatments
are in the order of 10~9 m/s, although higher cement addition (20%) results in lower conductivity values.
Measured conductivity values are four orders of magnitude lower than the value of 10"5 cm/s
recommended by U.S. EPA for land-burial of stabilized wastes (EPA, 1986).
Technical criteria for the performance assessment of S/S require low leachate concentrations, low
permeability, and high unconfmed compressive strength. For metal-containing mine waste, since all cases
produced acceptable unconfmed 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 was mixed with the waste consisting
of nearly 75 % fine (silt and clay size) particles.
The application of S/S for AOX in wastewater also gave successful results, with the achievement of
nearly 90% reduction in AOX concentration in the leachate.
10. REFERENCES
1. Malone, et al., "Guide To The Disposal Of Chemically Stabilized And Solidified Waste," SW-
872, Office of Water and Waste Management, U.S. EPA, Washington DC, 1982
2. Conner J. R. and Hoeffner S. L., "The History Of Stabilization/Solidification Technology,"
Critical Reviews in Environmental Science and Technology, vol: 28, no: 4, pp: 325-396, 1998
3. Smith M.A., 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, 1998
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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,
UK
Tell 44 1772 762566
Fax 44 1772762891
E-mail lie 1 (ojbnfl .com
Project Status
Final Report
Project Dates
Project accepted
1998
Final project report
1999
Costs Documented?
No
Contaminants
Metals
Technology Type
Biological
Treatment
Media
Effluents/Ground water
Project Size
Laboratory
Results Available?
Yes
Project 10 was completed in 1999.
1. INTRODUCTION
The development of Sulphate-Reducing Bacteria 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:
Employing a purpose designed biocell
Generating fundamental metal precipitation data from this biocell
Investigating factors affecting growth of sulphate-reducing bacterial (SRB) biofilms
Quantification of important biofilm parameters on metal immobilisation
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 favoured 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 2001
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 characterisation 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.
1. 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:
The separation of carbon source, or sulphate or heavy metal from the SRB biofilm.
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.
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.
2. 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 2001
2.1 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-utilisation 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 utilised, producing acetate. Varying the concentrations over a 10- to 20-fold range and allowed
determination of lactate utilisation kinetics, which was carried out by personnel engaged on process
modeling (K m @ 1,4 mM). Acetate was utilised very slowly by the biofilm culture and accumulated
during experiments on lactate utilisation as it was produced by SRB metabolising lactate.
When acetate was supplied as the sole carbon/energy source, its rate of utilisation and the accompanying
sulphate reduction were almost undetectable so that no kinetic parameters could be determined. The low
acetate utilisation 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-utilising mixed SRB culture was obtained, combined with the lactate-utilising culture and the
combined culture was maintained on mixed lactate and acetate as carbon/energy source. This combined
culture utilised 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-utilising culture led to increased acetate utilisation, it appears that the very
low rate of acetate utilisation in the original culture was due to the absence of acetate-degrading
organisms.
2.2 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.
3. Metal Precipitation studies
3.1 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 parameterise 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
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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
3.2 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 O.SmM 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.
4. Membrane Studies
4.1 Permeable membrane
Investigations into the flow characterisation 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.
4.2 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.
5 Modelling Studies
5.1 Biofilm
A model of the biological phenomena occurring within the sulphate reducing bacterial biofilms, has been
developed. The model is based upon the Generalised Repository Model (GRM) developed by BNFL. The
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 modelling 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Changes to the bulk chemistry due to microbial activity within the code are utilised as input data by the
chemical speciation component of the code, PHREEQE.
The main roles of PHREEQE are the modelling 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 utilisation 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 utilised 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
modelling tasks in the future, taking advantage of the full extent of it capabilities.
5.2 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:
- Sulphide production is zero order in sulphate concentration and exhibits a Monod rate dependence on
carbon substrate composition (ignoring complications from acetate utilisation),
- 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,
- 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,
- 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.
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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
not realised at the outset of the project and has not, hitherto, been discussed or analysed in the literature.
Nonetheless, the experimental and theoretical work in the project has:
- 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),
- Allowed estimates of the rate of biofilm capture of colloidal material to be made, and
- 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 III)
January 2001
Project No. 1 1
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.
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: 01 14 222 5744
Fax: 01142225700
E-mail: iiJLJiiomlxMi^shcffe
Project Status
Final report
Project Dates
Accepted 1998
Final Report 1999
Costs Documented?
Not applicable
Media
Groundwater
Technology Type
Intrinsic
bioremediation, natural
attenuation
Contaminants
Coal tars, phenol, cresols, xylenols,
BTEX
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 NH4), 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 <5mbgl) and the aquifer is 250 m thick in the vicinity
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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 modelling 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 2001
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 modelling of biodegradation processes in the plume is ongoing. An initial modelling
study was undertaken with the biodegradation code, BIO REDOX, to test the conceptual process model of
the plume and to identify additional modelling objectives. Further transport modelling 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 modelling 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 fieldscale.
4. ANALYTICAL APPROACH
Groundwater samples have been collected, anaerobically, for analysis of organic contaminants, dissolved
gases (e.g., N2, CO2, CFL^, 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 modelling 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 a/., 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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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 provide 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 III) January 2001
8. Thornton, S. F., Davison, R. M. Lerner, D. N. and. Banwart, S. A. (1998). Electron balances in field
studies of intrinsic remediation. M. Herbert and K. Kovar (eds), GQ 98—Ground-water Quality:
Remediation and Protection. Proceedings of a conference held at Tubingen, September 1998. IAHS
publication 250: 273-282.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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
To be determined
To be determined
Project Status
Interim Report
Media
Groundwater
Technology Type
In Situ Bioremediation
Technical Contact
Lt. Lisa Ackert
AFRL/MLQ
139 Barnes Drive, Suite 2
Tyndall AFB, FL 32403
Tel: 850-283-6308
Fax: 850-283-6064
Project Dates
Accepted 1999
Final Report 2001
Contaminants
tetrachloroethylene (PCE) and
trichloroethylene (TCE)
E-mail:
Catherine Vogel
DoD SERDP/ESTCP
Cleanup Program Manager
901 N. Stuart Street, Suite 303
Arlington, VA 22203
Tel: (703) 696-2 118
Fax: (703)696-2114
E-mail: vogclc@acq.osd.mil
Costs Documented?
Soon
Project Size
Field
Treatability
Testing
Results Available?
Soon
Please note that this project summary was not updated since the 1999 Annual Report.
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 2001
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.
/H 2H HC! (^ /H
/c—<\
Cl Cl Cl Cl Cl Cl H Cl H H
PCE TCE DCEs VC ETH
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
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.
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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 determined.
3. TECHNICAL CONCEPT
Site # 1: Cape Canaveral Air Station. FL
Site Description: Facility 1381, the Ordnance Support Facility at Cape Canaveral Air Station, contains a
shallow, 110-acre volatile organic contaminant (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; however these contaminants have been detected in a surface water body adjacent to
the site. This has prompted the state and federal environmental regulators to require a corrective measures
study of various remedial options.
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 ft to 50 ft bgs,
sands show a decrease in grain size and the silt and clay content increases. From 48.5 ft 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 umhos/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.
RABITT Testing: The ability of yeast extract, propionate, lactate, butyrate, and lactate/benzoate to
stimulate anaerobic dechlorination of TCE was evaluated in laboratory microcosm studies using
contaminated aquifer material. Butyrate and the lactate/benzoate mixture stimulated the complete
conversion of TCE to ethene. Based on these laboratory results, the decision was made to proceed with
the field treatability test.
The standard RABITT field treatability test design consists of an extraction/amendment/reinjection
system within a small test plot. Contaminated groundwater is extracted near the end of the treatment plot,
amended with nutrients and/or electron donor, and then reinjected near the head of the treatment plot.
This design creates a hydraulic gradient to direct the flow of groundwater through the treatment plot.
Multi-level monitoring points are placed within the treatment plot, in between the injection and extraction
wells. Groundwater extraction and injection are optimized to achieve a 30-day hydraulic residence time
within the treatment plot.
This standard RABITT design had to be 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 above ground.
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. 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.
The tri-level groundwater monitoring probes are positioned around the treatment cell to provide three-
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
dimensional data that are 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 modified system was installed at Facility 1381 in March 1999 and will operate for six months. The
electron donor selected for field-testing was lactic acid. Lactic acid is added to the treatment cell at a
concentration and flow rate to achieve an in situ concentration of 2-6 mM.
Site #2: Naval Air Station Alameda. CA
Site Description: Building 360 (Site #4) at Naval Air Station Alameda was selected for the 2nd
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 30-70% solutions of sodium
hydroxide. Site characterization activities performed by the facility revealed elevated levels of chlorinated
solvents, primarily TCE (24 ppm), DCE (8.6 ppm) and VC (2.2 ppm) detected between 5.5 and 15.5 feet
bgs.
Depth to groundwater in the Building 360 area ranged 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.
RABITT Testing: The ability of yeast extract, propionate, lactate, butyrate, and lactate/benzoate to
stimulate anaerobic dechlorination of TCE was evaluated in laboratory microcosm studies using
contaminated aquifer material. Yeast extract, butyrate, and lactate stimulated the complete conversion of
TCE to ethene. Based on these laboratory results, the decision was made to proceed with the field
treatability test.
The standard RABITT field treatability test was installed at the Alameda site. The system was installed in
May 1999 and will operate for six months. The electron donor selected for field-testing was a mixture of
butyric acid and yeast extract. Butyric acid and yeast extract are added to the treatment cell at a
concentration and flow rate to achieve in situ concentrations of 3 mM butyric acid and 20 mg/L yeast
extract.
4. 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.
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, CFLt, C2H4, C2H6, NO3, NO2,
SO4, Cl, Br, alkalinity, and total iron.
Performance Monitoring of the Field Test Cell: Table 1 presents the performance monitoring parameters
and their measurement frequency during field-testing.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Table 1: Performance Monitoring Parameters
Parameter
TCE, cis-DCE, VC, ethene
Volatile Fatty Acids (electron
donor)
Bromide
Dissolved Oxygen
pH
Conductivity
T^ +2
Fe
CrLj, C2ri4, C2ri6
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
5. RESULTS
Results from the RABITT field treatability testing at Cape Canaveral Air Station, Naval Air Station
Alameda, and Fort Lewis will be presented in the next interim report.
6. 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.
7. 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.
8. COSTS
Detailed costs for all phases of the RABITT treatability approach will be presented in the final report.
9. CONCLUSIONS
Two of the five planned RABITT treatability test systems have been installed and are currently being
monitored. By the time of the Year 2000 NATO/CCMS meeting, three of the tests should be completed
and the final two systems will be operating.
10. REFERENCES
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 Methanogenesis."
Applied and Environmental Microbiology 57(8): 2287-2292.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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.
Gossett, J.M., T.D. DiStefano, and M.A. Stover. 1994. Biological Degradation ofTetrachloroethylene in
Methanogenic Conditions. U.S. Air Force Technical Report No. AL/EQ-TR-1983-0026, USAF
Armstrong Laboratory, Environics Directorate, Tyndall AFB, FL.
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.
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 61(11):
3928-3933.
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.
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.
Zinder, S.H., and J.M. Gossett. 1995. "Reductive Dechlorination of Tetrachloroethene by a High Rate
Anaerobic Microbial Consortium." Environmental Health Perspectives 103: 5-7.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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:
rcctcrcv(rt}vfcsc.navv.mil
Project Dates
Accepted 1999
Final Report 2000
Contaminants
Chlorinated solvents:
DCE
PCE, TCE, and cw-1,2-
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:
Costs Documented?
Yes, in this report
and in more detail in
the Final Report
(March 2000)
Project Size
Field Demonstration
Pilot-scale
Results Available?
Yes, in this report
and in more detail in
the Final Report
(March 2000)
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 2001
(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
(Gavaskaretal., 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 for this project are 5 ug./L of PCE and TCE, 70 ug/L of cis-1,2
dichloroethene (cis-1,2 DCE), and 2 ug/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 ug/L of PCE and TCE, 70 ug/L of cis 1,2-dichloroethene (DCE), and 2 ug/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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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
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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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Battelle, 1997. Design/Test Plan: Permeable Barrier Demonstration at Area 5, Dover AFB. Prepared for
Air Force Research Laboratory by Battelle, Columbus, Ohio.
Gavaskar, A., N. Gupta, B. Sass, R. Janosy, and J. Hicks. Design Guidance for the Application of
Permeable Reactive Barriers for Ground-water Remediation. Prepared for Air Force Research Laboratory
by Battelle, Columbus, Ohio on March 31, 2000.
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 III)
January 2001
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: ncwmark@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
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.
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2. BACKGROUND
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)
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).
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
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.
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
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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.
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
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.
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.
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
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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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
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.
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.
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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.
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
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.
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
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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
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
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).
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; 9 pp.
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-JC126636, 1997; 18pp.
Knauss, Kevin G.; Dibley, Michael J.; Leif, Roald N.; Mew, Daniel A.; Aines, Roger D. "Aqueous
Oxidation of Trichloroethene (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.
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Knauss, Kevin G.; Dibley, Michael J.; Leif, Roald N.; Mew, Daniel A.; Aines, Roger D. "Aqueous
Oxidation of Trichloroethene (TCE): A Kinetic analysis." Accepted for Publication, Applied
Geochemistry; 1998b.
Knauss, Kevin G.; Dibley, Michael J.; Leif, Roald N.; Mew, Daniel A.; Aines, Roger D. "Aqueous
Oxidation of Trichloroethene (TCE) and Tetrachloroethene (PCE) as a Function of Temperature
and Calculated Thermodynamic Quantities, Submitted to Applied Geochemistry; 1998c.
Leif, Roald N.; Chiarrappa, Marina; Aines, Roger D.; Newmark Robin L.; and Knauss, Kevin G. "In Situ
Hydrothermal Oxidative Destruction of DNAPLS 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.; Battelle Press, Columbus,
OH, 1998; pp 133-138. Also available as Lawrence Livermore National Laboratory, Report,
UCRL-JC-129933, 1998a; 8 pp.
Leif, Roald N.; 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).
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 of Flourene at Temperatures Up To 150°C; Lawrence Livermore National Laboratory,
Report, UCRL-CR-129938, 1997a; 32pp.
Leif, Roald N.; 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, 1997b; 21 pp.
MSE 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.
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).
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.
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.
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.
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. 1,39-52.
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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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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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
All 3 projects are
on-going and the
latest observations
are presented in this
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: CQmptonJiarryja^crja.gQY
Steve Hirsh (Aberdeen Site)
U.S. EPA, Region 3 (3HS50)
1650 Arch Street
Philadelphia, PA 19103-2029
Tel: 215-814-3352
E-mail: hirsh.steven@epa.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: grincg_.geoigg;J7lepj|.gov
Greg Harvey (Carswell AFB Site)
U.S. Air Force, ASC/EMR
1801 10th Street-AreaB
Wright Patterson AFB, OH
Tel: 937-255-7716 ext. 302
Fax: 937-255-4155
E-mail:
G regory. Harvey@wpafb. af. mil
Project Dates
Accepted
1998
Contaminants
Chlorinated solvents: TCE, 1,1,2,2-
TCA, PCE, 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
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will demonstrate the use of hybrid poplars to hydraulically control the sites and ultimately to remove the
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 various hole 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
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downgradient end of the site during the three-year demonstration period was 11 percent. Increases in
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 dicloromethane (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 semiconfming unit for water
and contaminants percolating down toward an unconfmed 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.
Cars-well 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.
• 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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.
WJEGTA515
.WJEGTA527
WJEGTA509
-WJEGTA508
UEGTA507
EXPLANATION
• MONITORING WELL: Well * STREAM-STAGE GAGE
number indicates well was sampled
throughout the entire location + TENSIOMETER NEST
I MONITORING WELL WITH
WATER-LEVEL RECORDER
WEATHER STATION
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 1m) remained
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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.
Cars-well 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.
• 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.
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5. RESULTS AND EVALUATION
Aberdeen Proving Grounds, Maryland
• 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).
• Groundwater sampling indicated that the contaminated plume has not migrated off-site during the
growing seasons.
• There is no ecological impacts that are attributable to the plantation area. Sampling data have
shown non-detectable off-site migration of emissions from transpiration gas.
• Peak transpiration is estimated to occur in approximately 10 to 15 years.
• 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.
• Contaminant uptake is minimal at this time but is expected to improve as the trees mature.
• 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.
• 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 without cold trap, indicate 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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
• 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).
CarswellAFB, 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 >
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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
observations 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 2.5m 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.
• 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
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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 the to 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 cmVsec) 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.
• 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-l,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
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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
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
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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 2001
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
Media
Groundwater
Contaminants
Heavy metals (zinc,
cadmium, arsenic, lead,
chromium, nickel,
copper)
sulfate
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.
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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
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 + IT"
H2S + Me++ ==> MeS + 2 FT
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 ofin-situ bioprecipitation of heavy metals on sites should therefore be evaluated case by
case.
Outline of the project:
1. Preliminary study
• Site evaluation
2. Lab-scale treatability testing in batch and column experiments
• The presence of SRBs in the aquifers will be examined by microbial countings,
measurements of SRB-activity, and PCR-technology.
• Selection of a suitable organic substrate
• Determination of optimal physico-chemical conditions: required concentration of the electron
donor, nutrients requirement, sulfate requirements, influence of temperature, etc.
• 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.
• The stability of the formed metal sulfides will be checked.
• Further is clogging due to biomass production and metal precipitates an important issue that
has to be evaluated.
3. Field demonstration on pilot or full scale
4. Monitoring
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January 2001
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 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 HgCl2), 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 +
0.5mMHgCl2
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 SO42V1). Only after the addition
of extra sulfate (2000 mg SO4271) 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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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
316
mV
173
mV
197
mV
44 mV
144
mV
278
mV
-129
mV
-398
mV
T4
203
mV
341
mV
132
mV
290
mV
-308
mV
6mV
-212
mV
-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
315
mV
198
mV
145
mV
-284
mV
143
mV
-168
mV
-460
mV
-241
mV
T19
247
mV
301
mV
143
mV
142
mV
-316
mV
73 mV
-88 mV
-380
mV
-198
mV
NOTES: 5 ml K-acetate (25%); Postgate C 10X concentrated; 10 g FeA4;
TO: at time zero; Tl: after 1 week; T4: after 1 month; T8: after 2 months; T12: after 3 months; T19: after 5 months.
Table 3: Ni Concentrations at Different Conditions from 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
Total
62
54
62
37
424
57
65
48
34
Sol.
54
45
52
34
82
51
51
33
24
Tl
Total
52
44
45
54
270
51
72
28
42
Sol.
45
42
51
60
103
34
63
<20
25
T4
Total
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
Total
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
Total
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 2001
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., Cricka L.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.
7. Van der lelie, D., L. Diels, J. Vangronsveld, H. Clijsters. 1998. De metaalwoestijn herleeft. Het
ingenieursblad 11/12.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 17
GERBER Site
Location
SERMAISE - Department of
ESSONNE - ILE DE
FRANCE Region
Technical Contact
Rene Goubier
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
Please note that this project summary was not updated since the 1999 Annual Report.
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 important quantity of drums were 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: 3700 drums were excavated and
treated and 14,000 tons of polluted soil was confined on the site. The treatment of this polluted soil is
carried out at the present time by solvent washing. The total cost of these first phases of clean up is about
65 millions francs.
2. THE NEW PROJECT
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 will be:
• to improve the knowledge of the contamination source and to prepare the clean up of the
remaining hot spots
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
• to 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 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. 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 III)
January 2001
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
Please note that this project summary was not updated since the 1999 Annual Report.
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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
operation and competitive development in technology under real-wo rid conditions. The technologies
tested in the first phase of the pilot plant are:
• 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 ventilated 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
Weiss H., Teutsch G., Daus B. (ed.)(1997): Sanierungsforschung in regional kontaminierten Aquiferen
(SAFIRA) - Bericht zur Machbarkeitsstudie fur den Modellstandort Bitterfeld.-UFZ-Bericht 27/1997,
Leipzig
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Weiss H., Daus B., Fritz P., Kopinke, F.-D., Popp, P. & Wiinsche, L. (1998): In situ groundwater
remediation research in the Bitterfeld region in eastern Germany (SAFIRA); In: M. Herbert & K. Kovar
(Ed.): Groundwater Quality: Remediation and Protection.- IAHS Publication no. 250, 443-450.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 19
Succesive Extraction-Decontamination of Leather Tanning Waste Deposited Soil
Location
University of Istanbul
Technical Contact
Dr. Erol Ercag
University of Istanbul
Faculty of Engineering,
Department of Chemistry
Avcilar, 34850
Istanbul, Turkey
Tel: 02 12 593 84 7, Ext.
1191
Fax: 0212 591 1998
ErcagiSiistanbul .edn.tr
Project Dates
Accepted 1998
Final Report 2001
Costs Documented?
No
Report Status
Interim
Results Available
None
Contaminants
Organic and
inorganic
Project Size
Laboratory/field
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.
5. COSTS, HEALTH, AND SAFETY
Not yet available.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
6. CONCLUSIONS
Insufficient data to draw any meaningful conclusions.
7. REFERENCES
Not applicable.
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January 2001
Project No. 20
Interagency DNAPL Consortium Side-by-Side Technology Demonstrations at
Cape Canaveral, Florida
Location
Cape Canaveral, FL,
USA
Technical Contact
Tom Early
Oak Ridge National
Laboratory
P.O. Box 2008
Oak Ridge, TN 37831-
6038
Tel: 865/576-2103
Fax: 865/574-7420
Project Status
Ongoing/Interim
Project Dates
1999-2001
Costs Documented?
2001
Contaminants
DNAPL
Technology Type
3 Technologies
Side-by-Side
Media
Soil and Ground Water
Project Size
2 Acres
Results Available?
2001
1. INTRODUCTION
An important step in reducing technology risk and increasing user and regulatory acceptance of DNAPL
remediation, characterization and monitoring technologies involves conducting concurrent, "side-by-side"
field demonstrations. These side-by-side" demonstrations result in comparative cost and performance data
collected under the same field conditions. Through appropriate documentation, the resulting cost and
performance data can be evaluated for site-specific applications. Side-by-side demonstrations help to fill
an important "gap" in the process of technology development and deployment and will accelerate
technology privatization.
2. BACKGROUND
Dense non-aqueous phase liquids (DNAPLs) pose serious, long-term ground water contamination
problems due to their toxicity; limited solubility in ground water; and significant migration potential in
soil gas, ground water, 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 ground water contamination. Many agency and private-sector sites have DNAPL
contamination problems, including federal, state, and local government agencies. 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.
While various DNAPL remediation, characterization and monitoring technologies have been
demonstrated in the past, it is difficult, if not impossible, to make meaningful comparisons of either
performance or cost among these technologies because of the variable conditions at the demonstration
sites. As a result, "problem holders" and regulatory officials have been reluctant to deploy these
technologies for site clean up. In order to expedite the regulatory acceptance and use of these innovative
remedial technologies, comparative cost and performance data must be collected.
3. TECHNICAL CONCEPT
In 1998, a multiagency consortium was organized by the United States Department of Energy/Office of
Environmental Management (DOE/EM) and the Department of Defense (DOD) through the Air Force
Research Laboratory (AFRL) in cooperation with the 45th space wing, the National Aeronautics and
Space Administration (NASA) and the United States Environmental Protection Agency (EPA) to
demonstrate innovative DNAPL remediation and characterization technologies at a NASA remediation
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
site on Cape Canaveral Air Station, Cape Canaveral, FL. This Interagency DNAPL Consortium (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);
• cost-share the demonstration and comparison of these remediation and monitoring system
technologies;
• accelerate both the demonstration and deployment of DNAPL remediation, characterization and
monitoring technologies for the purpose of reducing the perceived technology risk associated
with 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 addition to ex situ treatment and disposal.
In order to conduct this side-by-side demonstration, an IDC Core Management Team was organized. The
IDC consists 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 utilizes a Technical Advisory Group (TAG) for support in making decisions that
concern individual evaluation of remediation systems. The IDC TAG is comprised of experts from
industry, academia and federal agencies. With the support of the TAG, the Team selected three of the
most promising remediation technologies for deployment and evaluation at Launch Complex 34.
4. ANALYTICAL APPROACH
In Situ Chemical Oxidation
In situ oxidation using potassium permanganate is a potentially fast and low cost solution for the
destruction of chlorinated ethylenes (TCE, PCE, etc), 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, 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 carbon
dioxide, chloride ions and manganese dioxide. The permanganate solution typically is applied at
concentrations of one to three percent solution via injection wells. This solution is easily handled, mixed
and injected and is non-toxic and non-hazardous.
Bench-scale laboratory tests of potassium permanganate with trichloroethylene have resulted in up to a
90% reduction of trichloroethylene 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Benefits
• Chemically oxidizes a wide range of organic compounds to innocuous end-products over a wide
pH range
• Visible (purple) solution makes it easy to track the injection influence or the degree of treatment
• Chemically stable in water (very slow auto-degradation)-stays in solution until it is reacted
• No off-gas treatment required
Six Phase Soil Heating
The Six Phase Soil Heating technology removes contaminants from soil and ground water by passing an
electrical current through the soil matrix. The passage of current generates heat due to electrical resistance
within the soil. This is the same process used in any electrically heated device (e.g., clothes iron, heater,
stove). Heat is generated throughout the soil in the remediation area and the temperature of the soil is
increased to the boiling point of water. Soil moisture becomes steam that is captured by vapor recovery
wells for removal. Soil contaminants are vaporized concurrently and are captured for ex situ treatment.
Benefits
• Heat is generated uniformly throughout the treatment volume. While low permeability lenses
reduce the performance of other technologies that rely on the vertical movement of a fluid or
vapor though the soil matrix, soil heterogeneity or low permeability does not adversely effect Six
Phase Soil Heating. In fact, low permeability soils tend to carry greater current than do sandy
soils, thus, become hotter, and boil constituents faster.
• Anaerobic dechlorination of solvents will add conductive chloride ions to "hot spots", likewise
attracting current for faster remediation of the impacted regions of the site.
• The boiling of soil moisture in clay lenses forms steam to "sweep out" volatile organic
compounds. This steam stripping process effectively increases the permeability clay soils.
• Because Six Phase Soil Heating treats all soils in the treatment volume, there are no untreated
regions from which contaminants could diffuse later and cause rebound. Rebound has not been
observed at any Six Phase Soil Heating site.
• The presence of perched water does not reduce the effectiveness of Six Phase Soil Heating.
In Situ Thermal Remediation (Steam Injection)
Thermal remediation by steam injection and recovery uses Dynamic Underground Stripping, Steam
Enhanced Extraction, Hydrous Pyrolysis/Oxidation, and Electrical Resistance Tomography. Combining
these technologies the Dynamic Underground Stripping System uses boilers to generate steam which is
then pumped into injection wells that surround the contaminants. The steam front volatilizes and
mobilizes the contaminants as it pushes the resulting steam front toward a central network extraction well
where it is vacuumed to the surface. Direct electrical heating of soils, clay and fine-grained sediments
causes trapped water and contaminants to vaporize and forces them into steam zones where vacuum
extraction removes them. Electrical Resistance Tomography is used as a process control method to
measure electric resistance and temperatures in the subsurface that allow for real-time control of the
heating process.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Benefits
• Faster clean-up, potential closure within months to years, not decades
• Removes source contaminants effectively
• Treats contamination both above and below the water table, with no practical depth limitation
5. RESULTS
In situ chemical oxidation and six phase heating technologies were implemented in 2000 on the two
outside plots of the three plots in the study. Steam stripping will be initiated in January 2001. Preliminary
data from the first two demonstrations are being analyzed. Complete results will be presented at the
September 2000 Pilot Study meeting in Belgium.
6. HEALTH AND SAFETY
To be determined.
7. ENVIRONMENTAL IMPACTS
To be determined.
8. COSTS
To be determined.
9. CONCLUSIONS
To be determined.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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:
bMDJSDJlIi^igLbaug^ethz.ch
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
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 10m 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"4m/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 50%).
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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
(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.
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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 22
Thermal In-Situ Using Steam Injection
Location
Former hazardous waste
disposal site, Miihlacker,
Germany
Technical Contact
Dr. H.-P. Koschitzky
Research Facility for Subsurface
Remediation, VEGAS,
University of Stuttgart,
Pfaffenwaldring 6 1
D-70569 Stuttgart, Germany
^oi^iMMMM^^MMSMLd^
Project Status
New project
Project Dates
July 1999 -January
2001
Costs Documented?
Not yet
Contaminants
TCE, BTEX
Technology Type
Steam injection
Media
Unsaturated zone
Project Size
Pilot-scale
Results Available?
Not yet
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
subsurface 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 Miihlacker 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 Miihlacker. 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. Detailed site investigation led 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 conventional 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 where steam can be injected in the highly
contaminated zone between 7 and 15 m below ground surface. The total volume of soil to be treated is
approximately 3000 m3.
The pilot plant is operated by two companies: Ziiblin Umwelttechnik GmbH and Preussag Wasser-
technik 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 Miihlacker, represented by the
consultant company Weber-Ingenieure GmbH.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
3. TECHNICAL CONCEPT
The egg-shaped test field has a diameter of about 20 m and 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 15m.
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 with a total of 100 sensors were installed at spaces 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 extent 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 weekly in the extracted vapours and liquids
using GC and HPLC methods and a flame ionization detector (FID).
5. RESULTS
First results of the pilot test can be found in Theurer et al. (2000).
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
Not yet available.
10. REFERENCES
1. 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 III) January 2001
2. Schmidt, R., Koschitzky, H.-P. (1999): Pilothafte Sanierung eines BTEX Schadens an einem
ehemaligen Gaswerksstandort mit der thermisch unterstiitzten Bodenluftabsaugung (TUBA)
durch Dampfmjektion, Wiss. Bericht WB 99/5 (HG 262), Institut fur Wasserbau, Universitat
Stuttgart (in German).
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 23
Bioremediation of Pesticides
Location
Stauffer Management Company
Superfund Site, Tampa, FL
Technical Contact
Brad Jackson
U.S. EPA, Region 4
6 IForsyth Street, SW
Atlanta, GA 30303-8960
Tel: 404-562-8925
Fax: 404-562-8896
E-mail: iackson.brad'ojcpa.gov
Project Status
New project
Project Dates
Accepted 2000
Final Report 2001
Costs Documented?
Yes - Field
Demonstration
Contaminants
Chlordane, DDT, ODD,
DDE, dieldrin, molinate,
toxaphene
Technology Type
Composting process
(Xenorem™)
Media
Soil
Project Size
Field Demonstration: 500
yd3
Full-Scale: 16,000 yd3
Results Available?
Yes - Field
Demonstration
Soon - Full-Scale
1. INTRODUCTION
The Stauffer Management Company (SMC) 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 has shown concentration reductions of more than 90 percent for ODD and
nearly 90 percent reduction for chlordane. Beginning in May 2000, the project has been operating under
full-scale conditions. The full-scale remediation is expected to be completed by 2002.
2. BACKGROUND
Located in Tampa, Florida, the SMC site manufactured and distributed agricultural chemical products
(organochlorine and organophosphorus 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. Typical pesticide concentrations
measured in the soil were chlordane (47.5 mg/kg), ODD (162.5 mg/kg), DDE (11.3 mg/kg), DDT (88.4
mg/kg), dieldrin (3.1 mg/kg), molinate (10.2 mg/kg), and toxaphene (469 mg/kg).
The site received final status under the Superfund program in 1996. Thermal desorption was initially
chosen as the remedial option. However, due to 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.
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. If these objectives were met, full-scale deployment of the technology would
ensue to treat 16,000 yd3 of pesticide contaminated soil.
3. TECHNICAL CONCEPT
AstraZeneca Group PLC, the affiliate of SMC, developed a patented composting process called
Xenorem™ for remediating soils contaminated with pesticides. Xenorem™ uses anaerobic and aerobic
cycles to bioremediate pesticides with indigenous bacteria and addition of amendments.
Using 500 yd3 of excavated soil from "hot spots" at the site, a field demonstration was conducted in an
enclosed on-site warehouse from June 1997 until September 1998. Soil amendments, including organic
wastes or byproducts (cow manure and straw), were added to the compost pile to maintain desired
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
conditions of temperature, oxygen, pH and nutrient availability. The addition of amendments took place
initially and at several intervals throughout the length of the project. The total volume of the compost pile
reached 1,193 yd3 at the conclusion of the demonstration. The process used an initial aerobic environment
with high levels of nutrients, followed by an anaerobic cycle when the pile was covered with a tarp. The
demonstration was conducted during hot and cold weather periods and used to assess amendment quality
effects and use of various mixing equipment.
4. ANALYTICAL APPROACH
Standard operating procedures were performed for soil sampling and collection of composite samples.
5. RESULTS
Table 1 shows the cleanup levels specified for selected constituents, the initial (T0) and end (T64)
concentrations for the field demonstration, and the percent reduction in concentration over that period.
Table 1: Concentrations of Selected Contaminants during the SMC Field Demonstration
Contaminant
Chlordane
ODD
DDE
DDT
Dieldrin
Toxaphene
Molinate
Cleanup Level
(mg/kg)
2.3
12.6
8.91
8.91
0.19
2.75
0.74
TO Concentration
(mg/kg)
47.5
242*
11.3
88.4
3.1
469
10.2
TM Concentration
(mg/kg)
5.2
23.1
6.8
1.2
BDL
29
BDL
Reduction in
Concentration (%)
89
90.5
40
98
NA
94
NA
* Consists of original DDD value (162.5 mg/kg), plus the amount converted from DDT in the first few weeks of
treatment, NA - Not Applicable, BDL - Below Detection Limit
6. HEALTH AND SAFETY
Not Available.
7. ENVIRONMENTAL IMPACTS
Not Available.
8. COSTS
Although specific costs are not available for the field demonstration, the vendor provided typical costs for
a cleanup using the Xenorem™ process. Total project costs were estimated at $192/yd3, including
$132/yd3 for treatment using Xenorem™ and $50/yd3 for non-technology expenses such as soil
excavation costs.
9. CONCLUSIONS
Based on the results from the field demonstration, the Xenorem™ technology is being deployed at full-
scale at the SMC site to treat approximately 16,000 yd3 of soil. The initial full-scale operation entails
treating 4,000 yd3 batches of contaminated soil. The field demonstration also has established amendment
quality specifications for full-scale use, along with experience on a broader range of amendment types.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
10. REFERENCES
1. Frazar, Chris. 2000. The Bioremediation and Phytoremediation of Pesticide Contaminated Sites.
www.clu-in.org. August.
2. U.S. Environmental Protection Agency. 2000. Cost and Performance Report: Bioremediation at the
Stauffer Management Company Superfund Site, Tampa, Florida, www.frtr.gov/cost. August.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 24
Surfactant-Enhanced Aquifer Remediation
Location
Marine Corps Base,
Camp Lejeune, NC
Project Status
New project
Contaminants
tetrachloroethylene
(PCE)
Technology Type
Surfactant flushing
Technical Contact
Laura Yeh
Naval Facilities Engineering
Service Center
560 Center Drive
PortHueneme, CA 93043
Tel: 805-982-1660
Fax: 805-982-1592
E-mail: yehsl@nfesc.naw.mil
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: vaiic.lcland@cpa.gov
Gary A. Pope, Ph.D.
The University of Texas
Austin, TX 78712
Tel: 512-471-3235
Fax:512-471-3605
E-mail:
gar\! popc@pc.utcxas.cdu
Project Dates
Accepted 2000
Final Report 2001
Media
Groundwater
Frederick J. Holzmer
Duke Engineering & Services
4433 NW Seneca Ct.
Camas, WA 98607
Tel: 360-834-6352
Fax: 360-834-7003
E-mail:
fjholzmc@dukccnginccring.c
om
Costs Documented?
Yes - Under
Review
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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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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, NC. 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 in the extraction well
effluent from 1.1 to 5 percent by weight (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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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
6. HEALTH AND SAFETY
No significant health and safety issues are associated with the implementation of SEAR, other than the
health and safety considerations normally associated with a remediation field demonstration.
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 injectant, 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, 2000; draft version). The report also includes a comparison of costs for full-scale SEAR at a
high-permeability site, as well as cost comparisons to alternative remedial technologies. The alternative
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technologies were compared only on a cost basis since there is no performance data for these technologies
at Site 88, MCB Camp Lejeune.
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 only treated 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, 2000 (draft version currently in review). Cost and
Performance Report for Surfactant-Enhanced DNAPL Removal at Site 88, Marine Corps Base
Camp Lejeune, North Carolina. Prepared for NFESC by Battelle Memorial Institute, Columbus,
OH and Duke Engineering & Services, Austin, TX.
2. Naval Facilities Engineering Service Center (NFESC), 2000. Final Technical Report for
Surfactant-Enhanced DNAPL Removal. Prepared for ESTCP Program Office by NFESC, Port
Hueneme, CA and Duke Engineering & Services, Austin, TX.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Project No. 25
Liquid Nitrogen Enhanced Remediation (LINER): A New Concept for the
Stimulation of the Biological Degradation of Chlorinated Solvents
Location
Netherlands
Technical Contact
Arne Alphenaar, Emile
Marnette, Haimo Tonnaer,
Chris Schuren, Frank
Spuij, Andre Lokhorst
(Tauw), Robert Nijhuis
(AGA-gas)
Project Status
New project
Project Dates
Costs Documented?
Media
Soil and groundwater
Technology Type
Contaminants
VOCls
Project Size
Results Available?
1. INTRODUCTION
One of the major problems involved in soil remediation today is the treatment of deep groundwater
contaminated with chlorinated hydrocarbons (VOCls). Biological degradation through microorganisms
often will 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 infiltration systems tend to clog easily
and the limited radius of influence of an infiltration well requires a dense network of wells.
In cooperation with AGA gas, engineering consultancy Tauw has developed a new remediation concept,
which overcomes most of the limitations inherent to the conventional in situ biological systems for
degradation of VOCls.
2. REMEDIATION OF SOIL CONTAMINATED WITH VOCLS
The Netherlands count large numbers of sites contaminated with VOCls. The remediation approach
commonly applied concerns extraction of contaminated groundwater followed by above ground
treatment. However, authorities more 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 contamination located in relatively
shallow soil layers.
Over the past few years, a few methods have been developed to enhance indigenous biological
degradation of ntaminants situated at greater depths; the local bacteria are stimulated such that they clean
up the VOCls contamination. All these methods involve the infiltration of a substrate (to feed the
bacteria) into the soil.
Clogging
imited radius of
ifluence
Bioavailability
Figure 11: Schematic of the drawbacks of liquid substrate addition
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January 2001
Problem: substrate transportation in the groundwater
All methods are based on adding and mixing substrate to the soil. Infiltrated substrate flowing along with
groundwater will be degraded by all kinds of soil bacteria before it reaches other contaminated areas
downstream. In consequence, the network of infiltration points required to effectively stimulate the
existing natural attenuation processes will have to be very dense. The cost of such networks makes them
practically unfeasible, particularly for contaminants located at large depths. Again, another problem
involved in infiltration of substrates in liquid form is clogging of the wells by biomass.
Solution: Gas injection substrate by means of infiltration.
The flow rate at which gas is distributed both horizontally and vertically within the soil is much higher
than that of water, making the injection of gas a much more effective procedure. Another advantage lies
in the relatively low cost of injecting gas into great depths.
Due to the (anaerobic) nature of microbiological processes, the use of compressed air is impossible. On
the basis of recently obtained insights into the behaviour of indigenous microorganisms, the injection of
nitrogen gas saturated with methanol (substrate) or of nitrogen-hydrogen mixture is currently under
consideration.
Figure 12: Schematic view of the advantages of
anaerobic sparging (the liner gas injection system)
A favourable side-effect of the method is
that due to the stirring created in the soil
by the injected gas (input of energy),
contaminants will become more readily
available for biological degradation or
physical removal.
LINER - Liquid Nitrogen Enhanced
Remediation
LINER involves the injection of nitrogen
gas saturated with a substrate. In April
2000, a pilot investigation began to test the
feasibility and efficiency of LINER. It is
expected that the project will serve to
demonstrate in practice that gas injection is a feasible alternative to the in-situ remediation methods
commonly applied to VOCls contamination. The following aspects of gas injection are investigated:
Substrate injection
procedures; particularly
the injection of methanol
as a substrate, in the
form of a fine mist, has
not reached the final
development stages yet;
Radius of influence and
distribution pattern of
the injected gas; and
Effects of the injected
substrate on the
degradation rate of PCE,
the original contamination.
5 m -mv /
25 m -mv
45 m -mv '
j
),
ip [
^f====^-r~^,
Ml
'P IT
1
.
P
6 m
Figure 13: Set-up of the Pilot Tests
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
The pilot will be integrated into a full-scale remedial operation. At two other sites, LINER will be applied
at full scale as a remediation technique for VOCls. This approach offers a unique opportunity. The new
technique can simultaneously be tested on a practice scale on three sites, with each site differing from the
other ones in terms of soil structure, contamination situation, and remediation target.
The picture shows the LINER pilot setup.
Liquid nitrogen is evaporated. The built up
pressure is reduced to the appropriate
injection pressure. Via nozzles, methanol
is nebulized into the nitrogen gas-flow.
The injection well is situated H m below
grade. At several distances monitoring
wells are installed for monitoring the
distribution of methanol in the groundwa-
ter and for assessing the enhancement of
biological degradation of VOCls.
3. PRELIMINARY RESULTS
The methanol has been retrieved in high
concentrations—over 500 mg/L at a depth
of 5 m below grade and approximately 200
mg/1 at 45 m below grade (the depth of
injection). There has been a considerable distribution of methanol in a vertical direction. This observation
indicates that the methanol vapor is stable enough to be distributed by the nitrogen gas flow.
Up until now, no methanol has been retrieved in monitoring wells that are located at lateral distances from
the injection well. However, a large increase has been observed in degradation products of PCE and
sulphate reduction.
LINER pilot setup
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January 2001
Project No. 26
SIREN: Site for Innovative Research on Monitored Natural Attenuation
Location
United Kingdom
Technical Contact
Sarah Macnaughton
AEA Technology
E6, Culham
Abingdon
OXON OX 14 3DB
Project Status
New project
Project Dates
September 1999-
2003 (or longer)
Costs Documented?
Yes
Contaminants
Organic solvents
Technology Type
Monitored natural
attenuation (MNA)
Media
Consolidated and non-consolidated aquifer
Project Size
>£1 million
Results Available?
Partly
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 that 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 characterised,
will be open to any bonafide researcher to conduct research on natural attenuation funded by other
bodies. AEA Technology, Shell, and the Environment Agency developed the project. In phase 1 of the
programme, the project team formulated criteria for research site selection. These criteria were developed
to locate a site available for 3-5 years that contained a mixture of contaminants in an aquifer characteristic
of UK conditions. Herein, we present the results of the site selection process.
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 a/., 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.
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.
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4. ANALYTICAL APPROACH
In phase 1 of the project, the objective has been to identify a suitable demonstration site for monitoring
natural attenuation. As part of this analysis, criteria were identified to assess the suitability of a number of
sites. It was considered that the ideal site should:
• Contain potentially biodegradable contaminants in a groundwater plume and should not contain
large amounts of free product.
• Be available for research for at least 3 years, although preferably 5 years.
• Have a plume of contamination that will not impact a receptor within 3 years of the project. The
plume should be contained within the site boundary or access should be available to areas of the
plume off-site.
• Have no current or impending legal and/or regulatory disputes.
• Have a limited number of identified source areas.
• Have sufficient initial site characterisation information to identify sources, pathways, and
receptors.
• Have historical monitoring data that could act as a benchmark.
• Be situated on a minor sedimentary aquifer, with preference given to a consolidated formation,
such as sandstone.
• Have groundwater within 10 to 15m of the surface, and the water table should not be subject to
wide fluctuations with recharge.
• Have no operating remediation scheme that could interfere with the potential study area.
• Be secure with no outstanding HS & E issues.
5. RESULTS
Over 200 sites were considered. Of these, more than 60 were petrol and oil depots, 117 were
infrastructure sites and more than 10 were landfills. Only 41 sites of this initial list were situated on a
minor sedimentary aquifer. After taking into account site availability, that the contaminants need to be
amenable to MNA, and that active remediation was not already underway or pending, just 4 sites were
left for further ranking against the criteria in section 4.
The short-listed sites were 1) a landfill in the south of England; 2) a waste transfer station; 3) a petroleum
distribution plant; and 4) a chemical plant. Although the landfill had received large amounts of liquid
solvent waste (mainly toluene), the contamination plume was either already attenuated or ill defined.
Moreover the presence of a deep unsaturated zone increased potential investigation costs. Consequently,
the landfill was considered a low priority. The waste transfer station was leased to a chemical company
and was located on 9 m of blown sand overlying Upper Carboniferous sandstone. Contaminants included
PAHs, chlorinated hydrocarbons, and CFCs. However, further investigation indicated that the
contaminants had migrated off-site with access to that part of the plume unlikely. In addition, the CFCs
were regarded as non-biodegradable and, as such, this site was also designated "low priority." The
petroleum distribution site was located on a consolidated aquifer, with plume flow towards a nearby river.
It was a multi-occupant site with contamination that included fuel oils, petroleum hydrocarbons, and
diesel. There were a limited number of source areas that had mainly been cleared. MNA had not been
investigated in detail at this site, but in general the site did agree with the selection criteria. However, due
to legal issues that could potentially arise from multi-ownership of the site, it was not ranked the highest
of the short-listed sites.
The highest ranking was given to the chemical plant site with mixed contaminants including BTEX,
chlorinated solvents, LNAPL, and DNAPL. It has both perched aquifers and a major consolidated aquifer
that are contaminated and a number of receptors identified nearby. There is no evidence to date that these
receptors have been impacted by contamination. The plume is not believed to have migrated off-site. The
site has just one owner. The project team agreed that the contamination could be managed successfully by
monitored natural attenuation (MNA). The chemical plant was, therefore, found to be the most compliant
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with all of the site selection criteria. Moreover, a nested monitoring well network was already in place
and being extended. As such, this site was chosen as the preferred location for the SIREN project.
6. HEALTH AND SAFETY
All projects proposed for the site will undergo a formal health and safety review. All staff involved with
projects at the chosen SIREN site will undergo an initial site health and safety induction course.
7. ENVIRONMENTAL IMPACTS
Environmental impacts at the site will be marginal. Utilisation of MNA at this site will be a low
energy/low impact approach.
8. COSTS
The Environment Agency is expected to contribute in the region of £25Ok to the project with £25k
provided for the phase 1 project. During this initial phase of work, more than £1M worth of site
investigation work has been reviewed. In phase 2 of the work, in kind contributions from the project team
should total about £35Ok. Through phase 3, the project team is looking to manage in the order of £1M per
year in research grants.
9. CONCLUSIONS
During this first phase of SIREN, 203 sites were considered as possible field locations. Of these sites,
about 20% were identified as being on minor sedimentary preferably consolidated aquifers. This is not
surprising considering the fact that many contaminated sites in the UK are located in coastal regions or in
valley deposits. The remaining stringent selection criteria eliminated the majority of these 41 sites, with
the result that only 4 were considered to be serious candidates. Of these, a petroleum storage plant and a
chemical plant were considered to be the most appropriate sites with the ownership issues weighing the
final selection in favour of the chemical plant.
The site owners have since granted permission for phase 2 of the SIREN project to go ahead, and in
principle have agreed for the site to be used as a demonstration site for 3-5 years subject to certain
conditions of confidentiality and safety. A further advantage of this site is that its operator is already
conducting a considerable amount of additional site characterisation and monitoring that will be made
available to project SIREN. Taken as a whole, the contamination at the site is too complex to fit
comfortably within SIREN without further site characterisation to enable clear objectives to be set for this
project. This work will be carried out in phase 2.
10. REFERENCES
1. ASTM (1998) 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.
2. Brady P.V., Brady, M., and Borns D.J. (1997). Natural Attenuation: CERCLA, RBCAs and the
Future of Environmental Remediation. Lewis Publishers, USA.
3. Wickramanayake G.B., and Hinchee R.E. (1998) Natural Attenuation of Chlorinated and
Recalcitrant Compounds. Battelle Press, USA.
4. 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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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
5. 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.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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
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:
1. To 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. To assess in situ biodegradative activity in the vadose/unsaturated zone and evaluate potential for
enhanced bioremediation.
3. To 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. To 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.
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
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
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.
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,
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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. UK Nirex 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. UK Nirex 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 2001
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 Road
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
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
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these "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 2001
Project No. 29
Automatic Data Acquisition and Monitoring System for Management of Polluted Sites
Location
Italy
Technical Contact
Dr. Claudio Mariotti
Dr. Leonardo Zan
Aquater
Via Mirabello 53
61047 S. Lorenzo in Campo
Italy
Tel: +39 0721 7311
E-mail:
claudio .mariotti(Ojaq uatcr .cni .it
Project Status
In progress
Project Dates:
Start:
January 1998
End:
December 2000
Costs Documented?
Not yet
Contaminants
TPH, BTEX
Technology Type
Monitoring
Media:
Groundwater and soil
Project Size:
Test site
Results Available?
Not yet
1. INTRODUCTION
This project is focused on an automatic remote controlled monitoring system of parameters and polluting
processes for remediation of sites contaminated with petroleum products and byproducts. This project
summary outlines the general procedure for project development.
The above-mentioned remediation works are both in situ or on site, based on integrated chemical-physical
or microbiological processes, such as bioventing, air sparging and natural attenuation for in situ
technologies, or biopile for on site technologies.
The main objectives of this monitoring and control system are:
• To assess environmental impact and ongoing polluting processes;
• To verify the level of contaminant removal achieved in the contaminated environmental
components;
• To optimize the acquisition methods for physical, chemical and biological data;
• To substitute the manual sampling activities and laboratory analysis.
Development of this system is achieved through the following steps:
• Definition of process and environmental parameters to be monitored;
• Selection of suitable measuring gauges and analysis apparatus;
• Design of system architecture;
• System implementation; and
• Testing of system.
2. BACKGROUND
The project is a logical follow-up of a preliminary monitoring network developed under RESCOPP
project. Project RESCOPP (REmediation of Soil Contaminated by Petroleum Products) (Project number
Eu-813) was a cooperation between Italian and French companies carried out under EU EUREKA
Funding Program during the period of 1993-1997.
The objective of the project was to develop innovative tools for monitoring and remediation of sites
polluted by petroleum products.
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3. TECHNICAL CONCEPT
Controlled process parameters
To achieve effective remediation that interacts with the three environmental components in the subsoil
(interstitial gas, soil, and groundwater), the minimum set of parameters to be controlled in order to assess
both the evolution of ongoing processes and the system's quality are:
Interstitial gas:
• VOCs;
• CO2;
02;
• CH^; and
• pressure;
Soil in the vadose zone:
• temperature; and
• humidity;
Groundwater:
• level;
• temperature;
• pH, Eh, electrical conductivity; dissolved O2;
• TPH;
• BTEX; and
• total heterotrophs.
It is also necessary to monitor the meteorological parameters that affect both data quality and the
evolution of all processes involved during remediation. These parameters are:
Meteorological parameters:
• temperature;
• barometric pressure;
• humidity;
• solar radiation;
• wind speed and direction; and
• rainfall.
4. ANALYTICAL APPROACH
Measuring principles
The analysis apparatus and measuring gauges that compose the monitoring system must meet the
following requirements:
• The quality of analytical data must be comparable to those obtained in the laboratory in regard to
precision and accuracy of measurements.
System architecture
The elements that compose the automatic system are:
• Monitoring and sampling points;
• Measuring gauges;
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• Analytical equipment for gas and water samples;
• Gas and water sampling apparatus;
• Interface for measuring signals with data acquisition units;
• Local data acquisition and system management unit;
• Management software;
• Data transmission;
• Remote data acquisition and control unit;
• Monitoring of chemical-physical variations induced by the system; and
• Final control of remedial system.
5. RESULTS
Results of the onsite test on a biopile will be available in December 2000.
6. HEALTH AND SAFETY
The system is totally health safe; in fact it avoids any direct contact with toxic chemicals.
7. ENVIRONMENTAL IMPACTS
The goal of the project is to monitor the progress of remediation techniques in a polluted site and
contaminant environmental evolution by an early and remote warning system. The system itself does not
imply any particular environmental impact.
8. COSTS
The total project cost is estimated in about 300,000 US $.
9. CONCLUSIONS
Work is still in progress.
10. REFERENCES
RESCOPP project report (Eureka Eu-813)
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COUNTRY TOUR DE TABLE PRESENTATIONS
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
ARMENIA
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 %lm
Content of useful metals %lm2
Level of dispersion
Possibility to conduct measures to prevent hazardous impact
Grading unit (point)
-3
-5
-5
-2
-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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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.
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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 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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January 2001
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
0.082
0.085
II
Waste
content
Mo
Cu
SiO2
A12O3
MgO
CaO
TiO2
FeO
Na2+K2
O
P205
s
Zn
Pb
rare
metals
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
AUSTRIA
1. LEGAL AND ADMINISTRATIVE ISSUES
Austria has a Federal Act on the Clean-up of Contaminated Sites (ALSAG) since 1989. The main focus of
this act is to provide a state-fund for remediation via a waste tax. The amount of waste tax depends on the
technical standard of the landfill to which waste is brought to today. 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 Ministry for Agriculture, Forestry, Environment and
Water Management is working on an amendment to 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. Also the polluter-pays-principle should be strengthened in the amendment.
The EU DG Competion wants to launch a guideline restricting state funding for remediation projects for
companies even more. For Austria this will cause a significant slow-down of remediation of contaminated
sites because all remediation activities up to now are based on state funding. So Austria supports the
statement of Clarinet to rethink this guideline and to exclude remediation funding from that guideline.
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 Ministry for Agriculture, Forestry, Environment and Water Management registered by January 2000
2.499 suspected sites of which 2.316 are landfills and 183 are industrial sites. Detailed risk assessments
showed that 148 sites pose a considerable risk to human health or the environment and therefore were
classified as contaminated sites.
For the time being 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 Ministry for Agriculture, Forestry, Environment and Water Management. In the last ten
years 97 remediation projects, with a total cost of ATS 3,4 billion (approx. 283 US$) were funded.
3. TECHNOLOGY DEVELOPMENT PROGRAM
There is no specific technology development program on a federal level. Initiatives are set by defining a
list of priorities for funding research via the Kommunalkredit Austria AG.
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
"Contaminated Sites - Risk Assessment concerning the Pollution of Soil-Air," Austrian Standards
Institute
"Application of Bioassays for Risk Assessment and Risk Monitoring of PAH-contaminated Sites," IFA-
Tulln
"Investigation and Assessment of Potential Waste Sites in Styria (Austria)," Joanneum Research, Graz
"Evaluation and Preliminary Assessment of Old Deposits," Landesakademie Lower Austria
"Mechanico-biological Treatment of Mass Waste," University Leoben
"Comparison of Elution Tests on Solidified Waste," University for Agriculture, Vienna
"Material-technological Examinations on Solidified Waste," University Innsbruck
"Evaluation of Testing Methods and Models for Valuing the Medium and Long-term Emissions of an
Organic Waste," University for Agriculture, Vienna
"New Models for Waste Tax," Quantum, Klagenfurt
"Examination of Heavy Metals in Thermal Treatment Residues," University for Agriculture, Vienna
"Guideline for Treatment of Electronic Waste," Technisches Euro fur Technischen Umweltschutz,
Vienna
"Treatment of old Wood, especially from Furniture," TechSET, Vienna
"Treatment of Laqueur Waste," AFC Aforma Consult GmbH, Vienna
"Treatment of Galvanic Sludge," AFC Aforma Consult GmbH, Vienna
"Treatment of used Batteries," OekoConsult GmbH, Vienna
"Realisation of the Concept of Treating Medical waste," 1C Consulenten ZT GmbH/KMB, Vienna
"Technologies for cleaning Air from mechanico-biological Treatment," Institute for Industriell Ecology,
St. Polten
"Mechanical Treatment of Electronic Waste," University for Agriculture, Vienna
"Treatment of old Oil and Fat," AFC Aforma Consult GmbH, Vienna
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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 few 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.
B. Summary of Legislation
Until now, only Flanders has adopted a full legislative framework. 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 (see Annual Reports 1996 and 1998). They
cover five key-issues:
• a register of polluted sites;
• the distinction between historical and new soil contamination;
• the distinction between duty and liability for remediation;
• the soil remediation compulsory procedure and control;
• the transfer of land.
Soil standards, background levels, and intervention values have been adopted by the Flemish
Government. The intervention values depend on future land use. Exposure scenarios have been defined
for four land use classes (agricultural, residential, recreational, and industrial). Plus nature areas, requiring
a separate approach. There is also a list of activities, which could create soil pollution, and need to be
investigated.
The two others Regions, Brussels and Wallonia, have partial legislations, based mainly on Waste Decrees
and on Town and Country Planning provisions. Since 1999, both Regions 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 uses authorized in the
surrounding area. Those new 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 was adopted, in April 2000, providing for the creation of a common fund for the remediation
of gas stations. The fund will be financed on equal basis by the oil companies and the consumers (through
a special levy).
Last but not least, in May 2000, the Walloon Government has launched a Strategic Programme for
Contaminated Soils and Brownfield Sites, including the preparation of a comprehensive Soil Decree. This
programme should be implemented and presented to the Walloon Parliament for adoption within the next
24 months, after hearings involving all public and private stakeholders.
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During this period, transitory measures will enhance the rhythm of brownfield sites reclamation; they will
also provide new means for a thorough updating of existing inventories of derelict and brownfield sites,
and for preliminary investigations of these sites.
C. Administrative Aspects
For institutional reasons (see § l.a), there is no Federal Agency for the Environment:
• OVAM (Public Waste Agency of Flanders) is the responsible authority for soil control and
remediation in the Flemish Region.
• In Brussels 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
• and whenever the license has to be renewed.
All information on soil pollution is compiled in the soil register, which serves as a database 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 remediation, in order to avoid to be listed as
contaminated in the register.
For more details, see previous NATO/CCMS Annual Reports.
Wallonia:
A registration system has existed since 1978 for derelict land and brownfield sites, based on Town and
Country Planning legislation and aiming at the redevelopment of those sites (see previous reports). The
transitory measures (see § l.b) will not only update this registration system, but also enlarge its scope and
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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 a list of sites for which a remediation
plan should be prepared, has been approved, or is into execution (+/- 850 sites registered in 1999).
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 cleanup 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 microorganisms in a slurry-reactor.
3. Phytoextraction 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.
In Flanders, a risk-evaluation model was evaluated and approved by OVAM. Research has been
implemented on the prioritization of historical soil pollution, and a decision-supporting system has been
developed to estimate which technologies are most appropriate at this moment, taking the costs into
account.
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 pollution;
• circumventing bio-availability limitations for bioremediation of PAH and mineral oil;
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• 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 soil remediation, there has been a growing recognition of
soil and groundwater contamination issues in Belgium. Forthcoming months might see new
developments, this time in Wallonia.
In the Flemish Region, the Decree has a highly positive influence on soil management and soil
environmental quality.
However, the main problems will probably remain in the three Regions:
• the lack of resources of many liable parties, for the cleanup of historical pollution;
• the cost-efficiency and environmental merit of the remediation programs, whether funded by
public or private money; and
• how will it be possible to reconcile 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
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 that 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 of fish 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 cleanup 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.
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
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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, $250 million (50%
federal) National Contaminated Sites Remediation Program. The program remediated 45 orphan sites—
sites for which the owner cannot be found, or is unable to pay for remediation—demonstrated over 50
technologies, and assessed 325 and remediated 18 federal sites. Scientific tools such as soil quality
guidelines and the National Classification System, which ranks sites based on health and environmental
risks, were also developed.
These tools are still used by many federal departments and by provincial and municipal governments.
Since the program ended in 1995, significant progress on the assessment and remediation of federal
contaminated sites has been made by federal government departments. Current spending on this issue
averages about Can$ 94 million per year.
Sydney Tar Ponds
In 1998, the federal government approved Can$41.5M over 3 years to address the Muggah Creek
Watershed in Nova Scotia, which rests within an urban area setting and is home to the worst hazardous
waste site in Canada. The watershed is 22.44 square kilometers (22,400 hectares) and encompasses the
Tar Ponds, the former Coke Ovens site and the Municipal Landfill site. The contamination includes
polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, PCBs and heavy metals.
Selection of appropriate remediation technologies to remediation this site will involve bench and field-
scale evaluations. This technology demonstration program is currently underway at an estimated cost of
Can$ 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.
In-situ Remediation of Soil and Groundwater
• Soil Vacuum Extraction
• Bioremediation (bioventing, bioslurping, land treatment)
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• 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,
reuse/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.
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 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
In previous years we've informed you about remediation experience in the Czech Republic with emphasis
on remediation works in localities, which left the Soviet Army. Allow me please today, to introduce you
to more experience gained in the Czech Republic in the field of the environment, namely, in the process
of large-scale privatisation because I receive more and more questions on this topic.
The rehabilitation of environmental burdens requires large financial resources; therefore, in the Czech
Republic the principle of finding a socially acceptable (reasonable) level of environmental as well as
health hazards has been applied also bearing in mind that attaining of "zero risk" is not always necessary
from the environmental point of view and often is accompanied with unreasonably high costs incurred.
In context of the Czech Republic joining to the member states of the European Union, certainly a major
emphasis is put on remedial of contaminated sites also, among other things, for the reason that this is the
condition of foreign investors' interest in investments into Czech companies.
There is no specific act providing for remedial of environmental burdens in general in the Czech
Republic. The legislation, which is especially important for environmental burdens in rocks and in
groundwater, comprises of the Act No. 92/1991 Code, on conditions and terms of the transfer of
government property onto other entities, Act No. 171/1991 Code, about Fund of National Property (FNP)
of the Czech Republic and also the Act no. 138/1973 Code, on water as amended by the Act No. 14/1998
Code, and the Act No. 125/1997 Code, on waste.
Remedial measures done by privatised companies are reimbursed by the FNP from finances gained in the
privatisation process, which do not belong to the state budget.
The principle documents governing remedial of contaminated sites in the privatisation process are the
Decisions of the Government of CR No. 123/1993 and No. 810/1997. These documents establish that
every obligation to environmental burdens (contaminated sites) are transferred onto the proprietor to be of
the property privatised. Government, however, as the former proprietor is responsible for remedial of
contaminated sites, which contamination occurred before they were privatised. The decisions include
concrete lists establishing environmental damages (as groundwater contamination, soil contamination,
existence of hazardous waste landfills on the company sites, and contaminated structures and sites or
portions thereof). These two decisions further establish the procedure, which these damages to the
property may be solved.
The first step that the proprietor of the privatised property shall make on the basis of the Act No. 92/1991
Code is to elaborate eco-audit of the property privatised. Then, based on the consent of the Government
of the Czech Republic, the Fund of National Property shall conclude an agreement with the transferee (so
called environmental agreement) in which the Government undertakes the reimbursement of costs made
in remedial actions of contaminated sites. Maximum of the costs is limited to the amount of purchase
price of the property privatised, or to equity capital of the company in case of joint-stock companies.
The next step is making a risk analysis. This works are covered by the Fund of National Property from the
account budgeted for rehabilitation of contaminated sites and the supplier thereof is selected in a tender.
On the basis of the risk analysis results, the administrative body of the Ministry of the Environment of the
Czech Republic, which is the Czech Environmental Inspection (CEI) here, shall make a decision on
remedial measures establishing concrete extent of the environmental burden and concrete levels (values)
and deadlines that shall become the targets of the future on-site remedial action. A separate tender is
called for the supplier of the remedial action.
From 1991 to March 15, 2000 the number of the environmental agreements approved by the Government
and concluded by the Fund of National Property reached 234 resulting in guaranteed amount about CZK
136 billion, while it is assumed that actually drawn amount to be CZK 32 billion. By December 31, 1999
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FNP spent approximately CZK 7.2 billion for cleanup of contaminated sites, out of the amount about
CZK 1.8 billion (approximately 200 million USD) in 1999. FNP has registered approximately 220
actions, in which cleanup of old contaminated sites has been implemented. Five cleanups were finished
and 60% of the rest are in the preparatory phase (tenders for risk analysis elaboration or the administrative
procedures for issuing of the CEI decision have started). In case of the remaining 40% of the actions,
remedial works are carried out or post cleanup monitoring is performed under control of supervisors who
control usefulness of the finances spent.
The estimate of future guarantees for contaminated sites, in cases of further privatisation and condition to
that the Government approves further environmental agreements, is at the amount of roughly CZK 165
billion, while it is assumed that actually drawn amount to be CZK 46 billion.
Last year, however, the solving process of environmental obligations in privatisation was sluggish due to
FNP, yet in the end a series of hard negotiations resulted in the Government Decision No. 917, adopted
on September 8, 1999, and ordering the continuation in reimbursing of environmental obligations based
on already signed environmental agreements and also in concluding of new environmental agreements in
accordance with the effective rules.
As of yet substantial contaminated sites, for example, in companies privatised in the first wave of the
privatisation when the duty to elaborate the eco-audit was not established yet have not been solved. The
manner of cleanup actions on lands not belonging to the entities, who are bound to perform remedial
measures, and in case of proprietors of restituted property has not been fully set. The government
participation has not been completely defined even in case of companies in process of dissolution, which
finances do not cover the necessary cleanup, and in case of residual companies as well. Concerning these
cases for some of them the legislation that became effective at the beginning of 1998 is important. The
importance is based on section 27 of the Act No. 14/1998 Code, modifying and amending the Act No.
138/1973 Code, on water, which establishes the state of facts, in which costs related to the remedial
measures are reimbursed by appropriate district government in cases as listed in the Act if there is a risk
of delay (for example, the incomplete or not performed remedial action may pose a risk to a water
source).
At present a bill amending the water act defining the area more exactly especially in determining the duty
of district governments to allocate the annual reserve at the amount of CZK 50 million for the actions that
are inevitable to be performed in the area, is ready for negotiations.
The contaminated sites are assessed form the point of view if they pose substantial risk to the
environment and human yet so far they have not been prioritised in accordance with officially established
priorities. It follows from the fact that decisions on privatisation were also made step by step and so there
was impossible to wait till decisions on all companies, which had substantially contaminated sites, are
made. A list of all contaminated sites (irrespectively there are finances for funding appropriate remedial
measures at present) that are necessary to be cleaned-up with high priority has been worked out at the
Ministry of the Environment in co-operation with CEI and Territorial Departments of the ME. Respective
lists of every region were completed and work on list of whole the CR will continue. The Ministry set up
additional criteria for objective assessment of seriousness of contamination based on a rather broad
context. Basic criterion is the potential of putting at risk resources of mass supplies of drinking water.
Mention should also be made of the database that originated at ME in connection with projects to support
the environment. This is the SESEZ database (list of environmental burdens from the past), which
constitutes a step of ME towards gradual filing of information on all environmental burdens. The database
is filled with records of investigation and decontamination work at individual locations. There are several
sources of data, consisting in the databases of gradually created records of cases resolved by the
Department of Environmental Burdens and the National Property Fund, including records of
decontamination of pollution caused by the stay of the Soviet Army. Another source in the future should
consist in information from the District Authorities on decontamination or other work that is not paid for
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by the state budget or from the funds of ME or NPF. This is an instrument intended for the District
Authorities and state administration for keeping records of environmental burdens from the past. At the
present time, the central database contains records of about 900 locations and the work has not yet been
completed (contact: JANfficnv.cz)
At present the discussion on whether remedial of contaminated sites is sufficiently effective goes on in the
Czech Republic, as elsewhere in the world, and the entire system has been gradually improved by adding
more and more check elements.
I believe that my contribution made you confirmed that we in the Czech Republic thoughtfully devoted
our attention to the environment already at the beginning of establishing of privatisation rules.
It is a matter of fact that not all decisions on privatisation came right but, there is no doubt that it was the
privatisation process, which started the entirely different approach in practical reality to the environment
compared to that, which had been in the country before, and the privatisation has had clearly beneficial
influence on the quality of the environment in our country.
Besides, the remedial of contaminated sites that left the Soviet Army has been financed through the state
budget.
In the period from 1990 till the end of 1999 the amount allocated in the state budget for survey and
cleanup works, including risk analysis and supervisory assessments reached approximately CZK 974
million. Today it is expected that by 2008 there shall be a need for further CZK 300 - 400 million. We
still work on 6 localities. Total costs just for works of cleanup of groundwater, soil, and uncontrolled
dumpsites shall account for approximately CZK 1.3 to 1.4 billion. These finances shall cover the
achievement of just acceptable, and that I must emphasize, level of environmental pollution and enable
for reasonable use of such areas in the Czech Republic.
The sites with the most extensive contaminated areas and degree of risk include the former Hradcany
airport in the Ralsko area and around Milovice (originally the Mlada Military Training Area). Extensive
contamination of ground waters and soil by aircraft kerosene and chlorinated hydrocarbons has been
found in the area of the Hradcany airfield. The usual chief centers of contamination mostly lie in the
vicinity of the original locations of warehouses of automotive fuels and uncontrolled hazardous waste
dumps. The seriousness of this contamination is increased at this site by the fact that the territory lies in a
very important hydrogeological region (the territory is located in a protected area of natural accumulation
of water from the North Bohemian Cretaceous and the amount of water in the geological basement has
been estimated at several billion m3). The usable supplies of underground water equal 2380 l.s"1.
An area of approximately 15 ha is designated for remediation with the target of attaining a limit of 5000
mg.kg"1 of dry matter of petroleum hydrocarbons (NES) in the soil and 5 mg.l"1 NES in the ground water.
The maximum pollution is located in the vicinity of the ground water surface level, which is 4-6 m under
the surface. The average concentration of NES in soils is 11000 mg.kg"1 and a separate phase of these
substances is also frequently present on the surface of the underground water. The decontamination of the
ground water (collection of the phase of petroleum products, stripping), decontamination of the soil air
(venting) and decontamination of soil in situ by air sparging is continuing. Autochtonnic microorganisms
are used and nutrients (nitrogen, phosphorum) are added to increase the biodegradation activity; the effect
of surfactants is also being tested. So far, approx. 1 150 tons of petroleum hydrocarbons have been
removed and a further minimally 1 500 tons of contaminants will have to be removed to achieve the set
limit. It is expected that decontamination of territory will be completed by the year 2008.
In the former Mlada MTA work is continuing primarily at the Milovice camp and Milovice airfield at
Bozi Dar. Contamination at these sites consists mainly of aircraft kerosene, gasoline, diesel fuel, oil, and
paint thinners. This area is also of great importance for water supplies, from the Dolni Pojizefi area. These
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are sources with an extensive collection system that are significant not only for their yields - a total of
1800 l.s"1, but also for their quality. They provide 20% of the overall requirements of Prague.
Decontamination of groundwater is progressing at both of these localities (collection of the separate phase
of petroleum substances, stripping), along with decontamination of the soil and decontamination of soil
air by venting. It is expected that the decontamination work will be completed at the Milovice airfield site
in the year 2005 and at the Milovice campsite in the year 2007.
RESEARCH AND DEVELOPMENT PROJECTS
In the year 2000, the Ministry of the Environment is providing support for specific research and
development programs. Calls for tenders have been announced for work on the following programs
related to the subject of elimination of environmental burdens from the past:
Environmental Economics
• Draft strategy of financing environmental protection
The goal of the project is to prepare proposals for financial provision for decisive targets for the future, in
accord with the new environmental policy, in particular to analyze current sources of financial protection
of the environment—especially the State Environmental Fund, the state budget, the National Property
Fund, sources at a local (regional) level, private sources, foreign sources, etc. In addition, it is required to
specify the necessary financial sources for protection of the environment, primarily on the basis of
completed quantification of expenditures connected with harmonization with the EU. It is necessary to
elaborate the basic principles of financial policy for the area of protection of the environment.
Time period: 2000-2001
Number: VaV/320/5/00
Support: 2 463 000 CZK
Environmental Burdens from the Past
The goal of the program consists in theoretical evaluation of the risk entailed in biodegradation of
aromatic chlorinated hydrocarbons and preparation of basic principles for identification of natural
biodegradation of important contaminants in the geological environment and decontamination technology
for liquidation of the contamination. The target of the project also consists in study of the transformation
of specified contaminants (PAH, phenols), the toxicological properties of the intermediates in their
degradation, monitoring of their migration, the detection and decontamination limits, and determining the
conditions, effects and specifications controlling transformations of specified contaminants and
monitoring in practice at selected locations.
Time period: 2000-2001
Number: VaV/730/1/00
Support: 988 000 CZK
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Waste
The goal of the program consists in waste management and replacement of technical fuels, more intensive
collection, transportation and separation of municipal waste, development of new composite materials
made from recycled plastics for more competitive products, proposal of technology for processing of the
biodegradable components of waste.
Time period: 2000 - 2003
Number: VaV/720/1/00
VaV/720/2/00
VaV/720/4/00
Support: 6 182000CZK
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FINLAND
I have a pleasure on behalf of the Ministry of Environment in Finland to present the tour de table about
progress in Finland.
In Finland, problems related to contaminated soil have been tackled systematically since the late 1980s.
The first policy statement on contaminated soil question was given in 1988 by the Council of State:
According the objective of that statement "contaminated land will be studied and cleaned systematically.
Urgent cases will be cleaned as the need is established. Studies will be made of contaminated areas and
steps will be taken as necessary to clean them systematically."
According this statement there was also "necessary to arrange the environmental authorities, to
investigate cleanup techniques, and to make revisions in legislation. In any case as far as possible the
polluter pays principle will be held in to meeting costs," said the Council of State.
At the moment almost all that is done first survey and after that started remediation phase in 1995.
Legal background has been refreshed in many steps. The last two most modern acts are:
1. New Act for Environmental Protection entered in force in 1.3.2000. This new piece of legislation
includes soil protection, groundwater protection and also remediation procedure questions all
together in one act.
2. New Building and Construction Act entered in force 1.1.2000. According that act, the
construction site must be clean and land quality must be taken in account in physical planning and
all land use.
Administrative structure is now simple and effective. Ministry is responsible on strategic and policy and
also legislative issues, 13 regional authorities: environmental centres are responsible of allocation public
funding, planning and decision making in permitting all - public and private remedial actions on
contaminated sites. Finnish environmental institute conducts environmental R&D. In generally the owner
of real estate has environmental and economical responsibility of all old soil contamination. Secondary
responsibility is shared between municipalities and state.
Ministry on Environment, the Association of Finnish Local Authorities and The Finnish Petroleum
Federation have programme for the remediation of sites, which have been used for retail sale of petroleum
products. Since 1996 has hundreds of those gasoline stations successful been cleaned up. Older, already
closed cases are paid by The Finnish Oil Pollution Compensation Fund and those that will be closed are
paid by oil companies.
In Finland are according the updated mapping about 20 000 preliminary suspected case of which will be
cleaned approximately 10%. Current soil contamination will be cleaned in some ten years. Typically
contaminated sites are in general civil sites instead of few military sites, land was not occupied under last
great war, chemical industry is young, post war built, population is small and land great.
At the moment Finnish environmental centres are reporting quite broad survey and risk assessment
project on soil pollution on shooting ranges caused by lead. Hundreds civil shotgun ranges are spreading
lead broadly to surroundings, forest soil and groundwater. Rifle ranges, military or civil ones do not
spread contamination to large area.
There are no derelict former industrial or military sites, so called brown fields, in Finland. All former
important industrial sites near cities has until now-as well in future-been remediated and taken to other
use, such as housing. The owners of the site are liable for the cleanup.
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FRANCE
In France, after one year, there are very limited changes in the field of polluted sites, and the situation
described in the tour de table presented in Angers and included in the 1999 Annual Report remain valid.
The only new element is the issue, on December 10, 1999, by the Ministry in charge of the Environment
of a circular letter on "the principles of fixation of rehabilitation objectives."
According to this circular letter, the rehabilitation objectives are determined on the bases of a detailed
evaluation study (in depth diagnosis) that describes and quantifies pollution source(s), pollution transfers,
human and environmental receptors associated with a detailed (quantified) risk assessment considering
human health and the environment (water, ecosystems). The application of the procedure takes in account
the present and future use of the site and for human risk assessment the calculation of total exposure has
to be compared to the tolerable daily intake for non-cancer effect substances and for carcinogens the
maximum acceptable dose corresponds to a supplemental cancer risk of 10~5 for lifetime exposure.
A technical guide describing the methodology for this in depth diagnosis and detailed risk assessment will
be published in the middle of this year.
GERBER SITE IN SERMAISE
A. Final Report On the Treatment of Polluted Soils by Solvent Extraction
During the previous NATO CCMS meeting in may 1999 in Angers a technical tour was organized to the
Gerber site in Sermaise and the participants visited the on going treatment of polluted soils previously
extracted.
The pollutants were mainly organics (BTX), chlorinated organics (solvents), PCB, heavy metals (lead,
zinc) and the soil was specially difficult to treat because of heterogeneity, compacity, and high percentage
of fine material. The treatment was realized by solvent extraction, named SOLVIS of the GEOCLEAN
Company, using dichloromethane. Because of the risks associated with the extracting solvent a strict
control of the operation has been continuously carried out (safety of workers and impact on the
environment). The soil to be treated was classified in two categories stored separately: storage T of
heavily polluted soil, lagoon L of mean polluted soil.
The management of treated soil was realized as it follows:
As a general result, the total quantity of polluted soil has been treated according to the depollution goals
for organics and chlorinated organics and is stored on the site.
Part of the treated soil did not reached the objectives for heavy metals (the treatment is not effective for
inorganics) and was transported to be landfilled in a site authorized for the storage of special industrial
waste.
Limited quantities of stones and waste (plastics and distillation residues) were separated before the
treatment of polluted soil, stones being reused on the site after washing and waste being transported for
treatment off site.
B. Results
1. Total quantity of soil treated: 10 650 tons
Treated soil remaining of the site: 9 085 tons
Treated soil transported and landfilled: 1 575 tons
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January 2001
2. Treatment of T storage
PCB
BTX
Chi SOLVENTS
Average pollution levels
before treatment (ppm)
370
2400
960
Average pollution levels
after treatment (ppm)
9.85
19.2
10.3
Efficiency (%)
97
99.2
98.9
3.
Treatment of L storage
PCB
BTX
Chi SOLVENTS
Average pollution levels
before treatment (ppm)
80
79
360
Average pollution
levels after treatment
(ppm)
4.3
4.9
6.4
Efficiency (%)
94.6
93.8
98.2
C. Present Situation and Perspectives
The treatment of the polluted soils stored above ground was completed at the end of October 1999. Since
then a new step has been initiated including:
• a first project of source reduction with the objective to extract and treat waste and heavily
polluted soil still remaining under concrete covered area; and
• an additional study to complete the risk assessment realized in 1998 and to have a detailed
description and quantification of the mechanisms of natural attenuation that appears to occur on
this site.
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GERMANY
1. LEGAL AND ADMINISTRATIVE ISSUES
The enforcement of the contaminated site remediation, which generally includes the steps registration,
risk assessment and remediation is with the 16 Federal States (Lander) of Germany. Together with the
Lander regulation more than 35 lists exist all over the country containing different values for risk
assessment and cleanup. In order to harmonize regulations and values the Federal Government submitted
the Federal Soil Protection Act (FSPA), which has been enacted on March 1st, 1999. To complete the
federal legal framework on contaminated land in Germany sublegal regulations have been laid down in an
ordinance submitted later on. This Federal Soil Protection and Contaminated Sites Ordinance came into
force in July 1999.
The FSPA includes precaution issues as well as remediation of contaminated soils and sites. The main
purpose of the FSPA is to protect against harmful changes in the soil. Harmful changes in the soil exist
when the soil functions are impaired and when this leads to danger, to considerable adversely affects for
the individual or for the general public. The definition of the FSPA includes natural soil functions and
functions of the soil utilization.
The two terms harmful changes in the soil and contaminated sites in the FSPA cover all burdens of the
soil that causes hazards for human beings and the environment. Contaminated sites (CS) are defined as
follows:
• closed-down waste disposal facilities or other estates on which wastes have been treated, stored, or
disposed (abandoned waste disposal sites-AWDS); and
• estates of closed-down facilities and other estates on which environmentally hazardous substances
have been handled (abandoned industrial sites-AIS), which cause harmful changes in the soil or other
hazards for the individual or for the general public. Sites which are suspected to be contaminated
(SCS) are by definition of this law AWDS and AIS, which are suspicious for harmful changes in the
soil or other hazards for the individual or the general public.
Following regulations for the remediation of contaminated sites are a substantial part of the FSPA:
• the authorities are responsible for registration, investigation and assessment of SCS;
• authorities may require under certain conditions remedial investigations and a remedial plan by
those who are obliged for remediation;
• the remedial plan should provide in the case of serious and complex CS transparency and by that
provide a substantial contribution to the acceptance of the necessary remedial measures by the
affected persons;
• the remedial plan should cover a summary of the risk assessment and the remedial investigations
as well as the remedial goals and the remedial measures;
• by the rule the remedial plan is worked by an expert;
• in the cases of CS and SCS, responsible persons are obliged to announce these sites and to carry
out self-control measures; the authorities are responsible for the supervision;
• together with the remedial plan the obliged person can submit a public contract for the remedial
measures; and
• to enhance the approval procedure the official obligation of the remedial plan as well as the
official order for remediation concentrates all necessary permissions from other laws.
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2. REGISTRATION OF CONTAMINATED SITES
The registration of suspected contaminates sites (SCS) is carried out by the Federal States (Lander).
Inventories of suspected contaminated sites have been set up by the Lander, however, they are based on
their specific definitions and specific local regulations. Consequently, comparison of the Lander figures is
only possible to a restricted extent. The focus of all Lander inventories are the numbers of abandoned
waste disposal sites (AWDS) and abandoned industrial sites (AIS). These figures had been summed up to
a nationwide number lately in December 1998 to more than 300,000 SCS excluding military
contaminated sites and former armament production sites. More than 100,000 are AWDS and nearly
200,000 are AIS. The table with the individual figures from the Federal States is published in the 1999
annual report of the Pilot Study.
3. REMEDIAL METHODS IN USE
According to the definitions of the Federal Soil Protection Act remediation are measures:
• for the removal or reduction of contaminants (decontamination measures);
• that prevent or reduce the spreading out of contaminants on a long-term basis without removing
contaminants (safeguarding measures); and
• for the removal or reduction of harmful changes of the physical, chemical and biological nature of
the soil.
Generally, the technological standard for the treatment of contaminated soil is high. Public funding has
contributed significantly to the development of soil treatment technologies. Expenses spent by the public
sector for R&D are estimated being added up to 300 million Deutsche Mark for about 200 projects within
the last 20 years. Industry investments in the range of approximately 900 million Deutsche Mark have
been take place only for soil decontamination. Meanwhile, there are more than 100 soil treatment plants
in operation providing a total treatment capacity of almost 4 million t/year. The technologies available for
field application cover a broad range of on and off site techniques as well as in situ strategies for soil
treatment by means of biological treatment, soil washing and thermal treatment. However, due to cost
constraints, also safeguarding measures like encapsulations, surface sealing or excavation and disposal
became more meaningful in the last few years. It is estimated that about 50% of all remedial action in
Germany are done by safeguarding measures.
The decision on weather to use safeguarding or decontamination measures for remediation is a complex
procedure determined by a multitude of factors (remedial investigation). The Soil Protection Act sets
priority on the warding off of hazards. According to the legal framework it hardly makes difference
regarding the technical procedure to reach this. From a purely environmental point of view, however,
decontamination of contaminated soil is still the better option for remediation. It is an important tool to
support the recycling of wastes, to protect natural resources and landfill space and thus to contribute to the
principles of a sustainable development.
In this context UBA has conducted a survey on soil management in Germany arising from contaminated
land. The objective was to analyze the soil streams from soil treatment plants regarding their recycling
potential and their contribution to the reuse of contaminated soil. 85 soil treatment plants, out of 108
plants written to, took part in the survey; this corresponds to a response rate of approx. 80%. Thus a
coverage rate of approx. 65% of all the plants in Germany has been achieved which for 1997 document an
input of approx. 1.8 million t and an output of approx. 1.6 million t (Table 1). During the period covered
by the study (1993-1997) the input quantities (quantities actually treated in the plant) of the plants
participating in the study rose from approx. 409,000 tons to more than 1.8 million tons. Accordingly the
output also rose (soil cleaned in the plants) from approx. 341,0001 to approx. 1,574,0001. Of that, in
1993 approx. 335,0001 was recycled. In 1997, 1,568,000 t was recycled. Thus the recycling rate almost
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reaches 100% (Fig. 1). The figures obtained in the survey show, however, that the average degree of
usage was about 60%.
Table 1: Development of the capacities, treated, cleaned and recycled soil quantities from 1993 to 1997
for the soil treatment units covered by the study
Industrial capacity
Soil accepted
Plant input
Plant output
thereof recycled
1993
(t/a)
1,460,800
539,120
408,586
341,396
335,306
===>
===>
===>
===>
1997
(t/a)
3,224,700
1,843,030
1,791,890
1,574,287
1,567,610
5s
Soil washing Microbiology Thermal treatment
Figure 14: Recycling rate for all soil treatment measures
4. TECHNOLOGY DEVELOPMENT PROGRAM/RESEARCH AND DEVELOPMENT
ACTIVITIES
The technology development program, which is mainly funded by the Federal Ministry for Education and
Research (BMBF), is executed by the BMBF Project Management Agency for Waste Management and
Remediation of Contaminated Sites within the Federal Environmental Agency (UBA). The high standard
of available soil treatment facilities being reached in Germany (see above) is particularly due to the
funding policy of the BMBF in the past.
This, of course, is also the reason that the focus for future research and development moved to
optimizations of available solutions in terms of cost-effective technologies and strategies. In this context
mainly bioremediation techniques for soil, groundwater treatment walls including permeable reactive
barriers and natural attenuation strategies have to be mentioned.
A Joint Research Group, Processes for the Bioremediation of Soil, comprises seven joint projects with
more than 30 single projects. This interdisciplinary group is working on the development of innovative
processes for the bioremediation of contaminated soils. After the laboratory phase, not only their
effectiveness is tested under application-oriented conditions, but also their success is monitored by a
complex control system that goes far beyond a conventional chemical analysis of pollutants. A
comprehensive handbook on the results will be published within this year.
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Currently starting is a joint research project on the "Application of Treatment Walls for the Remediation
of Contaminated Sites." Proposals for 38 single projects have been submitted to UBA for evaluation. A
committee of experts (chair: Harald Burmeier) has selected about 10 research projects on this subject for
funding within the next two years. The financial contribution of the BMBF will be in the range of 10
million Deutsche Mark. They cover a broad range of application purposes and technological principles.
The final objective of the joint research project is the elaboration of a handbook on the selection, design
and planning of permeable treatment walls to be used by consultants and administration.
A further joint research project is currently under final preparation. Based on an announcement by the
BMBF universities and consultants have been requested to submit proposals for research projects in the
field of monitored natural attenuation. Deadline for the call was the end of April 2000. At this date 212
proposals have been submitted. They will be further evaluated for final funding by a committee of experts
that is currently being set up. It is expected that about 50 projects will be funded as part of this joint
research project for a period of five years. The total amount of public funding is estimated to 50-60
million Deutsche Mark. The focus on the intended research activities regarding natural attenuation will be
in the following fields:
1. Mining and smelting
2. Refineries and tank storage facilities
3. MTBE
4. Gas work sites
5. Chemical and textile industries, arsenic
6. Landfills and dump sites
7. Abandoned Armament Sites
8. Military sites
9. Agricultural Sites
10. Sediments
The main objectives of the project are:
1. Identification of frame conditions for economic and environmental useful self-cleaning processes
(Note: Within the scope of the project the term "Natural Attenuation" is considered to encompass
both, dilution and reduction processes like absorbtion and/or degradation of pollutants in soil or
groundwater
2. Identification of substances that can be accessed by natural attenuation or enhanced natural
attenuation
3. Assessment of the behavior of pollutants in soil or groundwater regarding natural self cleaning
processes
4. Requirements on soil and groundwater schemes regarding the application of natural attenuation
5. Design and conduction of long term monitoring measures to quantify the reduction of contamination
and to predict the long-term behavior of the contamination under the aspects of future use options.
The joint research project on natural attenuation is desired to start in late summer 2000.
5. CONCLUSIONS
With the enactment of the Federal Soil Protection Act and the Federal Soil Protection and Contaminated
Sites Ordinance, Germany has for the first time a comprehensive legal framework to deal with
contaminated land. Registration of contaminated sites and research and development of remediation
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technologies are also far advanced. Thus, contaminated land management in legal and technical terms will
become more in the focus of enforcement than of research and development in the future. However,
experiences with the enforcement and execution of the legal framework will be vital over the next few
years for further optimizations.
Nevertheless, the contaminated land problem is far away from being solved in Germany. The legal
framework and the availability of remediation technologies are undoubtedly essential tools to overcome
the environmental risks. But they are not specifically designed to promote site redevelopment in terms of
attracting new investors for new uses. Thus, future activities in Germany will focus on the development of
new strategies and economic instruments for bringing the land really back into beneficial use under urban
planning aspects. Brownfield redevelopment in the context of legal, environmental, social, urban planning
and economic issues will be the wider context of contaminated land activities in the future.
Actually, UBA is involved in a couple of national and international activities so far. Especially, the
ongoing international co-operation of the UBA led working group 1 "Brownfield Redevelopment" as part
of EU funded Concerted Action CLARINET made quite clear that brownfield is a subject of international
concern.
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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 for soil quality, there are several components in Greek law
that 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 (JMD 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 waste 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)
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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:
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:
1. In situ chemical stabilisation of heavy metal polluted soils
2. Removal of heavy metals from contaminated soils by chemical extraction techniques
3. Bioremediation of soils contaminated by heavy metals and metalloids
4. Remediation of polluted ground waters using permeable reactive barriers
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ITALY
1. LEGAL AND ADMINISTRATIVE ISSUES
1.1 Legal Background
The first legal provision for the assessment and remediation of contaminated sites in Italy dates back to
the Environment Ministry Decree (DM) of May 16th 1989. This law established the general guidelines for
drawing up regional plans for contaminated sites assessment and management according to the following
processes:
• identification of potentially contaminated sites
• evaluation of the level of contamination
• definition of priority sites to be cleaned on a short-term basis
• definition of priority sites to be cleaned on a mid-term basis
From early 90's a number of regions elaborated own technical regulations relating to contaminated sites
characterization and assessment, setting soil quality standards and application of cleanup technologies.
Criteria for site-specific assessment of risks were envisaged. Several regions compiled regional
remediation plans and in 1997 preliminary results were summarized on a national basis.
The legislation relevant to contaminated sites has been recently detailed and expanded: by the beginning
of 1997 the Waste Act (D. Lg.vo 22/97) was adopted; this law provided the institutional framework for
contaminated sites assessment and management, and established the requirements for the development of
the technical and administrative procedures relevant to contaminated sites inventory, characterization and
assessment, cleanup, safety measures and monitoring (Art. 17). The norm contains provisions on the
administrative procedures for site decontamination and remediation and on the necessary steps to bring
concentration of pollutants within legally binding limits. Art. 17 also sets obligations for the person
responsible for a case of contamination to clean it up, and provides for sanctions on the violation of
administrative duties. In cases of difficult or impossible liability definition or in case of negligence from
the polluter, the public authority, municipality or region takes care of safety actions and site remediation.
Public cleanup represents a legal binding restrain of the area. The public authority keeps ownership
privileges on the site until costs of remediation are recovered from the responsible party or site owner.
The public authority can initiate legal actions to recover costs from the polluter or site owner.
Cleanup operations represent a "real burden" placed on the site to be decontaminated, which results from
the "site destination certificate" and which follows the site also when it is transferred to a different owner.
The only way to remove the burden will be to clean up the contaminated site.
Another major step in legislation was the enforcement of Law 426 of December 9, 1998 that established a
first list of sites of national interest that deserve special attention for environmental, economical and
social reasons, and are object of direct involvement and funding from the government. The Ministry of
the Environment together with the ANPA (National Agency for the Protection of the Environment)
together with other competent national and local institutions are responsible for approving and issuing
permits relevant to site investigation, assessment and remediation projects. ANPA has the task to define
(comparative) risk based criteria to establish the inventory and priorities for actions on sites of national
interest.
The list includes major industrial poles, partly or entirely dismissed. The law assigns public funds for the
remediation of those sites and direct government responsibility, through the Ministry for the
Environment, the National and Regional Environment Agencies together with other technical institutions
that have the task to issue the permits for characterization, for preliminary and final remediation projects
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or directly plan remedial actions in case of owner negligence. In some cases projects are carried out
according to agreements between stakeholders and control bodies.
Technical and more specific administrative guidelines have been then adopted with Environment Ministry
Decree (DM) 471 of October 25, 1999, which is actually the "implementation decree" of Art. 17 of
D.Lg.vo 22/97. The decree provides:
• definition for contaminated and potentially contaminated sites, emergency and permanent safety
measures, cleanup and cleanup with safety measures, environmental restoration;
• polluter and site owners obligations for site registration and cleanup;
• criteria and administrative procedures to be followed by site owner to carry out characterization
and remediation projects;
• tasks of the different local administrative levels: municipality, province, region;
• definition of acceptable contaminant limits for soil (two land use categories), surface water and
groundwater for approximately one hundred chemicals;
• criteria for soil and water sampling and analysis;
• criteria for site investigation and remedial actions design, together with stepwise licensing
procedures.
1.2 General Principles and Definitions
A site is defined contaminated, and registered as such, when even only one chemical exceeds the
acceptable limit concentration (limit values) in soil for the specific land use, surface water, or
groundwater. A site is defined as potentially contaminated when, because of actual or historic activities, a
potential exists that concentrations of polluting chemicals in soil, groundwater or surface water, may
determine a hazard to public health or the environment.
• Whenever limit values are exceeded, or an actual risk exists that it can be exceeded, local
authorities must be informed and cleanup or safety actions have to be taken on the site to remove
sources of pollution and remove or reduce pollution in the environmental media within limit
values.
• Cleanup is defined as the remedial action that removes pollutants or reduces their concentrations
to a level equal or below limit values.
• Emergency safety measures are urgent interim actions to remove polluting sources, to contain
their diffusion and to prevent contact with the sources themselves.
• Cleanup with safety measures is an integration of actions to reduce concentrations to residual
concentrations higher than limit values together with safety and monitoring measures. This
applies when best available technologies at affordable costs show that legal limit values, for the
specific land use destination, cannot be reached as cleanup targets. Under these circumstances,
site-specific residual concentrations in soil or groundwater are accepted, as long as a site-specific
risk assessment, demonstrates that they are protective of human health and the environment.
• Permanent safety measures are meant as long-term isolation actions to confine polluting sources
on site, when best technologies at affordable costs show that sources cannot be removed.
• Site-specific risk assessment guidelines are described within the remediation design steps. Sites
treated under a risk assessment procedure, i.e., when generic limit values are not reached, need
additional safety measures and are not considered thoroughly cleaned up.
• The general principle that in-situ techniques, rather than digging and landfilling techniques, must
be encouraged, is established.
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2. REGISTRATION OF CONTAMINATED SITES
Preliminary inventory data, on the basis of the Regional plans completed after DM of 1989, for potentially
contaminated sites, accounted for about 9000 sites from 14 out of 20 regions. 1200 sites were assigned a
short and mid term priority class for remediation.
The more recent laws distinguish between "census" (censimento) of potentially contaminated sites and
"register" (anagrafe) of contaminated sites. DM 471/99 defines criteria and procedures for registration of
contaminated sites.
2.1 Procedures for Registration of Sites
Three different procedures are envisaged to register and to initiate actions on contaminated sites:
1. a notice that is communicated to local authorities from the polluter;
2. an ordinance that is issued by controlling authorities;
3. 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 (Art. 7).
Tasks and powers of local authorities and competent institutions in issuing ordinances to parties
responsible of pollution are defined under procedure 2. (Art.8). Ordinances are issued by competent
Municipality.
For procedure 3., which requires a formal registration of the site to local authorities, the deadline has been
established within current year 2000. Registered contaminated sites will be included in regional registers
that will have to be drawn up and completed by the end of year 2000. Regions will decide about priorities
of actions according to criteria formulated by the ANPA.
2.2 Procedures for the Implementation of Remedial Actions
Administrative steps and technical requirements for preparing and authorizing projects of remedial
actions are defined: Three sequential project levels have to be followed (Art. 10):
1. a characterization plan
2. a preliminary proj ect
3. a final project
Particular projects have to follow also EIA procedures and comply with the relevant legislation to obtain
the specific permit. Financial warranties, not lower than 20% of estimated remediation costs, are provided
to the competent Regional administration as an engagement for correct execution and completion of the
remediation project.
Owners of a plurality of sites may stipulate special agreements for stepwise remedial programs with local
and central authorities.
After completion of site cleanup, certification and compliance monitoring is duty of the Province
authority.
Remedial projects relevant to polluted soil volumes less than 100 m and cleanup projects not requiring
safety measures and no EIA procedures, are not subject to the formal licensing procedure described
above.
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General criteria for the choice and implementation of cleanup and containment actions are given. In situ
and on site methods are encouraged together with the reuse of off-site treated soils. Solutions that reduce
long-term control and monitoring needs are privileged. Proposed innovative technologies must be tested
in laboratory experiments and verified in pilot tests. Provisions are provided for the use of GMOs in
bioremediation projects.
3. TECHNOLOGY DEVELOPMENT PROGRAM AND REMEDIAL METHODS IN USE
There is no specific national program for technology development. Several initiatives have taken place on
a case-by-case basis. Development of innovative technologies initiated after decree of 1989 and after
enforcement of regional laws in the following years.
Several remediation technologies have been applied in the past, but a comprehensive statistics of
completed cases is not available. A summary of methods implemented by major companies operating in
the country follows:
Summary of methods and number of applications completed by six major companies (more than one
method might have been applied at the same site):
Remedial techniques
Static containment (capping, impermeable
barriers, landfilling)
Hydraulic containment
Dual phase extraction
Soil vapor extraction, Soil venting
Bioventing, In situ Bioremediation, Air sparging
Biopile
Landfarming
Thermal desorption
Soil washing
Immobilization
Incineration
Reactive barriers
Natural attenuation
Total
Number of applications
205
36
49
89
72
9
17
3
3
-
1
3
4
377
%
54.3
9.5
13.0
23.6
19.1
2.4
4.5
0.8
0.8
0.5
0.5
0.8
1.1
100
4. RESEARCH AND DEVELOPMENT ACTIVITIES
The largest program for research and development of remediation technologies has been launched by the
Ministry for Scientific and Technological Research under National Research Program n. 15 (PNR15).
Main contractor is AREA; partners are the Center for Environmental Research Montecatini, the
University of Bologna and the Institute for Cancer Research. The program started in 1997 and is expected
to last till end of 2001. Funds provided for the program are approximately 6,5 million euros. The program
includes the following subprograms:
• R&D for bioremediation techniques in-situ and on-site
• R&D for vitrification techniques in situ
• training courses
A number of other individual research projects are being considered by the Ministry for the Environment
and others are presently funded by the Ministry for Scientific and Technological Research and by the
ANPA.
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Bioremediation and phytodepuration deserve particular attention. One research project aims at integrating
phytodepuration and biodegradation processes in order to achieve synergic effects for the degradation of
PCBs and PAHs in soil.
Other research activities on technology development are carried out within international and EU funding
programs or by research investment and by specific initiatives from the national holding for
hydrocarbons. One important EU funded project (under ESPRIT program) deals with the implementation
of models to simulate bioremediation processes in contaminated soils.
From a wider point of view other research projects have been carried out and are still ongoing for the
development of:
• risk assessment methodologies for contaminated site management
• decision support systems for risk assessment
• ecological risk assessment of soil and sediments
• remote sensing investigation methods
5. CONCLUSIONS
National procedures and technical requirements for remediation of contaminated sites have been enforced
very recently in Italy. Established provisions for legally binding and stringent acceptable contamination
limits, together with economic considerations, may perhaps hinder the application of several remediation
technologies. In this frame, site-specific risk assessment may have a critical role.
Criteria for registration of contaminated sites have also been established recently and it is perhaps too
early to comment on their efficacy in the definition of the real dimension of the contaminated sites
problem.
Even though wide national research programs have not been formulated yet, it is already evident that the
new legislation will provide a strong impulse to the development of new technologies.
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JAPAN
1. LAW CONCERNING SPECIAL MEASURES AGAINST DIOXINS
In Japan, dioxin pollution has been the serious social problem because high concentrations of dioxins
(8,500-52,000,000 pg-TEQ/g) have been detected in soils around the incineration facility of municipal
solid waste. In response to this concern, the Law Concerning Special Measures against Dioxins was
promulgated on July 16, 1999, and enforced on January 15, 2000.
Dioxins may cause serious effects on human life and health. Thus, this law has established the necessary
environmental standards, emission regulations and control measures (particularly for soil contamination)
in order to attempt the removal and prevention of the environmental pollution by dioxins. "Dioxins" are
defined as polychlorinated dibenzofurans, polychlorinated dibenzo-para-dioxins, and co-planar
poly chlorinated biphenyls.
1.1 Soil Pollution Control Measures under the Law Concerning Special Measures against Dioxins
Under the Law Concerning Special Measures against Dioxins, the Government shall establish
Environment Quality Standard, and the prefectural governors shall monitor and survey the pollution of
the soil caused by dioxins periodically.
As a result of monitoring and surveillance, prefectural governors shall be able to designate as the
controlled areas against soil contamination by dioxins, i.e., the area where the level of soil contaminated
by dioxins fails to comply with Environmental Quality Standard, and where is accessible to citizens. After
designating controlled areas, prefectural governors shall, without delay, establish Plans of Measures
against Soil Contamination by Dioxins, and conduct the removal and reduction of dioxin-derived risk.
Designation of Controlled Area
Central Environment Council
Report
'.'Establishment of Environment
Quality Standard
?Establishment of requirements
for designation of controlled area
Plan of Measures against Soil Contamination
Implementation of survey to findcauses
(Sources/Degree of contribution)
Measures
(Soil removal etc.)
Planning of Cost-bearing Plan
Pollution Control Publie Works
Cost Allocation Law
Cancellation of designation
Request for Application of
Financial Special Measures Law
I
T
Law Concerning Special
Government Financial Measures
for Pollution Control Projects
Figure 1: Scheme for implementation of soil pollution control measures
under the Law Concerning Special Measures against Dioxins
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The provision of the Pollution Control Public Works Cost Allocation Law shall be applied to projects
based on the Plans of Measures, when the causal relation based on scientific knowledge is clear between
the discharge of dioxins by a business establishment and contamination by dioxins. All or a part of the
cost which is necessary for the measures can be charged to cause persons.
And the provision of Law Concerning Special Government Financial Measures for Pollution Control
Projects shall be applied to the control measures, i.e., the measures conducted by local government will be
subsidized by the national government.
1.2 Environmental Quality Standard
The Environmental Quality Standard of dioxins in soil was established as 1,000 pg-TEQ/g or less
(Environment Agency Announcement No.68, 1999). The Survey Guideline Criterion in which additional
detailed surveys should be required from the viewpoint of prevention of progress of the pollution was also
established as 250 pg-TEQ/g or more. The Environmental Quality Standard has been set to generally
apply to all soils except for the soil of where waste landfills, and other facilities distinguished
appropriately from the general environment.
1,000 pg-
250 pg-
Prefectural governors shall be able to designate the area where soil
concentration of dioxins is more than 1 ,OOOpg-TEQ/g and where is
accessible to citizens, as the Controlled Area.
* Designation of controlled area
• Plans of measures against soil contamination
• Removal of contaminated soil
Environment Quality
Requirements for Designation of Controlled
Detailed
• Records review for source finding
• Additional soil survey
• Effect survey including air or water
• Continuous monitoring of soil
Survey Guideline
Monitoring and Surveillance
Figure 2: Environmental Quality Standard and Survey Guideline Criterion
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This Environment Quality Standard was established through evaluation of the exposure from soil. There
are the following possible exposure pathways for the dioxins in soil to be transferred into the human
body.
/* Human Body
Scattering/ Vaporization
;^n n
Direct skin contact
Direct ingestion
Penetration
k,
Erosion
Adhesion
/Absorptio
/Ingestion
Ground water
River
i
1
etc.
r
\
r
Aquatic life
i
r i
r Atmosphere \*~ II Inhalation II
Precipitation ^ It II
/Adhesion i^^^^s^^^^
^~ || absorption II
Oral
»- k. •
1, * Drinking water P ingc^tioii
1 ^
-
Marine products •_
-
Foodstuffs
*L Livestock
Figure 3: Exposure pathway of dioxins to human populations from soil start points
In the process for calculating to estimate the exposure from soil, "direct ingestion" and "direct skin
contact" were considered. The average daily exposure over a lifetime can be represented by the following
expression:
(Average daily exposure over a lifetime)(pg-TEQ/kg/day)=
(child's daily exposure) x 6 (adult daily exposure) x (exposure period 6)/70(years)x50(kg)
a) Exposure from ingestion
(soil concentration) x (daily quantity of soil ingestion) x (absorption rate) x (frequency of exposure)
Daily quantity of soil ingestion: child 200 mg/day, adult 100 mg/day
Absorption rate: 25
Frequency of exposure: 1 (everyday)
b) Skin exposure
(soil concentration) x (contact quantity per unit area) x (surface area of skin) x (absorption rate) x (frequency
of exposure)
Contact quantity per unit area: 0.5 mg/cm2
Surface area of skin: child 2,800 cm2, adult 5,000 cm2
Absorption rate: 1
Frequency of exposure: 0.6 (fair weather ratio) x [child 7/7 (everyday), adult 2/7 (weekend)]
Assume a soil concentration of 1,000 pg-TEQ/g, calculating the exposure to dioxins from soil gives an
estimate of 0.31pg-TEQ/kg/day. In considering the exposure from diet and atmosphere in the same way
as TDI (Tolerable Daily Intake: 4 pg-TEQ/kg/day), it is probably appropriate to use 1,000 pg-TEQ/g as
the Environmental Quality Standard value at which measure action should be implemented.
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1.3 Monitoring and Surveillance
Prefectural governors shall, in consultation with the heads of local administrative agencies of the national
government and heads of local governments, conduct surveys and measurements of the status of pollution
of the soil caused by dioxins in the areas under the jurisdiction of the prefecture concerned.
The scheme about the monitoring and survey is as follows.
a) Regional Survey
Ambient Soil Survey: Surveys not to think about the influence of a specific source of emission
in advance and to grasp the conditions of the pollution of the general environment widely.
Emission Source Surrounding Survey: Surveys to grasp the influence of a source of emission
Site Assessment Survey: surveys to grasp the conditions of the area with fear of the pollution by
dioxins
b) Detailed Survey
Surveys to confirm the conditions of the circumference area for the sampling point of 250pg-
TEQ/g or more
c) Contaminated Area and Depth Identification
Surveys to identify the area and depth of the soil more than l,OOOpg-TEQ/g
d) Evaluation of Measures
Surveys to confirm the effect after measures such as the removal of the pollution were
conducted
e) Continuous Monitoring
Surveys to carry out after 3-5 years to grasp the change of the concentration of dioxins in the
soil
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_£
Ambient Soil Survey
Regional Survey
Records Review
Emission Source Surrounding Survey
1
Site Assessment Survey
: All of these surveys conducted by !
: prefectural government will be |
: subsidized by the national |
! government. j
L :
Contaminated Area and Depth Identification
Measures
Evaluation of Measures
Figure 4: Scheme of surveys for soil contaminated by dioxins
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2. REMEDIATION TECHNOLOGIES FOR DIOXIN-CONTAMINATED SOIL
The Environment Agency of Japan invited submissions on 28 May 1999 for ideas on practical
technologies that are safe and reliable for purification of soil contaminated with dioxins. Within about one
month 48, submissions were received.
The Investigative Panel on Remediation Technologies for Dioxin-Contaminated Soil (Chairperson: Dr.
Masaaki Hosomi, Professor of Tokyo University of Agriculture and Technology) was established for the
purpose of investigating methods of remediation. As a result of examination, the following two methods
were selected as demonstration technologies which can be proven in the field, based on criteria such as
soundness of theory, safety and efficiency of purification. Testing of these methods is now being
discussed with interested local governments.
Table 1: Demonstration Technologies That Can Be Proven in the Field
Method
Principle
In Situ Vitrification Method
An electrode is placed in a container in the ground, which
holds contaminated soil. Electricity is passed through the
electrode, generating heat (1,600-2,000°C) 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°C.
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°C 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 300°C in a liquid BCD reactor.
The following four technologies were also selected as seed technologies, since they are at the final stages
of development. These technologies are considered likely to find practical applications quickly and are
suitable for small-scale testing. At the next NATO/CCMS meeting, the experimental result s for
demonstration and seed technologies will be introduced.
• Supercritical Water Oxidation Method
• Mechano-chemical Method
• Vacuum Thermal Cracking Method
• Bioremediation Method
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LITHUANIA
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.
5
-5
8
60
•3
o.
5
T3
5
f/s
•3
O
300
250
200
150
100
50
O Nitrogen fertilisers
D Potassium fertilisers
• Phosphorus fertilisers
1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996
Figure 1: Total Usage of Nitrogen, Phosphorus and Potassium Fertilisers in Lithuania (1986-
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).
D Insekticides
D Fungicides
• Herbicides
D Retard ants
• Defoliants
10000
8000
6000
4000
2000
1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996
Figure 2: Total Usage of Various Pesticides in Lithuania
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
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products (21% of military bases) and wastes (17% of military bases) prevail, alongside with the damage
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 m 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:
• Hazardous Substances: Maximum Permitted and Temporary Permitted Concentrations in Soil.
Hygiene Norm - HN 60-1996.
• Recommendations for Evaluation of Soil Chemical Contamination, 1997.
• The Maximum Permitted Level of Oil Products in the Upper Lithosphere (Ground) Layer - LAND
(Lithuanian Environmental Normative Document) 12-1996.
• 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 EURO. The Netherlands is now
spending about 0.5 billion EURO 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 cleanup on the basis of suitability for use. At the same time, the government
proposed other changes to soil protection legislation, including greater devolution of responsibility for
cleanup 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 cleanup. 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 that 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, the Dutch government wants to achieve ambitious objectives. 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 was 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: 1) anyone
intending to excavate and to move soil for building activities, has to report the quality of the soil to
provincial authorities; and 2) 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
Year Seriously contaminated sites Estimated costs (EURO) !
|1980 J350 ] a5bilhon j
[1986 |T600 | 3 billion j
|][9^
* based on new policy
3. REMEDIAL METHODS [1]
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. [1]
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 topsoil and the subsoil. In the approach to
the topsoil, 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
to as limited as possible care about residual contamination. At calibration times, the remediator checks
whether the desired remediation result is being obtained.
[1] Van trechter naar zeef W. Kooper, October 1999 ISBN 90 12 08843 7
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Routes
There are three routes for obtaining an approved remediation plan:
1) via a standard approach per case or cluster of cases. By this means the decision-making may be
simpler.
2) 2) via custom-made work per case or cluster of cases. This is obvious if the standard approach offers
no solutions.
3) 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."
Top soil
In the standard approach for the topsoil 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 that 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.
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 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 behind in the soil in
many cases. Therefore, care is required. This care may consist of registration (establishment), monitoring
(measuring), and 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.
Responsibility
The cause 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.
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Reduction in costs
The previous Cabinet accepted that with a new consideration method for a remediation goal, a cost
savings of 35-50 percent could 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 percent by the new standard approach;
• approximately 10 percent by cleaning and draining off less contaminated groundwater;
• approximately 5 percent by custom work per area.
Monitoring will show the extent to which the cost reduction will be achieved.
Decision-Making
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 licenses "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
Starting January 1, 1999, most of the research on contaminated land is organised in one centre: The
Centre for Soil Quality Management and Knowledge Transfer (8KB). The 8KB is a cooperative 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.
The mission of 8KB is to develop and transfer 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 BEVER, i.e., functional remediation and cost-effective
contaminant removal.
A decisive approach to soil contamination and the development of new forms of co-operation must put an
end to the stagnation that hampers the optimal use of the little space available in the Netherlands. The
8KB wants to achieve this not only through smarter and cheaper technical solutions, but also by devoting
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attention to managerial processes, rules and regulations, planning and, last but not least, communication.
This requires applying existing knowledge on the one hand and developing knowledge via applied and
strategic/fundamental research on the other.
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 gasworks sites.
Restructuring natural areas
Nature development and redesignation of agricultural areas in combination with the remediation of
former dumpsites 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.
A Supervisory Board is responsible for the policy and officially takes all decisions. Important decisions
concern the direction in which the programme will be developed, long-term plans, annual action plans,
and the budget. All parties involved in soil management are represented in the board, namely the
ministries of VROM (Housing, Planning Environment), LNV (Agriculture, Nature Management and
Fisheries), V&W (Transport and Public Works), Defence, OC&W (Education and Science) and EA
(Economic Affairs).
The demand side of the market includes trade and industry, provincial and municipal authorities, water
boards and managers of rural areas. The supply side of the market includes trade and industry,
consultants, knowledge institutions and universities. Other relevant parties are funding organisations,
property developers, environmental groups, insurance companies and branch organisations.
The 8KB is organised as a demand-driven body for the development and transfer of knowledge. This
implies that the organisation does not determine the activities itself, but rather formulates the demand for
knowledge and the supply of solutions and avenues for solutions with the interested parties.
The 8KB is financed by government (18 million EURO) and by the public private market (8 million
EURO) for 4 years: 1999-2002.
As of June 2000, about 50 projects have been started; only some has been completed.
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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 (June 2000) about
50 on-going projects.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
NORWAY
LEGAL AND ADMINISTRATIVE ISSUES
The Pollution Control Act from 1981 is the main law regulating the cleanup 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 landowner may be held liable for
investigations and remedial actions.
The Pollution Control Act gives the authorities a very strong legislative tool for cleanup of contaminated
land. Consequently industrial companies may be held responsible for historic contamination that occurred
before they took over the site or on their property before contaminated soil was regulated (i.e., before the
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-specific acceptance criteria can be generated and also allows
qualitative methods.
Two simple computer applications are available as Excel spreadsheets and on the Internet at the following
addresses: ht||x//wwwuisil«^ and httj3;//wmvj!iiljo™ They will also be
available on SFTs homepage http://www.sft.no.
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 cleanup of contaminated land in October
1999. These are:
• The most seriously contaminated sites shall be cleaned by end of 2005 (about 100 sites) decisions on
investigation and cleanup on the secondly most contaminated sites by end of 2005 (500 sites).
• Investigations and cleanup will be carried out and paid for by private 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.
For further information please see tour de table abstract from 1999.
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
SLOVENIA
1. INTRODUCTION
June 25, 2000, marked exactly nine years since the Republic of Slovenia seceded from the Federation of
Yugoslavia to become an independent state. Among other consequences of this historic occasion,
Slovenia had to rapidly establish its own comprehensive legal and state administration systems to replace
the former Yugoslavia systems, which had been far less specific to the needs of Slovenian citizens and
their wider environment. Such systems were needed to underpin freedom and democracy and support the
flowering of modern life in the newly independent state-of the kind that Western European countries had
been able to establish much earlier.
Protection and enhancement of the environment was an important part of this new focus, which was also
underwritten by the Constitution. Indeed, the previous political and economic systems had resulted in the
serious neglect of the environment. At the end of the 1990's much hope had been put on the Zeleni
movement (the Greens) to help improve the focus on the environment. The only environmental movement
allowed under the former Yugoslavia system, the Zeleni were quite well supported by ordinary people. In
the first democratically elected Slovenian government the Green movement had considerable influence,
with representatives in many important positions. For example, included in the Slovenian State
Presidency of four was one representative from the Greens. The movement also had a vice president in
the government as well as four ministers while in the National Assembly there were more than ten
deputies plus a vice-president.
The Green movement supporters were hopeful that there would be a new emphasis on achieving positive
results for the environment. But despite the high expectations, actual results have been very
disappointing-the Greens have turned out to be much more interested in preserving their well-paid
positions than preserving and enhancing the environment.
So it followed, in the 1992 elections the Greens won only a few seats in the National Assembly and had
just one minister who soon resigned. The incumbent Minister for the Environment and Physical Planning
had previously been a member of the Green movement but changed parties a few months before the
elections to help keep his ministerial position. With all this, the Zeleni movement and political party
practically collapsed and by the start of 1994 a Liberal Democrat MP became minister, even though that
party had previously shown little concern for the environment.
2. SUMMARY OF ENVIRONMENTAL PROTECTION LEGISLATION ADOPTED AND
AMENDED SINCE INDEPENDENCE
The legislation drawn up and adopted over the last nine years includes the so-called "umbrella" acts from
which specific regulations governing individual areas have been adopted. The most important umbrella
act has undoubtedly been the Environmental Protection Act (Ur.l. RS, no. 32/1993). From this act, a total
of eighty decrees and twenty-seven regulations, orders and instructions governing individual areas have
been adopted, as follows:
• 64 decrees, regulations, orders and instructions concerning water (discharges into water,
protection of water, etc.);
• 16 decrees and regulations dealing with protection of the atmosphere, gas emissions into the
atmosphere, etc;
• 4 decrees and instructions dealing with waste, the most important of which are the two
implementation acts: the Regulation on Waste Management (Ur.l. RS, no. 84/1998) and the
Regulation on Waste Disposal (Ur.l. RS, no. 5/2000); and
• 23 decrees and other implementation acts dealing with other areas of environmental protection
(disposal of toxic substances into the soil, etc).
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Another extremely important act adopted last year was the Chemicals Act (Ur.l. RS, no. 36/1999) which,
coupled with five implementation acts, comprehensively governs this area of extreme sensitivity for the
environment. This legislation has been drawn up in accordance with EU directives.
Below is a chronological list of the legislation adopted since 1993:
1993
Environmental Protection Act
Decree on the Founding and Appointing of the Environmental Protection Board
Decree on Temporary Restriction of Use of Water from Water Courses
Decree on the Protection of Endangered Animal Species
Decree on Methodology for Drawing Up Opening Balance Sheets
Forestry Act
Commercial Public Services Act
Urban and Environmental Planning Amendment Act
1994
Decree on Limit Values, Alert Thresholds and Critical Emission Values for Substances Emitted into the
Atmosphere
Decree on the Emission of Substances into the Atmosphere from stationary sources of pollution, heating
plants, from waste incinerators and during the incineration of waste, from aluminum production plants,
from plants for the production of ceramics and brick products, from cement production plants, from the
processing of light alloys, ferrous alloys and steel, from stationary internal combustion engines and
stationary gas turbines, from heat-galvanising plants, from lacquering plants, from plants for the
production and processing of wood products, from plants for the production of lead and alloys from
secondary raw materials
Decree on the Prohibition of the Sale and Import of Vehicles without Catalytic Converters
Decree on the Management of Infective Wastes which Appear in the Performance of Health Care
Activities
Decree on the Protection of Wild Fungi
Statute of the Ecological Development Fund
Decree on Concession for Commercial Exploitation of Ground Drinking Water from the Source by the
Nemiljscica Stream and Proseek Stream in Kneske Ravne
Decree on Temporary Declaration of the Skocjan Cave as a Nature Reserve - Fund for Financing
Disassembling the Krsko Nuclear Power Plant and the Its Radioactive Waste Disposal Act
Organisation and Field of Work of Ministries Act
Local Self-Administration Act
1995
Decree on the Quality of Liquid Fuels with Respect to Sulphur, Lead and Benzene Content
Decree on Noise in the Natural and Living Environment
Decree on Noise Owing to Road and Railway Traffic
Decree on Water Pollution Tax
Decision Determining the Amount of Tax per Unit of Water Pollution for 1995
Decree on the Prohibition of Driving Vehicles in the Natural Environment
Decree on Concessions for the Commercial Exploitation of Water of the Individual Sections of 26 water
Courses for Breeding Salmonidae Fish
Decree on Concessions for the Commercial Exploitation of Water of the Individual Sections of 26 Water
Courses for the Generation of Electricity
Decree on Concession for the Commercial Exploitation of Water Sources in the Republic of Slovenia for
Supplying Drinking Water
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
1996
Decree on Electromagnetic Radiation in the Natural and Living Environment
Decree on Tax for Atmosphere Pollution by Carbon Dioxide Emission
Decree on the Limit, Warning and Critical Emission Values of Toxic Substances in Soil
Decree on Input of Toxic Substances and Plant Nutrients into the Soil
Regulations on the Types of Activity for which an Environmental Impact Assessment is Mandatory
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for the
Production of Leather and Fur
Decree on the Emission of Substances in the Drainage of Wastewater from Plants and Facilities for the
Production, Processing and Treatment of Textile Fibre
Decree on the Emission of Substances in the Drainage of Wastewater from Municipal Wastewater
Treatment Plants
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for the
Production of Metal Products
Decree on the Emission of Substances and Heat in the Drainage of Wastewater from Pollution Sources
Regulations on Toxic Substances Which May Not be Released into Water
Decree on the Concession for the Exploitation of Forests Owned by the Republic of Slovenia
Regulations on Initial Measurement of Noise and Operational Noise Monitoring for Sources of Noise and
on Conditions for Their Execution
Regulations on Initial Measurements and Operational Monitoring of the Emission of Substances into the
Atmosphere from Stationary Sources of Pollution and on the Conditions for their Execution
Regulations on Initial Measurements and Operational Monitoring for Sources of Electromagnetic
Radiation and on Conditions for their Execution
Regulations on Initial Measurements and Operational Monitoring for Wastewater and on Conditions for
Their Execution
Decree on the Conditions and the Procedure for Obtaining Authorisation for Preparing Reports on
Environmental Impact
Decree on the Export, Import and Transit of Wastes
Instructions on the Methodology for Preparing a Report on Environmental Impact
Statute of the Ecological Development Fund of the Republic of Slovenia
Skocjanske Jame Regional Park Act
1997
Decree on Asbestos Emission into the Atmosphere in the Drainage of Wastewater
Decree on the Tax Return Form for the Drainage of Technological Wastewater
Regulations on Operational Monitoring in Input of Toxic Substances and Plant Nutrients into the Soil
Decree on Handling the Substances Causing the Depletion of the Ozone Layer
Regulations on Procedures and Conditions for Using the Ecological Development Fund of the Republic
of Slovenia Funds
Ordinance on Prices for Charging Work and Tasks of the Water Management Public Service
1998
Decree on Concessions for the Commercial Exploitation of Water from the Meza Watercourse for
Additional Snow-making in Crna na Koroskem Ski Trail, the Crnovski Potok Watercourse for Additional
Snow-making in Stari Vrh Ski Trail, and from Underground Water Wells in Cezsoca..., Sujica pri
Horjulu, Dobrusa pri Mosnjah for Breeding Salmonidae Fish
Statute on Treating Waste
Decree on the Form of the Report on Periodical or Permanent Measurements within the Operational
Monitoring of Wastewater
Regulations on Management of Waste Oils
Instructions on the Methodology for the Formation of Prices for Compulsory Local Public Services for
Municipal Waste Management and Disposal of Municipal Waste Remains
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
1999
Preservation of Nature Act
Decree on Prohibition against Alarming Protected Bird Species in the Cliffs in the Karst Margin
Decree on Temporary Declaration of the Soca River and its Tributary for Nature Reserve
National Programme for the Protection of the Environment
Decree on the Emission of Toxic Halogenous Hydrocarbons in the Drainage of Wastewater
Decree on the Emission of Cadmium in the Drainage of Wastewater
Decree on the Emission of Mercury in the Drainage of Wastewater
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for Plant
Protection Products
Decree on Concessions for Economic Exploitation of Sea in the Piran Bay for Breeding Sea Fish
Decree on the Method, Subject and Conditions for Performing Commercial Public Services of
Radioactive Waste Management
Decree on the Emission of Volatile Organic Compounds into the Atmosphere from the Equipment for
Storage and Decanting of Motor Fuel
Decree on the Emission of Substances in the Drainage of Wastewater from Chlorine-alkaline Electrolysis
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants: for the
production of glass and glass products, from domestic animal breeding facilities; from stations for
supplying motor vehicles with fuels; from maintenance and repair of motor vehicles facilities and car
washes; from the production of plant and animal oils and fats; from facilities for performing healthcare
and veterinary activities; from carcass disposal plants; from facilities for the production, processing and
conservation of meat and the production of meat products; from milk processing and production of milk
products; from the production of beer and malt plants, from paper, carton and cardboard production
plants; from cellulose production plants
Decree on the Tax Return Form and Content for Pollution of Atmosphere with the Emission of Carbon
Dioxide for Inflammable Organic Substances
Decree on Setting Up Standards for Forest Works
Decision Determining the Amount of Tax per Unit of Water Pollution for 2000
Instructions for the Formation of Prices for Compulsory Local Public Services for Drainage and
Treatment of Municipal Wastewater and Precipitation Water
Decree on Concession for Management of the Skocjan Cave Nature Reserve
Ordinance on Protection and Development of the Skocjan Cave Nature Reserve
Chemicals Act
Regulations on Special Conditions for Trade in Toxic Chemicals
Regulations on Communicating Data on Chemicals
Rules on the Classification, Packaging and labeling of Toxic Substances
Decision on Restricting Trade in Toxic Preparations for General Use Containing Monoethyleneglycol
Decision on Restricting Trade in Toxic Products for General Use Containing Naphthalene
Decision on Prohibition of Trade in and use of Toxic Substances and Products Made Thereof used as
Plant Protection Products
Chemical Weapons Act
Transport of Toxic Goods Act
2000
Decree on Temporary Protection of Fossil Vertebrates near Kozina
Decree on Temporary Protection of the Mlak Area
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for Coal
Extraction and Production of Briquettes and Coke
Decree on the Emission of Substances into the Atmosphere from Toxic Waste Incinerators
Decree on the Emission of Substances into the Atmosphere from Municipal Waste Incinerators
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for Water
Preparation
Decree on the Emission of Substances in the Drainage of Wastewater from Cooling Plants and Steam and
Hot Water Production Plants
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for
Smoke Gases Treatment
Decree on the Emission of Substances in the Drainage of Leach Waters from Landfills
Decree on the Emission of Substances in the Drainage of Wastewater from Alcohol Beverages and
Alcohol Production Facilities
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for
Production of Mineral Water and Soft Drinks
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for the
Production of Fish Products
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for
Processing of Fruit and Vegetables and Food Production and Deep-Frozen Vegetables
Decree on the Emission of Substances in the Drainage of Wastewater from Facilities and Plants for Potato
Processing
Decree on Concessions for the Commercial Exploitation of Water of the Individual Sections of the
Watercourses of Artisnica, Zaplaninscica, Limovski Graben and Susica for Breeding Salmonidae Fish
Regulations for Removal of Poly chlorinated Biphenyl and Polychlorinated Terpheny
Regulations on Monitoring Toxic Substances Pollution of Underground Water
Regulations on Waste Disposal
Instructions for the Formation of Prices for Compulsory Local Public Services for Drinking Water Supply
Decree on the Method of Performing National Public Service in Water Management
Instruction for Registration in the List of Legal and Natural Persons Carrying Out Production and/or
Trade in Toxic Chemicals Kept by the Chemicals Office of the Republic of Slovenia
Rules for Annual Reports on Performed Supervisions of Toxic Goods Transport
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
3. SURVEY OF CHANGES IN THE ENVIRONMENT SITUATION OVER NINE YEARS
A survey by individual parameter and change in the environment is specified only for the areas with
available data. Data involving changes in the atmosphere have been processed to the highest extent, here,
however, only data on water and some data on changes in the soil are specified.
Quality of Water
Until 1980, the quality of ground water was acceptable. Between 1986 and 1990, the researchers
performing the analyses of water sources began to warn that certain underground sources were
contaminated, which started systematic research and measurements within the Special Programme of
Ground Water Measurements funded by the Republic of Slovenia. The underground areas in Sorsko
Polje, Ljubljansko Polje, Dravsko Polje, and Mursko Polje have been systematically analysed.
The following has been established for the period between 1986 and 1990:
• Ground water in Sorsko Polje was heavily polluted with pesticides, nitrites, phenol compounds,
mineral oils, mercury, ammonium, organic solvents, and chlorinated phosphor compounds.
• Ground water in Ljubljansko Polje showed the presence of phenol compounds, trichloroethylene, tri-
and hexavalent chrome and mineral oils.
• Ground water of Dravsko Polje contained pesticides.
• Ground water of Mursko Polje showed only few exceeded values of pesticide content; the water was
mostly acceptable.
After 1990, analyses expanded to other fields so that systematic analyses of ground water were performed
all over Slovenia. Monitoring consisted of the sampling and analysis of water in 84 places in 18 ground
water fields.
A comparison between the analyses performed in 1990 and in 1995 in the same fields has demonstrated
the following changes:
• Ground water in Sorsko Polje was polluted with phenol compounds, chlorinated solvents and
poly chlorinated biphenyls.
• Ground water in Ljubljansko Polje was polluted with pesticides, chrome and organic solvents.
• Ground water of Dravsko Polje contained excessive concentrations of nitrates, pesticides, zinc, and
chlorinated solvents.
• Ground water of Mursko Polje contained nitrites, pesticides and in some places halogenated solvents.
The latest data show the following results on nitrate and pesticide content in ground water in individual
fields:
197
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
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Quality of the Soil
Pollution of the soil is the consequence of contaminants accumulating in the soil over a longer period.
Sources of such pollution are usually individual producers of these substances, which means that they
could be classified as point sources or strictly local sources. It has been established that in Slovenia the
pollution of the soil involves mainly unsuitable management of special waste, emissions of contaminants
into the atmosphere, composting waste substances, incorrect disposal of sediments and mud from
municipal and other treatment plants, inappropriate management of agricultural waste, inappropriate use
of pesticides, etc.
Measurements of the soil began before 1990, but only in certain areas where the environment was heavily
polluted by industry and emissions into the atmosphere and water, and an increased number of certain
diseases was established. This was the reason for the analyses. The region around the town of Celje was
researched the most. The results of the measurements, which had taken place in 1989, showed that the
concentrations of selenium, mercury, titanium, copper, and chromium did not exceed the standards in
force in the European Community at that time. The DDT, DDE, and TDD values were increased, but only
in individual locations. The concentrations of cadmium, lead, zinc, arsenic, nickel, and certain fluorides,
however, were exceeded. Table 3 demonstrates the measured values.
Table 3: Content of Certain Metals in Soil Samples in the Area of Celje Municipality
Metal
Copper
Zinc
Lead
Chromium
Cadmium
Nickel
Arsenic
Content of the Element in the
Celje Region
(ug/g of dry substance)
5.6- 100
55-3010
15-810
4.8-61.1
0.1-21.4
1.9-76
< 1-85
EGS and Alps Adriatic
Countries Standards
(ug/g of dry substance)
100
300
100
100
2
60
20
Source: Bio-technical faculty of the University in Ljubljana 1989
Note: All samples were taken in 1989
After 1990, the research of the soil began to be performed more intensively, with various institutions,
such as faculties, research institutes, etc. introducing a type of research studies involving the monitoring
of the soil with respect to different contaminants. Via its official institutions, such as the Ministry of the
Environment, the state started to become involved in this monitoring much later and much less
intensively than expected and was necessary. Therefore, the data that are the result of these analyses have
been obtained from the University and different doctorate theses that consisted of analysing and
measuring the environmental pollution parameters.
At the beginning of 1990, the monitoring of the soil encompassed mainly farmland and forests, on the
basis of the Decree on Establishing Pollution of Farmland and Forest (Ur.l. RS, no. 6/1990) and later
pursuant to Regulations on Normatives, Analytic Procedures and Methods of Establishing Pollution of the
Soil and Vegetation, and Conditions for the Use of Certain Substances in Agriculture and Forestry fUr.l.
RS, no. 7/1990).
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The parameters, such as cadmium, zinc, and lead content have been measured in the same area (the Celje
region) as in 1989. At the same time, systematic measurements of the soil in different regions have begun,
as shown in the Table 4.
Table 4: Regional Soil Measurements
Place
Celje
Ljubljana
Ljubljana
Jesenice
Krsko polje
Ptujsko polje
Koprsko
Ljutomer
Celje
Domzale
Novo mesto
Anhovo
Year
1989
1991
1991
1991
1991
1991
1991
1991
1993
1994
1994
1995
TOTAL
Number of
Samples
126
5
26
11
15
21
16
1
5
3
21
4
254
Number of
Samples of Soil
378
11
70
28
45
63
48
3
15
9
59
9
738
Number of
Samples of Plants
40
0
22
10
12
18
16
5
5
*0
21
4
153
After 1995 the Ministry of the Environment and Physical Planning adopted, pursuant to the Environment
Act, a number of decrees with the view of regulating the protection of the soil by law:
• Decree on the Limit, Warning and Critical Emission Values of Toxic Substances in Soil
• Decree on Input of Toxic Substances and Plant Nutrients into the Soil
• Regulations on Operational Monitoring in Input of Toxic Substances and Plant Nutrients into the Soil
These regulations set up limit and critical emission values for a number of contaminants and their input
into the soil. These values have been taken over from foreign legislation.
Systematic monitoring of the content of certain contaminants in the soil has shown that Slovenia has
some areas that are heavily polluted. In the most polluted areas, it has been established that in the regions
with intensive agriculture the main contaminants were pesticides, in the vine-growing regions the main
contaminant was copper, in the regions with excessive use of fertilisers, ground water was polluted with
nitrates, and in the areas where industrial waste had been inappropriately disposed the main contaminants
were heavy metals and aromatic hydrocarbons. The lead content near the main motorways was also high.
4. AN OVERVIEW OF CONDITIONS IN THE AREA OF WASTE MANAGEMENT AND
DISPOSAL
Waste
Waste management in Slovenia is still not institutionally regulated on a state level. Despite many
documents prepared on the subject, practical measures have not yet been undertaken.
The situation in 1990 was as follows: Sixty-five percent of the population was included in the public
municipal waste disposal system. In 1987, 320,000 tonnes of municipal waste were created in Slovenia,
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or 1,800,000 m3. Between 1981 and 1987, the quantity of municipal waste increased by a minimum of 5%
and by a maximum of 10% in major cities (Table 5).
Table 5: Quantity of Municipal Wastes Produced in Regions of Slovenia in 1981 and 1987
Region
Pomurska
Podravska
Savinj ska
Koroska
Zasavska
Posavska
Ljubljanska
Dolenj ska
Notranjska
Obalno-kraska
Goriska
Gorenjska
TOTAL
1981
Quantity of
wastes (tons)
20871
51234
39013
11191
7409
11589
75221
15724
7934
14900
18931
28680
302697
Number of
Inhabitants
130442
320215
243834
69945
46304
72432
470130
98276
49589
93127
118320
179250
1891864
1987
Quantity of
Wastes (tons)
21111
52532
40998
11767
7595
11642
82752
16344
8060
15896
19252
30364
318313
Number of
Inhabitants
131946
328425
256240
73546
47470
72764
517202
102153
50372
99349
120322
189773
1989462
Index (87/81)
101,1
102,5
105,1
105,1
102,5
100,5
110,0
103,9
101,6
106,7
101,6
105,9
105,2
Table 6: The Composition of Municipal Waste
Material
Paper
Plastics
Glass
Metals
Textile
Organic compounds
Inorganic compounds
TOTAL
Part(%)
15
10
5
7
4
41
18
100
Quantity of Wastes
Produced in 1 Year
45000
30000
15000
21000
12000
123000
54000
300000
Quantity of Wastes
Collected in 1 Year
30150
20100
10050
14070
8040
82410
36180
201000
In 1995, around 900,000 tonnes of municipal waste were created in Slovenia, which represented 10% of
all wastes created in Slovenia in that year. In that same year, the percentage of the population included in
the public municipal waste disposal system reached 76%. The composition of municipal waste in 1995
was similar to that in 1987. Approximately 100,000 tonnes of waste were separated and recycled, while
750,000 tonnes were disposed of in landfills only.
The conditions in the area of special types of waste management have changed greatly over the past few
years, in terms of structure as well as quantity. This is attributed to the changes in the political and
economic systems and to the concern for the environment connected to this, as well as to cost-cutting in
production, the closing of industrial plants in various unprofitable branches, and so on. Table 7 shows the
quantities of special types of waste created in 1987.
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Table 7: Quantities of Special Types of Waste Generated in 1987
Category
I.
II.
III.
Type of Waste
Particularly hazardous wastes
Hazardous wastes
Special wastes
TOTAL
Quantity
(tons)
447
24.118
740.384
764.949
(m3)
4.293
385.573
1.160.872
1.550.738
In practice, the management of special types of waste was completely unregulated on the state level. Such
waste was mostly disposed of in mono landfills, in municipal waste landfills and in various "illegal"
landfills. Secondary raw materials were only rarely recycled from such waste. Table 8 shows the recycled
quantities of secondary raw materials from 1985 to 1988.
Table 8: Recycled Quantities of Secondary Raw Materials from 1985 to 1988
Raw Material
Steel and castings
Heavy metals
Copper and alloys
Aluminium and alloys
Lead and alloys
Zinc and alloys
Paper
Plastics
Glass
Rubber
Textiles
Others
TOTAL
Quantity (tons)
1985
272728
16215
-
-
-
-
84210
2715
17448
3248
4244
6549
407357
1986
259660
-
7063
6323
3042
380
89197
2312
17516
3439
5841
945
395718
1987
293395
-
7663
6932
2688
358
80613
2212
17427
2369
5445
753
419855
1988
367291
-
6222
5709
2974
340
80027
1715
16283
2453
5234
780
489028
Structure
1988 (%)
75,1
-
1,3
1,2
0,6
0,1
16,4
0,4
3,3
0,5
1,1
0,2
100,0
Index
1988/86
141
-
88
90
98
89
90
74
93
71
90
83
124
Classification and measurements of special types of waste between 1993 and 1996 shows that the
quantities and variety of waste changed greatly. Table 9 shows these quantities and varieties over the
years, according to the definitions in legal acts passed after 1992 and still in force today.
Table 9: Quantity of Dangerous Waste Between 1993 and 1996
Type of Waste
Medical waste
Pharmaceutical production and
preparation
m3
1993
416
/
t
1993
324
269
m3
1994
474
1030
t
1994
286
868
m3
1995
831
931
t
1995
28
1226
m3
1996
631
892
t
1996
329
921
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Type of Waste
Pharmaceutical products,
narcotic drugs, and
medicaments
Production, preparation and use
of pesticides and plant
protection products
Production, preparation and use
of chemicals for wood
protection
Production, preparation and use
of organic solvents
Heat treatment and hardening
that contains cyanides
Mineral oil waste, waste
unsuitable for initially-
designated use
Waste mixtures oil/water,
hydrocarbons/water, and
emulsions
PCB, polychlorinated
triphenyls (PCX) and
polybrominated biphenyls
(PBB)
Residues of tar from refining,
distillation and pyrolitic
treatment
Production, preparation and use
of inks, dyes, pigments, coats,
and varnishes
Production, preparation and use
of pitches, latex, plastic
additives, glues
Chemicals from research and
development
Explosive wastes not regulated
by other laws
Production, preparation and use
of photographic chemicals
Superficial treatment of metals
and plastic
Residue from removing
industrial waste
Metal carbonyls
Beryllium, beryllium
compounds
Hexavalent chrome compounds
Copper compounds
Zinc compounds
Arsenic, arsenic compounds
Selenium, selenium compounds
m3
1993
0
2
936
4407
2
3125
258
2009
5
2
80
82
11
1
t
1993
7
696
849
1003
72
36
566
512
84
34
102
1141
55
3
1064
m3
1994
0
21
1084
2141
0
1293
123
1166
32
2
438
7
4
2
0
t
1994
21
272
913
279
17
30
572
172
4
918
132
1198
34
3
885
m3
1995
1057
3724
2
1123
101
3742
14
1
987
4
4
1
2
t
1995
27
157
719
703
28
410
142
2
1121
42
20
18
0
1254
m3
1996
2
1241
3007
4
1128
226
3981
11
1
1163
4
11
t
1996
104
204
753
800
14
555
184
2
961
49
19
0
1201
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
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Type of Waste
Cadmium, cadmium
compounds
Antimony, antimony
compounds
Tellurium, tellurium
compounds
Mercury, mercury compounds
Thallium, thallium compounds
Lead, lead compounds
Inorganic fluorine compounds
without calcium fluoride
Inorganic cyanides
Acid solutions or solid acids
Basic solutions or solid bases
Asbestos
Organic phosphor compounds
Organic cyanides
Phenol, phenol compounds
including chloro-phenols
Ethers
Halogenated organic solvents
Organic solvents without
halogenated solvents
All ingredients related to
polychlorinated dibenzofuran
All ingredients related to
polychlorinated dibenzo-p-
dioxin
Organo-halogenated
compounds not specified under
Y39,Y41,Y42,Y43,Y44
Waste from households
Waste from incinerating
household waste
Sum
m3
1993
1
9
938
720
39
744
522
1289
3
15601
t
1993
7558
17
162
1358
662
3417
616
2
238
2050
0
22897
m3
1994
8
449
558
839
179
543
1
10394
t
1994
45
158
151
642
6081
13
1
186
2405
3
16289
m3
1995
0
0
490
728
220
71
347
0
807
15187
t
1995
0
50
202
141
1218
4775
603
0
159
3840
2
56
16943
m3
1996
0
442
774
1
158
44
200
1
0
13922
t
1996
0
428
133
1727
599
4892
588
0
205
4496
56
19221
Management of such wastes has not changed greatly since 1987, which means that in the majority of
cases it is still collected and disposed of in more or less unregulated landfills. The separation and
recycling of raw materials from waste is in decline compared to the period between 1985 and 1988 (Table
8); therefore, raw material potential is being wasted due to a lack of appropriate economic measures. Even
though certain well-developed recycling procedures for specific types of special waste in certain branches
have been in use for a number of years, a large quantity of such waste is still disposed of in landfills,
completely unutilised.
In terms of energy, the caloric value of waste is harnessed in two incinerators for special types of
industrial waste, specifically for pharmaceutical waste (capacity 700 tonnes/year) and phytopharma-
ceutical waste (capacity 100 tonnes/year).
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Landfills
The most problematic activity in waste management is disposal in landfills. A comparison of the number
and fittings of landfills in Slovenia shows that waste treatment has not significantly changed. A total of 54
official municipal waste landfills were located in Slovenia before 1990 (see Figure 2).
Figure 2: Official municipal waste landfills in Slovenia
.^MAUI .
9 ,%'»
«*«*«'
™ '
^
/
*^
jll
™ -
All of the described landfills operate without fulfilling the required technical and geological demands, and
only 16 of them have legal operational permits. Between 1991 and 1994, 18 landfills were reconstructed,
but advanced technical solutions, such as treatment of water leakage, elimination of gases, monitoring,
disposal techniques, and so on, were used in only four. In addition to these landfills, approximately 600
"black" or illegal landfills for all types of waste are thought to exist. Their locations are known, but they
operate without operational permits and are not officially registered.
Apart from the above, several years ago various non-governmental organisations began to search for,
register and mark various pits where industries were disposing of their waste, and also registered waste
illegally disposed of, which had been mostly covered with earth. Such landfills were mostly discovered
due to toxic substances leaking into ground water, and often quite accidentally during construction works
or the like. The number of these sites exceeds 10,000.
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January 2001
Figure 3: Registered Caves in the Land Register of Slovenian Caves
«- %>. 'Ufc1*^**'
x^-*5
•^•sl*""1 i. «, ^W*»
Figure 4: Polluted or Damaged Caves in the Same Land Register
k4 tVl /V)J
,.-'' >^l*\\/
A/* ^ y^%
** X * JHh. -V. "1
v / * -
,,,'^|%(pii»S..
*2rO-s%'
;rs-r ./i «IFX|
4^^i^S^ A
^teS^SN^
Hi
^-"Jf"-' i .-IF
There are also 13 landfills in Slovenia for industrial waste and waste from prospecting of mineral
resources (see Figure 5).
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January 2001
Figure 5: Locations of 13 Industrial Waste and Mining Landfills
The capacity of all registered official municipal waste landfills (54 in number) is approximately
13,000,000 m3. Waste is compressed prior to disposal in these landfills to reduce its size. These landfills
are also the end destination of waste discovered in illegal landfills; their capacities are projected to suffice
only for the next five to seven years. Figure 6 shows the disposal of waste in registered official municipal
waste landfills.
The consequences of water leakage from illegal landfills already surfaced several years ago as water
contamination in certain areas. This was most evident in the northeastern part of the country where
drinking water had to be supplied by tankers to more than 60,000 people.
5. National Programme for the Protection of the Environment
The most important document drawn up by the Ministry of the Environment and Physical Planning in the
last ten years is, in addition to the Environmental Protection Act, the National Programme for the
Protection of the Environment. It contains goals, guidelines and the strategy for the protection of the
environment for the period of a minimum often years.
The document was published in official documents in September 1999 but it has not yet been adopted by
the National Assembly. With the National Assembly not adopting and confirming the legitimacy of the
document, all guidelines and plans defined in the document have not yet become operational.
The document consists of sets of basic goals, which are placed in the document with respect to meaning
and time plan of the implementation.
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Figure 6: Disposal of Wastes in Registered Official Municipal Waste Landfills
Polno 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2007 2010 2015 2020 2025
Leto
These goals are:
Water
• reducing emissions from point sources
• reducing emissions from diffusing sources
• clear-up of old pollution posing a threat to the aquatic environment
• clear-up and prevention of unsuitable encroachments into the aquatic environment
Waste management
• reducing the generation and risk potential of waste at the source
• increasing the exploitation of waste in terms of substance and energy, and reducing the emission of
greenhouse gases
• establishing an effective system of waste management
• gradual elimination of old pollution
Biotic diversity and genetic sources
• preventing the reduction of biotic diversity at the ecosystem level
• preventing further threats to the natural balance due to inappropriate exploitation of plant and animal
species
Atmosphere
• reducing the pollution of the atmosphere by industrial sources
• reducing the emissions from coal-fired power plants
• controlling pollution of the atmosphere due to traffic
• reducing emissions from individual and joint combustion chambers in residential areas
• reducing the causes for photochemical smog and troposphere ozone
• elimination of CFC use
• reducing the emissions of greenhouse gases
• controlling the problems of long-distance atmosphere pollution
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Soil and Forest
• limiting chemical soil pollution and implementation of urgent cleanups
• limiting physical degradation of soil
• limiting further degradation of forest soil
Noise
• reducing road-traffic-induced noise
• reducing noise from other sources
Ionic radiation
• providing for effective management of radioactive waste
• controlling radioactive radiation in the external environment
Non-ionic radiation
• identifying and gradually controlling individual sources of non-ionic radiation
Risks
• providing for suitable procedures for handling chemicals and genetically altered organisms in their
production, traffic and use
• establishing appropriate storage, transport and disposal of chemicals.
According to this document Slovenia's priority goals for the first five years of this millennium are the
following:
• effective completion of the set programmes for the protection of the atmosphere supplemented by the
programmes for reducing industrial concentrations of troposphere ozone and emissions of greenhouse
gases
• improving the situation in the aquatic environment
• establishing modern methods of waste management
• preserving and protecting biotic diversity and genetic sources.
The concept of the National Programme for the Protection of the Environment takes into consideration
the principles of the effectiveness of every sector or activity, which affect the environment, and does not
release any activity of its responsibility toward the environment. The document defines programmes for
individual industrial activities that affect the degradation of the environment by industry and mining,
power industry, agriculture and forestry, and tourism.
At the same time the document deals with specific environmental problems of sensitive areas the coast,
countryside, and mountainous areas. A question that comes to mind is whether the national programme
will receive its verification in the National Assembly and its implementation in practice.
6. FINANCIAL PROBLEMS
Slovenia's state administration, and the Ministry of the Environment and Physical Planning in particular,
are well aware that environmental care and rehabilitation and the organisation of activities for keeping
pollution-causing parameters within reasonable and legal boundaries are extremely costly and demanding
processes. In formulating the Strategic Orientation on Waste Management, the legislature envisaged
economic measures that would be necessary in order to enable these activities to commence and function.
Table 10 shows that the proponents of the Strategic Orientation on Waste Management in the Republic of
Slovenia have envisaged activities in connection with landfills, application of technical and technological
measures and introduction of heat processing of waste, and also in connection with the management of
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industrial, agricultural and forestry waste. They have also determined the amounts to be invested in
individual stages of each of these activities.
Table 10: Catalogue of the Main Activities and Investments
Number Of Activities Related To Deposit Sites
1. Land filling deposit sites by 2000, closing down and covering
over according to EU standards
2. Land filling by 2000, and closing down according to EU
standards
3. Land filling by 2000, reconstruction according to EU standards
4. Possibility of exploitation by 2000 along the reconstruction
according to EU standards
5. Reconstruction according to EU standards because of the
possibility of exploitation of the capacities after 2000
6. Expansion and reconstruction according to EU standards for
bridging transitional period
7. Reconstruction and additional construction of deposit sites with
long-term perspective according to EU standards
8. Construction of new deposit sites in accordance with EU
standards
9. Preliminary works for new deposit site
16
2
2
10
11
8
2
3
1
Investment (in
DEM million)
32
11
5
54
77
145
103
210
5
No.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Activities for the Implementation of Technical/Technological Complex:
Capture, Treatment, Processing, Exploitation of Substance
Collection systems for,
biological, green waste
other waste
dangerous waste in household waste
Recycling collectors: paper,
glass (white, coloured)
metal (cans)
artificial mass (selected)
Collection and conversion centres for potential secondary raw materials
Compost places:
4 major ones: Ljubljana, Maribor, Celje, Kranj (20,000 tonnes/yr or more)
40 small ones (up to 6,000 tonnes per year)
Collection and processing centre for glass
Seven collection centres, and one collection and processing centre for tyres
Portable devices for disinfecting infective waste
Collection, sorting and processing centre for artificial masses
Mechanised separation (3)
Portable and stationary condensers of sump sediments
Compost places for the mud of municipal BCN
Equipment for preparing soil for clear-up
Drying plants for mud BCN (three plants)
(depends on heat treatment of waste)
Disassembly of disposed cars and piece waste (three facilities)
Containers and reloading stations for other waste
Vehicles for transport to collection and conversion, and collection and
processing centres
Investment (in
DEM million)
17
25
15
84
45
2
7
7
3
30
9
13
25
10
25
5
5
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No.
1.
2.
3.
Activity for the implementation of heat treatment of waste, and realisation
and construction of suitable deposit sites
Preliminary works for two plants
Preliminary works and construction of one plant
Construction of the second plant for heat treatment of waste (after 2000)
Investment
(in DEM
million)
30
220
300
No.
1.
2.
3.
Activities for Realisation of Solutions in the Area of Waste from Industry,
Power Industry, and Construction
All investment from long-term reservations within the ownership
transformation, and the exploitation of up to 30 percent of slag and ashes from
coal-fired plants and metallurgy in construction
Stationary systems for re-cycling construction waste (five plants), mobile
recycling devices (two devices), portable sowing devices (two), five mono
deposit sites, investment into plants for exploitation of energy and metallurgy
slag in construction
Funds for technological upgrading, production for reducing quantities of waste
Investment
(in DEM
million)
230
192
200
No.
1.
2.
3.
4.
Activities for the Implementation of Solutions in the Area of Waste from
Agriculture and Forestry
Change of technologies for breeding cattle in farms (five farms), technical and
technological measures for reducing the amount of slurry, measures for
optimisation of possibilities for use of liquid manure and slurry in agricultural
areas
Upgrading the equipment of carcass disposal plant
Construction of compost places (or co-investment)
Construction of plants substantial exploitation of wood bio-mass
Investment
(in DEM
million)
50
25
15
0,1
Investment estimate is -20 to +30 percent.
The state has also planned certain economic measures for the implementation of other environmental
protection directives. One of the most important was the founding of Ekosklad (Ecofund), which may
only finance environmental projects. The fund was made possible by the Environmental Protection Act.
Ekosklad is a non-profit organisation, fully owned by the state, which functions as a joint-stock company.
Ekosklad grants loans from its own assets at an interest rate lower than that of commercial rates. The fund
does not grant non-returnable loans. All loans are intended exclusively for the financing of projects of
environmental rehabilitation, improvement or conservation (such as technologies for lower energy
consumption in the * industry, construction industry, etc.).
Table 11: Budgetary Spending on the Environment between 1994 and 1996 (in SIT million)
Total expenditures
Investment expenditures
Current expenditures
Transfer into companies
1994
Value
4,565
3,074
1,491
1,191
1994
Share
100%
67%
33%
26%
1995
Value
4,107
3,085
1,021
406
1995
Share
100%
75%
25%
10%
1996
Value
3,913
1,834
2,079
1,092
1996
Share
100%
47%
53%
28%
Note: Data may be changed since the methodology is being drawn up.
Source: The state budget
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Expenditures are exclusively for environmental purposes or for items with evidently favourable effects on
the environment (e.g., expenditures for improving energy efficiency). The difference between the
protection of the environment and the protection of nature has not yet been determined. Estimates do not
include non-returnable funds in the form of past income from tax deductions, relief, exemptions, loans or
other forms of fiscal incentives for environmental expenditures. State guarantees for environmental
projects are not included either.
Table 12: Ekosklad's Performance in 1994, 1995, and 1996
Income Statement (in SIT million)
Interest
Income form securities
Net charges and commissions
Other operating income
General administrative expenditures
Depreciation
Other operating expenditures
Write-offs and adjustment
Of non-repaid loans
Income from revoked commissions
Operating profit or loss
Extraordinary profit or loss
Total profit (loss)
1996
110.2
90.7
(1.3)
7.5
(129.7)
(12.1)
(198.7)
(31.6)
(128.4)
(37.3)
39.9
2.5
1995
44.4
20.7
(1.4)
2.0
(69.5)
(9.6)
(8.6)
(11.5)
(104.0)
70.5
(5.4)
65.1
1994
21.6
(0.1)
(18.7)
(0.4)
(2.3)
0.1
0.1
Eco Fund is a joint stock company. It is presently owned by the state. By statute, any legal entity and/or
natural person may become Eco Fund shareholder. The Fund is a non-profit organisation and does not
give dividends. If, in addition to the state, the owners of the Fund shares are also other shareholders, they
may benefit only from preference loans. A new shareholder may not own more than 33% of Eco Fund's
capital stock. Shareholders have no right to vote. The Fund is managed by the board-appointed by the
government (chair and four members).
The Director of the Fund is appointed by the management board and confirmed by the government. The
Fund performs its activities in four main areas: the reduction of the pollution of the atmosphere,
discontinuation of ozone-harmful substances, development of municipal infrastructure and the reduction
of industrial pollution. In June 1996, the Fund took up a loan at the World Bank in the amount of DEM 30
million for funding the transition to cleaner heating systems. The PHARE programme raised ECU
400,000 for institutional consolidation and projects of reducing the pollution of the atmosphere.
The Trust Fund at the Global Environmental facility has assigned USD 6.2 million of non-returnable
funds to six Slovene companies for the implementation of the project of discontinuation of ozone-harmful
substances. As a financial agent the Eco Fund has been dividing funds and is responsible for other
procedures. In November 1995, the Eco Fund started to carry out the projects of municipal infrastructure.
It published a tender for municipalities that wished to obtain loans for projects related to the sewage
system, waste, systems of treating wastewater, disposal of solid waste and water system. By the spring of
1996, the loans amounted to DEM 7 million.
A similar project started in June 1996, with the tender for industrial companies that wished to obtain loans
for projects related to the reduction of the pollution of the environment (atmosphere, water, solid waste
and ozone-harmful substances). By November DEM 11 million loans were assigned (Table 13).
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Table 13: Balance Sheet (in
Cash
Loans to banks
Loans to clients
Securities on the market
Tangible fixed assets
Other assets
Total assets
Generated expenditures and
Deferred income
Other liabilities
Reservations
Registered capital
Reserves
Revaluation adjustment to capital
Net profit carried over
from previous year
Net annual profit (loss)
Total liabilities and ownership capital:
1996
42.5
710.7
4,313.7
676.7
13.5
17.2
6.157.3
6.7
12.6
403.4
4,721.0
65.3
571.7
2.5
6,157.3
SIT million) for
1995
42.6
825.8
3,251.8
459.8
16.7
14.2
4.610.8
10.3
6.0
482.3
3,8712
0.1
175.7
0.1
65.1
4,610.8
31 December
1994
25.6
131.6
2,244.0
84.2
21.5
9.1
2.515.9
-
5.0
479.0
2,031.8
0.1
0.1
2,515.9
Implementation costs of the National Programme for the Protection of the Environment
The document divides the implementation costs of the programme into individual goals. The estimate has
been made for the initial five years from 1999 to 2003.
Table 14: Survey of Estimated Implementation Costs (in million SIT)
Year
1999
2000
2001
2002
2003
Total
Water
27.122
27.002
26.974
26.974
26.974
135.046
Waste
17.570
17.520
17.520
17.520
17.520
87.650
Biodiversity
2.095
2.095
2.071
2.093
1.809
10.163
Atmosphere
6.047
6.021
5.975
5.945
5.895
29.883
Soil
49
49
28
28
28
182
Noise
50
11
9
9
8
87
Radiation
56
40
10
10
12
128
Risk
58
58
9
5
5
135
Measures
142
94
2
238
Total
53.189
52.890
52.598
52.584
52.251
263.512
SIT 100 = DEM 1
The estimated costs by individual sectors and priority goals have been defined in detail. The financial
plans of funding sources have also been defined:
public sector
the budget
charge for the pollution of the environment (charge for polluting water with wastewater, charge for
waste disposal, charge for gas emissions, etc.)
municipal budgets
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• foreign sources (international loans, etc.)
• the Eco Fund loans.
Economic Instruments
The Environmental Protection Act provides the legal foundation for taxes and fees that the state may
collect from polluters. Slovenia finances its environmental protection activities from several sources, as
follows:
• the central budget (taxes and fees),
• municipal budgets (local taxes, donor contributions),
• company assets (companies in stages of privatisation reserve some of their assets for environmental
issues),
• foreign sources of funding (international loans, assistance on the basis of bilateral agreements, etc.).
• types of taxes:
• tax on polluted wastewater
• fee for drinking water
• tax on excess air pollution from carbon dioxide
• funds from concessions to use natural resources
7. CONCLUSION
Over the nine years since Slovenia gained its independence, Slovenia's citizens have expected much more
in the way of environmental protection than the state has actually provided. They expected great changes
in those areas where the state can actively interfere through its regulations; for example, the founding of
public companies for waste management, construction of landfills, water management, water
conservation, protection of nature, forests and biodiversity, linking of economic and environmental
developmental policies, introduction of cleaner, safer and more rational technologies in industry,
environmental protection in the energy sector, and similar issues. What they have in fact received are a
number of executive acts (and even those were issued under pressure from the EU, which Slovenia would
like to join in the near future) and some documents of a declarative nature such as the Strategic
Orientation on Waste Management in the Republic of Slovenia, the National Environmental Protection
Programme and the like, which have not been implemented to the full extent or within the deadlines
specified in the documents themselves. Unfortunately, many more years will have to pass before
Slovenia's environmental policy will achieve a level equal to that in EU member states, or as envisaged
by EU guidelines and directives.
8. SOURCES
1. GV Register of Currently Valid Legislation in the Republic of Slovenia 3/2000, published by the
Gospodarski Vestnik Publishing House, Ljubljana
2. An Overview of the Efficiency of Environmental Policy, Slovenia, United Nations Economic
Commission for Europe, No. 415-490/98 - MB/MC 1998
3. The Environment in Slovenia 1996, Administration of the Republic of Slovenia for the Protection
of Nature, Ljubljana 1998
4. The State of the Environment, a Proposal for the Report on the State of the Environment in 1995 -
EPA 1378, Reporter - Journal of the National Assembly of the Republic of Slovenia, year XXII,
No. 6/1, Ljubljana 1996
5. Report on the State of the Environment in the Socialist Republic of Slovenia, Reporter - Journal
of the National Assembly of the Socialist Republic of Slovenia, year XVI, No. 5/1, Ljubljana
1990
6. The Second International Conference on WASTE MANAGEMENT IN SLOVENIA - WASTE
DISPOSAL, Institute for Technical Education, Ljubljana, Slovenia, 28-29 May 1996
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7. Statistical Yearbook 1998, Year XXXVII, Ljubljana 1998
8. Strategic Guidelines of The Republic of Slovenia in Waste Management - EPA 1595 Reporter -
Journal of the National Assembly of the Republic of Slovenia, year XXII, No. 36, Ljubljana 1996
9. B. Druzina, The Final Disposition of Remains from the Processing of Waste in the Republic of
Slovenia, Ljubljana, March 1996
10. Proposed National Programme for the Protection of the Environment (NPVO), EPA 669-11,
Official bulletin (Porocevalec) of the National Assembly, Year XXV, No. 65, Ljubljana, 10
September 1999.
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SWITZERLAND
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 CONTAMINATED 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 closed in 1975, it was sealed over, and a drainage system and wastewater 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 (i.e., the 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 is
possible, at a cost of about 200 to 300 million Euro. These costs are considerably less than estimates
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made about fifteen years ago, when (faced with an estimate of 700 Euro for decontamination) safety
measures were taken instead.
Finally: a Swiss specialty
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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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
TURKEY
1. LEGAL AND ADMINISTRATIVE ISSUES
There is 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 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 that 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.
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.
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
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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 AND RD&D
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 at few chemical spill
sites, pump and treat type technologies are being used for groundwater cleanup. Most probably these sites
will set precedence, in terms of both cost and performance, for cleanup in other similar sites.
There is a pressing need for research and development of soil and groundwater cleanup technologies in
Turkey. The number of soil and groundwater remediation research projects supported financially by the
Turkish State Planning Organization, The Scientific and Technical Research Council of Turkey and other
governmental institutions is increasing. For example, a project regarding the performance assessment of
solidification/stabilization (S/S) technology for remediation of a large group of wastes (e.g., soils, mining
residue and paper and pulp industry sludge) containing organic contaminants (PCB and AOX) and heavy
metals has been initiated. The main purpose of this project is to investigate the reliability of S/S
technology for remediation of certain waste groups and provide technical and economical guidance for its
field-scale applications. The General Directorate of State Hydraulic Works is about to finish a couple of
pilot projects to update hydrogeologic investigations of two major groundwater basins. The main
objectives are to develop comprehensive database and appropriate groundwater management plans using
recent technologies such as GIS, RS and advanced numerical groundwater modeling and to set the
standards for similar studies for the other major basins.
4. 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 has 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.
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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
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
1. LEGAL AND ADMINISTRATIVE ISSUES
At the first two meetings of the Pilot Study, the 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 fully described.
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. 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, it is anticipated that the provisions of the 1990 Act will come into force in mid-July.
More 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 certain 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 importance of urban regeneration and the beneficial reuse of brownfield land continue to be a major
topic of debate in the UK. In June 1999, the Government appointed Urban Task Force reported its
conclusions and recommendations about reversing urban decline in England after a 14-month study. The
challenges posed by dealing with land contamination represented a significant issue in the brownfield
debate. In considering the issues, the report concluded that:
• Most contaminated land is capable of safe remediation using modern technology at reasonable cost.
• The present barriers to redevelopment are largely to do with the perception of risk.
• There is a need to simplify and consolidate the regulatory systems that seek to protect the
environment from the consequences of contamination.
• There is a need to promote greater standardisation in the way that the UK manages the risks involved
in redeveloping contaminated sites, and thereby promote a better and consistent understanding of the
situation.
2. TECHNOLOGY DEVELOPMENT PROGRAMMES
At the last Pilot Study meeting in Angers, France, the launch of CLAIRE (Contaminated Land:
Applications in Real Environments) was reported. The objective of CLAIRE is to establish a network of
test sites to research and demonstrate cost-effective techniques for the investigation and remediation of
land affected by contamination in the UK. It aims to address the key issue of how to get over the
information barrier limiting the use of process-based remediation technologies in the UK.
In the past year, CLAIRE has received 11 applications for research and demonstration projects. The first
CLAIRE Technology Demonstration project involved field-scale trials of low temperature thermal
desorption (LTD) technology carried out on 40 tonnes of hydrocarbon-contaminated soil. The project
report will be available shortly. CLAIRE is currently working with site owners to develop the range of
sites that might be available to the network for remediation projects—current discussions involve about
50 sites. In addition, the Technology and Research Group (TRG) within CLAIRE has been finalising the
key aspects of the CLAIRE Research Strategy. CLAIRE can be reached on the web at www.claire.cauk.
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January 2001
Summary of re mediation techniques used as a % of sites
surveyed. Process -based techniques have been
summarised as either in-situ or ex-situ [3]. Sample size 343.
inn -,^^^^^^^^^^^^^^^^^^^^^^^— ^^^^^^^^^^^^^^^^^^^^^^^—
sn
£r\
A(\
10
n
U % of sites surveyed
| | i ,
Civil Engineering In situ Ex situ
Civil engineering methods were
used on nearly all sites. Process-
based techniques were not used
exclusively but in combination
with civil engineering methods.
Key techniques used include
SVE, DVE, ex situ
bioremediation, and soil
washing.
Reported contaminant groups remediated
according to survey [3]. Sample size 357.
1 AA _,
1UU
OA
oU
f.f\
OU
/] A
4U
OA
ZU
D% of sites
surveyed
'
Ors^nics Metals Inorjpiics Gas /Vapour Asbestos
It should be noted that
more than one category of
contaminant might appear
on the same site.
The contaminants
identified are likely to be
the "risk-driver"
compounds (i.e., the most
memorable) and others
may have been present.
3. REMEDIAL METHODS IN USE
At the last Pilot Study meeting in Angers, France, it was reported that the Environment Agency had
commissioned a survey of remedial techniques that had been used in England and Wales for remediation
in recent years. This survey has now been completed and the report will be published in the next few
months [3]. However, it has been possible to illustrate some of its findings here.
In total, more than 1,500 sites were identified by the survey where remediation was carried out during the
period January 1996 to December 1999. The amount of information collected about each site varied
considerably. The majority of sites:
• Were small sites less than 5 hectares in size.
• Resulted from development led remediation (with most involving a change of use from industrial to
residential).
• Involved civil engineering-based remediation techniques (largely excavation and disposal, minor
regrading, and caps/cover systems).
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However, the survey also found evidence that multiple remediation techniques are being used on sites to
match contaminant distribution patterns, end-use layout, and the drive to minimise costs. Although only a
minority of sites was found to be subject to formal options appraisal there was evidence that cost, while
being a key consideration, was not the only factor taken into account. Cost data was found to be
extremely difficult to collect.
The charts on the following page illustrate some of the preliminary findings of the survey.
Research and Development Activities
Table 1 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 1: Recent UK R&D Projects on remediation of land affected by contamination
(not intended to be inclusive)
PROJECT
STATUS
RESEARCH COUNCILS
Disposal of Oiled Beach Sand in Coastal Soils.
Dual anaerobic system for bioremediation of
metal/organic wastes
Bioremediation and microbial population
dynamics
Cyanide biodegradation: a model for the
development of molecular probes for
optimisation of bioremediation
Phytoremediation: an integrated biological
approach to the decontamination of polluted soils
An integrated, multifunctional system for
bioremediation of waters containing xenobiotics
and toxic metals
Non-invasive characterisation of NAPL-
contaminated land by spectral induced
polarisation (SIP) tomography
New sensor system for monitoring solvent
migration from contaminated sites
Studies into metal speciation and bioavailability
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
Published in 2000.
Available from the Institute of Terrestrial
Ecology, Furzebrook Research Station,
Wareham, Dorset, BH20 5AS, United Kingdom
Supported by the Maritime Coastguard Agency
and the Natural Environment Research Council
BBSRC
Professor Macaskie, University of Birmingham
BBSRC
Dr Head, University of Newcastle
BBSRC
Professor Knowles, University of Oxford
BBSRC
Professor Thompson, Institute of Virology &
Environmental Microbiology
BBSRC
Professor Livingston, Imperial College of
Science, Technology, and Medicine
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
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Bacterial biosensors to screen in situ
bioavailability, toxicity, and biodegradation
potential of xenobiotic pollutants in soil
NERC
Professor Killham, University of Aberdeen
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 as part
of a selection process
Published in November 1999.
R&D Technical Report P316.
Natural Attenuation of Petroleum Hydrocarbons
and Chlorinated Solvents in Groundwater
To provide a review of current knowledge on
natural attenuation of two common organic
pollutants in groundwater systems: petroleum
hydrocarbons and chlorinated solvents.
Published in December 1999.
R&D Technical Report P305.
Costs and Benefits Associated with Remediation
of Contaminated Groundwater: A Review of the
Issues.
To provide guidance on the issues associated
with the costs and benefits of remediating
contaminated groundwater.
Published in December 1999.
R&D Technical Report P278.
Some 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.
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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
Project completed (available shortly).
R&D Technical Report P238.
Guidance on the Assessment and Monitoring of
Natural Attenuation of Contaminants in
Groundwater
To provide guidance on the assessment and
monitoring of natural attenuation of contaminants
in groundwater.
Project completed (available shortly).
R&D Publication 95.
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.
Guidance on monitoring the Operational and
Post-Remediation Performance of Remedial
Treatments for Land Contamination
To provide guidance on the monitoring
requirements for land remediation
On-going project.
Verification of remedial treatments
To develop guidance for the verification of
different remedial techniques to enable
performance to be established during remediation
and after works have been completed
On-going project.
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.
On-going project.
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 2000/01.
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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.
New start in 2000/01.
Valuation of environmental benefits of
remediation techniques in relation to land
contamination
To evaluate the feasibility for semi-quantitative
assessment of the environmental benefit resulting
from the remediation of land contamination
(including different remedial techniques).
New start in 2000/01.
A study of the long term management practices
and perceptions of remediated contaminated sites
To study long-term management practices and
perceptions of remediated contaminated sites to
improve our understanding of current practice
and the effectiveness of current guidance.
New start in 2000/01.
SCOTLAND AND NORTHERN IRELAND FORUM FOR ENVIRONMENTAL RESEARCH
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.
CONSTRUCTION INDUSTRY RESEARCH AND INFORMATION ASSOCIATION
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.
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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 disseminate information on good practice
using biological treatments in the UK.
New start in 2000/2001.
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.
New start in 2000/2001.
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.
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
www.environment.detr.gov.uk/contaminated/land/index.htm.)
[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 executive
summary is available on the web at www.regeneration.detr.gov.uk/utf/renais/index.htm)
[3] Environment Agency (in preparation) Survey of Remedial Techniques for Land Contamination in
England and Wales.
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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 September 30, 1999, over
397,000 confirmed releases had been reported, over 346,000 cleanups initiated, and over 228,000
cleanups completed.
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.
Anticipated Policy Developments
As debate continues on legislative changes to Superfund, there have been efforts to streamline the RCRA
Corrective Action program. EPA issued regulations simplifying the permitting process and modifying
land disposal restrictions for cleanups. EPA has also launched an initiative to expedite actions through
new guidance, rulemaking and public outreach. The Corrective Action program has set goals for the 1700
high priority facilities. The goals include control of human exposure at 95 percent of sites and control of
ground-water migration at 70 percent of facilities by the year 2005.
There is widespread and growing interest in using risk assessment to determine cleanup priorities, as may
be done under the Risk Based Corrective Action initiative in the UST program. There is also increasing
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interest in the issue of bioavailability of contaminants as an alternative to chemical concentrations alone
to set cleanup standards. Much scientific work and consensus building has yet to be completed on this
issue.
"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 100,000 to 450,000
such sites in the United States. A growing realization of their great potential has heightened interest in
their cleanup and redevelopment. EPA has funded over 300 Brownfield Assessment Pilots and 16
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 98 Brownfields Cleanup Revolving Loan Fund grants for up to
$500,000. In addition, EPA has provided Brownfields job training and development grants to 37
communities to provide environmental training for residents near the sites. Also, a $1.5 billion
Brownfields tax incentive has been enacted to further encourage cleanup and redevelopment.
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
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. However, in 1993 the
percentage of sites selecting some treatment began to decrease. In 1996, the number of containment or
off-site disposal projects exceeded the number of source control treatment remedies chosen for the first
time since 1986. The selection of treatment has stabilized in the last two years.
When treatment is selected, there is a trend toward greater use of in situ processes, as shown in the figure.
In 1996, in situ technologies made up 66 percent of source control technologies 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, 89 percent of
remedies selected for controlling ground-water plumes rely on conventional pump-and-treat technologies,
6 percent use in situ treatment in addition to pump-and-treat, and 5 percent utilize in situ technologies
alone. The most frequently selected processes include air sparging, bioremediation, and dual-phase
extraction. Many of the treatment technologies have only recently been selected and much work is
underway to develop and test new processes. One recently developed process involves permeable reactive
barriers, which have been rapidly deployed at full-scale. Early applications involved zero-valent iron to
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treat chlorinated solvents. Research and demonstration is focusing on materials to treat other
contaminants such as chromium, polynuclear aromatic hydrocarbons (PAHs), and radionuclides. Natural
attenuation has been used extensively to address petroleum contamination from underground storage
tanks. This approach relies primarily on naturally occurring biodegradation of contaminants in the
subsurface. It is also being selected at hazardous waste sites, but primarily as a final polishing step as
opposed to a sole remedy for a site.
Control of ground water plumes alone cannot always meet desired cleanup goals because of the presence
of NAPLs (non-aqueous phase liquids). The three most prominent technologies for treating DNAPL
(dense non-aqueous phase liquid) include three in situ processes: oxidation, flushing and thermal
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 so present at many sites.
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 is probably the single most important factor affecting our ability to attain
cleanup levels in ground water. Despite relatively few projects employing DNAPL treatment
technologies, very important results were reported using steam extraction at a wood-treating site in
Visalia, California. Pumping and treating was removing about 10 pounds of creosote per week. Using in
situ steam enhanced thermal treatment, over one million pounds of DNAPL were recovered in the first
two years of operation. These results have generated optimism in terms of our ability to address prevalent
DNAPL problems and helped encourage an important demonstration project to concurrently evaluate
three in situ technologies. This project involves a TCE (trichloroethylene) DNAPL problem resulting
from a spill at an old launch pad at Cape Canaveral, Florida. The project, led by the National Aeronautics
and Space Administration with support from the Air Force, DOE and EPA, should provide comparative
data for three selected in situ processes: six-phase thermal heating, steam injection and oxidation. The six-
phase heating and oxidation fieldwork has been completed and the steam injection effort is scheduled to
begin soon. At another level, member agencies of the Federal Remediation Technologies Roundtable
have agreed to coordinate efforts to speed the maturation of DNAPL technologies. Work Groups are
being established to improve coordination on research and information sharing from demonstration and
full-scale applications.
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 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 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. 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
software is warranted. Federal agencies are developing programs to identify opportunities to realize cost
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savings while maintaining acceptable levels of risk. Optimization is capable of producing substantial
savings.
As an alternative to pump-and-treat systems, monitored natural attenuation is receiving a lot of attention.
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.
A significant new challenge is resulting from the recent emergence of MTBE (the gasoline additive
methyl tertiary butyl ether), which is a contaminant being found with alarming frequency in ground-water
supplies around the country. 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.
4. RESEARCH, DEVELOPMENT, AND DEMONSTRATION
Federal agencies currently are coordinating several technology development and commercialization
programs. DOE is spending $238 million in Fiscal Year 2000 to develop new environmental cleanup
technologies. A DOE report released this year describes 20 new technologies that may lead to cost
savings in cleaning up DOE sites. These technologies are specific examples of the types of technologies
that DOE expects to need in the near future, such as bioremediation, electrokinetics, and biosorption of
uranium.
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 $61.8 million per year, which devotes 31 percent of its resources to remediation and site
characterization technologies. DOD's high priority cleanup technology needs include: detection,
monitoring and modeling (primarily related to unexploded ordnance [UXO] and DNAPLS); treatment for
soil, sediment, and sludge (primarily related to UXO, white phosphorous contaminated sediments,
inorganics, explosives in soil, explosives/organic contaminants in sediments); groundwater treatment
(explosives, solvents, organics, alternatives to pump-and-treat, and DNAPLs); and removal of UXO on
land and under water.
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 potential users can assess applicability to a particular site. A similar program that
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.epa.gov/ORD/SITE and www.epa.gov/etv. 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
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for future application. Led by EPA, the Remediation Technologies Development Forum (RTDF) is a
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 seven action teams, which are co-chaired by a government and industry
representative. Information is available from the RTDF home page at
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 78 new studies of full-scale
remediation and demonstration projects. This added to 140 studies that were published previously. The
reports are 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.
5. CONCLUSIONS
Legislative, regulatory and programmatic changes may alter the nature and sequence of cleanup work
done 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. EPA will continue
implementing administrative reforms and refining or improving them where necessary. EPA does support
new provisions that would provide targeted Superfund liability relief to qualified parties such as
prospective purchasers, innocent landowners, contiguous property owners, and small municipal waste
generators and transporters.
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 aboveground 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.
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January 2001
COUNTRY REPRESENTATIVES
Directors
Stephen C. James (Co-Director)
National Risk Management Research Laboratory
U.S. Environmental Protection Agency
26 Martin Luther King Drive
Cincinnati, Ohio 45268
United States
tel: 513-569-7877
fax:513-569-7680
e-mail: iamgjij5tgyg@gpa.gov
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: kovaliclewalter@gpa.gov
Co-Pilot Directors
Volker Franzius
Umweltbundesamt
Bismarckplatz 1
D-14193 Berlin
Germany
tel: 49/30-8903-2496
fax: 49/30-8903-2285 or -2103
e-mail: volkgr.franzius@uba.dg
H. Johan van Veen
TNE/MEP
P.O. Box 342
7800 AN Apeldoorn
The Netherlands
tel: 31/555-493922
fax: 31/555-493921
e-mail: hj_.yj|nvegn@mgp.tn().n|
Country Representatives
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: gogaajjiiin^^
Nora Meixner
Federal Ministry of Environment, Youth and
Family Affairs
Dept. HI/3
Stubenbastei 5
A- 10 10 Vienna
Austria
tel: 43/1-5 15-22-3449
fax: 43/1-5 13-1679-1008
e-mail: Nora.Aueri@bmu.gv.at
Jacqueline Miller
Brussels University
Avenue Jeanne 44
1050 Brussels
Belgium
tel: 32/2-650-3183
fax: 32/2-650-3189
e-mail: jrriillerjSiulb_.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: lisa.keller@ec.gc.ca
235
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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 Dahlstrem
Danish Environmental Protection Agency
Strandgade 29
DK-1401 Copenhagen K
Denmark
tel: +45/3266-0388
fax: 45/3296-1656
e-mail: kda@mst.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: ajijicj3rjancji@jyyli.fi
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: bieber.andreas@bmu.de
Anthimos Xenidis
National Technical University Athens
52 Themidos Street
15124 Athens
Greece
tel: 30/1-772-2043
fax: 30/1-772-2168
Pal Varga
National Authority for the Environment
F6 u.44
H-1011 Budapest
Hungary
tel: 36/1-346-8310
fax: 36/1-315-0812
e-mail: vargap@mail5.ktm.hu
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: m.crowe@epa.ie
Francesca Quercia
ANPA - Agenzia Nazionale per la Protezione
dellAmbiente
ViaV. Brancati48
I-00144 Rome
Italy
tel. 39/6-5007-2510
fax 3 9/6-5 007-25 31
e-mail: qucrcia@anpa.it
Masaaki Hosomi
Tokyo University of Agriculture and
Technology
2-24-16 Nakamachi
Tokyo 184-8588
Japan
tel: +81-42-388-7070
fax:+81-42-381-4201
e-mail: hosomi@cc.tuat.ac jp
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: bjorn.bjornstad@sft.tclcmax.no
Marco Estrela
Institute de Soldadura e Qualidade
Centre de Tecnologias Ambientais
Tagus Park
EC Oeiras - 2781-951 Oeiras
Portugal
tel:+351/21-422 90 05
fax:+351/21-422 81 04
e-mail: maestrela@isq.pt
236
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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: ejjai5iniultinet.ro
Branko Druzina
Institute of Public Health
Trubarjeva 2-Post Box 260
6100 Ljubljana
Slovenia
tel: 386/61-313-276
fax: 386/61-323-955
e-mail: branko.dmzina@gov.si
Vitor A.P.M. dos Santos
Spanish National Research Council
Professor Aubareoal
18008 Granada
Spain
tel: 34/958-121-011
fax: 34/958-129-600
e-mail: vasantosfgleez.csis.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: inh'Slejiyiron.se
Bernard Hammer
BUWAL
3003 Bern
Switzerland
tel: 41/31-322-9307
fax: 41/31-382-1456
e-mail: bcmard.liammcr@buwal.admin.cli
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: kunlu@metu.edu.tr
Ian D. Martin
Environment Agency
Olton Court
10 Warwick Road
Olton, West Midlands
United Kingdom
tel: 44/121-711-2324
fax: 44/121-711-5830
e-mail:
237
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
ATTENDEES LIST
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^anmncacom
P.A. (Arne) Alphenaar
TAUW
P.O. Box 133
7400 AK Deventer
The Netherlands
tel: 31/570699911
fax: 31/570 699 666
e-mail: pah@tauw.nl
Paul Bardos
R? Environmental Technologies Ltd.
P.O. Box 58
Ware-Hertfordshire SG12 9UJ
United Kingdom
tel: 44/1920-484-571
fax: 44/1920-485-607
e-mail: p-bardos@r3-bardos.dcmon.co.uk
Paul M. Beam (c.r.)
U.S. Department of Energy
19901 Germantown Rd.
Germantown, MD 20874-1290
United States
tel: 301-903-8133
fax: 301-903-3877
e-mail: paul.bcaiii@cm.doc.gov
Jorg Becht
Hessisches Ministerium fur Umwelt,
Landwirtschaft und Forsten
Mainzer Str. 98-102
65189 Wiesbaden
Germany
tel: 49/611-815-1380
fax: 48/611-815-1947
e-mail: abteilung.3@mue.hessen.de
Eberhard Bellinger
WCI Umwelttechnik GmbH
Heinrich-Hertz-StraBe 3
63303 Dreieich
Germany
tel: 49-61 03-9 38 90
fax:49-6103-938999
e-mail:
Andreas Bieber (c.r.)
Federal Ministry for the Environment
Ahrstrasse 20
53 175 Bonn
Germany
tel: 49/228-305-305-3431
fax: 49/228-305-305-2396
e-mail: bieber.andreas@bmu.de
Bj0rn Bj0rnstad (c.r.)
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.bjornstad@telemax.no
Volker Bohmer
Hessische Industriemull GmbH
Bereich Altlastensanierung
Kreuzberger Ring 58
65205 Wiesbaden
Germany
tel: 49/61 1-7149-700
fax: 49/61 1-7149-322
e-mail: volkcr@bochmcr@him.dc
Michael Bosley
International Engineering Center
US Army Corps of Engineers-Europe
Konrad Adennauar Ring 39 Box 20
65 187 Wiesbaden
Germany
tel: 49-61 1-816-2692
e-mail:
MICHAEL.J.BOSLEY@nau02.usace.armv.mil
238
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
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.burmeierfi2lt-oiiline.de
Erol Er^ag
Istanbul University
Dept. of Chemistry
Avcilar Campus, Avcilar 34850
Istanbul
Turkey
tel: 90/212-5911-998
fax: 90/212-5911-997
e-mail: ismailbfiadstanbul.cdu.tr
Laurence Davidson
c/o EarthFx Inc.
2635 Ulster Crescent
K1V 8J5 Ottawa, Ontario
Canada
tel: 613.260.2020
fax: 613.260.252
e-mail: |d@cartlj.fx._com
Branko Druzina (c.r.)
Institute of Public Health
Trubarjeva 2-Post Box 260
6100 Ljubljana
Slovenia
tel: 386/1-313-276
fax: 386/1-323-955
e-mail: br_aiikgAuzina@jvzrrsji
Vitor A.P.M. Dos Santos (c.r.)
Spanish National Research Council
Professor Aubareoal
18008 Granada
Spain
tel: 34/958-121-011
fax: 34/958-129-600
David Edwards
Leader ExSite
VHE Holdings pic.
CEO's Office
Shafton, Barnsley, S72 8SP
United Kingdom
tel: 44/1977-683300
fax: 44/870-1314537
e-mail: exSite@ibtinternet.com
James Finnamore
WSP Environmental
Buchanan House
24-30 Holborn
London EC IN 2HS
United Kingdom
tel: 44/20-73 14-5 000
fax: 44/20-73 14-5 005
e-mail: jim.finnamore@wspgroup.com
Volker Franzius
Umweltbundesamt
Bismarckplatz 1
D- 14 193 Berlin
Germany
tel: 49/30-8903-2496
fax: 49/30-8903-2285 or -2103
e-mail: volker.franzius@uba.de
loan Gherhes (c.r.)
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: IGherf|ej3(iMa^
Detlef Grimski
Umweltbundesamt
Bismarckplatz 1
14 193 Berlin
Germany
tel: 49/30-8903-2266
fax: 49/30-8903-2103
e-mail: dctlcf.grimski(a;uba.dc
239
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Karl Grundler
Hessisches Ministerium fur Umwelt,
Landwirtschaft und Forsten
Mainzer Str. 98-102
65189 Wiesbaden
Germany
tel: 49/611-815-1373
fax: 49/611-81-1947
e-mail: abtrilung.3@muc.hcsscn.dc
Bernhard Hammer (c.r.)
Federal Office of the Environment,
Forests & Landscape (BUWAL)
Federal Department of the Interior
Buwal Laupenstrausse 20
3003 Bern
Switzerland
tel:+41/31-322-6961
fax:+41/31-382-1546
e-mail: BenihardJHanimerjSibjiwaLadjnilLch
Gregory Harvey
Aeronautical Systems Center
Environmental Safety and Health Division
1801 10th St.
Bldg. 8, Suite 200 - Area B
WPAFB, OH 45433
United States
tel: 937-255-7716 (ext. 302)
fax: 937-255-4155
e-mail: gregory.harvey@wpafb.af.mil
R.A.A. (Rolf) Hetterschijt
P.O. Box 6012
2600 JA Delft
The Netherlands
tel:+31 152696257
fax:+31 152564800
e-mail rjietterechjjt^riitgjnajil
Howard Hornfeld
Programme Coordinator for the Chemical
Industry
United Nations Economic Commission for
Europe
Palais des Nations 429-3
CH-1211 Geneva 10
Switzerland
tel.: 41 22 917 3254
fax.: 41 22 917 0178
e-mail: chem@un.ece.org
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: jamgs._stcvg@c|)a..gov
Harald Kasamas
EU Concerted Action CLARINET
Breitenfurterstr. 97
A- 11 20 Vienna
Austria
tel: 43/1-804 93 192
fax: 43/1-804 93 194
e-mail:
Lisa Keller
Environmental Technology Advancement
Directorate
Environment Canada - EPS
12th floor, Place Vincent Massey
Hull, Quebec K1A OH3
Canada
tel: 819-953-9370
fax: 819-953-0509
e-mail: Lisa.Kcllcr@cc.gc.ca
Peter Kontny
Probiotec GmbH
SchillingstraBe 33
52355 Duren-Giirzenich
Germany
tel: 49/2421-6909-65
fax: 49/2421-6909-61
e-mail: info@probiotgc_.acj^urcgia,dc
240
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Hans-Peter Koschitzky
Technical director, VEGAS, Research Facility
Chair for Hydraulics and Groundwater
University of Stuttgart
Pfaffenwaldring 61
D - 70550 Stuttgart
Germany
tel: 49/711-686-4717
fax: 49/711-685-7020
Kazuhide Kuzawa
Japan Environment Agency
1-2-2 Kasumigaseki
100-8975 Chiyoda-ku, Tokyo
Japan
tel: 81/3-5521-8322
fax: 81/3-3593-1438
e-mail: KAZUHIDE_KUZAWA@canct.go,ip
Walter W. Kovalick, Jr. (Co-Director)
Technology Innovation Office
U.S. Environmental Protection Agency
1200 Pennsylvania Ave. (5102G)
Washington, DC 20460
United States
tel: 703-603-9910
fax: 703-603-9135
e-mail: kovalick.walter@epa.gov
Hana Kroova (c.r.)
Czech Ministry of the Environment
Vrsovicka 65
100 10 Prague 10
Czech Republic
tel: 420/2-6712-1111
fax: 420/2-6731-0305
Andrea Lodolo
ICS-UNIDO
Pure and Applied Chemistry
Area Science Park Building L2
Padriciano, 99
34012 Trieste
Italy
tel.: 39-040-9228114
fax:39-040-9228115
e-mail: cmanucla.corazzi(rt}ics.tricstc.it
Ian D. Martin (c.r.)
The Environment Agency
Olton Court, 10 Warwick Road
Olton, West Midlands
United Kingdom
tel: 44/121-711-2324
fax: 44/121-711-5830
e-mail: ia|y]iartin^envHpmnent^geiicy_.gOT.uk
Nora Meixner (c.r.)
Federal Ministry of Environment, Youth and
Family Affairs
Dept. HI/3
Stubenbastei 5
A-1010 Vienna
Austria
tel: 43/1-515-22-3449
fax: 43/1-513-1679-1008
e-mail: Nora.Meixner@bmii.gv.at
Jochen Michels
DECHEMA
Theodor-Heuss-Allee 25
60486 Frankfurt am Main
Germany
tel: 49-69-75 64-2 35
fax: 49-69-75 64-2 35
e-mail: michels@dechema.de
Jacqueline Miller (c.r.)
Brussels University
Avenue Jeanne 44
1050 Brussels
Belgium
tel: 32/2-650-3183
fax: 32/2-650-3189
e-mail: jtriillerjSiulb_.ac.be
Walter Mondt
Ecorem n.v.
Zwartzustersvest 22
B-2800 Mechelen
Belgium
tel: 32/15-21 17 35
fax: 32/15-21 65 98
e-mail: ccorcm@glo.bc
241
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Christoph Munz
Env. Eng., Dept. Head Chemical Risk
Assessment
BMG Engineering AG
Ifangstrasse 11
CH-8952 Zurich
Switzerland
tel. 41/1-732-92 77
fax. 41/1-732-9221
e-mail: christoph.miinz^bmgcng.ch
Joop Okx
Tauw Milieu bv
PO Box 133
7400 AC Deventer
The Netherlands
tel: 3 1570 699911
fax: 3 1570 699666
e-mail: jpo@tauw.nl
Johannes Pastor
Bundesministerium fur Umwelt
Naturschutz und Reaktorsicherheit
Postfach 12 06 29
53048 Bonn
Germany
tel: 49-2 28-3 05-34-30
fax: 49-2 28-3 05-23 96
Simon Pollard
The Environment Agency
Steel House
1 1 Tothill Street
London SW1H 9NF
United Kingdom
tel: 44 20 7664 6832
fax: 44 20 7664 6836
e-mail: simon.pollardfficnvironmcnt-
Francesca Quercia (c.r.)
ANPA - Agenzia Nazionale per la Protezione
dellAmbiente
ViaV. Brancati48
I -00 144 Rome
Italy
tel. 39/6-5007-2510
fax 3 9/6-5 007-25 31
e-mail
Charles Reeter
Naval Facilities Engineering Service Center
U.S. Navy
1 100 23rd Avenue, Code 411
Port Hueneme, CA 93043
United States
tel: 805-982-4991
e-mail: reetoiciiSnfo
Mathias Schluep
BMG Engineering AG
Ifangstrasse 11
8952 Schlieren
Switzerland
tel: 41/1-730-6622
fax: 41/1-730-6622
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: An_.Sej3pangn@vyh_.fi
Rainer Siebert
Bundesministerium fur Umwelt,
Naturschutz und Reaktorsicherheit
Postfach 12 06 29
53048 Bonn
Germany
tel: 49-228-305-3434
fax: 49-228-305-2396
e-mail: sicbcrt.raincr@bnm.dc
Roberrt Siegrist
Colorado School of Mines
Environ. Science and Eng. Division
1500 Illinois Ave.
Golden, CO 80401-1887
United States
tel: 303-273-3490
fax: 303-273-3413
e-mail: rsiegris@mines.edu
242
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Sjef Staps
TNO Institute of Environment, Energy, and
Process Innovation
Department of Environmental Biotechnology
P.O. Box 342
7300AHApeldoorn
The Netherlands
tel: 31555493351
fax: 31 555493523
e-mail: sjjte^)s@mcj3jncyil
Kai Steffens
PROBIOTEC GmbH
Schillingsstra e 333
D 52355 Duren-Giirzenich
Germany
tel: 49/2421-69090
fax: 49/2421-690961
e-mail: steffens@probiotec.de
Rita Hermanns Stengele
Professor for Environmental Geotechnics
Institute of Geotechnical Engineering
ETH Honggerberg/HIL
CH-8093 Zurich
Switzerland
tel. 41/1-633-2524 or 633-2525 (secreatriat)
fax. 41/1-633-109
e-mail: hcrmanns@igt.baum.cthz.ch
Robert Stewart
University of Tennessee
1060 Commerce Park
Oak Ridge, TN 37830
United States
tel: 865-241-5741
fax: 865-574-0004
e-mail: u47@onil.gov
Terry Sullivan
Environmental Sciences Department
34 North Railroad Street, Building 830
Upton, NY 11973-5000
United States
tel: 631-344-3840
fax:631-344-4486
e-mail: tsul|ivan@bnl.goy
Jan Svoma
Aquatest a.s.
Geologicka 4
152 00 Prague 5
Czech Republic
tel: 420/2-581-83-80
fax: 420/2-5 8 1-77-5 8
e-mail:
Bert-Axel Szelinski
Bundesministerium fur Umwelt
Naturschutz und Reaktorsicherheit
Alexanderplatz 6
11 05 5 Berlin
Germany
tel: 49-30-2 85 50-42 70
fax: 49-30-2 85 50-43 75
e-mail: szgjinsM_.axgl@bmu_._dc
Safieh Taghavi
Vlaamse Instelling voor Technologisch
Onderzoek (Vito)
Environmental Technology Expertise Center
Boeretang 200
B.2400 Mol
Belgium
tel: 32/14-335162
fax: 32/14-580523
e-mail: safiyh .taghavi@vito . be
Georg Teutsch
University of Tubingen
Sigwartstrasse 10
72076 Tubingen
Germany
tel: 49/707-1297-6468
fax: 49/707-150-59
e-mail: gcorg.toutscli@uiii-tucbingcn.dc
Steven Thornton
University of Sheffield
Mappin Street
Sheffield
United Kingdom
tel: 44/1 14-222-5 700
fax: 44/1 14-222-5 700
e-mail: S.F.Thoniton@shcfficld.ac.uk
243
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III)
January 2001
Kahraman Unlii (c.r.)
Depratment of Environmental Engineering
Middle East Technical University
Inonii Bulvari
06531 Ankara
Turkey
tel: 90/312-210-1000
fax: 90/3 12-2 10- 1260
e-mail: kunlu@mctu.cdu .tr
H. Johan van Veen (c.r.)
TNO/MEP
P.O. Box 342
7800 AN Apeldoorn
The Netherlands
tel: 31/555-493922
fax: 3 1/555-493921
e-mail: HJ.yjmVcgii@mg|)_.tng.nl
Joop Vegter
The Technical Committee on Soil Protection
(TCB)
Postbus 30947
2500 GX The Hague
The Netherlands
tel: 31/70-339-30-34
fax 3 1/70-339-13-42
e-mail: tcb@euronet.nl
John Vijgen
Consultant
Elmevej 14
DK-2840 Holte
Denmark
tel: 45/45 41 03 21
+fax:45/45410904
e-mail:
^^
Stephan Volkwein
C.A.U.
DaimlerstraBe 23
63303 Dreieich
Germany
tel: 49-61 03-9 83-25
fax: 49-61 03-9 83-10
e-mail: c .a.u . (ait-online .dc
Christian Weingran
Hessische Industriemull GmbH
Mullerwegstannen 46
35260 Stadtallendorf
Germany
tel: 49/6428-9235-11
fax: 49/6428-9235-35
e-mail: as
Holger Weiss
UFZ-Umweltforschungszentrum
Leipzig-Halle GmbH
Postfach 2
Germany
tel: 49-3 41-2 35-20 58
fax:49-341-235-2126
e-mail: weiss@pro.ufz.de
Paul Wersin
Geochemist/Project Manager Safety Analysis
NAGRA (National Cooperative for the Disposal
of Radioactive Waste)
Hardstrasse 73
CH-5430 Wettingen
Switzerland
tel. 41/56-437-12 80
fax. 41/56-437-1317
e-mail: .we rsi n @nagra. ch
Dieter Weth
Mull & Partner Ingenieurgesellschaft
Osterlede 5
30827 Garbsen
Germany
tel: 49-5 13-1 46 94-0
fax:49-513-14694-90
e-mail: wethiSniullund^
Uwe Wittmann
Umweltbundesamt
SeecktstraBe 8-10
13581 Berlin
Germany
tel: 49-30-89 03-
fax: 49-30-89 03-38 33
e-mail: uwc .wittmaiin@uba.dc
244
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) January 2001
Anthimos Xenidis Mehmet AH Yukselen
National Technical University Athens Marmara University
52 Themidos Street Environmental Engineering Department
15124 Athens Goztepe 81040 Istanbul
Greece Turkey
tel: 30/1-772-2043 tel: 90/216-348-1369
fax: 30/1-772-2168 fax: 90/216-348 -0293
245
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NATO/CCMS Pilot Project on Contaminated Land and Groundwater (Phase III) Date 2000
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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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 a 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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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: United States of America
Lead Organization: U.S. Environmental Protection Agency
U.S. Directors:
Stephen C. James Walter W. Kovalick, Jr., Ph.D.
U.S. Environmental Protection Agency U.S. Environmental Protection Agency
Office of Research and Development Technology Innovation Office (5102G)
26 W. M.L. King Drive 1200 Pennsylvania Ave, NW
Cincinnati, Ohio 45268 Washington, DC 20460
tel: 513-569-7877 tel: 703-603-9910
fax: 513-569-7680 fax: 703-603-9135
E-mail: james.steve@epa.gov E-mail: kovalick.walter@epa.gov
Co-Partner Countries: 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
Scheduled Meetings: February 23-27, 1998, in Vienna, Austria
May 9-14, 1999, in Angers, France
June 26-30, 2000, in Wiesbaden, Germany
2001 in Canada or the United States
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