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Decontamination of Hydrocarbon Polluted Military Sites
to Decrease Environmental Risks Low - Cost Cyclodextrin Technology (SfP-973720) SUMMARY REPORTS |
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SfP - BIOREMEDIATION
SfP – 973720
Title: A
new Bioremediation Technology for Contaminated Sites: Pilot and Field
Application
Project Co-Directors:
Prof. Dr. Fabio Fava, University of Bologna, Bologna,
Italy (NPD)
Prof. Dr. József Szejtli, Cyclolab, Ltd., Budapest,
Hungary(PPD)
Dr. Katalin Gruiz, Technical University of Budapest,
Budapest, Hungary
Dr. Attila Murányi, Hungarian Academy of Science,
Budapest, Hungary
Edward G. Soméus, Thermal Desorption Technology (TDT-3R),
Budapest, Hungary
Approval Date: 30 November, 1999 Effective starting
date: 1 January, 2000
Duration: 3 years; expected
completion by 31 December, 2002
NATO Budget: 7,300,000 BEF
Information about the SfP
Project through Internet: Not available yet
Major Objectives
·
·
to establish a solid
scientific background for the cyclodextrin technology (CDT) which is a new
bioremediation technology particularly indicated for soils chronically
contaminated by hydrophobic pollutants, such as aliphatic and aromatic
hydrocarbons and polychlorinated biphenyls, based on the soil supplementation
with low-cost cyclodextrin as an agent non-toxic, biodegradable and capable of
improving the bioavailability (and therefore the biodegradability) of such
organic pollutants in the soil matrix;
Overview of
Achievements since the Start of the Project until 31 October 2000
·
·
The effects of a
low-cost randomly methylated b-cyclodextrin (RAMEB) (assayed at 4 initial
concentrations) on the pollutant mobilisation and biodegradation in soils were
studied by treating 3 different soils (a loamy, a humic and a sandy-soil)
supplemented singly with 3 types of pollutant mixes (a Diesel oil, a
transformer oil and a transformer oil with PCBs) at 2 or 3 initial
concentrations both in slurry- and solid-phase aerobic 50-250 g soil
microcosms.
·
·
An integrated
analytical methodology, consisting in 1) the qualitative and quantitative
analysis of the pollutants and of the pollutant break-down intermediates and
final products, 2) the quantitative analysis of the heterotrophic and
pollutant-degrading soil aerobic cultivable bacterial biomass, and 3) the
analysis of the soil ecotoxicity (by using both prokaryotic and eukaryotic
biomarkers), was developed.
·
·
The addition of RAMEB
resulted in an improved microbial growth and/or survival in all spiked soils,
thus indicating that RAMEB was 1) metabolised and used as an exogenous carbon source,
and 2) capable of improving the nutrient bioavailability in the soils. 3) RAMEB
was also found to significantly increase the bioavailability and the
biodegradation rates and extents of the pollutant mixes added to the soils.
·
·
A remarkable decrease
of Diesel oil content (60-70%) was observed in soils spiked with 50000 ppm
oil in slurry phase at 0.5 % RAMEB concentration. Especially
good results were obtained in case of soils spiked with transformer oil, which
was degraded to about 10 % of the initial within 3 weeks on the effect of as
low as 0.1 % RAMEB. This oil concentration is about ¼ of that achieved
without RAMEB.
·
·
Summarising the data
collected in this reported period, the highest biological decontamination
yields were observed by applying RAMEB in the following experimental
conditions: 1) at 0.1-0.5 % (w/w) and through a repeated supplementation, in
case of the soils spiked with Diesel oil or transformer oil, 2) at 3% (w/w) in
soils spiked with PCBs, 3) in solid-phase, for the Diesel- or transformer
oil-spiked soils, and in slurry-phase, for the same soils contaminated with
PCBs, and 4) in the presence of exogenous specialised bacteria, in case of
soils with Diesel and transformer oil, and without inoculation in case of
PCB-contaminated soils.
·
·
Relevant soil
ecotoxicity decrements, detected by using Photobacterium phosphoreum
bioluminescence inhibition test, Sinapis alba germination test and
Collembola (Folsomia candida) mortality test, were generally found to be
associated to significant pollutant concentration depletions in the soils. On
the contrary, a poor correlation between pollutant concentration and soil
ecotoxicity was generally observed using the Lepidium sativum and the Sinapis
alba root and shoot elongation test.
·
·
The new analytical
approach (application of integrated - chemical, physico-chemical, biological
and ecotoxicological - methods) proved to be efficient by producing a large
amount of data which help to get a better inside view into the black box of the
microcosm experiments. Physico-chemical analysis shows the amount of the
extractable contaminant. This amount is always the resultant of the occurring
biodegradation (decreasing process) and the increasing availability (contrary
process) caused by the increased biological activity of the soil and the
addition of CD. Concentration of heterotrophic cells shows the general
microbiological state of the treated soil, while concentration of the oil
degrading cells is selectively associated with the activity of the hydrocarbon
biodegradation. Results of toxicity testing characterise the environmental and
human health risks during remediation and the final soil quality
·
·
RAMEB additions were
found to remarkably modify the surface and pore properties (surface area,
general pattern of the adsorption energy, the micropore and mesopore volume and
radius) of clay minerals; the results of this study strongly suggest that RAMEB
enhances the bioavailability of the soil-adsorbed hydrophobic pollutants by
increasing the water permeability of the soil aggregates.
·
·
The first assessment
of the model territory (former soviet military base) has been performed, and
the area for the further, more detailed assessment have been selected.
Payments through NATO Project Funds: 2,588,899 BEF
Milestones for the
Next Six Months
·
·
Completion of
preliminary screening on spiked soils and of the laboratory experiments and
inter - unit joint evaluation of the results
·
·
Completion of the
laboratory scale technological experiments: determination of the RAMEB effects
on the bioremediation of chronically contaminated soils of the actual site both
in slurry- and solid-phase lab-scale conditions, optimisation of the use of
RAMEB on the bioremediation of these soils
·
·
Selection of the
technological parameters for the pilot scale experiments
·
·
Planning and starting
the pilot scale experiments
·
·
Perfection of the
assessment of the contaminated site
Implementation of
Results
Not started as yet
NATO Consultant
Dr. Bjørn Arne
Johnsen
Division for
Protection and Material, Norwegian Defence Research Establishment
Collaborating
Institutions
·
·
Cyclolab Cyclodextrin
Research and Development Laboratory, Ltd., Budapest, Hungary
·
·
Department of
Agricultural Chemistry, Budapest University of Technology and Economics,
Budapest, Hungary
·
·
Research Institute
for Soil Science and Agricultural Chemistry of Hungarian Academy of Sciences,
Budapest, Hungary
·
·
Thermal Desorption
Technology, Group LCC., TDT-3R, Budapest, Hungary
Abbreviations:
CDT- Cyclodextrin
Technology (the bioremediation technology using cyclodextrin as an additive to improve
the desorption and bioavailability of the contaminants adsorbed to the soil
particles)
RAMEB - randomly
methylated b-cyclodextrin
SfP – BIOREMEDIATION
SfP –973720
Decontamination of Hydrocarbon
Polluted Military Sites to Decrease Environmental Risks - Low-Cost Cyclodextrin
Technology
Project Co-Directors:
Prof. Dr. Fabio Fava, Department of Applied Chemistry and
Material Science, Engineering Faculty, University of Bologna, Bologna, Italy
(NPD)
Prof. Dr. József Szejtli, Cyclolab Cyclodextrin R&D
laboratory, Ltd., Budapest, Hungary (PPD)
Dr. Katalin Gruiz, Department of Agricultural Chemistry,
Budapest University of Technology and Economics, Budapest, Hungary
Dr. Attila Murányi, Research Institute for Soil Science and
Agricultural Chemistry of Hungarian Academy of Science, Budapest, Hungary
Edward G. Soméus, Thermal Desorption Technology, Group LCC.,
(TDT-3R), Budapest, Hungary
Approval Date: 30 November, 1999 Effective Date: 1 January, 2000
Duration: 3 years; expected
completion by December, 2002
NATO Budget: 7,300,000 BEF
Major Objectives
·
·
to establish a
solid scientific background for the cyclodextrin technology (CDT) which is a
new bioremediation technology particularly indicated for soils chronically
contaminated by hydrophobic pollutants, such as aliphatic and aromatic
hydrocarbons and polychlorinated biphenyls, based on the soil supplementation
with low-cost cyclodextrin as an agent non-toxic, biodegradable and capable of
improving the bioavailability (and therefore the biodegradability) of such
organic pollutants in the soil matrix;
·
·
to develop and
optimise a dedicated pilot plant for implementing the CDT;
·
·
to perform a field
experiment
·
·
to develop the
know-how of the new CDT
·
·
to run SWOT
analysis (Strengths, Weakness, Opportunities, Threats) of the CDT
·
·
to demonstrate the
technical efficiency and cost-effectiveness of the CDT
·
·
to run a
comparative evaluation of the CDT (e.g. cost, risk assessment on human health
& economy)
·
·
to use the field
site for demonstration to disseminate the results at the university &
industrial level
·
·
to compile the
criteria of utilisation of the CDT & selection of the potential end-users
Overview of
Achievements since the Start of the Project until 30 April 2001
·
·
The effects of a
low-cost randomly methylated b-cyclodextrin (RAMEB) (assayed at 4 initial
concentrations) on the pollutant solubilisation and biodegradation in soils
were studied by treating 3 different soils (a loamy, a humic and a sandy-soil)
supplemented singly with 4 types of pollutant mixes (a Diesel oil, a mineral
oil, a transformer oil and a transformer oil with PCBs) at 2 or 3 initial
concentrations both in slurry- and solid-phase aerobic 50-250 g soil microcosms
under various environmental conditions.
·
·
An integrated
analytical methodology, consisting in 1) the qualitative and quantitative
analysis of the pollutants and of the pollutant break-down intermediates and
final products, 2) the quantitative analysis of the heterotrophic and
pollutant-degrading soil aerobic cultivable bacterial biomass, 3)
characterisation of the soil bioactivity through respirometric measurement of
the CO2 production and 4) the analysis of the soil ecotoxicity (by using both
prokaryotic and eukaryotic biomarkers), was developed.
·
·
The scale up of
the technology has been started: experiments in 40 kg soil have been carried
out for 10 months using soil spiked with transformer oil. The highest
bioactivity and biodegradation rates were observed in the presence of 1 % (w/w)
RAMEB in solid phase pilot-scale reactors.
·
·
The effects of
aeration, nutrient availability, inoculation with specialised bacteria and other
environmental factors have also been studied.
·
·
The addition of
RAMEB resulted in an improved microbial growth and/or survival in all spiked
soils, thus indicating that RAMEB was 1) metabolised and used as an exogenous
carbon source, and 2) capable of improving the nutrient bioavailability in the
soils. RAMEB was also found to significantly enhance the biodegradation rate
and extents of the soil pollutants by 3) enhancing the growth and the
persistence of the pollutant-metabolising biomass 4) and increasing the
bioavailability of the pollutant mixes added to the soils.
·
·
Laboratory studies
have shown that the naturally occurring adapted soil microorganisms are capable
of removing the organic pollutants from the soil. Application of various
commercial inocula (the lab coculture ECO3 for PCBs and H10CS of BIO-REM, Inc.
for Diesel and transformer oil) has not accelerated the biodegradation of the
studied hydrophobic pollutants and had not influenced the efficacy of RAMEB.
·
·
RAMEB was proved
to be able to intensify the aerobic bioremediation of actual site soils aged
contaminated with PAHs and PCBs as well. The effect of RAMEB was found to often
depend on the type and level of contamination, on its concentration. In case of
actual site PAH-contaminated soil RAMEB has accelerated the biodegradation of
PAHs in small-scale microcosms at as low as 0.1 % (w/w) concentration. In case
of aged contaminated soils containing from 850 to 8,500 mg/kg Arochlor 1260,
RAMEB enhanced markedly (more than 50 %) the PCB bioavailability at
concentrations equal or higher than 1 % (w/w), the aerobic bioremediation of
such soils was, however, often only slightly enhanced by RAMEB. This may be
ascribed to the fact that the occurrence of toxic organic and inorganic
co-pollutants in the soils affected their biological treatability.
·
·
RAMEB additions
were found to remarkably modify the surface and pore properties (surface area,
general pattern of the adsorption energy, the micropore and mesopore volume and
radius) of clay minerals; the results of this study strongly suggest that RAMEB
enhances the bioavailability of the soil-adsorbed hydrophobic pollutants by
increasing the water permeability of the soil aggregates.
·
·
Having assessed
the previously selected model territory (former soviet military base) the
pollution was found to be under the limit. So the soil of this area can not be
used to demonstrate the efficacy of the new technology. The ex situ experiments
are planned to be carried out on this site using the soil of a nearby
industrial area. The site for the in situ experiments is still searched.
Payments through NATO
Funds: 3,290,539 BEF
Milestones for the
Next Six Months
·
·
Completion of the laboratory
experiments to understand the effect of aeration and soil characteristics on
the efficacy of RAMEB in bioremediation of soils contaminated with hydrocarbons
and inter - unit joint evaluation of the results;
·
·
Completion of the
laboratory scale technological experiments: determination of the RAMEB effects
on the bioremediation of chronically hydrocarbon- or PCB-contaminated soils of
actual site both in solid-phase and fixed-phase aerobic bioreactors with well
defined configurations, further optimisation of the use of RAMEB on the
bioremediation of these soils;
·
·
Starting the ex
situ field scale experiments;
·
·
Assessment of a
new contaminated site to select an area for the in situ field
experiment.
Implementation of
Results
The end-users have
received the progress reports and have been invited to the annual meetings to
be up-to-date in the project.
The new results have
been incorporated into the relevant seminars of Bologna University and Budapest
University of Technology and Economics.
NATO Consultant
Dr. Bjørn Arne
Johnsen
Division for Protection and Material, Norwegian Defence Research Establishment,
Oslo, Norway
Collaborating
Institutions
·
·
No collaborating institutions
which are not listed under Project Co-Directors have participated in the
project’s realisation
Abbreviations:
CDT-
Cyclodextrin Technology (the bioremediation technology using cyclodextrin as an
additive to improve the desorption and bioavailability of the contaminants
adsorbed to the soil particles)
RAMEB -
randomly methylated b-cyclodextrin
SfP - BIOREMEDIATION
SfP 973720
Title: Decontamination of Hydrocarbon Polluted Military Sites
to Decrease Environmental Risks - Low-Cost Cyclodextrin Technology
Project Co-Directors:
Prof. Dr. Fabio Fava, Department of
Applied Chemistry and Material Science, Engineering Faculty, University of
Bologna, Bologna, Italy (NPD)
Prof. Dr. József Szejtli, Cyclolab Cyclodextrin R&D laboratory,
Ltd., Budapest, Hungary (PPD)
Dr. Katalin Gruiz, Department of Agricultural Chemistry, Budapest
University of Technology and Economics, Budapest, Hungary
Dr.
Attila Murányi, Research Institute for Soil Science and Agricultural Chemistry
of Hungarian Academy of Science, Budapest, Hungary
Edward
G. Soméus, Thermal Desorption Technology, Group LCC., (TDT-3R), Budapest,
Hungary
Approval Date: 30 November, 1999 Effective Starting
date: 1 January, 2000
Duration: 3 years; expected
completion by December 2002
NATO Budget: 7,300,000
BEF
Information about the SfP Project through Internet: The web page is
under preparation
Ø
To establish a solid scientific background
for the CycloDextrin Technology (CDT) which is a new bioremediation technology
particularly indicated for soils chronically contaminated by hydrophobic
pollutants, such as aliphatic and aromatic hydrocarbons and polychlorinated
biphenyls, based on the soil supplementation with low-cost cyclodextrin as a
non-toxic, biodegradable and capable agent for
improving the bioavailability (and therefore the biodegradability) of
such organic pollutants in the soil matrix;
Ø
to develop and optimise a dedicated pilot
plant for implementing the CDT;
Ø
to perform a field experiment by the
application of a complex and integrated technology monitoring
Ø
to develop the know-how of the new CDT
Ø
to run SWOT analysis (Strengths, Weakness,
Opportunities, Threats) of the CDT
Ø
to demonstrate the technical efficiency and
cost-effectiveness of the CDT
Ø
to run a comparative risk based
cost-benefit evaluation of the CDT
Ø
to use the field site for demonstration and
disseminate the results at university & industrial level
Ø
to compile the criteria of utilisation of
the CDT & defining of the potential end-users.
Ø
The effects of a low-cost randomly
methylated b-cyclodextrin (RAMEB) (examined at 4 initial concentrations) on the
pollutant solubilisation and biodegradation in soils were studied by treating 3
different soil-types (loamy, humic and sandy-soil) supplemented singly with 4
types of pollutant mixes (Diesel oil, mineral oil, transformer oil and
transformer oil with PCBs) at 2 or 3 initial concentrations both in slurry- and
solid-phase aerobic 50-250 g soil microcosms under various environmental
conditions.
Ø
An integrated analytical methodology,
consisting of 1) the analysis of the pollutants and of the pollutant break-down
intermediates and final products, 2) the analysis of the heterotrophic and
pollutant-degrading bacterial biomass, 3) characterisation of the soil
bioactivity through respirometric measurements of the CO2 production
and 4) the analysis of the soil ecotoxicity (using both prokaryotic and
eukaryotic testorganisms), was developed.
Ø
In pilot-scale experiments 40 kg soil
spiked with transformer oil have been treated for 10 months. The highest
bioactivity and biodegradation rates were observed in the presence of 1 % (w/w)
RAMEB in solid phase reactors.
Ø
The efficacy of RAMEB has been also proved
with actual site soils contaminated with PAH, mazout and PCB, respectively. The
optimal RAMEB concentration increases with the concentration of the pollutant
and the absorptive capacity of the soil.
Ø
The effects of aeration, nutrient supply
and availability, inoculation with specialised bacteria and other environmental
factors have also been studied and the optimal conditions found.
Ø
In general, both on spiked and on actual
site contaminated soils the addition of RAMEB resulted in an improved microbial
growth and/or survival, thus indicating that RAMEB was 1) capable of improving
the nutrient bioavailability in the soils. RAMEB was also found to
significantly enhance the biodegradation rate of the soil pollutants studied by
2) probably enhancing the growth and the persistence of the
pollutant-metabolising microbial consortia 3) and the bioavailability of the
pollutants added to the soils.
Ø
Laboratory studies have shown that the
naturally occurring adapted soil microflora is capable of enhancing the removal
the organic contaminants from the soil. Application of various commercial
inocula has not accelerated the biodegradation of the studied hydrophobic
pollutants and had not influenced the efficacy of RAMEB.
Ø
RAMEB additions were found to remarkably
modify the surface and pore properties (surface area, general pattern of the
adsorption energy, the micropore and mesopore volume and radius) of clay
minerals and soils; the capillary water-rise and the hydraulic conductivity was
also found to be influenced.
Ø
Two pilot-scale ex situ experiments have been started with a heavy oil-contaminated
actual site soil and with a soil artificially polluted with used transformer
oil. The results of the 13 week-treatment period showed the benefit of RAMEB
application (enhanced biodegradation, improved microbial life). The experiments
called our note on the importance on the mode of application of RAMEB on soil:
form of CD, solution, dilution, mixing, rheological properties of the CD
treated soil, etc. The surprising physical effects of RAMEB observed on the
surface of the soil (a gradual increase in oil and cell concentration) will be
further studied.
Payments
through NATO Project Funds : … 4,800,000BEF
1.) Completion of the laboratory scale technological
experiments on two actual site PCB-contaminated soils by determining: a) the
ecotoxicity of both soils resulting from the recycled and solid-phase reactor
treatment by using the Lepidium sativum
germination test, b) the chemical nature of the aromatic metabolites produced
in the reactors during the soil treatments and c) heavy metal concentration in
the soils
2.) To perform a biochemical study on the indigenous
PCB-cometabolising bacteria detected in the soils based on the use of specific
gene probes will be performed.
3.)
To perform
a study on the environmental fate and the migration properties of RAMEB in
contaminated soils
4.) Finishing and evaluation of ex situ field experiments
5.) Assessment of a new contaminated site for the
selection an area for the in situ
field experiment, planning and starting the in
situ model experiment
Ø
A training course for students and young scientists on PCB
biodegradation was held at the Bologna University
Ø
The end-users have received the progress reports and have been invited
to the annual meetings
Ø
The new results have been incorporated into relevant curricula of
Bologna University and Budapest University of Technology and Economics and
presented at a NATO Advanced Study Institute
Dr. Bjørn Arne Johnsen
Division for Protection and Material, Norwegian Defence Research Establishment,
Oslo, Norway
Additional Collaborating
Institutions
Ø
Körte-Organica Ecotechnologies company,
joined recently to the project as an end-user, will be charged with the field
work of the in situ experiments.
Abbreviations: CDT- Cyclodextrin Technology (the
bioremediation technology using cyclodextrin as an additive to improve the
desorption and bioavailability of the contaminants adsorbed to the soil
particles)
RAMEB - randomly methylated
b-cyclodextrin
SfP - BIOREMEDIATION
Title: Decontamination of Hydrocarbon Polluted
Military Sites to Decrease Environmental Risks - Low-Cost Cyclodextrin
Technology
Project Co-Directors:
Prof. Dr. Fabio Fava, Department of
Applied Chemistry and Material Science, Engineering Faculty, University of
Bologna, Bologna, Italy (NPD)
Prof. Dr. József Szejtli, Cyclolab Cyclodextrin
R&D laboratory, Ltd., Budapest, Hungary (PPD)
Dr. Katalin Gruiz, Department of Agricultural
Chemistry, Budapest University of Technology and Economics, Budapest, Hungary
Dr.
Attila Murányi, Research Institute for Soil Science and Agricultural Chemistry
of Hungarian Academy of Science, Budapest, Hungary
Edward
G. Soméus, Thermal Desorption Technology, Group LCC., (TDT-3R), Budapest,
Hungary
Approval Date: 30
November, 1999 Effective
date: 1 January, 2000
Duration: 3 years; expected
completion by December 2002
NATO Budget: 180
962 EUR
![]()
Information about the SfP Project through Internet:
www.cyclolab.hu/nato
![]()
Ø
To establish a solid scientific background
for the CycloDextrin Technology (CDT) which is a new bioremediation technology
particularly indicated for soils chronically contaminated by hydrophobic
pollutants, such as aliphatic and aromatic hydrocarbons and polychlorinated
biphenyls, based on the soil supplementation with low-cost cyclodextrin as a
non-toxic, biodegradable and capable agent for improving the bioavailability
(and therefore the biodegradability) of such organic pollutants in the soil
matrix;
Ø
to develop and optimise a dedicated pilot
plant for implementing the CDT;
Ø
to perform a field experiment by the
application of a complex and integrated technology monitoring
Ø
to develop the know-how of the new CDT
Ø
to run SWOT analysis (Strengths, Weakness,
Opportunities, Threats) of the CDT
Ø
to demonstrate the technical efficiency
and cost-effectiveness of the CDT
Ø
to run a comparative risk based
cost-benefit evaluation of the CDT
Ø
to use the field site for demonstration
and disseminate the results at university & industrial level
Ø
to compile the criteria of utilisation of
the CDT & defining of the potential end-users.
Ø
In the laboratory experiments, the effects
of a low-cost randomly methylated b-cyclodextrin (RAMEB) (examined at 4 initial
concentrations) on the pollutant solubilisation and biodegradation in soils
were studied by treating 3 different soil-types (loamy, humic and sandy-soil)
supplemented singly with 4 types of pollutant mixes (Diesel oil, mineral oil,
transformer oil and transformer oil with PCBs) at 2 or 3 initial concentrations
both in slurry- and solid-phase aerobic 50-250 g soil microcosms under various
environmental conditions.
Ø
An integrated analytical methodology,
consisting of 1) the analysis of the pollutants and of the pollutant break-down
intermediates and final products, 2) the analysis of the heterotrophic and
pollutant-degrading bacterial biomass, 3) characterisation of the soil
bioactivity through respirometric measurements of the CO2 production
and 4) the analysis of the soil ecotoxicity (using both prokaryotic and
eukaryotic testorganisms), was developed.
Ø
In pilot-scale experiments 40 kg soil
spiked with transformer oil have been treated for 10 months. The highest
bioactivity and biodegradation rates were observed in the presence of 1 % (w/w)
RAMEB in solid phase reactors.
Ø
The efficacy of RAMEB has been also proved
with actual site soils contaminated with PAH, mazout and PCB, respectively. The
optimal RAMEB concentration increases with the concentration of the pollutant
and the absorptive capacity of the soil.
Ø
The effects of aeration, nutrient supply
and availability, inoculation with specialised bacteria and other environmental
factors have been studied in the technological experiments and the optimal
conditions found.
Ø
In general, both on spiked and on actual site
contaminated soils the addition of RAMEB resulted in an improved microbial
growth and/or survival, thus indicating that RAMEB was 1) capable of improving
the nutrient bioavailability in the soils. RAMEB was also found to
significantly enhance the biodegradation rate of the soil pollutants studied by
2) probably enhancing the growth and the persistence of the
pollutant-metabolising microbial consortia 3) and the bioavailability of the
pollutants added to the soils.
Ø
Laboratory studies have shown that the
naturally occurring adapted soil microflora is capable of enhancing the removal
the organic contaminants from the soil. Application of various commercial
inocula has not accelerated the biodegradation of the studied hydrophobic
pollutants and had not influenced the efficacy of RAMEB.
Ø
RAMEB additions were found to remarkably
modify the surface and pore properties (surface area, general pattern of the
adsorption energy, the micropore and mesopore volume and radius) of clay
minerals and soils; the capillary water-rise and the hydraulic conductivity
were also found to be influenced.
Ø
Two pilot-scale ex situ experiments have been started with a heavy oil-contaminated
actual site soil and with a soil artificially polluted with used transformer
oil. The results of the 37 and 31 week-treatment period, respectively, showed
the benefit of RAMEB application (slightly enhanced biodegradation, improved
microbial life). The experiments called our note on the importance on the mode
of application of RAMEB on soil: form of CD, solution, dilution, mixing, etc.
Ø
RAMEB was found slowly biodegraded by the
soils of the ex situ experiment
Ø
The great efforts to find a proper site
for the in situ experiment have succeeded and the field treatments will be
started soon.
Payments through NATO Project Funds : … 127 780.5 EUR
1.
Finishing
and evaluation of ex situ field experiments
2.
Performing
the in situ model experiment based on the results of the laboratory
trials with the soil of the site, evaluation
3.
Final
evaluation of the cyclodextrin technology
Ø
A training course for students and young scientists on PCB
biodegradation was held at the Bologna University
Ø
The end-users (Dunaferr Steal Company and Innopark Development-Construction-Service, both located
in Dunaujvaros, Hungary)have received the progress
reports and have been invited to the annual meetings
Ø
The new results have been incorporated into relevant curricula of
Bologna University and Budapest University of Technology and Economics,
presented at a NATO Advanced Study Institute in Prague and at 11th
International Cyclodextrin Symposium in Reykjavik.
Dr. Bjørn Arne Johnsen
Division for Protection and Material, Norwegian Defence Research Establishment,
Oslo, Norway
Additional Collaborating
Institutions
Ø
REM-FWS Water, Air and Soil Cleaning
Systems company, joined recently to the project as an end-user; it will be
charged with the field work of the in
situ experiments.
__________________________________________________________________________
Abbreviations: CDT- Cyclodextrin Technology (the
bioremediation technology using cyclodextrin as an additive to improve the
desorption and bioavailability of the contaminants adsorbed to the soil
particles)
RAMEB - randomly
methylated b-cyclodextrin
SfP - BIOREMEDIATION
SfP 973720
Title: Decontamination of
Hydrocarbon Polluted Military Sites to Decrease Environmental Risks - Low-Cost
Cyclodextrin Technology
Project
Co-Directors:
Prof. Dr. Fabio Fava,
Department of Applied Chemistry and Material Science, Engineering Faculty,
University of Bologna, Bologna, Italy (NPD)
Prof. Dr. József
Szejtli, Cyclolab Cyclodextrin R&D laboratory, Ltd., Budapest, Hungary
(PPD)
Dr. Katalin Gruiz,
Department of Agricultural Chemistry, Budapest University of Technology and
Economics, Budapest, Hungary
Dr.
Attila Murányi, Research Institute for Soil Science and Agricultural Chemistry
of Hungarian Academy of Science, Budapest, Hungary
Edward
G. Soméus, Thermal Desorption Technology, Group LCC., (TDT-3R), Budapest,
Hungary
Approval
Date: 30 November, 1999 Effective
date: 1 January, 2000
Duration: 3 years and 3 months;
completed by March 2003
NATO Budget: 181
500 EUR
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Information about the SfP Project through
Internet: www.cyclolab.hu/nato
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Ø To establish a solid scientific background
for the CycloDextrin Technology (CDT) which is a new bioremediation technology
particularly indicated for soils chronically contaminated by hydrophobic
pollutants, such as aliphatic and aromatic hydrocarbons and polychlorinated
biphenyls, based on the soil supplementation with low-cost cyclodextrin as a
non-toxic, biodegradable and capable agent for improving the bioavailability
(and therefore the biodegradability) of such organic pollutants in the soil matrix;
Ø to develop and optimise a dedicated pilot
plant for implementing the CDT;
Ø to perform a field experiment by the
application of a complex and integrated technology monitoring
Ø to develop the know-how of the new CDT
Ø to run SWOT analysis (Strengths, Weakness,
Opportunities, Threats) of the CDT
Ø to demonstrate the technical efficiency
and cost-effectiveness of the CDT
Ø to run a comparative risk based
cost-benefit evaluation of the CDT
Ø to use the field site for demonstration
and disseminate the results at university & industrial level
Ø to compile the criteria of utilisation of
the CDT & defining of the potential end-users.
Ø In the laboratory experiments, the effects
of a low-cost randomly methylated b-cyclodextrin (RAMEB) on the pollutant
solubilisation and biodegradation in soils were studied by treating 3 different
soil-types supplemented singly with 4
types of pollutant mixes (Diesel oil, mineral oil, transformer oil and
transformer oil with PCBs) at 2 or 3 initial concentrations both in slurry- and
solid-phase aerobic 50-250 g soil microcosms.
Ø An integrated analytical methodology,
consisting of 1) the analysis of the pollutants and of the pollutant break-down
intermediates and final products, 2) the analysis of the heterotrophic and
pollutant-degrading bacterial biomass, 3) characterisation of the soil
bioactivity through respirometric measurements of the CO2 production
and 4) the analysis of the soil ecotoxicity (using both prokaryotic and
eukaryotic testorganisms), was developed.
Ø In pilot-scale experiments 40 kg soil
spiked with transformer oil have been treated for 10 months. The highest
bioactivity and biodegradation rates were observed in the presence of 1 % (w/w)
RAMEB in solid phase reactors.
Ø The efficacy of RAMEB has been also proved
with actual site soils contaminated with PAH, mazout and PCB, respectively. The
optimal RAMEB concentration increases with the concentration of the pollutant
and the absorptive capacity of the soil.
Ø The effects of aeration, nutrient supply
and availability, inoculation with specialised bacteria and other environmental
factors have been studied in the technological experiments and the optimal
conditions found.
Ø In general, both on spiked and on actual
site contaminated soils the addition of RAMEB resulted in an improved microbial
growth and/or survival, thus indicating that RAMEB was 1) capable of improving
the nutrient bioavailability in the soils. RAMEB was also found to
significantly enhance the biodegradation rate of the soil pollutants studied by
2) probably enhancing the growth and the persistence of the
pollutant-metabolising microbial consortia 3) and the bioavailability of the
pollutants added to the soils.
Ø Laboratory studies have shown that the
naturally occurring adapted soil microflora is capable of enhancing the removal
the organic contaminants from the soil. Application of various commercial
inocula has not accelerated the biodegradation of the studied hydrophobic
pollutants and had not influenced the efficacy of RAMEB.
Ø RAMEB additions were found to remarkably
modify the surface and pore properties (surface area, general pattern of the
adsorption energy, the micropore and mesopore volume and radius) of clay
minerals and soils; the capillary water-rise and the hydraulic conductivity were
also found to be influenced.
Ø Two pilot-scale ex situ experiments have been carried out with a heavy
oil-contaminated actual site soil and with a soil artificially polluted with
used transformer oil on a former military site (see photo on the left). The results
of the 64 and 31 week-treatment period, respectively, showed the benefit of
RAMEB application (slightly enhanced biodegradation, improved microbial life
and the contaminant elimination by 15-30%). The experiments called our note on
the importance on the mode of application of RAMEB on soil. The revitalisation
of the soil could successfully decrease the toxicity.
Ø RAMEB was found slowly biodegraded by the
soils of the ex situ experiment, its half life time is about 1 year.
Ø The in situ experiment was performed on a transformer station where the
soil was historically contaminated with transformer oil (see photo on the
right). The results show the benefits of the combined technology: ventilation,
simultaneous addition of RAMEB and nutrients and a slight flushing together
resulted in a fast reduction of the EPH content both in the groundwater and in
the soil. The cost benefit assessment showed that the
application of RAMEB is beneficial in those cases, when the future land use
brings high benefit and the saved time will
compensate for the higher costs.
Ø The SWOT (Strengths, Weakness, Opportunities, Threats) analysis of CDT proved
that it is a possible alternative biotechnology for the reduction of
environmental risk of a site contaminated with hydrocarbons.
Ø A
training course for students and young scientists on PCB biodegradation was
held at the Bologna University
Ø Another
training course on biodegradation of hydrocarbons was held at the Budapest
University of Technology and Economics
Ø The
new results have been incorporated into relevant curricula of Bologna
University and Budapest University of Technology and Economics, presented at a
NATO Advanced Study Institute in Prague, at 11th International
Cyclodextrin Symposium in Reykjavik, and at the XII International Biodeterioration and Biodegradation Symposium, Prague, 8th International FZK/TNO Conference on Contaminated
Soil in Gent, and 2nd European Conference on Bioremediation, in
Chania


Dr. Bjørn Arne Johnsen
Division for Protection and Material, Norwegian Defence Research Establishment,
Oslo, Norway
Additional
Collaborating Institutions
Ø REM-FWS Water, Air and Soil Cleaning
Systems company, joined recently to the project as an end-user; it has been charged
with the field work of the in situ
experiments.
__________________________________________________________________________
Abbreviations:
CDT- Cyclodextrin Technology (the
bioremediation technology using cyclodextrin as an additive to improve the
desorption and bioavailability of the contaminants adsorbed to the soil
particles)
RAMEB
- randomly methylated b-cyclodextrin