Decontamination of Hydrocarbon Polluted Military Sites to Decrease Environmental Risks

Low - Cost Cyclodextrin Technology

(SfP-973720)

 

SUMMARY REPORTS

 

 

NOVEMBER 2000

 

MAY 2001

 

NOVEMBER 2001

 

MAY 2002

 

Final Report

 

 


November 2000

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

BACK


May 2001

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

BACK

 


November 2001

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

 

Major Objectives

 

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.

 

Overview of Achievements since the Start of the Project until 31 October 2001

 

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

 

Milestones for the Next Six Months

 

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

 

Implementation of Results

 

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

 

Overview of Patents or Patent Applications

 

NATO Consultant

 

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

 

 

BACK

 


 

MAY 2002

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

 


Major Objectives

 

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.

 

Overview of Achievements since the Start of the Project until 31 October 2001

 

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

 

 

Milestones for the Next Six Months

 

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

 

Implementation of Results

 

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.

 

Overview of Patents or Patent Applications

 

NATO Consultant

 

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

 

 


 

Final Report

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

 


Information about the SfP Project through Internet: www.cyclolab.hu/nato

 


Major Objectives

 

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.

 

Overview of Achievements

 

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.

 

Implementation of Results

 

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

 

 

 

 

 

 

 

 

 

 

 

 

 

 


NATO Consultant

 

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.

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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

 

 

 

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