Decontamination of Hydrocarbon Polluted Military Sites to Decrease Environmental Risks

Low - Cost Cyclodextrin Technology

(SfP-973720)

ACTIVITIES

 

Phase 1. Preliminary screening on artificially contaminated soils

In this phase, the influence of CDs on the biodegradation of different hydrocarbon mixtures in defined soils will be determined by analyzing the pollutant disappearance and the ecotoxicity depletion in artificially contaminated soils treated in fixed- and slurry-phase conditions (scale: 50-500 g). Several chemical and biological analytical procedures will be developed and jointly used at the beginning and at the end of the experiments to assess and quantify the occurrence of the soil detoxification and remediation in the different treatment conditions.

The CDs will be used in the concentration range: 0.1 to 5 % of dry soil.

Four different complex mixtures of organic compounds will be applied: Diesel oil, transformer oil, PAHs and PCBs. These groups of hydrocarbons highly differ from each other in biodegradability and in toxicity. Their concentrations will follow their usual occurrence at military sites.

- Diesel oil               10 000–50 000 ppm                         - PAHs              10–5 000 ppm

- Transformer oil        5 000–30 000 ppm                         - PCBs            100–1 000 ppm

Parallel experiments are planned to perform by using a CD-contaminant complex. These experiments will allow us to understand the possible action-mechanism of CDs.

This preliminary study will allow us to screen the potential role of CDs in the biological restoration of the military area chosen in this project and the influence of the main soil and treatment parameters that can affect their activity.

The experiments will be carried out by using three different types of soil (loamy, sandy and humic) to study the effect of soil characteristics on the CDs activity. Consistence of the soil according to the technology may be slurry or solid. Inoculation with the appropriate microflora may be useful to increase biodegradation or can be necessary for PCBs biodegradation. Two possibilities will be evaluated: indigenous, adapted microflora or commercially available mixture of bacterial strains. The optimal nutrient supply may vary depending on contaminant and CD concentration. The experiments will be carried out in batch aerobic reactors: in solid phase or in mixed slurry.

Phase 2. Laboratory experiments

After assessment of the site, laboratory experiments (scale: 100-1000 g) directed to evaluate the effects of RAMEB on the bioremediation and detoxification of actual site contaminated soil samples in fixed- and slurry-phase conditions will be performed. Aim of Phase 2 is to evaluate the effect of the concentration of CDs, and in their presence, the influence of temperature (20oC and 30oC), nutrients (N, P and microelements) and microbial inocula on the soil decontamination. Two consistencies will be applied: solid and slurry. Evaluation (analysis) will be carried out at the beginning and at the end of the experiments. Shaken and static aerated glass vessels will be used as batch reactors for the slurry and solid phase soil treatment.

Phase 3. Laboratory scale technological experiments

After the determination of optimal nutrient concentration and inoculation, we investigate the effect of two different CD concentrations, and the use-pattern of CD, as well as the effect of aeration on the decontamination process. In order to be able to identify the best technology for the next phase experiment we will evaluate these parameters both in slurry and in solid phase conditions.

Aim of the technological experiments (Scale: 500 - 1000 g) is not only to select the best (optimal) conditions for scaling up but also to develop reactors which are able to model the ex situ and in situ soil remediation technologies.

In this phase 1-2 liter of volume reactors will be applied with aeration. In case of slurry phase mixing will be applied, whereas in case of soil phase, packed columns or storage vessels will be used.

Phase 4. Pilot-scale experiments

Complex analysis to control and manage the technology on the basis of the continuous measuring of respiration and biological conditions of the soil originating from the contaminated site. Aims of these experiments (Scale: 20 kg) are to support the design and keeping the field experiments, to compare the homogenous ex situ system with the heterogeneous in situ system, and to get more information about the inside of the black box, i.e. the interactions between the soil, i.e. the CD, the contaminant and the microflora. In this phase special interest is given for the effect of a randomly methylated ß-cyclodextrin (RAMEB), which is currently the cheapest CD derivative on the market.

20 dm3 volume self-designed glass and plastic reactors will be used. The reactors are supplied with aeration, with an injection and sampling system. For modeling the in situ technology, a solid-phase reactor will be used in order to treat the soil in an undisturbed system. For modeling the ex situ technology, rotated plastic vessels will be applied. These more advanced reactors are equipped with a control system for O2 consumption, CO2 production and temperature

Phase 5. Application of the technology

Phase 5 has four further tasks: assessment of the site, design of the technologies and their field application in 30 and 70 m3. After completion of the remediation a monitoring system will be established and maintain.

Phase 5.1. Assessment of the contaminated site (see the map in Annex 2)

Two or three sites indicated in the map as contaminated sites will be selected on the basis of the contamination degree (which will be estimated on the basis of the uncomplete evaluation made available by Hungarian environmental authorities which characterized this military area in 1991) and location (accessibility); and 96 samples taken from different depths of each area will be subjected to an extensive characterization by using chemical, biological and ecotoxicological analyses. On the bases of the results we can select the most suitable site for the field experiments.

Phase 5.2. Design of the technology

Planning of the technology will be performed on the basis of the results of Phase 5.1., Phase2, Phase 3 and Phase 4. An ex situ and an in situ technology will be designed.

Phase 5.3. Field experiments (Scale: 100 m3)

Field experiments will be based on the results of the former small and medium size technological experiments. Two different remediation technologies will be investigated.

As ex situ bioremediation process 30 m3 of excavated and homogenized soil will be treated. Ex situ treatment is a controlled solid-phase biotechnology. The excavated soil will be supplemented with amendments and placed into a close reactor equipped with systems for leachate collection, and for air and nutrient addition.

CD, nutrients and microbes will be added according to the optimal schedule.

About 70 m3 of non-excavated contaminated soil will be treated by an in situ biological process. During the in situ bioremediation undisturbed soil will be aerated (regulated by CO2 production or O2 consumption) through vertical bore hole system supplied with perforated plastic tubes. Bioventing means a slow airflow within the soil matrix ensured a low capacity ventilator. Exhausted gas will be collected and treated. CDs and other additives will be applied to keep an optimal concentration.

The information from the completely homogeneous, ex situ system will be compared with the undisturbed in situ system, where all the parameters have a gradient or other kind of tendentious change according to the place and time. Differences and similarities in the two systems will give important basic information about the processes in the soil.

100 samples (10 times 10). To clear up the arising technological problems, additional small scale experiments will be carried out in the labs. Phase 5 experiments will be performed by TDT-3R, TUB, RISSAC and CYL. Biological investigations will be carried out by TUB, chemical-physical characterization of the soil by the RISSAC, the evaluation of the experiments by chemical analysis will be done by CYL and by BU.

Phase 5.4. Monitoring of the remedied site

Design and settlement of soil and ground water monitoring system to control of remedied site will be performed.

Phase 6. Demonstration and dissemination of the results

Demonstration and dissemination of the project result to the universities and scientific community through publications and conference presentations.

A complex methodology is applied to follow and evaluate the experiments:

-       Extraction: Soxhlet and/or ultrasonic extraction

-       Biological investigations: cell number of aerobic heterotrophic bacteria, oil-degrading bacteria and aerobic PCB- and chlorobenzoic acid-degrading bacteria, CO2 production and O2 consumption, ATP content in connection with biological activity of soil

-       Ecotoxicological methods: Photobacterium phosphoreum bioluminescence inhibition test, Sinapis alba and Lepidum sativum germination and root elongation test, Azotobacter agile dehydrogenase enzyme activity test and/or Folsomia candida (Collembola) mortality test

-       Chemical-physical investigations: physical characteristics of the soil, nutrient supply (for plants) of the soil, two and three phase water transport, pore-size distribution and humus content

-       Chemical analysis: oil content measured and PAH content measured by GC-FID and/or by CE and GC-MS, PCBs content measured by GC-ECD, chlorobenzoic acids and chloride ions produced by the PCBs break-down measured by HPLC-DAD and a CSE, respectively.

 

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