![[logo] US EPA](https://webarchive.library.unt.edu/eot2008/20081106052538im_/http://www.epa.gov/epafiles/images/logo_epaseal.gif){kind=logo}
Final Report: Field Scale Bioremediation: Relationship of Parent Compound Disappearance to Humification, Mineralization, Leaching, Volatilization of Transformaiton Intermediates
EPA Grant Number: R825549C051Subproject: this is subproject number 051 , established and managed by the Center Director under grant R825549
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: HSRC (1989) - Great Plains/Rocky Mountain HSRC
Center Director: Erickson, Larry E.
Title: Field Scale Bioremediation: Relationship of Parent Compound Disappearance to Humification, Mineralization, Leaching, Volatilization of Transformaiton Intermediates
Investigators: Sims, Ronald C.
Institution: Utah State University
EPA Project Officer: Manty, Dale
Project Period: August 12, 1993 through May 17, 2000
Project Amount: Refer to main center abstract for funding details.
RFA: Hazardous Substance Research Centers - HSRC (1989)
Research Category: Analysis/Treatment of Contaminated Soil
Description:
Objective:Two specific goals were identified for this project. The first goal was to provide new information concerning the distribution of PAH and PCP associated with the solid fraction of soil and the parent compounds and transformation products associated with the water soluble extract (leachate) fraction. The second goal was to determine the effect of environmental variables and amendments on biodegradation and on chemical contaminant association with solid and aqueous phases due to microbial soil processes.
Summary/Accomplishments (Outputs/Outcomes):The rationale for the project is based on the lack of information concerning the behavior and management of PAHs and PCP in soil bioremediation systems with regard to establishing soil cleanup levels and evaluating the effectiveness of soil remediation systems treating wood-preservative contaminated soil. Specifically, the role of the humification, sequestration, or binding process, whereby a chemical is rendered non-solvent extractable, is currently unknown in prepared bed systems and ground water systems. The development of information addressing transformation and behavior of transformation intermediates with an emphasis on characterizing humification of target organic chemicals and non-humified intermediates in this project has increased our understanding of soil bioremediation processes with regard to protection of public health and the environment. Based on information developed in this project, techniques for the management of the humification process and for characterization of biochemical intermediates as indicators of biodegradation were identified and applied to soil bioremediation in prepared bed and ground water environments.
The approach in this project was to use samples of soil taken from field-scale bioremediation systems treating creosote and creosote/PCP contaminated soil at the Champion International Superfund site, Libby, Montana. A chemical mass balance was used for developing analytical and instrumental approaches and protocols as well as results for evaluating contaminant association with the soil solid phase (binding) and other soil phases. This approach was used to generate information concerning: (1) association of PAHs and PCP/intermediates with the soil solid phase and with leachate; (2) effects of environmental variables (temperature and soil moisture) on the humification process; and (3) effects of amending soil with electron acceptors (oxygen, manganese, and iron) on humification, mineralization, and volatilization; and (4) characterization of the microorganisms responsible for the biodegradation of PAHs and PCP. A second activity involved the characterization/identification of PAH and PCP transformation products that could be extracted from soils. Microtox? toxicity determinations were made during treatment to provide a relative index of toxicity reduction as a result of soil bioremediation.
To evaluate the effect of redox conditions of pH on humification, we designed, built, and tested an apparatus (Potentiostat) capable of maintaining a redox cell at a set reference voltage and a set pH. The Potentiostat apparatus has been used to evaluate humification. Tetrachloro-1,4-benzoquinone was the main oxidation product of PCP reaction with solid MnO2 surfaces. Other oxidation products included tetra- and trichlorophenols.
USU recently received access to the DOE funded Advanced Light Source (ALS) synchrotron located at the Lawrence Berkeley National Laboratory (LBNL), California, to further explore the process of microbial PAH degradation and bound residue formation. The technique utilizes photon energy from the synchrotron source as a light source for a Nicolet Nic-Plan Fourier-transform infrared (FTIR) spectromicroscope operating in the mid-IR region from 10,000 cm-1 to 450 cm-1. Since the source is a non-thermal source, the intensity of the synchrotron light source allows for the beam to be focused to small diameters with little loss of signal resolution. This provides the ability to focus the instrument on areas as small as 10 um in size whereas conventional thermal IR sources are limited to target sizes of 100 um or greater. The infrared radiation from the facility is also non-destructive to the biological material being studied. These observations make synchrotron-based FTIR spectromicroscopy an ideal tool for non-destructively studying ongoing biogeochemical processes on surfaces of environmental samples. The instrument has been used to characterize the biodegradation of pyrene on a magnetite (rock) surface by bacteria strains isolated from the treated Montana soil.
Results of non-solvent extractable binding of 14-C-pyrene to the Montana soil solid phase were obtained using the methyl isobutly ketone (MIBK) humic fractionation procedure. Binding increased through 294 days of treatment in biologically active microcosms for humic acid, fulvic acid, bound humic acid, and mineral-associated organic carbon fractions. The relative affinity of the added pyrene and transformation products was highest for the humic acid fraction. Bound residue formation in PAH-contaminated soil was observed to be an important behavior mechanism in the prepared bed bioremediation system at the Superfund site, and may be an acceptable endpoint in the remediation of contaminated soil (Nieman et al. 1999).
Laboratory tests indicated a significant effect of soil gas oxygen concentration on the degradation, mineralization, and binding of spiked 14-C-pyrene and nonspiked 16 priority pollutant PAHs in the Montana soil. Degradation rates of 14-C-pyrene and nonspiked PAH compounds were enhanced under soil gas oxygen concentrations between 2% and 21 % by volume in the contaminated soil. Between 45% and 55% of 14-C-pyrene was mineralized after 70 days at soil gas oxygen levels between 2% and 21%. No statistically significant mineralization was fond to occur at 0% oxygen concentration. Mineralization of 14-C-pyrene in contaminated soil poisoned with mercuric chloride was determined to be less than 0.5%. Chemical mass balance evaluation indicated insignificant volatilization (less than 0.3%), and non-solvent extractable binding of 15% in biologically active microcosms at soil gas oxygen concentrations above 2%. Soil binding was only 8% in non-poisoned microcosms held at 0% oxygen. Degradation of indigenous nonradiolabeled PAH in non-poisoned soil was statistically significantly greater than in poisoned soil. These results indicated that the degradation of 14-C-pyrene and PAH compounds was biological and would occur under low soil oxygen conditions. Application of these findings would be appropriate for soil aeration technology in order to achieve continued treatment for buried soil while new soil was added above, as practiced in landfarming and prepared-bed systems (Hurst et al. 1996).
Laboratory tests also indicated a significant effect of soil gas oxygen concentration on the behavior of pentachlorophenol (PCP) with the critical soil gas concentration at 2% (by volume). Similar to the trend in results obtained with 14-C-pyrene, between 48% and 64% of spikedl4-CPCP was mineralized after 70 days, and no significant mineralization was observed in microcosms incubated at 0% oxygen. In poisoned microcosms mineralization was less than 0.2%, volatilization less than 0.08%, non-extractable 14-C between 4% and 10%, and the dominant form was solvent extractable 14-C at 88% to 95%. For biologically active microcosms, non-solvent extractable 14-C ranged from 14% to 16% when soil gas oxygen was 2% or greater, and 4% when soil gas oxygen was 0%. Application of these findings would be similar to applications described for pyrene and PAH above (Hurst et al. 1997).
Microcosm tests of the biological stability of PAH parent compounds phenanthrene and anthracene, and metabolites, including 1-hydroxy-2-naphthoic acid and 2.3-dihydroxynaphthalene in the contaminated Montana soil indicated that there was no significant lag period in biodegradation of these metabolites. Oxygen consumption was used to indicate the rate and extent of degradation of the metabolites identified. At the 95% confidence interval, significant differences in first order rate constants associated with repeated spiking. Oxygen consumption rates were observed to increase with repeated spiking of test compounds, indicating increased acclimation of the Montana soil to the test chemicals. Rates of oxygen utilization of metabolites were observed to be lower than rates of oxygen utilization of parent PAHs. The extent of biodegradation was observed to higher after repeated addition of each test compound, again indicating acclimation (Ginn et al. 1996).
Results from this research project included the design, construction, and testing of a redox apparatus that controls Eh, pH, and temperature, referred to as a controlled environment potentiostat. The potentiostat was used to evaluate the behavior of PCP under simulated natural attenuation conditions and under engineered remediation conditions. Manganese dioxide was observed to oxidize PCP under controlled conditions at high Eh and low pH conditions (Petrie et al. 1998).
Results of an evaluation of environmental conditions, including soil moisture and temperature, on the behavior of 14-C-pyrene in the Montana soil indicated significant differences in mineralization and non-solvent extractable binding. Samples at higher moisture content (85% field capacity) mineralized from 25% to 30% of spiked 14-C, while samples at 45% field capacity mineralized minimal (less than 5%) 14-C over a 365 day treatment period. Arrhenius parameters were well suited to describing the rates of biodegradation during the first 125 days of treatment. However, first order mineralization rate constants from day 125 through day 365 at 10 C and 20 C were not significantly different, indicating that contaminant bioavailability may have controlled biodegradation at these temperatures. In addition, biologically active samples incubated at 85% field capacity were capable of binding 14-C significantly more effectively than samples at 45% field capacity. Incubation temperature had not effect on total bound 14-C and had little effect on the distribution of 14-C among humic fractions in soil incubated at 85%. Applications for this information indicate that moisture content plays an important role in affecting the rate and extent of PAH mineralization, and also affects contaminant binding (Nieman et al. 2000).
The information generated as a result of this research project was used by regulators and the wood preserving industry for evaluating soil bioremediation systems, especially in Region VIII where several wood preserving sites undergoing soil bioremediation are located. Information regarding the mineralization and binding of pyrene and PCP identified in chemical mass balance microcosms was requested and given to: (1) Mr. Jim Harris, U.S. EPA Region VIII, for application to the Montana Pole wood preserving site, (2) U.S. EPA, NRMRL, Ada, OK, Drs. Scott Huling and John Wilson, (3) CH2MHill, Denver, Colorado Office, and (4) U.S. EPA Region I, Boston. Dr. Sims presented findings of PCP and PAH behavior at wood preservative sites at the "Workshop on Utility Poles: Environmental Issues", October 13-14, 1997, Madison, Wisconsin, sponsored by the United States Telephone Association and the U.S. Department of Agriculture, Forest Products Laboratory. In addition, results from this project were presented at the U.S. EPA Training course on Natural Attenuation for U.S. EPA Region IV presented in Atlanta, Georgia, August 25-27,1998, and in Columbia, South Carolina, June 1-3, 1999, sponsored by the Robert S. Kerr Laboratory, Ada, Oklahoma, and at the U.S. EPA Training course on Innovative Treatment Technologies, San Francisco, September 13-15, 1999.
The results from this work are directly applicable to the Libby, Montana, site. In addition, presentations of the work on the effects of oxygen tension of PAH and PCP biodegradation have been incorporated into the U.S. EPA technology transfer course on Natural Attenuation that has been offered ten times thus far (Seattle, Washington (twice); Kansas City, Kansas; Denver, Colorado; Chicago, Illinois (twice); Boston, MA, San Francisco, California, and Atlanta, Georgia).
Journal Articles on this Report: 7 Displayed | Download in RIS Format
| Other subproject views: | All 21 publications | 9 publications in selected types | All 7 journal articles |
| Other center views: | All 900 publications | 231 publications in selected types | All 188 journal articles |
| Type | Citation | ||
|---|---|---|---|
|
|
Ginn JS, Doucette WJ, Smith D, Sorensen DL, Sims RC. Aerobic biotransformation of polycyclic aromatic hydrocarbons and associated metabolites in soil. Polycyclic Aromatic Compounds 1996;11(1-4):43-55 |
R825549C051 (Final) |
not available |
|
|
Hurst CJ, Sims RC, Sims JL, Sorensen DL, McLean JE, Huling S. Polycyclic aromatic hydrocarbon biodegradation as a function of oxygen tension in contaminated soil. C. Jestin Hurst, Ronald C. Sims, Judith L. Sims, Darwin L. Sorensen and Joan E. McLean. Journal of Hazardous Materials 1996;51(1-3):193-208. |
R825549C051 (Final) |
not available |
|
|
Hurst CJ, Sims RC, Sims JL, Sorensen DL, McLean JE, Huling S. Soil gas oxygen tension and pentachlorophenol biodegradation. Journal of Environmental Engineering, ASCE 1997;123(4):364-370. |
R825549C051 (Final) |
not available |
|
|
Nieman JKC, Sims RC, Sims JL, Sorenson DL, McLean JE, Rice JA. [C-14]Pyrene bound residue evaluation using MIBK fractionation method for creosote-contaminated soil. Environmental Science Technology 1999;33(5):776-781. |
R825549C051 (Final) R825549C058 (Final) |
not available |
|
|
Nieman JKC, Sims RC, McLean JE, Sims JL, Sorensen DL. Fate of pyrene in contaminated soil amended with alternate electron acceptors. Chemosphere 2001;44(5):1265-1271. |
R825549C051 (Final) |
not available |
|
|
Environmental variables affecting mineralization and sequestration of pyrene. J.K.C. Nieman, R.C. Sims, J.L. Sims, D.L. Sorensen, and J.E. McLean. |
R825549C051 (Final) |
not available |
|
|
Petrie RA, Grossl PR, Sims RC. Controlled environment potentiostat to study solid-aqueous systems. Soil Science Society of America Journal 1998;62(2):379-382. |
R825549C051 (Final) |
not available |
bioremediation, humification, mineralization, leaching, volatilization, Intermediates , Ecosystem Protection/Environmental Exposure & Risk, Toxics, Water, Scientific Discipline, Waste, Analytical Chemistry, Fate & Transport, pesticides, Environmental Chemistry, Contaminated Sediments, Ecology and Ecosystems, Geochemistry, Bioremediation, electron acceptors, biodegradation, fate and transport, creosote, humification, biotechnology, adsorption, chemical kinetics, contaminated sediment, contaminant transport, PCP, contaminants in soil, contaminated soils, bioremediation of soils, migration, wood treatment, Pentachlorophenol, agrochemicals
Relevant Websites:
http://www.engg.ksu.edu/HSRC
Progress and Final Reports:
Original Abstract
Main Center Abstract and Reports:
R825549 HSRC (1989) - Great Plains/Rocky Mountain HSRC
Subprojects under this Center:
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R825549C006 Fate of Trichloroethylene (TCE) in Plant/Soil Systems
R825549C007 Experimental Study of Stabilization/Solidification of Hazardous Wastes
R825549C008 Modeling Dissolved Oxygen, Nitrate and Pesticide Contamination in the Subsurface Environment
R825549C009 Vadose Zone Decontamination by Air Venting
R825549C010 Thermochemical Treatment of Hazardous Wastes
R825549C011 Development, Characterization and Evaluation of Adsorbent Regeneration Processes for Treament of Hazardous Waste
R825549C012 Computer Method to Estimate Safe Level Water Quality Concentrations for Organic Chemicals
R825549C013 Removal of Nitrogenous Pesticides from Rural Well-Water Supplies by Enzymatic Ozonation Process
R825549C014 The Characterization and Treatment of Hazardous Materials from Metal/Mineral Processing Wastes
R825549C015 Adsorption of Hazardous Substances onto Soil Constituents
R825549C016 Reclamation of Metal and Mining Contaminated Superfund Sites using Sewage Sludge/Fly Ash Amendment
R825549C017 Metal Recovery and Reuse Using an Integrated Vermiculite Ion Exchange - Acid Recovery System
R825549C018 Removal of Heavy Metals from Hazardous Wastes by Protein Complexation for their Ultimate Recovery and Reuse
R825549C019 Development of In-situ Biodegradation Technology
R825549C020 Migration and Biodegradation of Pentachlorophenol in Soil Environment
R825549C021 Deep-Rooted Poplar Trees as an Innovative Treatment Technology for Pesticide and Toxic Organics Removal from Soil and Groundwater
R825549C022 In-situ Soil and Aquifer Decontaminaiton using Hydrogen Peroxide and Fenton's Reagent
R825549C023 Simulation of Three-Dimensional Transport of Hazardous Chemicals in Heterogeneous Soil Cores Using X-ray Computed Tomography
R825549C024 The Response of Natural Groundwater Bacteria to Groundwater Contamination by Gasoline in a Karst Region
R825549C025 An Electrochemical Method for Acid Mine Drainage Remediation and Metals Recovery
R825549C026 Sulfide Size and Morphology Identificaiton for Remediation of Acid Producing Mine Wastes
R825549C027 Heavy Metals Removal from Dilute Aqueous Solutions using Biopolymers
R825549C028 Neutron Activation Analysis for Heavy Metal Contaminants in the Environment
R825549C029 Reducing Heavy Metal Availability to Perennial Grasses and Row-Crops Grown on Contaminated Soils and Mine Spoils
R825549C030 Alachlor and Atrazine Losses from Runoff and Erosion in the Blue River Basin
R825549C031 Biodetoxification of Mixed Solid and Hazardous Wastes by Staged Anaerobic Fermentation Conducted at Separate Redox and pH Environments
R825549C032 Time Dependent Movement of Dioxin and Related Compounds in Soil
R825549C033 Impact of Soil Microflora on Revegetation Efforts in Southeast Kansas
R825549C034 Modeling the use of Plants in Remediation of Soil and Groundwater Contaminated by Hazardous Organic Substances
R825549C035 Development of Electrochemical Processes for Improved Treatment of Lead Wastes
R825549C036 Innovative Treatment and Bank Stabilization of Metals-Contaminated Soils and Tailings along Whitewood Creek, South Dakota
R825549C037 Formation and Transformation of Pesticide Degradation Products Under Various Electron Acceptor Conditions
R825549C038 The Effect of Redox Conditions on Transformations of Carbon Tetrachloride
R825549C039 Remediation of Soil Contaminated with an Organic Phase
R825549C040 Intelligent Process Design and Control for the Minimization of Waste Production and Treatment of Hazardous Waste
R825549C041 Heavy Metals Removal from Contaminated Water Solutions
R825549C042 Metals Soil Pollution and Vegetative Remediation
R825549C043 Fate and Transport of Munitions Residues in Contaminated Soil
R825549C044 The Role of Metallic Iron in the Biotransformation of Chlorinated Xenobiotics
R825549C045 Use of Vegetation to Enhance Bioremediation of Surface Soils Contaminated with Pesticide Wastes
R825549C046 Fate and Transport of Heavy Metals and Radionuclides in Soil: The Impacts of Vegetation
R825549C047 Vegetative Interceptor Zones for Containment of Heavy Metal Pollutants
R825549C048 Acid-Producing Metalliferous Waste Reclamation by Material Reprocessing and Vegetative Stabilization
R825549C049 Laboratory and Field Evaluation of Upward Mobilization and Photodegradation of Polychlorinated Dibenzo-P-Dioxins and Furans in Soil
R825549C050 Evaluation of Biosparging Performance and Process Fundamentals for Site Remediation
R825549C051 Field Scale Bioremediation: Relationship of Parent Compound Disappearance to Humification, Mineralization, Leaching, Volatilization of Transformaiton Intermediates
R825549C052 Chelating Extraction of Heavy Metals from Contaminated Soils
R825549C053 Application of Anaerobic and Multiple-Electron-Acceptor Bioremediation to Chlorinated Aliphatic Subsurface Contamination
R825549C054 Application of PGNAA Remote Sensing Methods to Real-Time, Non-Intrusive Determination of Contaminant Profiles in Soils
R825549C055 Design and Development of an Innovative Industrial Scale Process to Economically Treat Waste Zinc Residues
R825549C056 Remediation of Soils Contaminated with Wood-Treatment Chemicals (PCP and Creosote)
R825549C057 Effects of Surfactants on the Bioavailability and Biodegradation of Contaminants in Soils
R825549C058 Contaminant Binding to the Humin Fraction of Soil Organic Matter
R825549C059 Identifying Ground-Water Threats from Improperly Abandoned Boreholes
R825549C060 Uptake of BTEX Compounds by Hybrid Poplar Trees in Hazardous Waste Remediation
R825549C061 Biofilm Barriers for Waste Containment
R825549C062 Plant Assisted Remediation of Soil and Groundwater Contaminated by Hazardous Organic Substances: Experimental and Modeling Studies
R825549C063 Extension of Laboratory Validated Treatment and Remediation Technologies to Field Problems in Aquifer Soil and Water Contamination by Organic Waste Chemicals