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OF PETROLEUM CONTAMINATED SOILS Biological, Physical, and Chemical Processes © 1998 by CRC Press LLC... This comprehensive technology survey describes and compares the many biological, c

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OF PETROLEUM CONTAMINATED

SOILS

Biological, Physical, and Chemical Processes

© 1998 by CRC Press LLC

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LEWIS PUBLISHERS

Boca Raton London New York Washington, D.C

REMEDIATION

OF PETROLEUM

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This comprehensive technology survey describes and compares the many biological, chemical, andphysical processes available for remediating soils contaminated by jet fuels, gasoline, bunker oil, hydrau-lic and lubricating oils, and related petroleum products Many details have been collected from theliterature and assembled under one cover to provide a convenient and informative reference source forthose who must contend with the critical worldwide problem of environmental contamination by thesecompounds

The survey was initially conducted for the Naval Civil Engineering Laboratory (NCEL), Port eme, CA, which is now merged with other commands in the new Naval Facilities Engineering ServiceCenter (NFESC) The survey was performed in connection with the installation restoration effort atTwenty-nine Palms, a marine corps base training and staging facility at Twenty-nine Palms, CA, onPurchase Order Number N62583/88 P 2085 It was later expanded and updated for this publication.Bioremediation is emerging as an important tool for treating petroleum-contaminated soils, whetherused as a stand-alone technology or in combination with other physical or chemical methods Bioreme-diation was considered to be the desired primary approach for remediating the contaminated soil atTwenty-nine Palms, supplemented, as necessary, by other processes Also, because of heightened worldinterest in the phenomenon of bioremediation and its appropriation as a viable treatment option, thisbook presents an in-depth coverage of its application for contaminated soils

Huen-The results of current research are combined with essential background information to cover allaspects of in situ and ex situ bioremediation of petroleum-contaminated soils This information elaborates

on the numerous factors affecting biodegradation of petroleum hydrocarbons and describes how theycan be enhanced to optimize bioremediation The susceptibility of individual petroleum components tobiodegradation by specific microorganisms is reported, as are the chemical reactions and metabolicpathways involved All groups of microorganisms are considered for their potential contribution, andthe effects of both aerobic and anaerobic conditions are discussed

This survey also contains an extensive overview of current in situ and ex situ physical and chemicalsoil remediation processes for dealing with petroleum contamination, including many innovativeapproaches It investigates means of controlling release of volatile organic compounds (VOCs) to theatmosphere and leachate that could migrate to the groundwater during remediation Methods for col-lecting and treating VOCs and leachate are included to address these secondary waste streams generatedduring soil treatment, whether in situ or ex situ The importance of selecting appropriate technologiesfor each contamination incident and the potential value of combining processes for maximum efficiencyare discussed The expansive coverage of these subjects will furnish the reader with a wide range ofoptions for developing treatment strategies and for customizing remediation procedures to the specificsite requirements

Information for this report was obtained through API (American Petroleum Institute), NTIS (NationalTechnical Information Service), DTIC (Defense Technical Information Center), and Dialogue searches,and by extensive use of the library facilities of the University of California at Santa Barbara, in Goleta,CA

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ABOUT THE AUTHOR

Eve Riser-Roberts, Ph.D., received her doctoral degree in microbiologyfrom the University of London, England She has over 30 years’s expe-rience in the life and physical sciences as a consultant, researcher, tech-nical writer, copywriter, and editor She has conducted and directedresearch and written for scientists, engineers, and the general publicwhile working in England, Germany, and the United States

Dr Riser-Roberts compiled two major reports for the U.S Navy onremediation of the environment contaminated by petroleum products.Her previous book, Bioremediation of Petroleum-Contaminated Sites,

was published in 1992 by Lewis Publishers

At the University of Arizona, Tucson, she wrote for the Lunar andPlanetary Laboratory (LPL), Department of Planetary Sciences, Depart-ment of Physics, and the Department of Agriculture She also conductedresearch in the university’s Department of Geosciences, and coordinatedthe first microbiological research ever performed on hydroponic systems at the Environmental ResearchLaboratory Prior to that she conducted medical research at the University Health Sciences Center at theUniversity of Arizona; at the Royal Free and Middlesex Hospitals in London, England; at the TechnicalUniversity in Munich, Germany; and at the University of Tübingen and Max Planck Institute in Tübingen,Germany

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Thanks must be given to all the practitioners and researchers in the many diverse areas related toremediation of soils contaminated by petroleum products The information they contribute from theirwork and studies help facilitate restoration of our contaminated world

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This book is dedicated to Richard M (Mike) Roberts, my personal, in-house chemical and environmentalconsultant, whose help in so many ways made this book possible

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Section 1Introduction

1.1 Background

1.2 Biodegradation as a Treatment Alternative

1.3 Combined TechnologiesSection 2

Current Treatment Technologies

2.1 On-Site or Ex Situ Processes

2.1.1.2.3 Adsorption with Brown Coal

2.1.1.2.4 Wet Air Oxidation (WAO)

2.1.1.2.5 Supercritical Fluid (SCF) Oxidation

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2.1.2.2.1.3 Microbial Accumulation of Metals

2.1.2.2.1.4 Combination Aerobic Reactors/Microbial

Adsorption

2.1.2.2.1.5 Bioreactor for Aromatic Solvents

2.1.2.2.1.6 Sequencing Batch Reactor (SBR)

2.1.2.2.2.1 Anaerobic Bioconversion Process

2.1.2.2.2.2 Suspended Growth Systems

2.1.2.2.2.3 Fixed-Film Systems

2.1.2.2.3 Combined Aerobic/Anaerobic Treatment

2.1.2.2.3.1 Aerobic/Anaerobic Biofilm Reactor

2.1.2.2.3.2 Sequential Anaerobic/Aerobic Treatment

2.2 In Situ Processes

2.2.1 Physical/Chemical Soil Treatment Processes

2.2.1.1 Shallow Soil Mixing (SSM)

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2.2.1.14.1 Hot Air Injection/Flushing

2.2.1.14.2 Steam Injection/Steam Flushing/Steam Stripping

2.2.1.14.3 Radio Frequency (RF) Heating

2.2.2.6 Deep Soil Fracture Bioinjection™

2.2.2.7 Combined Air–Water Flushing

Constituents and Associated Heavy Metals

3.1 Chemical Composition of Fuel Oils

3.2.1.4 Degradation of Aromatic Compounds

3.2.1.5 Degradation of Specific Compounds

3.2.1.5.1 Mononuclear Aromatic Hydrocarbons and Derivatives

3.2.1.5.2 Polycyclic Aromatic Hydrocarbons

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3.2.2.4.1 Mononuclear Aromatic Hydrocarbons

3.2.2.4.2 Polycyclic Aromatic Hydrocarbons

Factors Affecting Biodegradation in Soil–Water Systems

4.1 Chemical and Physical Factors

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5.1.4.5 Soil Oxygen Delivery Approaches

5.1.4.6 Commercial Soil Oxygen Delivery Approaches

5.1.4.7 Creating Anaerobic Conditions

5.1.4.8 Combination Aerobic/Anaerobic Treatment

Volatile Organic Compounds in Petroleum Products

6.1 Emissions Produced from Soil Contamination

6.1.1 Gasoline Vapor Composition

6.1.2 Human Health Criteria

6.2 Parameters Affecting Volatilization

6.2.1 Temperature

6.2.2 Operating Surface Area

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6.2.3 Wind/Barometric Pressure

6.2.4 Soil Moisture/Volumetric Water Content

6.2.5 Mass Transfer Coefficient/Partition Coefficient

6.2.23 Diffusion Travel Times

6.3 Control of VOC Emissions

6.3.1 Design and Operating Practices

6.3.1.1 Surface Area Minimization

6.3.1.2 Freeboard Depth

6.3.1.3 Inflow/Outflow Drainage Pipe Locations

6.3.1.4 Operating Practices

6.3.1.4.1 Temperature of Influent

6.3.1.4.2 Dredging, Draining, and Cleaning Frequency

6.3.1.4.3 Handling of Sediments and Sludge

6.3.1.4.4 Collecting Samples for Monitoring

6.3.2 In Situ Controls

6.3.2.1 Air-Supported Structures and Synthetic Membranes

6.3.2.2 Vapor Extraction Systems (VES)

6.3.3 VOC Pretreatment Techniques

6.3.3.1 Pretreatment Processes for Organic Liquids

6.3.3.2 Pretreatment Processes for Sludge with Organics

6.3.3.2.1 Air Stripping with Carbon Adsorption

6.3.3.2.2 Evaporation with Carbon Adsorption

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6.3.3.3.4 Soil Vapor Extraction (SVE)

6.3.3.3.5 Soil Vapor Extraction/Shallow Soil Mixing (SSM)

7.1.1 Methods for Enumerating Subsurface Microorganisms

7.1.1.1 Direct Microscopic Counts

7.1.1.2 Direct Counts with Acridine Orange

7.1.1.3 Direct Viable Counts by Cell Enlargement

7.1.1.4 Direct Viable Counts from Cell Division

7.1.1.5 Dip Slides

7.1.1.6 INT Activity Test

7.1.1.7 ATP Content

7.1.1.8 Direct Epifluorescence Filtration Technique (DEFT)

7.1.1.9 Microcolony Epifluorescence Technique

7.1.1.10 Immunofluorescence Microscopy

7.1.1.11 Plate Counts

7.1.1.12 Enrichment Techniques

7.1.1.13 Fume Plate Method

7.1.1.14 Drop Count Method

7.1.1.15 Droplette Method

7.1.1.16 Broth Cultures

7.1.1.17 Most-Probable-Number (MPN) Method

7.1.1.18 Membrane Filter Counts

7.1.1.19 Rapid Automated Methods

7.1.1.20 Fatty Acid Analysis/Lipid Biomarkers

7.1.1.21 Dehydrogenase-Coupled Respiratory Activity

7.1.2 Counts in Uncontaminated Soil

7.1.3 Counts in Contaminated Soil

7.1.4 Effect of Biostimulation on Counts

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7.2 Other Monitoring Methods

7.2.1 Biomolecular/Nucleic Acid–Based Methods

7.2.4 Other Organic Indicators

7.2.5 Electron Acceptor Concentration

7.2.6 Soil Gas Monitoring

7.2.6.1 Carbon Dioxide and Oxygen

7.2.12 Intermediary Metabolite Formation

7.2.13 Monitoring Conservative Tracers

7.2.14 Gas Chromatography and Mass Spectrometry (GC/MS)

7.2.15 Thin-Layer Chromatography–Flame Ionization Detection

8.1 Limitations of Soil Treatment Systems

8.1.1 Physical/Chemical Treatment Systems

8.3.3 Processes for Treatment Trains

8.4 Examples of the Use of Treatment Trains

References

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GLOSSARY TERM/ACRONYM DESCRIPTION

ABF: Activated biofilters

Abiotic reactions: All reactions not biological in origin, including inorganic, photolytic, catalyzed, sorptive, and transport processes

surface-Absorption: Retention of the solute within the mass of the solid rather than on its surface

Acclimation: The lag time during which organisms acquire the ability to degrade novel compounds

Acetogens: Microorganisms that convert higher volatile acids to acetate and hydrogen

ACGIH: American Conference of Governmental Industrial Hygienists

Acidophilic: Favors acidic conditions

Adaptation: The modification of characteristics of organisms to improve ability to survive and duce in a particular environment

repro-Adsorption: Retention of solutes in solution by the surfaces of the solid material

Aerobic: In the presence of oxygen

AFCEE: U.S Air Force Center for Environmental Excellence

AGP: Attached growth ponds

Alfonic 810-60: A nonionic alcohol ethoxylate surfactant

Alkalophilic: Favors basic conditions

Allochthonous: Nonindigenous microorganisms

Ambersorb 563: Activated carbon

Anaerobes: Microorganisms that require anoxic conditions and oxidation-reduction potentials of lessthe –0.2 V

Anaerobic: The absence of oxygen

Anisotropic: Exhibiting properties with different values when measured along axes in different directions

Anoxic: Oxygen free

Anthropogenic: Of man-made origin

AODC: Acridine orange direct counting method

API: American Petroleum Institute

Assimilatory: Results in the reduction of nitrate to ammonia for denitrification cellular synthesis

ATAB: Autothermal aerobic bioreactor

ATA MBR: Autothermal aerobic membrane bioreactor

ATF: Automatic transmission fluid

ATP: Adenosine-5′-triphosphate

Attenuation: Mixing of contaminated soil with clean soil to reduce concentration of hazardouscompounds

ATTIC: Alternative Treatment Technology Information Center (EPA database for technical tion on innovative treatment technologies for hazardous waste and other contaminants)

informa-Autochthonous: Indigenous or native bacteria found in soil in relatively constant numbers that do notchange rapidly in response to the addition of specific nutrients

Autotrophic: The ability to use reduction of carbon dioxide as major source of organic compoundsneeded for growth

Autotrophs: Organisms that can survive autotrophically

Axenic: Free from other living organisms

BAC: Biological activated carbon

BARR: Bioanaerobic reduction and reoxidation; a remedial technique for in situ biodegradation insoil and groundwater

BCP: Bacterial chromosomal painting

BDAT: Best demonstrated available technology

Bioaccumulation: Accumulation of organic contaminants or metals by some microorganisms

Bioaugmentation: Supplementation of microorganisms to a contaminated site to enhance ation; see Enhanced biodegradation

bioremedi-BIOCELS: Bioreclamation with Innovative On-Site Controlled Environment Landtreatment Systems

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Biodegradation: Breakdown of organic substances by microorganisms by breaking intramolecular

bonds; e.g., involving substituent functional group or mineralization As a result, the microorganisms

derive energy and may increase in biomass

Bioemulsifier: An emulsifier produced by a microorganism

BIOFAST: Biological forced-air soil treatment for biopiles

Biofiltration: Treatment of off-gases using biological filters to remove VOCs

Biolog ® system: Measures metabolic potentials to describe bacterial communities (Biolog, Inc.)

Biopiles: Mounds of excavated contaminated soil for controlled ex situtreatment

BIOPUR ® : A patented, aerated, packed-bed, fixed-film reactor using PUR as a carrier material for

microorganisms

BioPurge SM : Technology using bioventing with a closed-loop concept to regulate soil moisture and

release of nutrients, oxygen, and microorganisms into the vadose zone

Biorecalcitrance: Resistance of a compound to biological attack

Bioreclamation: A natural or managed process involving biodegradation of environmental contaminants

Bioremediation: A natural or managed process involving biodegradation of environmental contaminants

Biorestoration: A natural or managed process involving biodegradation of environmental contaminants

BioSparge™: Technology using bioventing with a closed-loop concept to regulate soil moisture and

release of nutrients, oxygen, and microorganisms below groundwater level

Biostim: Uses “Tysul” WW H2O2 to circulate oxygen in the soil (Biosystems, Inc.)

Biotic reactions: Reactions that are biological in origin

Biotransformation: Microbial or enzymatic alteration of the molecular structure of a chemical; i.e.,

microbial metabolism

Bioventing: Process of aerating subsurface soils to stimulate in situ bioremediation using SVE systems

Bio XL: Process employing stabilized solutions of H2O2 to increase level of oxygen in soil (Aquifer

BTEX: Benzene, toluene, ethylbenzene, and xylenes

BTX: Benzene, toluene, and xylenes

C8PE9.5, C9PE10.5: Nonionic alkylphenol ethoxylate surfactants

C12-E4: Nonionic alkylethoxylate surfactant

Catox: Catalytic/thermal oxidation units for controlling VOC emissions

Cedephos FA-600: Anionic surfactant mixture of mono- and diorganophosphate esters

CEQ: Council on Environmental Quality

CERCLA: Comprehensive Environmental Response, Compensation, and Liability Act (Superfund)

CFU: Microbial colony-forming unit

CGAs: Colloidal gas aphrons (foams); e.g NaDBS

Chemoautotrophic: Derives energy from the respiration of inorganic electron donors

CO-601 carbons: Coal-based or coconut shell carbons for removal of hydrocarbons from gas streams

with the Detoxifier™

CoA: Coenzyme A

COD: Chemical oxygen demand

Commensalism: Sequential degradation of a compound by two or more microorganisms in a

relation-ship that may benefit only one partner

Cometabolism or Cooxidation: The indirect metabolism of a recalcitrant substance; the process by

which microorganisms, in the obligate presence of a growth substrate, transform a nongrowth substrate

Composting: A form of biodegradation involving mesophilic and thermophilic microorganisms

Conjugation: Reaction between a normal metabolite and a toxicant

Convective Transport: Passive transport of microorganisms through soil by transport addition of water

or aqueous nutrient feed solution

Corexit 0600: A surfactant

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