Ert Student Manual 3ppg 2012-01-09

Off ce of Solid Waste andEmergency Response(5201G)

December 2011www.epa.gov/superfund

Environmental Remediation Technologies

Superfund

United StatesEnvironmental ProtectionAgency

Student Manual

ENVIRONMENTAL REMEDIATION TECHNOLOGIES TABLE OF CONTENTS

Section 1 ................................... Successful Treatment Design

Section 2 ................................... Fate and Transport

Section 3 ................................... Capping and Containment

Section 4 ................................... Basic Water Treatment

Section 5 ................................... Chemical Reactions and Separations

Section 6 ................................... Sediment Remediation

Section 7 ................................... Bioremediation

Section 8 ................................... Monitored Natural Attenuation

Section 9 ................................... In-situ Treatments

Section 10 ................................. Soil Washing and Immobilization

Section 11 ................................. Thermal Treatment

Section 12 ................................. Phytoremediation

Section 13 ................................. Process Testing

Section 14 ................................. Technology Selection

Section 15 ................................. Exercises

Acronyms and Abbreviations

ENVIRONMENTAL REMEDIATION TECHNOLOGIES 3 DAYS

This introductory-level course provides participants with an overview of the treatment technologies most frequently used for cleanups of contaminated media. The emphasis of the course is on the technology description, applicability, and limitations of appropriate treatment technologies. It is intended for new On-Scene Coordinators, Remedial Project Managers, Waste Site Managers, and other environmental personnel interested in remediation.

Topics that are discussed include site characterization; fate and transport; technology screening; capping and containment; basic water treatment; chemical reactions and separations; in-situ treatments; sediment remediation; phytoremediation; bioremediation; soil washing and immobilization; thermal treatment; and process testing.

Training methods include lectures and group problem-solving exercises. Case studies are used to demonstrate applications of the treatment technologies. Group discussions relevant to the course are encouraged.

After completing the course, participants will be able to:

Evaluate appropriate techniques to assess, stabilize, and screen potential remedies for contaminated sites.

Identify the processes and explain the limitations of the most frequently used treatment technologies.

Identify resources that describe innovative treatment technologies.

Note: Calculators are recommended.

Continuing Education Units: 1.9

Orientation and Introduction

ENVIRONMENTAL REMEDIATION TECHNOLOGIES

presented byTetra Tech NUS, Inc.

for theU.S. Environmental Protection Agency'sEnvironmental Response Team

OSWER

U.S. EPA

Office of Solid Waste and Emergency Response (Superfund)

United States Environmental Protection Agency

Environmental Response TeamERT

Office of Superfund Remediationand Technology Innovation

OSRTI

Are offered tuition-free for environmental and response personnel from federal, state, and local agenciesVary in length from one to five daysAre conducted at EPA Training Centers the United States

1



Course Descriptions, Class Schedules, and Registration Information are available at:

www.trainex.org

www.ertpvu.org

Evaluate appropriate techniques to assess, stabilize, and screen for potential remedies for contaminated sites

Identify the processes and explain the limitations of the most frequently-used treatment technologies

Identify resources that describe innovative treatment technologies

Student Registration Card

Student Evaluation Form

Course Agenda

Student Manual

Facility InformationStudent Handouts

2



Parking

Classroom

Restrooms

Water fountains, snacks, refreshments

LunchTelephones

Emergency telephone numbers

Alarms and emergency exits

3

Environmental Remediation Technologies - REFERENCES

SUCCESSFUL TREATMENT DESIGN U.S. EPA. Guidance for Conducting Remedial Investigations and Feasibility Studies Under CERCLA. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC. October 1988.

Wong, Jimmy H. C. et al. Design of Remediation Systems. Lewis Publishers reprint of CRC Press, Inc. Boca Raton, FL. 1997.

Nyer, Evan K. et al. In Situ Treatment Technology. Lewis Publishers reprint of CRC Press, Inc. Boca Raton, FL. 1996.

Rodriguez, Rey and Rosenfeld, Paul. Successful Remediation Technologies. National Groundwater Association. Columbus, Ohio. October 2003.

Monroe, James S. and Wicander, Reed. Physical Geology, Exploring the Earth. West Publishing Company. Saint Paul, MN. 1995

Heath, Ralph C. Basic Ground-Water Hydrology. U.S. Geological Survey. Water Supply Paper 2220. U.S. GPO. Washington, DC. 1987.

Interstate Technology & Regulatory Council. Technical and Regulatory Guidance for the Triad Approach: A new Paradigm for Environmental Project Management. Interstate Technology & Regulatory Council. Sampling, Characterization, and Monitoring Team. Washington, DC. December 2003.

Dupont, R. Ryan et al. Bioremediation, Innovative Site Remediation Technology: Design and Application. American Academy of Environmental Engineers. Annapolis, MD. 1997.

FATE AND TRANSPORT OF CHEMICAL CONTAMINANTS Brady, Wyle. The Nature and Properties of Soils. 8th ed. Macmillan Publishing Co. New York, NY. 1974.

Dragun, James. The Soil Chemistry of Hazardous Materials. 2nd ed. Amherst Scientific Publishers. Amherst, MA. 1998.

Ney, Ronald. Where Did That Chemical Go? A Practical Guide to Chemical Fate and Transport in the Environment. Van Nostrand Reinhold. New York, NY. 1990. Schwarzenbach, Rene et al. Environmental Organic Chemistry. John Wiley & Sons, Inc. New York, NY. 1993.

U.S. EPA 1989. Transport and Fate of Contaminants in the Subsurface (Seminar Publication). EPA/625/4-89/019. U.S. Environmental Protection Agency. Center for Environmental Research Information. Cincinnati, OH. 1989

U.S. EPA 1990. Subsurface Contamination Reference Guide. EPA/540/2-90/011. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC. 1990.

U.S. EPA 1991a. Assessing UST Corrective Action Technology - A Scientific Evaluation of the Mobility and Degradability of Organic Contaminants in Subsurface Environments.

5

EPA/600/2-91/053. U.S. Environmental Protection Agency. Office of Research and Development. Washington, DC. 1991.

U.S. EPA 1991b. Seminar Publication - Site Characterization for Subsurface Remediation. EPA/625/4-91/026. U.S. Environmental Protection Agency. Office of Research and Development. Washington, DC. 1991.

U.S. EPA 1999. Groundwater Issue: Fundamentals of Soil Science as Applicable to Management of Hazardous Waste. EPA/540/5-98/500. U.S. Environmental Protection Agency. Office of Research and Development/Office of Solid Waste and Emergency Response. Washington, DC. 1999.

CAPPING AND CONTAINMENT U.S. EPA. Requirements for Hazardous Waste Landfill Design, Construction, and Closure. Pub. EPA/625/4-89/022. Center for Environmental Research Information. Office of R & D. U.S. Environmental Protection Agency. Cincinnati, OH. 1989

U.S. EPA. Evaluation of Subsurface Engineering Barriers at Waste Sites. Pub. EPA542-R-98-005. U.S. Environmental Protection Agency. Office of Solid Waste and Emergency Response (5102G). Washington, DC. 1998

BASIC WATER TREATMENT Kemmer, Frank N. The NALCO Water Handbook. 2nd Edition. McGraw-Hill Book Company. New York, NY. 1988.

CHEMICAL REACTIONS AND SEPARATIONS U.S. EPA. E. I. Dupont De Nemours and Company/Oberlin Filter Company Microfiltration Technology. EPA/540/A5-90/007. U.S. Environmental Protection Agency. Risk Reduction Engineering Laboratory. Cincinnati, OH. 1991.

IN-SITU TREATMENTS; NATURAL ATTENUATION, SVE, AND AIR SPARGING. National Research Council. Natural Attenuation for Groundwater Remediation. National Academy Press. Washington, DC. 2000.

ITRC. Innovative Site Remediation Technology: Technical/Regulatory Guidelines, Natural Attenuation of Chlorinated Solvents in Groundwater: Principles and Practices. Interstate Technology and Regulatory Cooperation Work Group. Washington, DC. 1999

Wong, Jimmy H. C. and et al. Design of Remediation Systems. Lewis Publishers reprint of CRC Press, Inc. Boca Raton, FL. 1997.

Nyer, Evan K. and et al. In Situ Treatment Technology. Lewis Publishers reprint of CRC Press, Inc. Boca Raton, FL. 1996.

IN-SITU TREATMENTS; PERMEABLE REACTIVE BARRIERS AND CHEMICAL OXIDATION U.S. EPA. Permeable Reactive Barrier Technologies for Contaminant Remediation. U.S. Environmental Protection Agency. Office of Solid Waste and Emergency Response. Washington, DC. 1998.

6

ITRC. Innovative Site Remediation Technology: Technical/Regulatory Guidelines, Technical and Regulatory Guidance for In Situ Chemical Oxidation of Contaminated Soil and Groundwater. Interstate Technology and Regulatory Cooperation Work Group. Washington, DC. 2001.

ITRC. Innovative Site Remediation Technology: Regulatory Guidance for Permeable Reactive Barriers Designed to Remediate Chlorinated Solvents. Interstate Technology and Regulatory Cooperation Work Group. Washington, DC. 1999. Wong, Jimmy H. C. and et al. Design of Remediation Systems. Lewis Publishers reprint of CRC Press, Inc. Boca Raton, FL. 1997.

Nyer, Evan K. et al. In Situ Treatment Technology. Lewis Publishers reprint of CRC Press, Inc. Boca Raton, FL. 1996.

BIOREMEDIATION U.S. EPA. 1992b. Engineering Bulletin: Rotating Biological Contractors. Office of Emergency and Remedial Response. U.S. Environmental Protection Agency. Washington, DC.

Wolfe, David W. Tales From the Underground: A Natural History of Subterranean Life. Perseus Publishing. Cambridge, MA. April, 2001.

Dupont, R. Ryan. Innovative Site Remediation Technology: Design and Application, Bioremediation. American Academy of Environmental Engineers. U.S. EPA. Manual, Ground-water and Leachate Treatment Systems. Office of Research and Development. U.S. Environmental Protection Agency. Washington, DC. January, 1995.

In Site Bioremediation When does it work? Committee on In Situ Bioremediation. National Academy Press. Washington, DC. 1993

Operation of Wastewater Treatment Plants. Subcommittee on Operation of Wastewater Treatment Plants. Water Pollution Control Federation. Washington, DC. 1976.

U.S. EPA. Use of Bioremediation at Superfund Sites. Office of Solid Waste and Emergency Response. U.S. Environmental Protection Agency. Washington, DC. 2001.

Norris, Robert D. et al. Handbook of Bioremediation. Lewis Publishers reprint of CRC Press, Inc. Boca Raton, FL. 1994.

PHYTOREMEDIATION Pivetz, B. E. Ground Water Issue-Phytoremediation of Contaminated Soil and Ground Water at Hazardous Waste Sites. USEPA-ORD EPA/540/S-01/500. U.S. Environmental Protection Agency. Washington, DC. 2001.

ITRC. Technical and Regulatory Guidance Document-Phytotechnology. ITRC Phytotechnologies Work Team. Interstate Technology and Regulatory Cooperation Work Group. Washington, DC. 2001.

U.S. EPA. Introduction to Phytoremediation. EPA/600/R-99/107. National Risk Management Research Laboratory. U.S. Environmental Protection Agency. Cincinnati, OH. 2000.

7

Schnoor, J. L. Phytoremediation. TE-98-01. Ground-Water Remediation Technologies Analysis Center. Pittsburgh, PA. 1997.

MONITORED NATURAL ATTENUATION National Research Council. Natural Attenuation for Groundwater Remediation. National Academy of Sciences, Washington, DC, 2001.

U.S. EPA. How to Evaluate Alternative Cleanup Technologies for Underground Storage Tank Sites a Guide for Corrective Action Reviewers. EPA 510-R-04-002. Solid Waste and Emergency Response. Washington D. C. May 2004.

SOIL WASHING AND SOLVENT EXTRACTION U.S. EPA. Engineering Bulletin: Soil Washing Treatment. EPA/540/2-90/017. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC; and Office of Research and Development. Cincinnati, OH. 1990.

U.S. EPA. Engineering Bulletin: In Situ Soil Flushing. EPA/540/2-91/021. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC; and Office of Research and Development. Cincinnati, OH.1991a.

U.S. EPA. Guide for Conducting Treatability Studies Under CERCLA: Soil Washing. (Quick Reference Fact Sheet). EPA/540/2-91/020B. U.S. Environmental Protection Agency. Office of Solid Waste and Emergency Response; and Office of Emergency and Remedial Response. Washington, DC. 199lb.

U.S. EPA. Guide for Conducting Treatability Studies Under CERCLA Solvent Extraction. (Interim Guidance). EPA/54O/2-92/016a. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC. 1992a.

U.S. EPA. Guide for Conducting Treatability Studies Under CERCLA: Solvent Extraction. (Quick Reference Fact Sheet). EPA/5401R-92/016b. U.S. Environmental Protection. Agency. Office of Solid Waste and Emergency Response; and Office of Emergency and Remedial Response. Washington, DC.1992b.

U.S. EPA. Applications Analysis Report: Resources Conservation Company B.E.S.T. Solvent Extraction Technology. EPA/540/AR-92/079. U.S. Environmental Protection Agency. Office of Research and Development. Washington, DC. 1993.

U.S. EPA. Engineering Bulletin: Solvent Extraction. EPA/540/S-94/503. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC; and Office of Research and Development. Cincinnati, OH.1994a.

U.S. EPA. Superfund Innovative Technology Evaluation: Technology Demonstration Summary: EPA RREL's Mobile Volume Reduction Unit.EPAI54O/SR-93/508. U.S. Environmental Protection Agency. Risk Reduction Engineering Laboratory. Cincinnati, OH. 1994b.

8

IMMOBILIZATION U.S. EPA. Immobilization Technology Seminar: Speaker Slide Copies and Supporting Information U.S. Environmental Protection Agency. Risk Reduction Engineering Laboratory. Cincinnati, OH. 1990

U.S. EPA. Stabilization/Solidification of CERCLA and RCRA Wastes: Physical Tests, Chemical Testing Procedures, Technology Screening and Field Activities. U.S. Environmental Protection Agency. Office of Research and Development. Washington, DC. 1989

U.S. EPA. Stabilization/Solidification of Organics and Inorganics. EPA/540/S-92/015. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response, Washington, DC; and Office of Research and Development, Cincinnati, OH. 1993

U.S. EPA. Engineering Bulletin: In-situ Vitrification Treatment. EPA/540/S-94/504. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC. 1994

THERMAL TREATMENT U.S. EPA. Engineering Bulletin: Mobile/Transportable Incineration Treatment.EPA/540/2-90/014. U.S. Environmental Protection Agency. Office of Research and Development. Risk Reduction Engineering Laboratory. Cincinnati, OH. 1990.

U.S. EPA. Superfund Engineering Issue: Issues Affecting the Applicability and Success of Remedial/Removal Incineration Projects. EPA/540/2-91/004. U.S. Environmental Protection Agency. Office of Research and Development. Office of Solid Waste and Emergency Response. Washington, DC. 1991a.

U.S. EPA. Treatment Technologies. 2nd Ed. ISBN: 0-86587-263-5. U.S. Environmental Protection Agency. Office of Solid Waste. Government Institutes, Inc. Rockville, MD. 1991b.

U.S. EPA. Engineering Bulletin: Thermal Desorption Treatment. EPA/540/S-94/501. U.S. Environmental Protection Agency. Office of Emergency and Remedial Response. Washington, DC; and Office of Research and Development. Cincinnati, Ohio. 1994.

TECHNOLOGY SELECTION Federal Remediation Technologies Roundtable. Remediation Technologies Screening Matrix and Reference Guide, Version 4.0. Web address http://www.frtr.gov/matrix2/top_page.html U.S. EPA. How to Evaluate Alternative Cleanup Technologies for Underground Storage Tank Sites. EPA 510-R-04-002. Office of Solid Waste and Emergency Response. U.S. Environmental Protection Agency. Washington, DC. 2004

U.S. EPA. Seminar Publication, Guide for Conducting Treatability Studies under CERCLA. Publication EPA/540/R-92/071a. Office of Solid Waste and Emergency Response. Office of Research and Development. U.S. Environmental Protection Agency. Washington, DC. 1992

U.S. EPA. Presumptive Remedy for CERCLA Municipal Landfill Sites. EPA 540-F-93-035. Office of Solid Waste and Emergency Response. Office of Research and Development. U.S. Environmental Protection Agency. Washington, DC. 1993

9

U.S. EPA. Presumptive Remedies: Site Characterization and Technology Selection for CERCLA Sites with Volatile Organic Compounds in Soils. EPA 540-F-93-048. Office of Solid Waste and Emergency Response. Office of Research and Development. U.S. Environmental Protection Agency. Washington, DC. 1993

U.S. EPA. Presumptive Response Strategy and Ex-Situ Treatment technologies for Contaminated Ground Water at CERCLA Sites. EPA/540/R-96/023. Office of Solid Waste and Emergency Response. Office of Research and Development. U.S. Environmental Protection Agency. Washington, DC. 1996

U.S. EPA. Presumptive Remedies for Soils, Sediments, and Sludges at Wood Treater Sites. EPA/540/R-95/128. Office of Solid Waste and Emergency Response. Office of Research and Development. U.S. Environmental Protection Agency. Washington, DC. 1995

PROCESS TESTING U.S. EPA. Innovative Site Remediation Technology-Design and Application-Thermal Desorption Volume 6. EPA 542-B-93-011. U.S. Environmental Protection Agency. Washington, DC. 1993.

Chu, C. Observations of Performance Test. WA#R1A00111, Trip Report. FCX Engineering. April 17, 2000.

WEBSITES www.epa.gov www.clu-in.org www.frtr.gov

10

Student Performance ObjectivesUpon completion of this unit, students will be able to:

1. Understand the general principles of the Triad approach

2. Describe the key components of the conceptual site model

SUCCESSFUL TREATMENT DESIGN

11

Successful Treatment Design


A successful treatment design requires a clear understanding of specific site conditions.

During many earlier environmental restoration projects, the collection of site-specific data proved to be a lengthy and expensive process.

Clear project goals are established through the use of:

Systematic Project Planning

Dynamic Work Strategies

Real-time Measurement Technologies

13



Image Courtesy of USGS

Initial investigation for the source of the oil release discovered high Concentrations of a chlorinated solvent (TCE) north of the mill building

In developing a CSM, key elements include:

General physical site description

Regional environmental setting

Land use

Contaminant information and site activities

Potential exposure pathways and risk estimation

On-going data evaluation and data gap identification

14




General physical site descriptionRegional environmental setting

Land use




Facility descriptionSite addressGeneral site operation

Physical settingArea topographyArea land use

Chem-Dyne general site operations:

Operated from 1974 to 1980 on a 10-acre site

Stored, recycled, and disposed of many types of industrial chemical wastes

Thousands of 55-gallon drums

15



Facility descriptionSite addressGeneral site operation

Physical settingArea topographyArea land use

Site

Site is bounded to the south by residential property

16



Site is bounded to the north by the Ford Hydraulic Canal and, further north, by agricultural fields



Regional environmental settingLand use




Geology

Site is located on the Great Miami River alluvial deposits glacial outwash materials consisting of poorly sorted, poorly bedded silt and sand.

Depth of Ordovician limestone bedrock is greater than 100 feet below the surface.

17



Hydrogeology

Site is located on permeable sand and gravel deposits in ancestral drainage channels

Deep aquifer groundwater wells yield 5001000 gpm

Site includes a shallow unconfined aquifer and a deep confined aquifer

Site

Site

18



Ecological ProfileDescribes the physical relationship of the organisms on the developed and undeveloped portion of the site and adjacent off-site properties




Land useContaminant information and site activities



Land use descriptionsLand use historyCurrent land use

The Triad approach works toward a viable end use of the land. Current use and proposed use are important.

Example Chem-Dyne site:Currently a remediation project operated by the Chem-Dyne TrustNo future use has been proposed at this time

19



Federal, state, and local operating permitsReported releases or spillsFacility RecordsPublic Records

Title historyCity directoriesAerial photographsSanborn Fire Insurance MapsLocal agencies

Public records (title history & city directories):1910 to 1960s Ford Motor Co. 1960s to 1974 Nimrod Camping Trailer 1974 to 1980 Chem-Dyne Recycling Facility1980 to present Chem-Dyne Trust

(remediation project)

Chem-DyneHamilton, OH

Aerial photoDecember, 1979

20



Sanborn Fire Insurance maps:1927 Ford Motor Co. forge and

manufacturing facility1950 Ford Motor Co. metal

stamping and wheel manufacturing facility

1969 Ward Manufacturing (Nimrod Camping Trailer Division)

Local agency reports (ChemDyne):

Hamilton Fire Department reported numerous fire responses. Firemen became ill and fire hoses dissolved in standing puddles. Reports led to a health department and Ohio EPA investigation. Site operations were suspended in 1980.

In developing a CSM, key elements include:General physical site description


Land use

Contaminant information and site activitiesPotential exposure pathways and risk estimation


21



This component of the CSM includes the following information:

Previous site activitiesContaminants of concernPotential contaminant source areasContaminant fate and transportContaminant susceptibility to treatment options


Previous site activitiesContaminants of concern

Potential contaminant source areas

Contaminant fate and transport

Contaminant susceptibility to treatment options

Removal Action

Stabilization

22



General rule at many sites:80% of the contamination removed during immediate remedial action often is completed for 20% of the total project cost

Chem-Dyne:Removal of drums and standing liquidExcavation of grossly contaminated soil


Previous site activities

Contaminants of concernPotential contaminant source areas



23



Identification from recordsLocal Emergency Planning CommitteeRCRA listingOperator knowledge

Identification by sample analysisField screeningTarget Compound List (TCL) and Target Analyte List (TAL) analysisRegulatory agency-specific list

At the Chem-dyne site, many TCL and TAL hazardous materials were detected, including:

Volatile organic compounds (VOC)Semi-volatile organic compoundsPCBsTAL (metals)



Contaminants of concern

Potential contaminant source areasContaminant fate and transport


24



Areas where hazardous material is stored, used, or disposed, such as:

Drum padsAST & USTsWaste storage & Disposal areas

Hazardous material usage areas:Paint boothsPlating operationsTreating operationsPipe runs





Contaminant fate and transportContaminant susceptibility to treatment options

25



Relates how a contaminant reacts or travels through the environment to a receptorBased on the Contaminant characteristics:

VolatilitySolubility

Characteristics of the medium, using soil as an example, could include:

PermeabilityOrganic carbon contentGrain size distribution







Contaminants detected at the Chem-Dyne site included:

Volatile organic compoundsSemi-volatile organic compoundsPCBsTAL (metals)

26





Land use


Potential exposure pathways and risk estimationOn-going data evaluation and data gap identification

Groundwater (Chem-Dyne site)

Source Onsite hazardous materials

Fate-and-transport mechanism

Through soil into shallow and deep Great Miami River Aquifers

Exposure route Ingestion and/or dermal contact

Receptors Residents using deep-aquifer groundwater

27



Surface Water (Chem-Dyne site)

Source Onsite hazardous materials


Surface water runoff during heavy rains

Exposure route Direct contact (e.g. burned feet)

Receptors Employees of adjacent business

Emissions (Chem-Dyne site)

Source Hazardous materials released by onsite activities


Fugitive dust released into the air, migrating off site

Exposure route Inhalation

Receptors Neighbors

EmissionsExposure pathway: contaminated fugitive dust migrated offsite to neighboring habitats

28



Ensures that the selected remedial activities will protect human health and the environment.

Examples:Risk Based Corrective Action (RBCA)Brownfield ProgramSite Specific Risk Assessment



Land use




As the CSM develops, data gaps may be identified and specific site information may need to be collected, such as:

Soil CharacteristicsHydrogeologic & geologic informationSurface water & sediment informationAdditional information

29



MeteorologicalAnnual rainfallAverage temperatureEvapotransporation

Offsite informationNearby populationOffsite land useZoning issues

Chem-Dyne Superfund Sitevs.

Pristine, Inc. Superfund Site

30



Remediation of Chem-Dyne included:Excavation of top 10 ft. of soil

Deeper contaminated soil remainedGroundwater pump-and-treat system through 25 wellsTreated groundwater through air stripperTreated air stripper emissions through granular activated carbon

Remediation of Chem-Dyne included:Re-circulated half of the treated water into unsaturated zone to further leach remaining soil contaminationDischarged remaining half of the treated water Constructed impermeable cap to prevent surface water infiltration

Cost$11.6 million constructionApprox $18 million operation and maintenance (20 years)

31



0

10000

20000

30000

40000

1988 90 92 94 96 98 2000

Year

Tota

l VO

Cs R

ecov

ered

Very similar to Chem-Dyne site:Urban industrial waste recycling facility located in Reading, Ohio

Operated from 1974 to 1981

Stored, treated, and incinerated hazardous wastes: 10,000 drums & gallons of waste onsite

Similar geology and hydrogeology

32



Excavation of all visibly contaminated soil to 4 bgs

Onsite thermal desorption of contaminated soil

SVE Treatment of unsaturated zone

Groundwater pump-and-treat system w/ GAC & air stripping

Cost$13.5 million construction

$6 million operation & maintenance (20 years)

On-track to reach cleanup goals

Triad approach supports the project goal of a successful treatment design by combining:

Site-specific informationContaminant-specific informationTreatment options

33

FATE AND TRANSPORTOF CONTAMINANTS

Student Performance ObjectivesUpon completion of this module you will be able to:

1. Describe how chemicals travel through environmental media,

such as rock or soil, air, and water.

2. Describe how chemicals can become associated with (stored

by) various environmental media.

3. Describe chemical parameters which model (predict) the

distribution of contaminants among media.

4. Describe environmental conditions which promote or retard

the movement of chemicals in the subsurface.

5. Describe factors that affect organic chemical degradation.

35

Fate and Transport of Chemical Contaminants


Pour one cup of TCE onto the ground, and it will cost you $1 million to get it out.

WHY?

1 CUPTCE

$1 MILLION

+ =

Why would it cost so much?

Contaminant behavior is a function of the properties of both the contaminant and the environmental media.

Contaminant

Soil Air

Water

37



Degradation

Volatilization PercolationRunoff

RetardationAdsorption

DispersionDiffusion

Surface Water

Vadose zone

Degradation

Adsorption

Diffusion

Retardation

Dispersion

Groundwater

SolubilityCapillary forces

SurfaceSubsurfaceDistributionDegradation

Physical stateVolatilizationRunoffSolubilityPercolation

38



Solid Liquid

Leastmobile

Mostmobile

Organic vs. InorganicTransition temperatures, e.g., melting point, boiling point

Gas

PHASE DIAGRAM

0C 20C 100C

Pressure(mm Hg)

Temperature

17.5

760

H2OSolid Liquid

A B

C

(Not to scale)

327 to 1620

-100-200C 0 100 200 30020

0 to 100

5.5 to 80.1

87 to 87

86 to 80

39.9 to 357

188 to 310 (decomposes @ 310)

189.9 to 42

H2O

Benzene

MEK

TCE

Propane

PCP

Hg

Pb

LIQUID TEMPERATURE RANGE

39



Function of: Molecular weight"Cohesive forces"

Van der Waals forcesPolarity

Temperature

Vapor Pressure (VP): Pressure exerted above a compound in liquid or solid phase

Compound VP (mmHg @ 20c)

Benzene 80.0TCE 63.0H2O 17.5PCP .00011

MORE VOLATILE

LESS VOLATILE

Function of: Hydraulic gradient"Cohesive forces" (e.g., internal friction)

40



Dynamic viscosity (): Indicates degree of resistance to flow

Compound (centipoise @ 20c)

TCE .57Benzene .65H2O 1.0Kerosene 2.5Phenol 8.5

MOST MOBILE

LEAST MOBILE

Function of: Cohesive forcesAdhesive forces

Van der WaalsPolarityIonization

OHH +

+

Met

al s

olub

ility

(mob

ility

)

7pH (s.u.)

Pb(OH)+1Pb(OH)2

Fe(OH)3

Fe(OH)+2

Al(OH)3Al(OH)+2

Al(OH)41

41



Function of:Fluid height or "head"Fluid densityCohesive forces ("surface tension")Adhesive forces ("wetting")

h

Compound (centistokes @ 20c)TCE .39Benzene .74H2O 1.0

MOST MOBILE

LEAST MOBILE

Kinematic viscosity (): Indicates degree of resistance to downward flow (combines density with dynamic viscosity)

Function of:Preferential pathways (channeling)

MacroporesMicropores

SolubilitySorptionVolatility

42



Physical movement stops when matric potential and hydrodynamic head are balancedMolecular movement continues as long as relative concentration remains "unbalanced"

Solubility

Organic carbon

NAPL

Pore water

Ped or particle

Pore air

Diffusion Process whereby molecules move from a region of higher concentration to a region of lower concentration as a result of Brownian motion.

43



Contaminant movement

Soil particles

Dispersion Tendency for a solute to spread from the path that it would be expected to follow under advective transport

Dispersion and Diffusion

Contaminant movement

Soil particles

PercolationThrough

Saturated Zone

DNAPL

DissolvedcontaminantGroundwaterflow

H2O

LNAPL

Soil

44



Air

Water

Water/Air

Water/soil

Vapor pressure (VP)

Solubility (Sol.)

Henry's Law (HL)

Sorption (KOC, CEC)

Compound VP (mmHg) Sol.(mg/L) HL

HL = VP Solubility

atm-m3mol

VC 2,300 1,100 6.9 10-1

Benzene 76 1,780 5.4 10-3

TCE 58 1,100 8.9 10-3

MEK 71.2 268,000 2.7 10-5

PCP 0 00011 1 2 8 10 6

Function of:ContaminantFraction of organic carbon in medium (fOC)Properties of soil, e.g., structure, texture (KOC)

The degree of attraction between a non-polar chemical and the natural organic matter associated with an aquifer (retardation)

45



Function of: Soil texture (e.g., clay, silt, sand)Soil surface area (clay type, e.g., kaolinite)Organic matter content

Total cations adsorbed on a unit mass of soil (centimoles/kg)

Break down chemically (organics only)Examples of degradation processes:

Hydrolysis

Redox

Biodegradation

Function of:pHBond strengths of contaminantProperties of attacking agentRedox potential"Hospitable" environment (biodegradation)

46



chloride

carbon tetrachloride

PCE

1.0

0.5

0

200 400

Rel

ativ

e co

ncen

trat

ion

in M

W1

dow

ngra

dien

t of s

ourc

e

Time (days)0

GW flow

Source MW1

GWflow

What are you going to do?

Problem: Saturated soil contaminated with TCE (enough to contaminate groundwater to solubility limit for 15 years)

Problem: Chrome plating bath solutions have been disposed into unlined lagoon (now dry).Most of chromium has been adsorbed by underlying clay soils.Groundwater contamination was not detected.

What are you going to do?

47

CAPPING AND CONTAINMENT


1. State the application, limitations, working mechanisms, advantages

and disadvantages of the following capping technologies:

a. Clay caps

b. Resource Conservation and Recovery Act (RCRA) multi-stage

caps

2. State the application, limitations, working mechanisms, advantages

and disadvantages of the following groundwater containment

technologies:

a. Slurry trench cutoff walls

b. Grout curtain walls

49

Capping and Containment


Capping controls airborne contamination and surface water infiltrationContainment controls groundwater movement

ApplicationsSlows the movement of airborne or dustborne contaminants

Slows the movement of surface water into the ground

LimitationDoes not directly remediate contaminants

Makes soil recovery and further treatment difficult

51



Capping materials may include natural or synthetic materials.

24" Clay

6" Gas-venting layer/soil cushion

6" Topsoil with vegetative cover

30 mil PVC Liner

Waste Material

Cap

Cap

5' Recompacted Clay

24" Pea Gravel60 mil PVC Liner

Ground

80 mil PVC Liner

Leachate Collection System

Atlanta, GA Hickory Ridge Landfill

52



Gas collection and process system

Phoenix Golf Course

California Gulch Superfund SiteCourtesy US EPA Region 8

53



Explore alternative and more aesthetically-pleasing ways to cover mine waste piles with materials that will help preserve the historic appearance of the mining landscape

Water management strategyDivert clean waterEnhance/ enlarge collection system for acid rock drainageGradually eliminate Leadville Mine Drainage Tunnel use, with exception of emergency

54



Alternative 1 Natural Face with Partial Cap (preserve areas visible from Mineral Belt Trail/roads)

Alternative 2 Shotcrete with No Liner on Slope

Alternative 2A Shotcrete with Liner on Slope

Alternative 3 Inert Mine Waste Rock with Liner

Alternative 4 Inert Mine Waste Rock with Cribbing

Before capping After capping


55



After capping



56



Virtual Forum Web Address: www.merid.org/leadville

EPA Web Address: www.epa.gov/region8/superfund/co

57



Bioreactor landfills are designed and operated by increasing the moisture content of the waste to enhance degradation and stabilization

Primary advantagesEfficient utilization of permitted landfill capacityStabilization of waste in a shorter timeReduced leachate handling costReduced post closure care

Secondary AdvantagesPotential for landfill gas can be a revenue streamPromotes more sustainable waste management Reduced air emissions containing VOC and hazardous air pollutants May possibly reduce long term costsReduced toxicity of leachate and waste materialConsistency with sustainable landfill design

58



Primary Disadvantages and Challenges Slope stabilityHigher capital costsOperator skillsTemperature control in aerobic bioreactorsConfusion over regulations to permit bioreactorsLiner chemical compatibilityOdor controlDesign & construction of liquid handling systemsWaste heterogeneity

Subsurface walls to control groundwater movement

Slurry trench cutoff wall

Grout curtain

Sheet piling

ApplicationsSlows movement of groundwater-borne contaminants using subsurface walls

Can be used to dewater a site for remediation

LimitationsDoes not directly remediate contaminants

59



Production well

Monitoring well

Aquitard

Groundwater flow

Keyed slurry trench cutoff wall

60



Production well

Monitoring well

Aquitard

Groundwater flow

LNAPLs

Recovery well

Hanging slurry trench cutoff wall

WallSoil

Drain

Stream

Waste

Groundwater flow

Stream

Extraction well

Groundwater flow

WallSoil

Waste

61



Soil

Injection tube

Grout curtain

Contaminant plume

Groundwater flow

62



Zone of influenceInjection tube

Z-typeStraight web type

Deep arch web type

T-fitting

63


ENVIRONMENTAL REMEDIATION TECHNOLOGIES 64


1. State the advantages and disadvantages of basic water treatment

systems.

2. State the working mechanisms of the following basic water

treatment subsystems and/or components.

- Oil/water separators

- Iron removal systems

- Filters

- Clarifiers

- Air strippers

- Scale control systems

- Carbon adsorption units

BASIC WATER TREATMENT

65

Basic Water Treatment


Treats most contaminantsHighly flexible and reliable

Could be very expensiveEnergy- and labor-intensiveRegulatory problems with dischargeFine-grained material a problem

67



Oil / Water Separator

Reactor Tank

Sand Filter

Reactor Tank

Air Stripper

Carbon Contactor

pH Control

Courtesy State of Washington, Department of Ecology

Water

68



Water

Oil

Sludge

69



Courtesy State of Washington, Department of Ecology

71



Physically separates volatile or semi-volatile contaminants, usually organics, from waterProcess applies to volatile and semi-volatile organics with a Henry's Law Constant of >0.003 atm/mol/m3

Storage tank

Off-gas treatment

Air blower

Effluent treatment

Packing Saddles Packing Rings

Snowflakes

72



aBsorption aDsorption

75


1. State the advantages and disadvantages and describe the working

mechanisms of the following chemical reaction systems:

- Neutralization systems

- Precipitation systems

- Reduction and oxidation systems

2. State the advantages and disadvantages and describe the working

mechanisms of the following separation systems:

- Microfiltration systems

- Reverse osmosis systems

- Ion exchange systems

CHEMICAL REACTIONSAND SEPARATIONS

77

Chemical Reactions and Separations


NeutralizationPrecipitationReductionOxidation

AdvantageEliminates corrosives

DisadvantagesProcess chemicals are hazardous

Generates a lot of heat

Heavy-duty process equipment may be needed

79



AdvantagesRemoves dissolved heavy metals

DisadvantagesProduces metal sludge

Often produces high pH wastewater

Doesn't always work on highly soluble metals

80



Chemicalprecipitants

Liquidfeed

Mixing tank

Chemicalflocculants/settling aids

FlocculationpaddlesFlocculation

well

Flocculationclarifier

Sludge

Baffle

Effluent

Source: U.S. EPA 1991

81



Chemical reactionsAdvantages

Reduces solubility of heavy metals

Oxidizes and destroys organics

DisadvantagesUnintended reactions

Acid feed

pH control Mixer

Reducing agent feed Limeslurry hopper

Effluent

Hydroxide sludgeChrome

precipitation

Chrome reduction tank

Chrome wastewaterfeed

SOX

Cr6+

Ca(OH)2

H+

Cr3+Cr3++OH- Cr(OH)3

82



UV lamps

Influent

EffluentO3

H2O2

MicrofiltrationReverse osmosisIon exchange

83



SeparationProcess

Relative Size of

Common Materials

Microns 0.001 0.01 0.1 1.0 10 100 1000

ReverseOsmosis

Microfiltration

Ultrafiltration

Nanofiltration

Particle Filtration

AqueousSalt

Endotoxin Pyrogen

Metal Ion

Oil Emulsion

Lactose

Sediment

Red Blood Cells

Virus Bacteria

ColloidalSilica Cryptosporidium

Dredge, Fox River, WI

84



Microfiltration is a process which removes contaminants from a fluid by passing though a microporous membrane.

Typical microfiltrations membrane pore size range is 1 to 10 micrometers.

AdvantageRemoves very small particles

DisadvantagesDoes not remove dissolved contaminants

85



Source: U.S. EPA 1991

Filtraterecirculation

Lime slurry tankProFix slurry tank

TyvekUsed Tyvek

GroundwaterTo disposal

Air

Staticmixer

Filter cake

Filter cakestorage

Microfiltrationunit

Microfiltration Treatment System



86



Pressure

Contaminated water

Treatedwater

Concentratedwastewater

87



Sludge

FiltersReverse osmosis unitFeed

tank

Storagetank Clarifier

NaOHcausticsoda

HCI

88



Removes dissolved metals via transfer of ionsUses resin beads

Removes low concentrations of soluble metalRecovers concentrated metal streams for recycling

89



Suspended solids and organicsRegeneration chemicals are hazardous

Acid regenerant

Caustic regenerant

Removal:OH [An(s)] + XX [An(s)] + OH

Regeneration:X [An(s)] + OHOH [An(s)] + X

Removal:H+ [Cat(s)] + M+M+ [Cat(s)] + H+

Regeneration:M+ [Cat(s)] + H+H+ [Cat(s)] + M+

Waste containing MX

Deionized effluent

Spent regenerant

Anion exchanger

Cation exchanger

90

SEDIMENT REMEDIATION

Student Performance Objectives

1. Defi ne Sediments2. List common sediment remedy options3. List the advantages and disadvantages for the three common sediment remedy options

91

Sediment Remediation


Define SedimentsList common sediment remedy optionsList the advantages and disadvantages for the three common sediment remedy options

Source: USEPA 1999

Sediments - The organic and inorganic materials found at the bottom of a water body. Clay, silt, sand, gravel, decaying organic matter, shells & debris.The most common sediment contaminants:

PesticidesPCBsPAHsDissolved phase chlorinated hydrocarbons (to a lesser extent)

Source: USEPA 1999

93



Pipeline or outfall dischargesChemical spills Surface runoff: waste dumps, chemical storage, mines, agricultural or urban areas Air emissions: Power plants, incinerators, pesticide applicationsUpwelling of contaminated ground waterShips, ship maintenance & in-water structures

Source: USEPA 1999

Health impacts from eating fish/shellfish and recreationEcological impacts on wildlife and aquatic speciesLoss of recreational & subsistence fishingLoss of recreational swimming and boatingLoss of traditional cultural practices by Indian tribes, etc.

Economic effects of loss of fisheriesEconomic effects on development and property valuesEconomic effects on tourismIncreased costs of drinking water treatmentLoss or increased cost of commercial navigation

94



Source: Adapted from EPA Region 5, Sheboygan Harbor and River Site

Sediment grab samplers: Surface sediment chemistryCoring devicesWater column probes: pH and DOSurface water samplers: Dissolved and particulate chemical concentrationsSemi-permeable membrane devices: Dissolved contaminants at the sediment-water interface

Benthic analysis: Population and diversityToxicity testing: Acute and long-term lethal effects on organismsTissue sampling: Bioaccumulation, modeling trophic transfer potential, and estimating food web effects Caged fish/invertebrate studies: Change in uptake of contaminants by biota

95



Monitored natural recoveryIn situ cappingDredging & Excavation (most common)

Allows natural processes to contain, destroy, or otherwise reduce the bioavailability or toxicity of the contaminant in the sediment.

This remedy should include site specific cleanup levels, remedial action objectives, and monitoring to assess whether risk is being reduced as planned.

Physical processes Sedimentation, advection, diffusion, dilution, dispersion, bioturbation, volatilization

Biological processesBiodegradation, biotransformation, phytoremediation, biological stabilization

Chemical processesOxidation/reduction, sorption, or other processes resulting in stabilization or reduced bioavailability

96



Human exposure is low (most important)Sediment bed is stable, cohesive, well-armoredContaminant concentrations decreasing on their own Contaminants are readily biodegradable or transform to lower toxicity forms Concentrations are low and cover diffuse areaContaminants have low ability to bioaccumulate

Long-term decreasing trend of contaminant concentrations in:

Higher trophic level biota (piscivorous fish) Water column (during low flow)Sediment core contaminant levelsSurface sediment

97



AdvantagesRelatively low implementation costsNon-invasive

LimitationsLeaves contaminants in placeSlower to reduce risks than active technologiesOften relies on institutional controls such as fish consumption advisories

Monitored natural recoveryIn situ cappingDredging & Excavation

In-situ capping is the placement of a subaqueous covering or cap of clean material over contaminated sediment.

In-situ capping is the placement of a subaqueous covering or cap of clean material over contaminated sediment.

98



Caps reduce risks by:

Physical isolation: Reduce exposure & bioturbation

Stabilization: Contaminant & erosion protection to reduce re-suspension

Chemical isolation:Prevent dissolved and bound contaminants from transporting into water column

Physical:Population density of organismsSand cap consolidation through compression

Stabilization: Potential erosion from bed shear stresses due to river, tidal, and wave-induced currents, turbulence generated by ships/vessels, etc.

ChemicalGas generation due to anaerobic degradation from organic content, can generate uplift forces on the cap (especially w/ less permeable cap material)

99



Upland sand-rich soils (preferred)Engineered clayReactive/adsorptive materials: activated carbon, apatite, coke, organoclay, zero-valent iron and zeolite Geotextiles: reduce mixing and displacement of cap materialImpervious materials: geomembranes, clay, concrete, steel, or plastic

Source: USEPA 1998d

Source: Modified from U.S. EPA 1998d

100



Advantages Quickly reduce exposureLess infrastructure for material handling, dewatering, treatment & disposalLess expensive than dredging or excavationQuick to implement

LimitationsRisk of re-exposure if cap is disturbed Cap materials may not promote native habitat

Monitored natural recoveryIn situ cappingDredging & Excavation

Dredging: Removal of contaminated sediment while it is submerged

Excavation: Removal of contaminated sediment after dewatering

Most often used treatment method at Superfund sites

Both include transport, treatment and disposal of impacted sediment and water

101



Suitable disposal site is nearby Suitable area for staging and handlingNavigational dredging is planned Water depth is adequateRisk reduction outweighs disturbanceContaminated sediment overlies clean sedimentContaminants cover discrete areas

Mechanical Dredging Clamshell: Wire supportedEnclosed bucket: Wire supported, watertightArticulated mechanical: Backhoe designs

Hydraulic DredgingCutterhead: pipeline dredge w/ cutterheadHorizontal auger: pipeline dredge with augerPlain suction: pipeline dredge w/ suctionPneumatic: Air operated submersible pump

Source: A = Cable Arm, Corp. B = Barbara Bergen, USEPA)

102



Source: A = Jim Hahnenberg USEPA: B = Ernie Watkins USEPA: C = Ellicott Corporation

Air or Gas Residue

Treatment

TreatmentPretreatmentStagingTransportSediment Removal

DebrisRemoval

Water Effluent Treatment

and/or Disposal

Disposal and/or Reuse

Disposal and/or Reuse

Solids

Solids

ContaminatedSolids

Contaminated Solids

103



Sheet piling & CofferdamsEarthen dams Geotubes, inflatable dams Rerouting the water body using temporary dams or pipesPermanent relocation of the water body

Example of excavation following isolation using sheet piling

Source: Pine River/Velsicol, EPA Region 5

Advantages Contaminant removal poses less risk uncertaintyLess limitation for water body uses

LimitationsComplex and costlyUncertainty of residual contamination Contaminant losses through re-suspension and volatilizationTemporary destruction of aquatic community

104



Fox River, WI

5 Operable Units (OU) due to large area of PCB contamination

PCB in Sediment includes 39 miles of river and 2700 square miles of Green Bay PCBs from a large number of papermills along the river producing and recycling carbonless copy paper (9 PRPs)PCBs released directly into the river or after municipal treatment plantFish consumption advisories have been in effect since 1976

105



Dredging and off-site disposal7-inch thick engineered cap of sand and armor stone3 to 6-inch sand cover where PCBs



Fox River MapBlue = Capping Areas

Capped 415 acres

Fox River MapYellow/Brown = Sand Cover Areas

Approximately 495 acres sand capped

Capping Slope Diagram

7-inch thick sand and armor stone3-6 inch sand cover where PCBs < 2 ppm

107



Cutterhead Dredge & Piping

Piping Suction Pump & Diesel Engine

Extended Ladder Cutterhead Dredge & Barge

108



Pipe flow to vibrating Screen of gravel and debris > 1/8 inchFurther hydrocyclone for fine grain sand removalThickening tanks using polymer addition for uniform flow & weir for water removalMembrane sediment cake press Conveyor to Transport off-site

Geotube Dewatering

Treated Sediment is Transported to landfill or TSCA landfill

Sand Filtration: fine vs. course sandBag FiltrationGAC FiltrationDiffuser to discharge treated water back to Fox River at ambient flow conditions to avoid disruption

109



EPA. 1998d. Assessment and Remediation of Contaminated Sediments (ARCS) Program Guidance for In-Situ Subaqueous Capping of Contaminated Sediments. Prepared for the U.S. Environmental Protection Agency, Great Lakes National Program Office, Chicago, Illinois. EPA 905/B-96/004. Available on the Internet at http://www.epa.gov/glnpo/sediment/iscmain.

USEPA. 1999. Introduction to Contaminated Sediments. EPA 823-F-99-006, Office of Science and Technology

USEPA. 2005. Contaminated Sediment Remediation Guidance for Hazardous Waste Sites, EPA-540-R-05-012. Office of Superfund Remediation and Technology Innovation

110


1. Discuss site considerations needed for the use of bioremediation

methods.

2. Discuss intrinsic and engineered bioremediation treatment methods

3. Discuss in-situ and ex-situ bioremediation treatment systems.

BIOREMEDIATION

111

Principles of Bioremediation


Define bioremediation Describe a basic oxidation-reduction reactionList the different microbial metabolic processesList the basic ways that microbes demobilize contaminantsList three indicators of microbial activityList factors that may complicate bioremediation

The treatment or remediation of contaminated soils, sediments, and groundwater through microbial metabolism.

112



Bioremediation

Ex-Situ

Natural AttenuationEngineered

Bio-stimulation Bio-augmentation

Addition of Oxygen, Nutrients & BacteriaAddition of oxygen-Bio venting

-Bio-sparging Addition of Oxygen & nutrients

In-Situ

Microbial metabolism is the basis of bioremediationIt is the transformation of organic and inorganic compounds by microscopic organisms

The biochemical transformation that occur in living organisms How cells derive energy and basic elements for reproduction Energy and essential elements are derived through oxidation-reduction processes

113



The breaking of chemical bonds and transferring electrons from electron donors to electron acceptors.

The organic contaminant often serves as the electron donor, yielding electrons (being oxidized) to microbial compounds (being reduced) to stimulate cell growth and reproduction.

The three modes of metabolism are:RespirationFermentationPhotosynthesis

114



Respiration process is either aerobic or anaerobicAerobic respiration uses oxygen as an electron acceptorAnaerobic respiration uses a chemical other than oxygen as an electron acceptor such as nitrate, iron, sulfate, and carbon dioxide

An organic compound is used as both electron donor and electron acceptor, converting the compound to fermentation products such as alcohols, organic acids, hydrogen, and carbon dioxide.

The metabolic process where plants convert radiant energy into chemical energy, most often stored initially in glucose.

115



The key microorganism involved in bioremediation of organic and inorganic compounds is bacteria. Other microorganisms that may be involved in bioremediation are protozoans, fungi, and algae.

BacteriaSingle-celled organismsMetabolize soluble foodReproduce by binary fissionCellular composition:

70 90% water10 30% dry mass

92% of dry mass composed of carbon, oxygen, nitrogen, and hydrogen

C5H7O2N

C5H7O2NC5H7O2N

116



Favorable physical and chemical conditions are necessary for optimum bacteria metabolism.

Physical conditions include:pHTemperaturePhysical structure for support

GROWTHAND

REPRODUCTION

NUTRIENTS

WATERCO2

Chemical requirements include:ENERGY SOURCE

CARBONSOURCECARBONHYDROGENS

ParentCell

DaughterCell

DaughterCell

117



Energy SourceChemical compounds (organic or inorganic)Sunlight and Substrates

Carbon SourceOrganic CompoundsCO2

NutrientsNitrogenPhosphorusTrace Nutrients (sulfur, potassium, and iron)

Organic and inorganic carbonOrganic compounds and CO2

Ammonia (NH3), nitrate (NO3-), or nitrogen gas (N2)Various sources of phosphates (PO43-)Trace nutrients

Amino acids, sulfate, potassium, magnesium, and iron

Aerobic respirationAnaerobic respirationFermentationSecondary utilization and co-metabolismReductive dehalogenationInorganic compounds as electron donors

118



C7H8 +9O2 7CO2 + 4H2O

Cell Growth and ReproductionAcceptorDonor

EnzymesBiological catalystsAre not altered by the reactionReaction specific

C7H8 +9O2 7CO2 + 4H2OENZYME

Anaerobic RespirationInorganic chemicals are used as electron acceptors

Nitrate (NO3-), sulfate (SO42-)Metals (Fe3+, Mn4+)C02

Byproducts = nitrogen gas, hydrogen sulfide, reduced forms of metals, and methane

119



C7H8 + Nitrate (NO3-) CO2 + N2

Benzylsuccinic acid

Benzoyl Coenzyme-A

Can play an important role in an anaerobic environmentOrganic contaminant serves as both electron donor and acceptorByproducts can be biodegraded by other species of microbes

Non-beneficial biotransformationThe microorganism transforms the contaminant but does not benefit from the reaction

120



Replacement of a halogen atom with an hydrogen atom.Electron donors include hydrogen and low-molecular weight compounds.

Ammonium (NH4+ ), nitrite (NO2-), reduced iron (Fe2+), reduced manganese (Mn2+), and H2SOxygen is usually the electron acceptorCarbon is most commonly taken from atmospheric CO2 (Carbon Fixation)

Water chemistry changesDecrease in parent compound, electron acceptorIncrease in byproducts Presence of specific metabolic products

C7H8 + 9O2 7CO2 + 4H2O

121



Changes in native microbial communitiesGrowth of predators

Unavailability of the contaminant to the microbesToxicity of contaminant to microbesMultiple contaminants and natural organic chemicals

Incomplete degradation of contaminantsInability to remove contaminants to low concentrationsAquifer clogging

122



Aqueous ex-situ treatment systemsTrickling filtersAerated lagoonRotating Biological ContactorAnaerobic digester

Solid ex-situ treatment systemIn-situ treatment systems

Trickling Filters

123



Aerated Lagoon

Rotating Biological Contactor

Rotating Biological Contactor

124



Anaerobic Digester

Contaminated soil

Water

Slurry

Nutrients

Mixer Bioreactor Centrifuge Water

Clean soil

Emission control

Vapor treatment

Vadose zoneGroundwater

Extraction wells Extraction wells

AirInjectionwell

125



Microbes

Pre-treatment

Nutrients Oxygen

126

Student Performance ObjectivesUpon completion of this unit, students will be able to:

1. Define monitored natural attenuation

2. Understand monitored natural attenuation processes

3. Review case studies that show monitored natural

attenuation processes

4. Understand two screening criteria for monitored natural

attenuation applicability

MONITORED NATURAL ATTENUATION

127

Monitored Natural Attenuation


Define monitored natural attenuationUnderstand monitored natural attenuation processesReview case studies that show monitored natural attenuation processesUnderstand two screening criteria for monitored natural attenuation applicability

Monitored natural attenuation (MNA) is the reliance on natural attenuation processes to achieve a site-specific remediation objective within a time frame that is reasonable compared to other more active methods (EPA,1999).

129



MNA is often used in conjunction with or as a follow-up process to another active remedial activity.

AdvantagesAn in-situ treatmentMay be a lower cost alternativeMay be effective as a final process to treat residual contaminants

DisadvantagesMay not be accepted by the regulatory

agency or publicMay not treat contaminant within a reasonable timeMay not treat desired contaminantsRequires detailed site characterization

and continued monitoring

130



The MNA natural processes are biological, chemical, and physical reactions.Under favorable conditions, these processes either transform contamination to less harmful forms or immobilize contaminants to reduce risks.

Examples of natural processes include:

Biodegradation by subsurface microbes

Naturally occurring chemical reactions

Physical sorption to subsurface media

Natural dilution of contaminants*

Physical volatilization of contaminants from the subsurface to the atmosphere*

* Not acceptable processes

Concerns MNA is site and contaminant specific. The success of MNA depends on many natural environmental conditions which will change as MNA proceeds.

131



Water table

For example, biodegradation will continue as long as an adequate supply of electron acceptors is available.

Aerobic respiration

DenitrificationIron (III) reduction Sulfate

reduction

Residual NAPL

Methanogenesis

Plume of dissolved fuel hydrocarbons

Groundwater flow

The following case studies show examples of successful and common failures of MNA projects.

South Glen Falls, NY

Natural attenuation of a chlorinate solvent

St. Joseph, Michigan

No natural attenuation of a chlorinate solvent

Edwards Air Force Base

Vandenberg Air Force Base BTEX and MTBE release

Hudson River Sediment Incomplete natural attenuation of PCBs

Pinal Creek, Arizona Natural attenuation of inorganic compounds

Natural attenuation of PAHs following source removal

132



This case study shows the value of source removal. In the 1960s, coal tar generated from an old manufactured gas plant was excavated and reburied in a sand sediment.During the 30 years the coal tar was left in place, an 200-foot by 1000-foot contaminated plume developed.

The contaminated plume consisted of PAHs including naphthalene from 0.01 ppm to >2 ppm. In 1991, the coal tar-contaminated soil was re-excavated, properly disposed, backfilled with clean native soil.Within 4 years of source removal, much of the plume was below detectable levels.

Evidence that biodegradation was the primary attenuation process that removed much of the contamination are:

Depletion of oxygen at the center of the plume where the concentrations were the highestRapid growth of the microbial population that consumed the contamination

133



Additional data that suggests natural biodegradation reduced the contamination once the source was removed:

Increase of the protozoan population (predator of bacteria) inside the plumeDetection of a unique transient intermediary metabolite showing biodegradation of the contaminants

TCE released from a former factory contaminated the groundwater with concentrations as high as 100 ppm. A nearby disposal lagoon also leached a large amount of organic matter into the groundwater.

Microbial activity had completely converted the organic matter into methane, creating a reduced environment that dechlorinated the TCE.TCE biodegradation occurred because of the high chemical oxygen demand (COD) placed on the aquifer, as a result of the organic matter that leached from the nearby disposal lagoon.

134



Evidence of biotransformation is supported by concentrations of cis-DCE, vinyl chloride, and ethene, daughter products of TCE reductive dechlorination. Samples collected near the source show that 825% of the TCE had been converted to ethene.

A site survey shows that the conversion of the TCE to ethene was most complete where methane production and loss of nitrate and sulfate by reduction were the highest.Although extensive dechlorinationtook place, complete breakdown of TCE and its daughter products did not occur.

Indicators of TCE reductive dechlorinationare:

Formation of cis-DCE, VC, and etheneLoss of COD in excess of what was needed for dechlorinationEvidence of anaerobic processes

135



Between 1958 and 1967, approximately 5,500 gallons of TCE were released creating a large groundwater plume (about 2,800-feet by 2,100 feet).Groundwater modeling shows the contaminant had migrated from its source area, however, no degradation of the TCE had occurred.

Electron acceptors (nitrate and sulfate) are present in the plume, but there is no dissolved oxygen content or organic material present. The probable reason that there is no biotransformation of the TCE is that no primary substrate (organic material) is present to create a reducing condition.

Vandenberg Air Force Base:

572 gallon release of gasoline containing MTBE Estimated groundwater velocity is 400 ft/yearBTEX plume stops within 50100 feet from source MTBE plume is 250 feet wide and extends 1,700 feet from source

NE

S

W

Approximate extent of MTBE above 2 ppb

(11/97)

Surface drainage

Approximate extent of detectable TPH / BTEX (11/97)

0 100 200

Scale: feet

136



Natural biodegradation appears to have affected the BTEX, but it had little or no affect on the MTBE.In general, simpler and naturally-occurring organic compounds, such as BTEX, are degradable. MTBE is notably resistant to biodegradation because of its stable molecular structure and its reactivity with microbial membranes.

A PCB release contaminated a 200 mile stretch of the Hudson River sediment from Hudson Falls to Manhattan. Studies show an incomplete natural attenuation of PCBs in the sediment.Studies show aerobic microorganisms present in the sediment. Active aeration pilot studies show co-metabolism created a reduced environment allowing the reductive dechlorination of the PCB.

Potential for PCB biodegradation exists in the Hudson River sediment, two requirements must be fulfilled for natural attenuation:

A mixing of deep and shallow sediments must occur to link aerobic and anaerobic process. This can occur naturally, but there is no guarantee it will occur often enough to achieve biodegradation.

Biodegradation must occur before the PCBs enter the food chain, e.g., the bioaccumulation of PCB in fish tissue.

137



A 1997 study showed significant dechlorination of PCBs, but, even after decades, complete dechlorination has not occurred. The rate of dechlorination is insufficient to ensure that monitored natural attenuation will meet regulatory standards.

Acid drainage from copper mining in Pinal Creek, Arizona area caused a 25-km plume of metal contamination from several unlined mine tailings ponds. It is suspected the pH of the ponds were 2 to 3.The acid part of the plume extended 12 km with several metals having concentrations above MCLs.Many physical, chemical, and biological processes have affected the metal contaminants.

Physical dilution likely accounted for a 60% contaminant concentration decrease for the first 2 km of the plume.Chemical reaction of the acid plume with natural carbonate material raised the pH to 5-6. This pH raise caused precipitation or sorption of the iron, copper, zinc, and other metals.The neutralization reactions depleted the carbonate allowing some metals to continue to migrate to a discharge point in Pinal Creek. The increase in pH and oxygen caused manganese oxides to precipitate.

138



The precipitation of the manganese oxides were enhanced by manganese-oxidizing bacteria which resulted in about 20% decrease of the dissolved manganese.Concentrations of other dissolved metals decrease because of sorption onto the manganese oxides.The natural process reduced the dissolved metals in groundwater. But as the carbonate material become depleted, the source may overwhelm the natural attenuation capacity of the aquifer.

The success of a project is based on:

The level of understanding of the dominant attenuation processesThe probability that site-specific conditions will result in an effective natural attenuation

139



A number of factors must be considered to determine if MNA will be effective:

Initial Screening of MNA ApplicabilityDetailed Evaluation of MNA Effectiveness

Do regulations allow MNA as a remedial method?Has the source been removed to the maximum extent practical?Is the plume shrinking such that remediation will be achieved within a reasonable time?Are there any receptors that could be affected within a 2-year period?

140



If the answer is "no" to any of the first three questions or yes to the fourth question:

MNA is not a remedial option at the site

If the answer is yes" to the first 3 questions and no to the fourth question:

MNA has the potential to be effective at the site, but a detailed evaluation should be conducted

Has the site been fully characterized in three dimensions?If groundwater is the issue, has the hydraulic conductivity of the most permeable transport zone been measured?If groundwater is the issue, has the retarded contaminant transport velocity been estimated?Have the geochemical parameters been measured for all monitoring points?

141



Have rate constants or degradation rates been calculated?Is the estimated time to achieve remediation objective reasonable?Is there no current or future threat to potential receptors?

If yes to all above, then MNA may be effective

Key components of a MNA corrective action plan include:

Documentation of adequate source control

Comprehensive site characterizationEvaluation of time frame for meeting remediation objectivesLong-term performance monitoringA contingency plan

142


1. Recognize the advantages and disadvantages of in-situ treatment.

2. Identify the different in-situ treatment methods for saturated and

unsaturated zones.

3. Describe the principles of natural attenuation, soil vapor

extraction, enhanced soil vapor extraction, and air sparging

treatment methods.

4. Understand the factors of a successful natural attenuation, soil

vapor extraction, enhanced soil vapor extraction, and air sparging

treatment system.

IN SITU TREATMENTS, PART ONE

143

In-situ Treatments, Part 1


In place treatment of contaminants in soil,sediment, or groundwater using physical,chemical, or biological mechanisms.

Eliminates mass removal process

Reduces potential exposure

Reduces surface destruction

May reduce cost

145



Increases treatment time

May be difficult to monitor results

May not treat all contamination

May cause contaminant to spread

Unsaturated Saturated

Physical

Chem

ical

Biological

Physical

Chem

ical

Biological

Monitored Natural Attenuation Soil Vapor Extraction (SVE)

SVE Enhancements Air Sparging Permeable Reactive Barriers Chemical Oxidation Soil Flushing * Bioremediation * Phytoremediation * Immobilization * *Covered in other lectures


Physical

Chem

ical

Biological

Physical

Chem

ical

Biological



146



An in situ method that relies on natural processes to remediate contamination.

Relies on:Volatilization of contaminant

Biological processes

Chemical processes

Success depends on:Type and amount of contaminant

Size and depth of contaminated area

Favorable soil and groundwater conditions

Sufficient time

147




Physical

Chem

ical

Biological

Physical

Chem

ical

Biological



Process draws fresh air through the unsaturated zone, allowing flux, mass transfer, and treatment.

VaporTreatment Blower

CondensateCollection



148



Flux: Contaminant vaporizes into the introduced fresh air.





Mass transfer: Vapors move to one or more extraction wells.

Treatment: Single- or multi-step process extracts and treats vapors.



149



Success depends on:

Contaminant characteristics

Soil properties

Site conditions

System design

Remediation manager can only control:


Soil properties

Site conditions

System design

Remediation manager can only control:


Soil properties

Site conditions (limited control)

System design

150



Success depends on:


Soil properties

Site conditions

System design

The single most important criterion for a successful soil-vapor extraction (SVE)system is the volatility of the contaminant.

Volatility of contaminant influenced by :

Primary factor

Henry's Law Constant

Secondary factors

Affinity to medium

Contaminant composition

151



Henry's Law Constant (KH)

Relationship between the contaminant's concentration in air and water

Function of vapor pressure (Pv) and its solubility (C) in water

KH =PvC

Expresses the ability of a contaminant to volatilize from a dissolved phase into a vapor.

Approximately 10-3 atm m3/mole

152



Expresses the affinity of a soil to a chemical compound.

KOC

A complex mix of contaminants may impede the effectiveness of an SVE system.

Success depends on:


Soil properties

Site conditions

System design

153



Coarse-grainedmaterial (gravel)

Fine-grainedmaterial (silt)

Soil permeabilitySecond only to Henry's Law Constant for success of an SVE system

Gravel

Silt

Soil permeability is affected by:Soil type and heterogeneity

Soil permeability is affected by:Soil type and heterogeneitySoil moisture content

High soil moisture content will limit vapor advection pathwaysOptimum soil moisture is less than 10% by weight

154



Success depends on:


Soil properties

Site conditions

System design

Site conditions refer to above-ground and below-ground conditions, and include:

Depth to groundwater surfaceSubsurface cond

Ert Student Manual 3ppg 2012-01-09

Documents

Transcript of Ert Student Manual 3ppg 2012-01-09