-------
Solid Waste EPA-542-R-05-006
and Emergency Response December 2005
(5102G) http://www.clu-in.org/POPs
Reference Guide to Non-combustion Technologies for Remediation
of Persistent Organic Pollutants in Stockpiles and Soil
Internet Address (URL) MtBl//www.g»a..gaY
Recycled/Recyclable. Printed with Vegetable Oil Based Inks on Process Chlorine Free Recycled Paper (minimum 50% Post consumer)
-------
CONTENTS
Section
Pas
ACRONYMS AND ABBREVIATIONS iii
NOTICE AND DISCLAIMER v
ACKNOWLEDGMENTS vi
EXECUTIVE SUMMARY vii
1.0 INTRODUCTION 1
1.1 Purpose of Report 2
1.2 Methodology 2
1.3 Report Organization 3
2.0 BACKGROUND 4
2.1 Stockholm Convention 4
2.2 Sources of POPs 4
2.3 Characteristics of POPs 4
2.4 Health Effects of POPs 5
2.5 Related Documents 5
3.0 NON-COMBUSTION TECHNOLOGIES 7
3.1 Full-Scale Technologies for Treatment of POPs 7
3.1.1 Anaerobic Bioremediation Using Blood Meal for Treatment of Toxaphene in Soil
and Sediment 11
3. .2 DARAMEND® 12
3. .3 Gas-Phase Chemical Reduction 14
3. .4 GeoMelt™ 15
3. .5 In Situ Thermal Desorption 16
3. .6 Mechanochemical Dehalogenation 18
3. .7 Xenorem™ 21
3.2 Pilot-Scale Technologies for Treatment of POPs 22
3.2.1 Base-Catalyzed Decomposition 22
3.2.2 CerOx™ 23
3.2.3 Phytotechnology 24
3.2.4 Solvated Electron Technology 26
3.2.5 Sonic Technology 26
3.3 Bench-Scale Technologies for Treatment of POPs 27
3.3.1 Self-Propagating High Temperature Dehalogenation 27
3.3.2 TDR-3R™ 27
3.3.3 Mediated Electrochemical Oxidation (AEA Silver II™) 28
3.4 Full-Scale Technologies with Potential to Treat POPs 28
3.4.1 Plasma Arc 28
3.4.1.1 PLASCON™ 28
3.4.1.2 Plasma Arc Centrifugal Treatment 29
3.4.1.3 Plasma Converter System 29
3.4.2 Supercritical Water Oxidation 30
4.0 INFORMATION SOURCES 32
5.0 VENDOR CONTACTS 33
6.0 REFERENCES 35
-------
Appendix
Technology Fact Sheets for Remediation of POPs
A Anaerobic Bioremediation Using Blood Meal for the Treatment of Toxaphene in Soil and
Sediment
B Bioremediation Using DARAMEND® for Treatment of POPs in Soils and Sediments
C In Situ Thermal Desorption for Treatment of POPs in Soils and Sediments
LIST OF TABLES
Table Page
1-1 POPs Identified by the Stockholm Convention 1
3-1 Summary of Non-combustion Technologies for Remediation of POPs 8
3-2 Performance of Non- combustion Technologies for Remediation of POPs 10
3-3 Performance of Anaerobic Bioremediation Using Blood Meal for Toxaphene Treatment 12
3-4 Performance of DARAMEND® Technology 13
3-5 Performance of GPCR™ Technology 14
3-6 Performance of GeoMelt™Technology 16
3-7 Performance of ISTD Technology 18
3-8 Soil Acceptance Criteria for the Mapua Site 19
3-9 Performance of MCD™ Technology at the Mapua Site 20
3-10 Performance of Xenorem™ Technology at the Tampa Site 22
-------
ACRONYMS AND ABBREVIATIONS
|lg/kg Microgram per kilogram
ART Adventus Remediation Technologies, Inc.
BCD Base-catalyzed decomposition
CCMS Committee on the Challenges of Modern Society
cy Cubic yard
ODD Dichlorodiphenyldichloroethane
DDE Dichlorodiphenyldichloroethylene
DDT Dichlorodiphenyltrichloroethane
Dioxins Polychlorinated dibenzo-p-dioxins
DRE Destruction and removal efficiency
EDL Environmental Decontamination Ltd.
EPA U.S. Environmental Protection Agency
ERT Environmental Response Team
ESVE Enhanced soil vapor extraction
FRTR Federal Remediation Technologies Roundtable
Furans Polychlorinated dibenzo-p-furans
GEF Global Environmental Facility
GPCR Gas-phase chemical reduction
gpd Gallon per day
GRIC Gila River Indian Community
HCB Hexachlorobenzene
HCH Hexachlorocyclohexane
HEPA High-efficiency particulate air
ICV In Container Vitrification
IHPA International HCH and Pesticides Association
ISTD In situ thermal desorption
LTR Liquid tank reactor
M Meter
MCD Mechanochemical dehalogenation
MDL Method detection limit
mg/kg Milligram per kilogram
mm Millimeter
ng/kg Nanogram per kilogram
NAPL Nonaqueous-phase liquid
NATO North Atlantic Treaty Organization
NCDENR North Carolina Department of Environmental and Natural Resources
ND Below detection limit
OSRTI Office of Superfund Remediation and Technology Innovation
PACT Plasma Arc Centrifugal Treatment
PAH Polycyclic aromatic hydrocarbons
PCB Polychlorinated biphenyl
PCS Plasma Converter System
POP Persistent organic pollutant
ppb Part per billion
ppm Part per million
ppt Part per trillion
REACHIT Remediation and Characterization Innovative Technologies
SCWO Supercritical water oxidation
SITE Superfund Innovative Technology Evaluation
in
-------
SPHTD Self-propagating high-temperature dehalogenation
SPY Subsurface Planar Vitrification
STAP Science and Technology Advisory Panel
SVOC Semivolatile organic compound
TCDD Tetrachlorodibenzodioxin
TNT Trinitrotoluene
UNEP United Nations Environment Programme
UNR University of Nevada at Reno
USD United States Dollar
VOC Volatile organic compound
IV
-------
NOTICE AND DISCLAIMER
This report compiles information about non- combustion technologies for remediation of persistent
organic pollutants, including technology applications at both domestic and international sites, but is not a
comprehensive review of all the current non- combustion technologies or vendors. This report also does
not provide guidance regarding selection of a specific technology or vendor. Use or mention of trade
names or commercial products does not constitute endorsement or recommendation for use.
This report has undergone EPA and external review by experts in the field. However, information in this
report is derived from a variety of references (including personal communications with experts in the
field), some of which have not been peer-reviewed.
This report has been prepared by the U.S. Environmental Protection Agency (EPA) Office of Superfund
Remediation and Technology Innovation, with support provided under Contract Number 68-W-02-034.
For further information about this report, please contact Ellen Rubin at EPA's Office of Superfund
Remediation and Technology Innovation, at (703) 603-0141, or by e-mail at aibin.ellen@epa.gov.
A PDF version of "Non- combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil" is available for viewing or downloading at the Hazardous Waste Cleanup
Information System web site at hUjy^_//www._clu=in.org/POP_s. A limited number of printed copies of the
report are available free of charge and may be ordered via the web site, by mail, or by fax from the
following source:
EPA/National Service Center for Environmental Publications
P.O. Box 42419
Cincinnati, OH 45242-2419
Telephone: (513) 489-8190 or (800) 490-9198
Fax: (513)489-8695
-------
ACKNOWLEDGMENTS
Special acknowledgment is given to members of the International HCH and Pesticides Association
(IHPA), and other remediation professionals for their cooperation, thoughtful suggestions, and support
during the preparation of this report. Contributors to the report include the following individuals:
Bryan Black, Environmental Decontamination Ltd.
Carl V. Mackey, Washington Group International
Charles Rogers, BCD Group, Inc.
Christine Parent, California Department of Toxic Substances Control
David Raymond, Adventus Remediation Technologies, Inc.
Edward Someus, Terra Humana Clean Technology Engineering Ltd.
Giacomo Cao, Centre Studi Sulle Reazioni Autopropaganti
John Vijgen, International HCH and Pesticides Association
Kevin Finucane, AMEC Earth and Environmental, Inc.
Matt Van Steenwyk, CerOx™
Paul Austin, Sonic Environmental Solutions, Inc.
Ralph Baker, TerraTherm, Inc.
Tedd E. Yargeau, California Department of Toxic Substances Control
Volker Birke, Tribochem
VI
-------
EXECUTIVE SUMMARY
This report provides a high level summary of information on the applicability of existing and emerging
non-combustion technologies for the remediation of persistent organic pollutants (POPs) in stockpiles and
soil. POPs are a set of chemicals that are toxic, persist in the environment for long periods of time, and
biomagnify as they move up through the food chain. POPs have been linked to adverse effects on human
health and animals, such as: cancer, damage to the nervous system, reproductive disorders, and
disruption of the immune system. In addition, restrictions and bans on the use of POPs have resulted in a
significant number of unusable stockpiles of POP-containing materials internationally. Deterioration of
storage facilities used for the stockpiles, improper storage practices, and past production and use of POPs
also have resulted in contamination of soils around the world.
Previously, POPs have been destroyed by combustion technologies (incineration). Many interested
parties have expressed concern about the potential environmental and health effects associated with this
type of treatment technology. Combustion of POPs can create by-products such as polychlorinated
dibenzo-p-dioxins (dioxins) and polychlorinated dibenzo-p-furans (furans) - known human carcinogens.
Two principal reports have identified the various non-combustion destruction technologies for POPs
(Review of Emerging, Innovative Technologies for the Destruction and Decontamination of POPs and the
Identification of Promising Technologies for Use in Developing Countries: Evaluation of Demonstrated
and Emerging Remedial Action Technologies for the Treatment of Contaminated Land and Groundwater
(Phase III)).
With the passage of time, some of the technologies discussed in these comprehensive documents that
were in the development stage are now commercialized; while other commercial technologies are no
longer being developed. Also, new promising destruction technologies for POPs have been developed.
This report is intended to summarize and update older reports in a concise reader's guide, with links to
sources of further information. The updated information was obtained by reviewing various websites and
documents, and by contacting technology vendors and experts in the field.
This report provides short descriptions of a range of non-combustion technologies and highlights new
performance data showing the various considerations associated with selecting a non-combustion
technology. Table 3-1 summarizes the selected technologies and provides information on waste strength
treated, ex situ or in situ technology, contaminants treated, cost information when available, pretreatment
requirements, power requirements, configuration needs, and links to individual fact sheets. Fact sheets for
the various technologies are available through the International Hexachlorocyclohexane (HCH) and
Pesticides Association website; new fact sheets are available in the appendices of this report.
vn
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
1.0 INTRODUCTION
POPs are toxic compounds that are chemically stable, do not easily degrade in the environment, and tend
to accumulate and biomagnify as they move up through the food chain. Serious human health problems
are associated with POPs, including cancer, neurological damage, birth defects, sterility, and immune
system suppression. Restrictions and bans on the use of POPs have resulted in a significant number of
unusable stockpiles of POP-containing materials internationally. In addition, deterioration of storage
facilities used for the stockpiles, improper storage practices, and past production and use of POPs have
resulted in contamination of soils around the world. Because of their chemical stability, tendency to
bioaccumulate, adverse health effects associated with POPs, and widespread POP contamination,
remediation technologies are needed to treat these pollutants.
Previously, POP-contaminated soil and stockpiles have been treated using technologies such as
incineration that rely on combustion to destroy the contaminants. However, site owners and operators,
remedial project managers, and other interested parties have expressed concern about the potential
environmental and health effects associated with combustion of POPs. Combustion technologies can
create polychlorinated dibenzo-p-dioxins (dioxins) and polychlorinated dibenzo-p-furans (furans).
Dioxins and furans have been characterized by EPA as human carcinogens and are associated with
serious human health problems. Also, combustion technologies that have historically been used for the
destruction of POPs may fail to meet the stringent environmental conditions or destruction and removal
efficiency (DRE) requirements established for POPs. Because of these concerns and an ongoing desire to
find more cost effective solutions, environmental professionals are examining the application of non-
combustion technologies to remediate POPs in stockpiles and soil (Ref 58).
Under the Stockholm Convention, countries committed to reduce or eliminate the production, use, and
release of the 12 POPs of greatest concern to the global community. In addition, the Basel Convention
invited the bodies of the Stockholm Convention to consider the development of information on best
available techniques and environmental practices with respect to POPs (Refs. 59 and 60). The Basel
Convention was adopted on March 22, 1989, by the Conference of Plenipotentiaries convened at Basel.
The Stockholm Convention obligated parties to remediate POPs stockpiles but did not obligate cleanup of
POPs-contaminated sites. Table 1-1 lists the 12 specific POPs identified by the Stockholm Convention,
which include nine pesticides and three industrial chemicals or by-products (Ref. 23).
Table 1-1. POPs Identified by the Stockholm Convention
Pesticides
Industrial Chemicals or By-Products
Aldrin
Chlordane
Dichlorodiphenyltrichloroethane (DDT)
Dieldrin
Endrin
Heptachlor
Hexachlorobenzene (HCB)
Mirex
Toxaphene
Polychlorinated biphenyls (PCB)
Dioxins
Furans
Source: Ref. 23
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
1.1 Purpose of Report
This report is intended to provide a high level summary of information for federal, state, and local
regulators, site owners and operators, consultants, and other stakeholders on the applicability of existing
and emerging non-combustion technologies for the remediation of POPs in stockpiles and soil. The
report provides short descriptions of these technologies and evaluates them based on the POPs treated,
media treated, pretreatment requirements, performance and cost. Case studies provided show the various
considerations associated with selecting a non- combustion technology.
Information on non- combustion technologies for the remediation of POPs is available in several more
comprehensive documents. With the passage of time, some of the technologies discussed in these
comprehensive documents were in the development stage and are now commercialized; while other
commercial technologies are no longer being developed. For all of these technologies, this report is
intended to update and summarize older reports in a relevant concise reader's guide with links to sources
of further information. In addition, this report provides information on several new technologies.
1.2 Methodology
INTERNATIONAL HCH AND PESTICIDES
ASSOCIATION
IN 2002, JOHN VIJGEN, THROUGH THE
INTERNATIONAL HCH AND PESTICIDES
ASSOCIATION, PUBLISHED 11 FACT SHEETS
ABOUT EMERGING NON- COMBUSTION
ALTERNATIVES FOR THE ECONOMICAL
DESTRUCTION OF POPS
(HTTP: //\\WW. j HP A. j NFO/U B R AR YN ATO.JJTM).
THESE FACT SHEETS WERE USED AS A KEY
INFORMATION SOURCE DURING DEVELOPMENT OF
THIS REPORT.
EPA identified non- combustion technologies for
remediation of POPs in stockpiles and soil by
reviewing technical literature, EPA reports, and
EPA databases such as the Federal Remediation
Technologies Roundtable (FRTR) (www.frtr.gov)
and the Remediation and Characterization
Innovative Technologies (REACHIT) system
(www.cparcachit.org). as well as by contacting
technology vendors and experts in the field.
REACHIT is a real time vendor supplied source of
information including data on emerging non-
combustion technologies for POPs. A key source of
information is the work done by John Vijgen of the
International HCH and Pesticides Association (see
box). Some of the information sources have not
been peer-reviewed.
A list of non- combustion technologies was prepared using the available information. For each
technology, the following types of information were compiled: commercial availability; the processes
used; advantages and limitations; POPs treated; sites where the technology was applied at full-, pilot- or
bench-scale; technology performance results; cost information; and lessons learned. Technologies that
have treated one or more of the 12 POPs or have the potential to treat POPs are discussed in this report.
Some technologies previously discussed in other sources were identified as no longer commercially
available or have not been used to treat POPs.
Based on the available information, EPA reviewed the types of waste and contaminants treated, and
summarized the results from use of the technology. Performance data were evaluated based on the
concentrations of specific POPs before-and after-treatment. For many of the specific projects described
in this report, gaps existed in the information available. For example, for some projects, little or no
performance data was available. EPA did not perform independent evaluations of technology
performance. However, where feasible, such data gaps were addressed by contacting specific technology
vendors and users.
-------
FURTHER INFORMATION ABOUT NON-
COMBUSTION TECHNOLOGIES FOR
REMEDIATION OF POPS IS PROVIDED AT
VVWW.CLU-IN.ORG/POPS.
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
1.3 Report Organization
This report includes six sections. Section 1.0 is an introduction discussing the purpose and organization
of the report. Section 2.0 provides background information about the Stockholm Convention and about
the sources, characteristics, and health effects of POPs. [^^^^^^^^^^^•^^^^^^^^^^^•i
Section 3.0 presents technology overviews, while more
detailed information for some technologies is provided in
the technology-specific fact sheets in the appendices of the
report. Seventeen technologies for POP treatment are
described in Section 3.0. Section 3.0 is divided into four
subsections based on the scale of application of the technologies. Section 3.1 contains descriptions of
full-scale technologies that treat POPs. Section 3.2 contains descriptions of pilot-scale technologies that
have treated POPs. Section 3.3 contains descriptions of bench-scale technologies that have been tested on
POPs. Section 3.4 contains descriptions of full-scale technologies that have treated non-POPs and that
are potentially applicable for POP treatment. Section 4.0 lists web-based information sources used for the
preparation of this report. Section 5.0 contains contact details for technology vendors. Section 6.0 lists
references used in the preparation of this report.
The appendices to this report provide fact sheets prepared by EPA for three technologies: anaerobic
bioremediation using blood meal for the treatment of toxaphene in soil, DARAMEND® technology for
treatment of POPs in soils, and in situ thermal desorption (ISTD) for treatment of POPs in soil. Fact
sheets for 11 other POP treatment technologies discussed in this report were previously published in
"Evaluation of Demonstrated and Emerging Remedial Action Technologies for the Treatment of
Contaminated Land and Groundwater (Phase III)," which was issued by the International HCH and
Pesticides Association (IHPA) in 2002. EPA examined the 11 technologies for which fact sheets were
prepared by IHPA (see list in Section 2.5) and evaluated whether additional, more recent information was
available for these technologies. Only one technology, mechanochemical dehalogenation (MCD), was
identified for which new information had become available after the original fact sheet was published;
this new information is included in Section 3.1.6 of this report. All other full-scale technologies listed in
this report were updated with site specific performance data and included in their respective sections.
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
2.0 BACKGROUND
This section provides background information about the Stockholm Convention and the sources,
characteristics, and health effects of POPs. It also identifies related documents that address technologies
for the treatment of POPs.
2.1 Stockholm Convention
The Stockholm Convention (Ref 49) is a global treaty intended to protect human health and the
environment from POPs. On May 23, 2001, 93 countries and regional economic integration organizations
such as the European Union signed the convention. As of April 25, 2005, 97 countries and one regional
economic integration organization had signed or ratified the treaty. The United States signed the treaty
but as of April 2005 has not ratified it.
2.2 Sources of POPs
Most POPs originate from man-made sources associated with production, use, and disposal of certain
organic chemicals. Some POPs are intentionally produced, while others are the by-products of industrial
processes or result from the combustion of organic chemicals. The POPs within the scope of the
Stockholm Convention include nine pesticides and three industrial chemicals or by-products (Ref. 18).
Table 1-1 lists these POPs.
The nine pesticides targeted by the Stockholm Convention were produced intentionally and used on
agricultural crops or for public health vector control. By the late 1970s, these pesticides had been either
banned or subjected to severe use restrictions in many countries. However, some of the pesticides are still
in use in parts of the world where they are considered essential for protecting public health (Ref. 18).
The three industrial chemicals and by-products within the scope of the Stockholm Convention are PCBs,
dioxins, and furans. PCBs were produced intentionally but are typically released into the environment
unintentionally. The most significant use of PCBs was as a dielectric fluid (a fluid which can sustain a
steady electrical field and act as an electrical insulator) in transformers and other electrical and hydraulic
equipment. Most countries stopped producing PCBs in the 1980s; for example, equipment manufactured
in the United States after 1979 usually does not contain PCBs. However, older equipment containing
PCBs is still in use. Most capacitors manufactured in the United States before 1979 also contain PCBs.
Dioxins and furans are usually produced and released unintentionally. They may be generated by
industrial processes or by combustion, including fuel burning in vehicles, municipal and medical waste
incineration, open burning of trash, and forest fires (Ref. 18).
2.3 Characteristics of POPs
POPs are synthetic chemicals with the following properties (Ref. 18):
• They are toxic and can have adverse effects on human health and animals.
• They are chemically stable and do not readily degrade in the environment.
• They are lipophillic (affinity for fats) and easily soluble in fat.
• They accumulate and biomagnify as they move up through the food chain.
• They move over long distances in nature and can be found in regions far from their points of
origin or use.
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
2.4 Health Effects of POPs
POPs are associated with serious human health problems, including cancer, neurological damage, birth
defects, sterility, and immune system defects. EPA has classified certain POPs as probable human
carcinogens1, including aldrin, dieldrin, chlordane, DDT, heptachlor, HCB, toxaphene, and PCBs.
Laboratory studies have shown that low doses of POPs can adversely affect organ systems. Chronic
exposure to low doses of certain POPs may affect the immune and reproductive systems. Exposure to
high levels of certain POPs can cause serious health effects or death. The primary potential human health
effects associated with POPs are listed below (Refs. 18 and 56).
• Cancer
• Immune system suppression
• Nervous system disorders
• Reproductive damage
• Altered sex ratio
• Reduced fertility
• Birth defects
• Liver, thyroid, kidney, blood, and immune system damage
• Endocrine disruption
• Developmental disorders
• Shortened lactation in nursing women
• Chloracne and other skin disorders
In addition, studies have linked POP exposure to diseases and abnormalities in a number of wildlife
species, including numerous species offish, birds, and mammals. For example, in certain birds of prey,
high levels of DDT caused eggshells to thin to the point that the eggs could not produce live offspring
(Ref 18).
2.5 Related Documents
Two organizations, the United Nations Environment Programme (UNEP) and IHPA, have recently
developed summary overview reports and fact sheets about non- combustion technologies for POP
treatment. These documents are listed below.
• UNEP, Science and Technology Advisory Panel (STAP) of the Global Environmental Facility
(GEF). 2004. "Review of Emerging, Innovative Technologies forthe Destruction and
Decontamination of POPs and the Identification of Promising Technologies for Use in
Developing Countries." GF/8000-02-02-2205. January. Online Address:
http://www.bascl.int/tcchmattcrs/rcvicw_pop_fcb04.pdf. This report (Ref. 57) provides a
summary overview of non- combustion technologies that are considered to be innovative and
emerging and that have been identified as potentially promising for the destruction of POPs in
stockpiles. The report was originally a background document for the STAP-GEF workshop held
in Washington, DC, in October 2003 and was based on work done by the International Centre for
1 Based on the 1986 EPA classification of carcinogens, "probable" carcinogens (Group B) include those agents for
which the weight of evidence of human carcinogenicity based on epidemiological studies is "limited" and those
agents for which the weight of evidence of human carcinogenicity based on animal studies is "sufficient" (Ref. 56).
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Sustainability Engineering and Science, Faculty of Engineering, at the University of Auckland,
New Zealand.
The report contains overviews of the following non-combustion technologies:
Base-catalyzed decomposition (BCD)
Bioremediation/Fenton reaction
Catalytic hydrogenation
DARAMEND® bioremediation
Enzyme degradation
Fe (III) photocatalyst degradation
Gas-phase chemical reduction (GPCR)
GeoMelt™ process
In situ bioremediation of soils
Mechanochemical dehalogenation
(MCD)
Mediated electrochemical oxidation
(AEA Silver II)
Mediated electrochemical oxidation
(CerOx™)
MnOx/TiO2 - A12O3 catalyst degradation
15. Molten salt oxidation
16. Molten slag process
17. Ozonation/electrical discharge
destruction
18. Photochemically enhanced microbial
degradation
19. Phytoremediation
20. Plasma arc (PLASCON™)
21. Pyrolysis
22. Self-propagating high-temperature
dehalogenation (SPHTD)
23. Sodium reduction
24. Solvated electron technology
25. Supercritical water oxidation (SCWO)
26. TiO2 - based V2O5AVO3 catalysis
27. White rot fungi bioremediation
IHPA. 2002. IHPA and North Atlantic Treaty Organization (NATO) Committee on the
Challenges of Modern Society (CCMS) Pilot Study Fellowship Report: "Evaluation of
Demonstrated and Emerging Remedial Action Technologies for the Treatment of Contaminated
Land and Groundwater (Phase III)." Online Address: http://w\vw.ihpa.info/libraryNATO.htm .
This report (Ref. 33) describes emerging non- combustion alternatives for the economical
destruction of POPs. Mr. John Vijgen of IHPA collected the technology data and authored the
report. The report contains fact sheets for the 11 technologies listed below:
1. BCD
2. CerOx™
3. Gas-phase chemical reduction process
4. GeoMelt™
5. In situ thermal destruction
6. MCD™
7. SPHTD
8. Silverll™
9. Solvated electron technology
10. SCWO
11. TDR-3R™
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
3.0 NON-COMBUSTION TECHNOLOGIES
This section provides a review of selected non- combustion technologies for POPs remediation, including
their implementation at both domestic and international sites. In this report, POPs include the 12
contaminants within the scope of the Stockholm Convention, and non-combustion technologies are
defined as processes that operate in a starved or ambient oxygen atmosphere (including thermal
processes). For this report, treatment technology is defined as the primary process where contaminant
destruction occurs. Pretreatment is defined as any process that precedes the primary treatment technology
wherein the contaminants are transferred from one media/phase to another.
Table 3-1 lists the selected technologies and summarizes available technology-specific information,
including capability to handle waste strength, ex situ or in situ application, scale, contaminant treated,
cost, pre-treatment needs, power requirements, configuration and location of fact sheets. Waste strength
refers to high- and low-strength wastes. High-strength waste includes stockpiles of POPs-contaminated
materials and highly contaminated soil. Low-strength waste includes soil contaminated with low
concentrations of POPs. The table indicates whether the technologies have been applied at a full2, pilot3,
or bench4 scale for treatment of POPs. Table 3-2 provides performance data for the selected technologies.
The performance data include the site location, contaminants treated, untreated and treated contaminant
concentration, and percent reduction of the contaminants. Section 5.0 provides contact information for
vendors of these various technologies.
3.1 Full-Scale Technologies for Treatment of POPs
This section describes seven technologies that have been implemented to treat POPs at full scale. Each
subsection focuses on a single technology and includes a description of the technology and information
about its application at specific sites. Fact sheets developed by EPA and IHPA contain additional details
on some of these technologies and their applications. The appendices to this report provide fact sheets
prepared by EPA for three technologies. Links to the IHPA fact sheets are included in the appropriate
subsections of this report.
2 A full-scale project involves use of a commercially available technology to treat industrial waste and to remediate
an entire area of contamination.
3 A pilot-scale project is usually conducted in the field to test the effectiveness of a technology and to obtain
information for scaling up a treatment system to full scale.
4 A bench-scale project is conducted on a small scale, usually in the laboratory, to evaluate a technology's ability to
treat soil, waste, or water. Such a project often occurs during the early phases of technology development.
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Stockpiles and Soil
Table 3-1. Summary of Non-combustion Technologies for Remediation of Persistent Organic Pollutants 1
Technology
Waste
Strength2
Ex/Miitu1
( 'oiitiiiiiiniint(s) Treated
POPi
PeitMde(i) 4
PCBi
Dioxiii
Furans
Non-POPs 5
Coit
Pre-
Treatment
Power
Requirement
Configuration
Fact Sheet
Full-Scale Technologies
Anaerobic
bioremediation using
blood meal for the
treatment of toxaphene
in soil and sediment
DARAMEND®
Gas Phase Chemical
Reduction (GPCR™)6
GeoMelt™
In-Situ Thermal
Desorption (ISTD)
Mechanochemical
Dehalogenation
(MCD™)
Xenorem™
Low
Low
High
Low/High
Low/High
High
Low
Ex situ
Ex/In situ
Ex situ
In/Ex situ
In situ
Ex situ
Ex situ
Toxaphene
Toxaphene
and DDT
DDT and
HCB
DDT,
chlordane,
dieldrin and
HCB
NA
Aldrin,
dieldrin and
DDT
Chlordane,
DDT,
dieldrin, and
toxaphene
None
None
Yes
Yes
Yes
None
None
None
None
Yes
Yes
Yes
None
None
None
ODD, DDE,
RDX, HMX,
DNT, and
TNT
PAH,
chlorobenzene
Metals and
radioactive
waste
VOCs,
SVOCs, oils,
creosote, coal
tar, gasoline,
MTBE,
volatile
metals
Lindane,
ODD, and
DDE
Molinate
$98 to
$296
per
cubic
yard (in
2004)
$55 per
cubic
yard (in
2004)
NA
NA
$200 to
$600
per
cubic
yard
(from
1996 to
2005)
NA
$132
per
cubic
yard (in
2000)
None
None
Thermal
desorption
None
None
None
None
None
None
High
High
High
NA
NA
Transportable
Transportable
Fixed and
transportable
Fixed and
transportable
Transportable
NA
Transportable
Appendix A
Appendix B
http://www.ihpa.info/li
brarvnato.hlni
http://www.ihDa.infb/li
brarvnato.hlm
Appendix C
httpj/LWWwjhpaJnfoli
brarvnato.hlm
None
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Stockpiles and Soil
Technology
Waste
Strength2
In/In situ1
( 'oiitiiiiiiniint(s) Treated
POPs
PeitMde(i) "
PCBi
Dioxin,
Furam
Non-POP» 5
Pre-
Cost Treatment
Power
Requirement
Configuration
Fact Sheet
Pilot-Scale Technologies
Base Catalyzed
Decomposition (BCD)
CerOx™
Phytoremediation
Sonic Technology
Low/High
Low
Low
Low/High
Ex situ
Ex situ
In/Ex situ
Ex situ
Chlordane
and
heptachlor
Chlordane
DDE, DDT,
and chlordane
None
Yes
Yes
Yes
Yes
Yes
Yes
None
None
a-BHC,
endosulfan
Aniline,
cyclohexanone,
and dibutyl
phthalates
NA
NA
NA
NA
NA
NA
Thermal
desorption
Blending to
produce liquid
influent
None
Mixing with
solvent to
produce a
slurry
High
NA
None
NA
Transportable
and fixed
Modular
Transportable
NA
littp://www.ilipa.iiifo/li
brarynato.lilin
http://www.ihpa.infb/li
brarvnato.h 1m
None
None
Bench-Scale Technologies
Self Propagating High
Temperature
Dehalogenation
TDR-3R™
High
High
Ex situ
Ex situ
HCB
HCB
None
None
None
None
None
PAH
NA
NA
None
Thermal
desorption
NA
High
NA
NA
1ittp:/'i'www.i1ipa.iiifb/li
brarMiato.1i tin
http://www.ihpa.info/li
brarvnato.hlni
Notes:
1: Data in this table is derived from various document, vendor information, and other sources - both peer reviewed and not.
1: Waste strength refers to high- and low-strength wastes. High-strength waste includes stockpiles of POP-contaminated materials and highly contaminated soil. Low-strength
waste includes soil contaminated with low concentrations of POPs.
3: Ex/In situ refers to Ex situ or In situ application of the technology.
4: Pesticides include the nine pesticides addressed within the scope of the Stockholm Convention.
5: Non-POPs include contaminants outside the scope of Stockholm Convention.
6: GPCR is currently not commercialized due to cost.
BHC: Benzene hexachloride
DDD: Dichlorodiphenyldichloroethane
DDE: dichlorodiphenyldichloroethylene
DDT: dichlorodiphenyltiichloroethane
DNT: Di-nitro toluene
HMX: High melting explosive, octahydro-
1,3,5,7-tetranitro-1,3,5,7 tetrazocine
MTBE: Methyl tert-butyl ether
NA: Not available
PAH: Polycyclic aromatic hydrocarbons
SVOC Semivolatile organic compound
VOC Volatile organic compound
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Table 3-2. Performance of Non-combustion Technologies for Remediation of Persistent Organic
Pollutants '
Technology
Examples of Treatment Performance2
Site Name or
Location
Contaminant
Untreated
Concentration
(mg/kg)
Treated
Concentration
(mg/lig)
Percent Reduction
Full-Scale Technologies
Anaerobic
bioremediation using
blood meal for the
treatment of
toxaphene in soil and
sediment
DARAMEND®
Gas Phase Chemical
TM
Reduction (GPCR )3
GeoMelt™
In-Situ Thermal
Desorption (ISTD)
Mechanochemical
Dehalogenation
(MCD™)
Xenorem™
Gila River Indian
Community, Arizona
T.H. Agricultural and
Nutrition Superfund
Site, Montgomery,
Alabama
NA
Parsons Chemical
Superfund Site,
Grand Ledge,
Michigan
Tanapag Village,
Saipan, Northern
Mariana Islands
Centerville Beach,
Ferndale, California
Fruitgrowers
Chemical Company
Site, Mapua, New
Zealand
Stauffer Management
Company Superfund
Site, Tampa, Florida
Toxaphene
Toxaphene
DDT
NA
DDT
Chlordane
Dieldrin
PCBs
PCBs
Dioxin/Furans
Aldrin
Dieldrin
DDX (total
DDT,DDD, and
DDE)
Chlordane
DDT
Dieldrin
Toxaphene
59
189
84.5
NA
340
89
4.6
10,000 (max)
860 (max)
0.0032
7.52
65.6
717
3.8
82
2.4
129
4
21
8.65
NA
<4
<1
<.008
<1
<0.17
0.00006
0.798
19.8
64.8
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
3.1.1 Anaerobic Bioremediation Using Blood Meal for Treatment of Toxaphene in Soil and
Sediment
This technology uses biostimulation with amendments to promote degradation of toxaphene in soil or
sediment by native anaerobic microorganisms. It involves the addition of biological amendments such as
blood meal (dried and powdered animal blood), which is used as a nutrient, and phosphates, which are
used as a pH buffer (Ref 2). In some applications, starch is also used to speed the establishment of
anaerobic conditions. The soil to be treated is mixed with the amendments and water. The technology
can use several methods to produce homogeneous soil-amendment mixtures, including blending in a
dump truck, mechanical mixing in a pit, and mixing in a pug mill. The homogenized mixture is
transferred to a lined cell, and water is added to produce a slurry. Up to a foot of water cover is provided
above the settled solids. The water cover helps to minimize the transfer of atmospheric oxygen to the
slurry so that anaerobic conditions are maintained. The lined cell is covered with a plastic sheet, and the
slurry is incubated for several months.
The slurry may be sampled periodically to measure contaminant degradation. The process continues until
the treatment goals are achieved, at which time the cell is drained. The treated slurry is usually left in the
cell; however, the slurry may be dried and used as fill material on site or as a source of microorganisms
for other applications of the technology. The end products of degradation are carbon dioxide, water, and
chlorides. Residual contamination can include low concentrations of toxaphene and camphenes with
varying degrees of chlorination (Refs. 3 and 19).
Anaerobic bioremediation using blood meal has been
implemented to treat low-strength waste contaminated with
toxaphene. Essential components such as mixing troughs
are typically constructed and left in place. Other
components such as mixing equipment and biological amendments are usually procured locally.
THE FACT SHEET PREPARED BY EPA IS
INCLUDED IN APPENDIX A.
POPs TREATED: TOXAPHENE
MEDIUM: SOIL AND SEDIMENT
RESIDUALS: Low CONCENTRATIONS OF
TOXAPHENE AND CAMPHENES WITH
VARYING DEGREES OF CHLORINATION
COSTS: $98 TO $296 PER CUBIC YARD
(COST IN 2004 USD)
FULL SCALE
EXSITU
The technology has been used to treat toxaphene at
numerous livestock dip vat sites. Dip vats are trenches with
a pesticide formulation used to treat livestock infested with
ticks. In 2004, cleanup costs in United States Dollar (USD)
for full-scale implementations ranged from $98 to $296 per
cubic yard (Ref. 19). Performance data from nine dip vat
site applications are presented in Table 3-3.
The technology was developed by EPA's Environmental
Response Team (ERT). This technology is publicly
available and is not patented (Ref. 3).
11
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Table 3-3. Performance of Anaerobic Bioremediation Using Blood Meal for Toxaphene Treatment
Site
Location
Period
(Days)
Quantity
of Soil
Treated
Scale
Untreated
Concentration
(ing/kg)
Treated
Concentration
(nig/kg)
Gila River Indian Community (GRIC)
GRIC Cell 1
GRIC Cell 2
GRIC Cell 3
GRIC Cell 4
Chandler,
Arizona
272
272
272
272
3,500 cy
Full
Full
Full
Full
59
31
29
211
4
4
2
3
Navajo Vats Chapter
Laahty Family
Dip Vat
Henry O Dip
Vat
Nazlini
Whippoorwill
Blue Canyon
Road
Jeddito Island
Ojo Caliente
Poverty Tank
Zuni Nation,
New Mexico
Zuni Nation,
New Mexico
NA
NA
NA
NA
Zuni Nation,
New Mexico
NA
31
68
108
110
106
76
14
345
253 cy
660 cy
3.5 tons
3.5 tons
NA
NA
200 cy
NA
Full
Full
Pilot
Pilot
NA
NA
NA
NA
29
23
291
40
100
22
14
33
4
8
71
17
17
o
5
4
8
Sources: Refs. 2, 3 and 19
Notes:
cy = Cubic yard
mg/kg = Milligram per kilogram
NA = Not available
The
3.1.2 DARAMEND®
DARAMEND® has been used to treat low-strength wastes contaminated with toxaphene and DDT.
DARAMEND® technology can be implemented ex situ or in situ. It is an amendment-enhanced
bioremediation technology for POP
treatment that involves the creation of
sequential anoxic and oxic conditions
(Ref. 41). The treatment process involves
the following steps:
1. Addition of a solid-phase
DARAMEND® organic soil
amendment of a specific particle
size distribution and nutrient
profile, zero valent iron, and water
to produce anoxic conditions
2. Periodic tilling of the soil to
promote oxic conditions
3. Repetition of the anoxic-oxic
cycle until cleanup goals are
achieved
Bioremediation using DARAMEND process. Source: Ref. 1
12
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
The addition of the DARAMEND® organic amendment, zero valent iron, and water stimulates the
biological depletion of oxygen, generating strong reducing (anoxic) conditions in the soil matrix.
Diffusion of replacement oxygen into the soil matrix is prevented by near saturation of the soil pores with
water. The depletion of oxygen creates a very low redox potential, which promotes dechlorination of
organochlorine compounds. The soil matrix consisting of contaminated soil and the amendments is left
undisturbed for the duration of the anoxic phase of the treatment cycle (typically 1 to 2 weeks). In the
next (oxic) phase, periodic tilling of the soil increases diffusion of oxygen and distribution of irrigation
water in the soil. The dechlorination products formed during the anoxic degradation process are
subsequently removed through aerobic (oxic) biodegradation processes, which are initiated and promoted
by the passive air drying and tilling of the soil. Addition of the DARAMEND® amendment and the
anoxic-oxic cycle continue until cleanup goals are achieved (Ref 15).
THE FACT SHEET PREPARED BY EPA IS
INCLUDED IN APPENDIX B.
The DARAMEND technology can be implemented ex situ or
in situ. In both cases, the treatment layer is 2 feet (ft) deep,
which is the typical depth reached by tilling equipment. For _
treatment to greater depths, the technology can be
implemented in sequential, 2-ft lifts. The DARAMEND® technology may be technically or economically
infeasible with excessively high contaminant concentrations in soils (Ref. 15).
DARAMEND® has been used to treat soil and sediment
containing low concentrations of pesticides such as toxaphene
and DDT as well as other contaminants. The technology has
not been used for treatment of other POPs such as PCBs,
dioxins, or furans. Adventus Remediation Technologies, Inc.
(ART), the developer of the technology, indicated that
DARAMEND® had not been successful in bench-scale
treatment of PCB-contaminated soil. DARAMEND® has been
used to treat POPs at the T.H. Agriculture and Nutrition
Superfund site in Montgomery, Alabama, and the W.R. Grace
site in Charleston, South Carolina. Table 3-4 presents the performance data from these applications. The
average treatment cost (in 2004 USD) at the site in Montgomery was $55 per ton; the vendor did not
specify the components included in this cost (Refs. 1, 22 and 42).
Table 3-4. Performance of DARAMEND® Technology
POPs TREATED: TOXAPHENE AND
DDT
MEDIUM: SOIL AND SLURRY
COSTS: $55 PER TON (COST IN 2004
USD)
FULL SCALE
EX SITU AND IN SITU
Site
T.H.
Agriculture
and Nutrition
Superfund site
W.R. Grace
site
Location
Montgomery,
Alabama
Charleston,
South Carolina
Year
Implemented
2003
1995
Period
(Months)
5
8
POP
Toxaphene
DDT
Toxaphene
DDT
Quantity of
Soil Treated
(Tons)
4,500
250
Scale
Full
Pilot
Untreated
Concentration
(mg/kg)
189
84.5
239
89.7
Treated
Concentration
(mg/kg)
21
8.65
5.1
16.5
Source: Ref. 1
Notes:
mg/kg = Milligram per kilogram
DARAMEND® is a proprietary technology provided by ART in Mississauga, Ontario, Canada. In the
United States, the technology is provided by ART's sister company, Adventus Americas, Inc. in
Bloomingdale, Illinois.
13
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
3.1.3 Gas-Phase Chemical Reduction
Gas-phase chemical reduction (GPCR™) has been used to treat high-strength wastes containing POPs.
GPCR™ is an ex situ technology and is available in both fixed and transportable configurations. It is
applicable to both solids and liquids.
The technology uses a two-stage process to treat soil
contaminated with POPs. In the first stage, contaminated soil is
heated in a thermal reduction batch processor in the absence of
oxygen to temperatures around 600 °C. This causes organic
compounds to desorb from the solid matrix and enter the gas
phase. The treated soil is non- hazardous and is allowed to cool
prior to its disposal on or off site. In the second stage, the
desorbed gaseous-phase contaminants pass to a GPCR™ reactor,
where they react with introduced hydrogen gas at temperatures
ranging from 850 to 900 °C. This reaction converts organic
contaminants into primarily methane and water. Acid gases
such as hydrogen chloride may also be produced when chlorinated organic contaminants are present. The
gases produced in the second stage are scrubbed by caustic scrubber towers to cool the gases, neutralize
acids, and remove fine particulates. The off-gas exiting the scrubber is rich in methane and is collected
and stored for reuse as fuel. Methane is also used to
generate hydrogen for the GPCR™ process in a
catalyzed high-temperature reaction. Spent scrubber
water is treated by granular activated carbon filters
prior to its discharge (Refs. 12 and 33).
POPs TREATED: HCB, DDT, PCBs,
DIOXINS, AND FURANS
PRETREATMENT: THERMAL
DESORPTION
MEDIUM: SOIL, SEDIMENT, AND
LIQUID WASTE
FULL SCALE
EXSITU
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP;//\V WW. 1H PA. 1N FO/IJ R V'N ATO. H TM.
GPCR™ has been implemented at both full and pilot scales to treat solids and liquids contaminated with
POPs. The POPs treated include HCB, DDT, PCBs, dioxins, and furans. Table 3-5 presents performance
information for the technology. In 1992, GPCR was field-tested by EPA's Superfund Innovative
Technology Evaluation (SITE) Program to evaluate the performance of the technology at the Bay City
Middleground Landfill located in Bay City, Michigan (Ref. 14).
Table 3-5. Performance of GPCR™ Technology
Site
Kwinana Commercial
Operations
Kwinana Hex Waste
Trials
General Motors of
Canada Limited
Location
Australia
Australia
Canada
Period
1995 to 2000
April 1999
1996 to 1997
POP
PCBs
DDT
HCB
PCB
Dioxins
Quantity of
Soil Treated
2,000 tonnes
(2,200 tons)
8 tonnes
(9 tons)
1,000 tonnes
(1,100 tons)
Scale
Full
Full
Full
Destruction
Efficiency
> 99.9999%
> 99.9999%
> 99.9999%
> 99.99999%
> 99.9995%
Source: Ref. 12
The technology has been selected by the United Nations Industrial Development Organization for a pilot-
scale project to treat approximately 1,000 tons of PCB-contaminated waste in Slovakia. The technology
has also been licensed in Japan for treatment of PCB- and dioxin-contaminated wastes (Refs. 33 and 58).
The technology was developed by Eco Logic International Inc. in Ontario, Canada. Bennett
Environmental Inc. in Oakville, Ontario, Canada, recently acquired exclusive patent rights to the
technology. An update from previous reports is that this technology is not currently marketed, as it is
14
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
considered to be cost prohibitive. However, Bennett Environmental Inc. is modifying the technology to
improve its cost effectiveness (Ref. 40).
3.1.4 GeoMelt™
POPs TREATED: DIELDRIN, CHLORDANE,
HEPTACHLOR, DDT, HCB, PCBS, DIOXINS,
AND FURANS
MEDIUM: SOIL AND SEDIMENTS
FULL SCALE
EX SITU AND IN SITU
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP:/AV w w. i H PA. i NFO/I , i BRA R vNATO.H T M.
GeoMelt™ has been used to treat high-strength wastes
containing POPs. The technology is available for both
in situ and ex situ applications and in both fixed and
transportable configurations. GeoMelt™ vitrification is
a high-temperature technology that uses heat to destroy
POPs and to permanently immobilize residual
contaminants by incorporating them into the vitrified
end product. GeoMelt's in situ process is available in
two main configurations, In-Situ Vitrification (ISV) and
Subsurface Planar Vitrification (SPY'"). Both configurations use electrical current to heat, melt, and
vitrify material in place. ISV is suitable for treatment to depths exceeding 10 feet. SPY is suitable for
more shallow applications. GeoMelt™ also provides a
variation of SPY called Deep-SPV which facilitates
focused vitrification of limited-thickness treatment
zones greater than 30 feet deep. Electric current is
passed through soil using an array of electrodes
inserted vertically into the surface of the contaminated zone. Because soil is not electrically conductive, a
starter pattern of electrically conductive graphite and glass frit is placed in the soil between the electrodes.
When power is fed to the electrodes, the graphite and glass frit conduct current through the soil, heating
the surrounding area and melting directly adjacent soil. Once molten, the soil becomes conductive. The
melting proceeds outward and downward. Typical operating temperatures range from 1,400 to 2,000 °C.
As the temperatures increase, contaminants may begin to volatilize. When sufficiently high temperatures
are attained, most organic contaminants are destroyed in situ through thermally mediated chemical
reactions, yielding carbon dioxide, water vapor, and sometimes hydrogen chloride gas (if chlorinated
contaminants are present). Gaseous reaction products (such as hydrogen chloride) and volatilized
contaminants that escape in situ destruction are collected by an off-gas hood and are processed through an
aboveground off-gas treatment system before their discharge to the atmosphere. When the heating stops,
the medium cools to form a crystalline monolith vitrified end product, encapsulating contaminants that
were not destroyed or volatilized (Ref. 26).
GeoMelt's ex situ process, which is called In
Container Vitrification (ICY™), involves
heating contaminated material in a refractory-
lined container. A hood placed over the
container collects off-gases. The heat is
generated by either two or four 12-inch-
diameter, graphite electrodes positioned
vertically in the container. Typical operating
temperatures range from 1,400 to 2,000 °C. At
these temperatures, the waste matrix melts,
and organic contaminants are destroyed or
volatilized. The off-gas from the process
enters an off-gas treatment system, which
includes a baghouse particulate filter, high-
efficiency particulate air (HEPA) prefiltration,
aNOx (oxides of nitrogen) scrubber, a
Geomelt ™ ICV process. Source: Ref. 24
15
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
hydrosonic scrubber, a mist eliminator, a heater, and one or two HEPA filters. After treatment, the hood
is removed and a lid is installed on the refractory-lined container. When the melt has solidified, the
vitrified waste-filled container is disposed in a landfill based on the results of EPA Toxicity Characteristic
Leaching Procedure (TCLP) analysis.
GeoMelt™ is a full-scale treatment technology and has been used to treat such POPs as dieldrin,
chlordane, heptachlor, DDT, HCB, PCBs, dioxins, and furans (Ref 26). GeoMelt™ has also been used to
treat radioactive waste. Table 3-6 provides performance information for the technology.
Table 3-6. Performance of GeoMelt™ Technology
Site
Parsons
Chemical/
ETM
Enterprises
Superfund
Site
TSCA
Spokane
Wasatch
Chemical
WCS-
Commercial
TSCA
cleanup
WCS-Rocky
Flats
Location
Grand
Ledge,
Michigan
Spokane,
Washington
Salt Lake
City, Utah
Andrews,
Texas
Andrews,
Texas
Period
1993 to 1994
1994 to 1996
1995 to 1996
2005
2005
POP
DDT
Chlordane
Dieldrin
PCBs
Dioxins
DDT
Chlordane
HCB
PCBs
PCBs
Quantity
of Soil
Treated
4,350 tons
5,375 tons
5,440 tons
5 tons
11 tons
Scale
Full
Full
Full
Full
Pilot
Untreated
Concentration
(mg/kg)
340
89
4.6
17,860
0.011
1.091
535
17
496
130
Treated
Concentration
(mg/kg)
<4
<1
0.08
ND
ND
ND
ND
<0.08
ND
ND
Source: Ref. 24 and 33
Notes:
mg/kg = Milligram per kilogram
ND = Below detection limit
TSCA = Toxic Substance Control Act
WCS = Wasatch Chemical Superfund
GeoMelt™ is commercially available from AMEC Earth and Environmental, the sole licensee of this
technology in the United States. AMEC Earth and Environmental owns several GeoMelt™ systems of
varying sizes that are currently available for use.
3.1.5 In Situ Thermal Desorption
THE FACT SHEET PREPARED BY EPA IS
INCLUDED IN APPENDIX C.
ISTD has been used to treat both high- and low-strength
wastes containing POPs. ISTD is primarily an in situ
technology but has also been used ex situ on constructed soil
piles. ISTD is a thermally enhanced, in situ treatment
technology that uses conductive heating to directly transfer heat to environmental media. "ISTD" has
been a nonspecific term used to refer to in situ technologies that use heat to enhance the removal of
16
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
volatile subsurface contaminants. The most common ISTD methods include steam and resistive heating.
Enhanced soil vapor extraction (ESVE) is a commonly used synonym for ISTD. However, this section
uses "ISTD" to refer to a specific proprietary technology that is distinct in its methods. ISTD, sometimes
also known as "In Situ Thermal Destruction" is a patented technology developed by Shell Oil Co. and
TerraTherm, which holds the exclusive license to the technology and is currently the only vendor.
There are three basic elements in the ISTD process (Ref 51):
1. Application of heat to contaminated media by thermal conduction
2. Collection of desorbed contaminants through vapor extraction
3. Treatment of collected vapors
ISTD uses surface heating blankets or buried,
electrically powered heaters to heat
contaminated media. In the most common
setup, a vertical array of heaters is placed in
wells drilled into the remediation zone.
Surface heating blankets are less commonly
used. As the matrix is heated, adsorbed and
liquid-phase contaminants begin to vaporize.
Once high soil temperatures are achieved, a
significant portion of the organic contaminants
either oxidizes (if sufficient air is present) or
pyrolizes. Desorbed contaminants are
recovered through a network of vapor
extraction wells. Contaminant vapors captured
by the extraction wells are conveyed to an off-
gas treatment system for treatment prior to
their discharge to the atmosphere. TerraTherm
offers two different methods of vapor
treatment. One method treats extracted vapor without phase separation and uses a thermal oxidizer to
break down organic vapors to primarily carbon dioxide and water. Thermal oxidation may be followed
by vapor phase activated carbon absorption. The second method uses a heat exchanger to cool extracted
vapors. The resulting liquid phase is then separated into aqueous and nonaqueous phases. The
nonaqueous-phase liquid (NAPL) is usually disposed of at a licensed treatment, storage, or disposal
facility. The aqueous phase is passed through liquid-phase activated carbon adsorption units and is then
discharged. Cooled, uncondensed vapor is passed through vapor-phase activated carbon adsorption units
and is then vented to the atmosphere (Refs. 6, 21 and 51).
ISTD process at the Alhambra site. Source: Ref. 51
POPs TREATED: PCBs, DIOXINS, AND FURANS
MEDIUM: SOIL AND SEDIMENT
COSTS: $200 TO $600 PER CUBIC YARD (COST
IN USD, DATA FROM 1996 TO 2005)
FULL SCALE
INSITU
Pilot- and full-scale applications of ISTD have been
used to remove PCBs, dioxins, and furans.
According to TerraTherm, laboratory-scale work
indicates that this technology can also effectively treat
other POPs, including aldrin, dieldrin, endrin,
chlordane, heptachlor, DDT, mirex, HCB, and
toxaphene. However, these contaminants have not
yet been treated using ISTD at full or pilot scale.
ISTD was field-tested by EPA's SITE Program to
evaluate the performance of the technology at the Rocky Mountain Arsenal (RMA) site near Denver,
Colorado. The site was contaminated with hexachlorocyclopentadiene, aldrin, chlordane, dieldrin,
endrin, and isodrin (Ref. 20).
17
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Four full-scale and two pilot-scale ISTD projects at POP-contaminated sites were identified. In general,
treatment costs in USD at these sites ranged from $200 to $600 per cy. Projects involving ISTD
treatment of larger volumes of waste will have lower unit costs. Available performance information for
the technology is presented in Table 3-7.
Table 3-7. Performance of ISTD Technology
Site
Former South
Glens Falls
Dragstrip
Tanapag Village
Centerville
Beach
Missouri
Electric Works
Former Mare
Island Naval
Shipyard
Alhambra
"Wood Treater"
Location
Moreau,
New York
Saipan,
Northern
Mariana
Islands
Ferndale,
California
Cape
Girardeau,
Missouri
Vallejo,
California
Alhambra,
California
Period
1996
July 1997 to
August 1998
September to
December
1998
March to
June 1997
September to
December
1997
May 2002 to
January 2005
POP
PCBs
PCBs
PCBs
Dioxins
and
Furans
PCBs
PCBs
Dioxins
Quantity of
Soil Treated
NA
1,000 cy
667 cy
NA
222 cy
16,200 cy
Scale
Full
Full
Full
Pilot
Pilot
Full
Untreated
Concentration
5,000 mg/kg
10,000 mg/kg
860 mg/kg
3.2|ig/kg
20,000 mg/kg
2,200 mg/kg
194 u.g/kg
Treated
Concentration
0.8 mg/kg
< 1 mg/kg
< 0.17 mg/kg
0.006 ug/kg
O.033 mg/kg
O.033 mg/kg
<1 ug/kg
Source: Refs. 7, 48, 50 and 51
Notes:
cy = Cubic yard
|lg/kg = Microgram per kilogram
mg/kg = Milligram per kilogram
NA = Not available
3.1.6 Mechanochemical Dehalogenation
MCD™ has been used to treat high-strength wastes
containing POPs. The MCD™ technology uses
mechanical energy to promote reductive dehalogenation
of contaminants. In this process, contaminants react with
a base metal and a hydrogen donor to generate reduced
organics and metal salts. The base metal is typically an
alkali-earth metal, an alkaline-earth metal, aluminum,
zinc, or iron. The hydrogen donors used include alcohols,
ethers, hydroxides, and hydrides. The process occurs ex
situ in an enclosed ball mill, and the grinding medium provides the mechanical energy and mixing. The
technology is applicable to soil, sediments, and mixed solid-liquid phases. The by-products generated at
the end of the process are nonhazardous organics and metal salts (Ref 54). Additional information about
the technology is available at http://www.ihpa.info/libraiyNATO.httn.
POPs TREATED: DDT, ALDRIN, AND
DIELDRIN
MEDIUM: SOIL, SEDIMENT AND LIQUID
WASTES
FULL SCALE
EXSITU
18
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
One MCD™ process developed by Environmental
Decontamination Ltd. (EDL) is being used at full
scale to treat soil at the Fruitgrowers Chemical
Company site in Mapua, New Zealand. The site is
the location of a former pesticide and herbicide
manufacturing plant that operated from 1950 to
1980. The site is approximately 8.4 acres in area
and contains about 706,280 cubic feet of soil
contaminated with DDT, ODD, DDE, aldrin,
dieldrin, and lindane. Proof of performance testing
of the MCD™ process was conducted at the site
between February 16 and April 23, 2004. The
objective of the testing was to demonstrate the
technology's ability to treat the contaminated soil to
meet the cleanup standards for commercial land use.
The cleanup criteria are listed in Table 3-8 and the
proof of performance testing results are listed in
MCD process at the Mapua Site. Source: Ref. 54
Table 3-9. The criteria are based on the concentration
of DDX (the sum of the concentrations of DDT,
dichlorodiphenyldichloroethane [ODD], and
dichlorodiphenyldichloroethylene [DDE]) and the
sum of the concentrations of aldrin, dieldrin, and
lindane.
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://\V ww. i H PA. i N FO/I \ BRA R vN ATO. H TM.
Table 3-8. Soil Acceptance Criteria for the Mapua Site
Land Use
Commercial
Depth
(meters)
0 to 0.5
Below 0.5
DDX (Total DDT, DDD, and DDE)
(mg/kg)
5
200
Aldrin + Dieldrin + Lindane
(nig/kg)
3
60
Source: Ref. 54
Notes:
mg/kg = Milligram per kilogram
At the Mapua site, soil greater than 10 millimeters (mm) size fraction has contaminant concentrations
below the soil acceptance criteria for the site and requires no treatment. EDL receives contaminated soil
which is less than 10 mm in size. The 10 mm size fraction soil is dried and then passed through a 2 mm
screen to segregate soil particles less than and greater than 2 mm size. Contaminated soil less than 2-mm
size is treated using the MCD™ process. Additional information on the soil drying and screening
processes and the MCD™ process are described below.
Soil Drying
The contaminated soil enters a temperature controlled, diesel-fired rotary drum unit. As the soil passes
through the drier, the soil particles undergo size reduction. The moisture content in soil exiting the drier
is typically less than 2 percent. Gaseous emissions from the drier are treated by an air quality control
system consisting of cyclones, a baghouse, a scrubber and an activated carbon filter.
19
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Soil Screening
Soil exiting the drier is passed through a rotary screen to separate soil particles by size range. Soil
particles less than 2 mm in size are separated from soil particles between 2 and 10 mm in size. Soil
samples are collected from the 2- to 10-mm fraction stream and analyzed. Thus far, DDX concentrations
in this size fraction have been at or below cleanup standards and have consequently not required
treatment. The less than 2-mm fraction stream and the fines from the cyclones and baghouse are fed into
the MCD™ reactor.
MCD™ Process
The dried contaminated soil (the less than 2-mm fraction) and the fines from the cyclones and baghouse
fed into the MCD™ reactor are mixed with metered quantities of a combination of metal salts and a
hydrogen donor at a rate of around 3 percent by mass. The reactor is a vibratory mill that has two
horizontally mounted cylinders containing a grinding medium. The grinding medium provide the
mechanical impact energy required to drive the chemical reaction. Treated soil exits the base of the
MCD™ reactor through enclosed screw conveyors and enters a paddle mixer, where the treated material is
wetted to minimize dust generation. The required residence time within the reactor is about 15 minutes.
The treated soil is then analyzed. Once treatment of soil to cleanup standards has been completed, treated
soil is placed in a clean backfill area.
During the proof of performance testing at the Fruitgrowers Chemical Company site in Mapua, New
Zealand, the MCD™ system exhibited a maximum treatment rate of 139 cubic meters per week. Table 3-9
lists the initial and final mean contaminant concentrations in the soil treated in the MCD™ reactor. The
concentrations listed in Table 3-9 are mean concentrations in samples collected between February 16 and
April 23, 2004. The treated soil met the cleanup criteria for soil more than 0.5 m below ground surface
but did not meet the criteria for soil from 0 to 0.5 m below ground surface.
Table 3-9. Performance of MCD™ Technology at the Mapua Site
POP
DDX
Aldrin
Dieldrin
Lindane
Aldrin+Dieldrin
+Lindane
Untreated
Concentration
(mg/kg)
717
7.52
65.6
1.25
73.245
Treated
Concentration
(mg/kg)
64.8
0.798
19.8
0.145
20.612
Percent
Reduction
91%
89%
70%
88%
72%
Soil Acceptance Criteria by Depth
(meters)
0 to 0.5
5
NA
NA
NA
3
>0.5
200
NA
NA
NA
60
Source: Ref 54
Notes:
mg/kg = Milligram per kilogram
NA = Not available
Subsequent to the Proof of Performance testing, EDL was commissioned to remediate the site with an
expected completion date in 2006. EDL has developed a proprietary reactor that eliminates the need for a
vibratory ball mill. Experience has indicated that soil composition affects the performance of the process.
Clays in particular have been shown to have a negative performance impact. EDL plans to conduct pilot
tests on its reactor in the United States during the later part of 2005. These trials will involve DDT,
lindane, and PCBs.
20
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
The MCD™ technology is available from EDL in Auckland, New Zealand (http://edl.net.nz/about.php').
and from Tribochem in Wunstrof, Germany (http://www.tribochem.com) (Ref 8). Information was
provided by EDL. Tribochem has not provided process details, performance data, or costs for its
technology.
3.1.7 Xenorem™
Xenorem™ is an ex situ bioremediation technology that has been used to treat low-strength wastes
containing chlordane, DDT, dieldrin, and toxaphene contamination. Xenorem™ uses an enhanced
composting technology consisting of aerobic and anaerobic treatment cycles. Organic amendments such
as manure and wood chips are added to contaminated soil, which can increase the final amended soil
volume by as much as 40 percent (Ref. 30). i^^^^^^^^^^^^^^^^^^^^^^^^^^^^=i
A self-propelled SCAT windrow incorporates
the amendments into the soil and provides
aeration creating aerobic conditions. The
presence of high levels of available nutrients MEDIUM: SOIL
from the amendment increases the metabolic
activity in the amended soil and depletes the
oxygen content, creating anaerobic conditions.
The anaerobic conditions promote „
EX SITU
dechlorination of organochlorine compounds.
POPs TREATED: CHLORDANE, DDT, DIELDRIN,
AND TOXAPHENE
COSTS: $132 PER CUBIC YARD (COST IN 2000
USD)
The length of the anaerobic phase is determined
by bench-scale studies. At the end of the anaerobic phase, the SCAT unit is used to mix the amended
soil, creating aerobic conditions again. The anaerobic and aerobic cycles are repeated until the desired
contaminant reductions are achieved. Typically, by the end of 14 weeks of treatment the organic
amendments are spent. Soil samples are collected from the treated soil, and if the contaminant
concentrations do not meet the cleanup goals, more organic amendments are added; the treatment is
continued as long as necessary.
This technology was applied in a full-scale cleanup at the Stauffer Management Company Superfund site
in Tampa, Florida. The site is the location of a pesticide manufacturing and distribution facility that
operated from 1951 to 1986 (Ref. 13). Soil on the 40-acre site was contaminated with chlordane, ODD,
DDE, DDT, dieldrin, molinate, and toxaphene. The Xenorem™ technology was applied to two 4,000-cy
batches of soil. The first batch was completed in 2001 and the second batch was completed in 2002. The
contaminated soil was excavated; screened; mixed; and amended with dairy cow manure, chicken litter,
and wood chips. The amended soil matrix was then placed in a compost windrow. The temperature,
oxidation-reduction potential, and moisture level of the amended soil matrix were continuously monitored
(Ref. 13). Table 3-10 presents the performance data for Batch 1 and Batch 2. Batch 1 was treated for a
total of 24 weeks and achieved the site cleanup goals for chlordane, ODD, DDE, dieldrin, and molinate.
After 12 weeks of treatment, Batch 2 achieved the site cleanup goals for chlordane, DDE, dieldrin, and
molinate. The treatment of Batch 2 extended beyond 12 weeks; the final performance data for Batch 2
are not yet available from the vendor. Neither batch achieved the site cleanup goals for DDT and
toxaphene. Typical treatment costs in USD using Xenorem™ were provided by the vendor and are
approximately $132 per cy of contaminated soil (Ref. 16)
The Xenorem™ technology was applied to a third batch of contaminated site soil. Batch 3 was treated for
one year but did not achieve the cleanup goals for chlordane, DDT, dieldrin, and toxaphene. Because the
selected remedy did not fully meet the cleanup goals, the remedial design for the site is being modified.
EPA is awaiting details of the modification proposal. Eventually EPA will prepare an Explanation of
Significant Difference (ESD) fact sheet explaining the selection of anew remedy (Ref. 29).
21
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Table 3-10. Performance of Xenorem™ Technology at the Tampa Site
Pesticide
Chlordane
DDD
DDE
DDT
Dieldrin
Molinate
Toxaphene
Site
Cleanup
Goal
(mg/kg)
2.3
12.6
8.91
8.91
0.19
0.74
2.75
Batch 1 a
Untreated
Concentration
(mg/kg)
3.8
26
6.6
82
2.4
0.2
129
Treated
Concentration
(mg/kg)
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
IIITP://mYW.IIIPA.INFO/LIBR4RYNATO.IITM.
At the Warren County PCB Landfill site in Warren
County, North Carolina, a full-scale demonstration
of BCD was proposed by the North Carolina
Department of Environment and Natural Resources
(NCDENR). After completing the first stage,
thermal desorption of contaminated site soil, NCDENR decided to incinerate the residual, highly
contaminated waste oil condensate instead of performing the second-stage BCD reaction (Ref 34). The
off-site incineration activities were completed in June 1996.
POPs TREATED: PCBs, DIOXINS,
AND FURANS
PRETREATMENT: THERMAL
DESORPTION
MEDIUM: SOIL AND LIQUIDS
PILOT SCALE
EXSITU
BCD has been implemented at a bench scale to treat soil
contaminated with POPs. In 2004, EPA sent a sample of
contaminated waste oil from the Warren County PCB Landfill
site to an analytical laboratory in order to perform a bench-scale
demonstration. Results from the bench scale study indicate that
total PCBs were reduced from 81,100 mg/kg to below the
detection limit of 5 mg/kg. Total tetrachlorodibenzodioxin
(TCDD) was reduced from 5,800 nanogram per kilogram
(ng/kg) to 9.1 ng/kg. A second bench scale study was conducted
by EPA in 2005. The second bench scale study indicated that
PCBs were reduced from 5,280 mg/kg to below the detection
limit of 5 mg/kg. Total TCDD was reduced from 5,800 ng/kg to
15.0 ng/kg (Ref. 37).
BCD was developed by EPA's National Risk Management Research Laboratory in Cincinnati, Ohio.
EPA holds the patent rights to this technology in the United States. The foreign rights for this technology
are held by BCD Group Inc., Cincinnati, Ohio. The technology has been licensed by BCD Group Inc., to
environmental firms in Spain, Australia, Japan and Mexico. Since the invention of the BCD technology
in 1990, considerable technology advancements have been made with the discovery of a new catalyst.
The catalyst used in the second generation BCD technology reduces the reaction time in the BCD reactor
(Ref. 44). This second generation technology has been in Australia, Mexico and Spain to treat PCB
contaminated oil. Two commercial BCD plants are being constructed in Czech Republic and will begin
operation in 2006. At this time, performance data for the BCD operations in Australia, Mexico, and
Spain are not available from the vendors.
3.2.2 CerOx™
CerOx™ is an ex situ electrochemical reaction technology
that has been used in pilot tests to treat low-strength liquids
containing POP
POPs TREATED: CHLORDANE, DIOXINS,
AND PCBS
PRETREATMENT: SOIL AND SEDIMENT
ARE MIXED WITH WATER TO PRODUCE A
FLUID INFLUENT
MEDIUM: LIQUIDS
PILOT SCALE
EXSITU
contamination.
CerOx™ uses
cerium in its
highest valence
state (IV) to
oxidize organic
compounds,
including
POPs, to form
carbon dioxide,
water, and inorganic acid gases. The technology uses an
electrochemical cell to produce cerium (IV) from cerium
23
CerOx™ treatment system,
Source: Ref. 9
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
(III). Prior to treatment, solid waste such as soil or sediment is mixed with water to produce a fluid waste
stream. This waste stream is injected with cerium (IV) from the electrochemical cell, agitated through
sonication, and transferred to a liquid-phase reactor. The liquid-phase reaction takes place at a
temperature between 90 and 95 °C and results in the destruction of organic compounds in the waste
stream. During this process, cerium (IV) is reduced to cerium (III). Cerium (III) and unreacted cerium
(IV) are returned to the electrochemical cell for recycling, and the treated medium is removed from the
system. Gases produced during the liquid-phase reaction usually include carbon dioxide, chlorine gas,
and unreacted volatile organic compounds Volatile Organic Compounds (VOC). These gases are
processed through a gaseous-phase reactor that uses cerium (IV) to destroy VOCs. The remaining gases
are passed through a scrubber to remove acid gases and are then vented to the atmosphere. Liquid from
the scrubber is discharged (Ref 9).
The information sources used to prepare this report did not describe any applications of CerOx™ systems
at a pilot or full scale for treatment of POP-contaminated soil or sediment. CerOx™ systems have been
used to treat POP-contaminated liquids. The first CerOx™ system was installed at the University of
Nevada at Reno (UNR) to destroy surplus chlorinated pesticides and herbicides from the university's
agricultural departments. Prior to use of this system by UNR, CerOx Corporation conducted proof of
performance tests in May 2000. The medium treated was a pesticide-water emulsion. In one test, 71
percent by mass chlordane was mixed with water and t
fed to the system. The system is reported to have
achieved a chlordane destruction efficiency of 99.995
percent in the gaseous-phase reactor (Ref. 4).
Chlordane concentrations in the liquid effluent were
not reported.
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://\V ww. i H PA. i N FO/I \ BRA R vN ATO. H TM.
The vendor later performed additional tests of the UNR system to determine the ability of CerOx™ to
treat PCBs and dioxins (Ref. 58). A treatment test was performed on August 29, 2000, using a feed
stream consisting of three commercially available dioxins dissolved in isopropyl alcohol. The dioxins in
the feed stream were present at a concentration of 5 parts per billion (ppb). Two of three samples
collected from the system's effluent contained dioxins at concentrations lower than their detection limit of
0.397 part per trillion (ppt). One sample had a dioxin concentration of 0.432 ppt. The UNR system was
tested again on August 30, 2000, using a liquid sample from a remedial operation being performed in
Fayetteville, North Carolina. The sample consisted of an isopropyl alcohol solution containing about 2
parts per million (ppm) PCBs. The system effluent contained PCB concentrations less than the minimum
detection limit of 0.4 ppb PCBs (Ref. 9).
The technology was developed by CerOx™ Corporation in Santa Maria, California. CerOx™ Corporation
offers a variety of CerOx™ treatment systems for commercial use. The systems range in size from
modules with 25-gallon per day (gpd) treatment capacities to multimodular plants with 100,000-gpd
treatment capacities (Ref. 9).
3.2.3 Phytotechnology
Phytotechnology is a process that uses plants to remove,
transfer, stabilize, or destroy contaminants in soil, sediment, and
groundwater. It may be applied in situ or ex situ to treat low-
strength soils, sludges, and sediments contaminated with POPs.
The mechanisms include:
MEDIUM: SOIL AND SEDIMENT
PILOT SCALE
EX SITU AND IN SITU
• Enhanced rhizosphere biodegradation (degradation in the soil immediately surrounding plant
roots),
24
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
• Phytovolatilization (the transfer of the pollutants to air via the plant transpiration stream),
• Phytoextraction (also known as phytoaccumulation, the uptake of contaminants by plant roots and
the translocation/accumulation of contaminants into plant shoots and leaves),
• Phytodegradation (metabolism of contaminants within plant tissues),
• Phytostabilization (production of chemical compounds by plants to immobilize contaminants at
the interface of roots and soil), and
• Hydraulic control (the use of trees to intercept and transpire large quantities of groundwater or
surface water for plume control).
In general more proven field studies have been conducted using phytostabilization and hydraulic control
mechanisms. Other proven uses of phytotechnologies include alternative landfill caps, the use of
wetlands to improve water quality, and treatment of certain contaminants (such as petroleum products and
chlorinated solvents).
Phytoremediation of POPs is not feasible for stockpiles of contamination but provides an appropriate
polishing technology for residual contamination in soils. Initial laboratory research identified enhanced
degradation of PCBs in the rhizosphere (Refs. 11, 27, and 36). Other researchers are finding promising
results for phytoextraction in the laboratory and at the pilot scale phase. The Connecticut Agricultural
Experimental Station's preliminary data has shown that a narrow range of plant species (certain
cucurbitas) can effectively accumulate significant amounts of highly weathered pesticide residues such as
DDE and chlordane from soil (Ref 61). The Royal Military College of Canada has also demonstrated
that certain plants species can extract and store significant levels of PCBs and DDT (Ref. 62). Both the
Ukraine and Kazakhstan have been conducting research on the use of plants to remediate soils laced with
pesticides. In the Ukraine, laboratory experiments have shown that bean plants can accumulate and
decompose DDT (Ref. 38). In Kazakhstan, native vegetation that can tolerate and accumulate pesticides
has been identified (Ref. 39).
While research is still active and needed, field scale
projects are also occurring. A clean-up project was
conducted at a 40 year old scrap yard site with PCB
contaminated soils at the 225 ppm level. The site
contamination was approximately 2 acres in area and
three feet deep. The clean-up project demonstrated
that PCB concentrations decreased (over 90%) in the
presence of red mulberry trees and bermuda grasses
within 2 years (Ref. 31). Another example is an
Evapotranspiration Cover that will be constructed at
the Rocky Mountain Arsenal (RMA) National
Wildlife Refuge near Denver, Colorado; the cover will
address contaminants including aldrin, chlordane,
DDT, dieldrin, and endrin. A field demonstration
project was used as the basis of the final design, which
will include five projects that encompass 400 acres.
The selected seed mix for the site includes ten grass
species and ten wildflower species native to the site
(Ref. 34).
25
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Furthermore, two EPA Superfund sites have utilized phytotechnology as a treatment for POPs:
• Aberdeen Pesticides Dumps in North Carolina is utilizing phytotechnology for residual
contaminants (dieldrin and HCB) using poplar trees and grasses. This is an on-going project.
• Fort Wainwright in Alaska utilized ex-situ phytotechnology for aldrin and dieldrin with willow
trees. After treatment, the soil was deposited in the site landfill rather than a hazardous waste
landfill.
3.2.4 Solvated Electron Technology
Solvated electron technology uses solvated electron
solutions to reduce organic compounds to metal salts
and the parent dehalogenated molecules. Solvated
electron solutions are formed by dissolving alkali or
alkaline earth metals such as sodium, calcium, and
lithium in solvents such as anhydrous liquid ammonia.
Commodore Solution Technologies, Inc., the vendor of the technology, is not currently marketing the
technology because of its high treatment costs.
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
IITTP;//W\V\V.IHPA.INFO/LIBRARYNATO.HTM.
POPs TREATED: PCBs
PRETREATMENT: SOIL is MIXED WITH
SOLVENT TO PRODUCE A SLURRY
MEDIUM: SOIL
PILOT SCALE
EXSITU
3.2.5 Sonic Technology
Sonic technology is an ex situ technology that is used
to treat low- and high-strength soils containing PCB
contamination.
In this process, contaminated soil is first mixed with a
solvent. The mixture is then subjected to sonic energy
generated by a proprietary low-frequency generator.
Using sonic energy, the mixture is agitated and the PCBs from the soil are extracted and suspended in the
solvent. The solvent is then separated from the mixture using multistage liquid separators. The solvent is
then mixed with elemental sodium, and subjected to sonic energy again. The sonic energy activates
dechlorination of the PCBs in the solvent. The spent solvent can then be recycled through the system.
Any off-gas from the process is treated using condensation, demisting, and multistage carbon filtration
(Ref. 45).
In a pilot scale application of the technology to
treat PCB-contaminated soil, the concentrations
of PCBs before treatment were 388 to 436
mg/kg, and the concentrations after treatment
were 0.35 to 0.81 mg/kg. The technology is
being implemented at full scale to treat
approximately 3,000 tons of PCB-contaminated
soil at the Juker Holdings site in Vancouver,
British Columbia, Canada (Ref. 45). Additional
performance data of the full scale application of
this technology are not currently available.
The technology was developed by Sonic
Environmental Solutions Inc. in Vancouver,
Canada.
Sonic technology process. Source: Ref. 45
26
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
3.3 Bench-Scale Technologies for Treatment of POPs
This section describes the technologies that have been implemented to treat POPs at the bench scale.
Each subsection focuses on a single technology and includes a description of the technology and
information about its application at specific sites. Fact sheets developed by IHPA contain additional
details on some of these technologies and their applications. Links to the IHPA fact sheets are included in
the appropriate subsections of this report.
3.3.1 Self-Propagating High-Temperature Dehalogenation
Self-Propagating High-Temperature Dehalogenation (SPHTD) is an ex situ technology used to treat
stockpiles containing HCB contamination.
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://W\VW.IIIPA.LNTO/LIBRARYNATO.IITM.
HCB containing stockpiles are mixed with calcium
hydride or calcium metal, and the mixture is placed in
a reaction chamber containing a tungsten coil.
Addition of purified argon gas causes the reaction
chamber to become pressurized, and an electrical
pulse to the tungsten coil initiates the reaction. Once initiated, the reductive reactions that occur in the
reaction chamber are exothermic and self-propagating. The reaction chamber can reach a temperature of
3,727 °C, which creates thermochemical conditions that convert HCB to calcium chloride, carbon, and
hydrogen (Ref 58).
POPs TREATED: HCB
MEDIUM: POP STOCKPILES
BENCH SCALE
EXSITU
SPHTD has been tested at bench scale using materials contaminated
with HCB, but no bench-scale test results are available (Ref. 32). The
information sources used to prepare this report did not provide
information about application of the technology at the pilot or full
scale. The SPHTD technology is being developed by Centre Studi
Sulle Reazioni Autopropaganti in Italy.
3.3.2 TDR-3R
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
TDR-3R™ is an ex situ technology used to treat high-
and low-strength soils containing HCB contamination.
The TDR-3R™ technology uses a continuous low-
temperature thermal desorption process conducted in the absence of air. The main component of this
process is a specially designed, indirectly fired, horizontally arranged rotary kiln. Contaminated soil is
heated in the kiln to a temperature typically between 300 and 350 °C under an applied vacuum of 0 to 50
Pascal. In some instances, the kiln is heated to higher temperatures when POPs are being treated. The
contaminants in the soil desorb and vaporize in the kiln. The vaporized contaminants are recovered from
the kiln and combusted in a thermal oxidizer for at least 2 seconds at a temperature exceeding 1,250 °C.
Off-gas from the thermal oxidizer is rapidly cooled, passed through a wet gas multi-venturi scrubber, and
i^^^^^^^^^^^_^^^^^^^^^^^^i discharged. Process water from the scrubber is treated
and discharged. Treated soil exiting the kiln is cooled
indirectly and removed (Refs. 33 and 52).
POPs TREATED: HCB
PRETREATMENT: THERMAL DESORPTION
MEDIUM: SOIL
BENCH SCALE
EXSITU
TDR-3R™ has been implemented at a bench scale in
Gare, Hungary, to treat 100 kilograms (kg) of soil
contaminated with HCB. Treatment occurred at a
temperature of 450 °C under a vacuum of 30 Pascal.
27
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
The technology reduced the soil's HCB concentration from 1,215 to 0.1 mg/kg (Ref. 53).
TDR-3R™ is marketed by Terra Humana Clean Technology Engineering Ltd. in Hungary. This firm is a
subsidiary of Thermal Desorption Technology Group LLC in the United States. The firm has developed
pilot scale kilns that operate at a throughput of 0.1 tons per hour. Larger kilns that operate at throughputs
from 5 to 70 tons per hour are still conceptual (Ref. 52).
3.3.3 Mediated Electrochemical Oxidation (AEA Silver II™)
AEA Silver II™ is an ex situ technology used to treat low-strength wastes containing POPs.
The AEA Silver II process uses Ag ions to oxidize I THE FACT SHEET PREPARED BY IHPA is
organic compounds, including POPs, to form carbon II AVAILABLE AT
dioxide, neutral salts, and dilute acid solutions. The II IITTP://WWW^
process operates at low temperatures (60 to 90 °C) and 11^^^^^^^^^^^—^^^^^^^^^^^—
at atmospheric pressure.
According to AEA Technologies Inc., the vendor of the technology, AEA Silver II™ is not applicable for
soil or sediment. The contaminant has to be in an aqueous phase for the technology to be applied.
Therefore, pretreatment is needed to extract the contaminant from the solid phase to an aqueous phase.
AEA Technologies Inc. is not currently marketing this technology.
3.4 Full-Scale Technologies with Potential to Treat POPs
This section describes technologies that have been implemented to treat non-POPs at full scale and that
are potentially applicable for treatment of POPs. Each subsection focuses on a single technology and
includes a description of the technology and information about its application at specific sites. Fact sheets
developed by IHPA contain additional details on some of these technologies and their applications. Links
to the specific IHPA fact sheets are included in the appropriate subsections of this report.
3.4.1 Plasma Arc
Plasma arc technologies use a thermal plasma field to treat contaminated wastes. The plasma field is
created by directing electric current through a gas stream under low pressure to form a plasma with a
temperature ranging from 1,600 to 20,000 °C. Bringing the plasma into contact with the waste causes
contaminants to dissociate into their atomic elements. The separated elements are subsequently cooled,
which causes them to recombine to form inert compounds. The process may also destroy organic
compounds through pyrolysis. The end products are typically gases, such as carbon monoxide, carbon
dioxide, hydrogen and inert solids. If chlorinated compounds are present in the waste, acid gas is also
generated as an end product. The off-gas from the plasma arc system passes through an off-gas treatment
system and is then discharged. The plasma arc technologies that are used to treat organic wastes include
PLASCON™, Plasma Arc Centrifugal Treatment (PACT), and the Plasma Converter System (PCS). The
PLASCON and PCS may potentially remediate POPs; however, the PACT technology has treated POP
contamination at pilot scale. These technologies are described below (Ref. 58).
3.4.1.1 PLASCON™
PLASCON™ is an ex situ technology that can be used to treat both solid and liquid waste streams. It is
potentially applicable to both low- and high-strength wastes containing POP contamination.
28
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
discharge through argon gas to create plasma with a *^ PREPARE° BYIHPAK
The PLASCON™ technology passes a direct current
discharge through argon gas to create plasma with a
temperature greater than 10,000 °C. Liquid or gaseous „ , .,. „_
...... , • , , 01-7 • iiiiP://wwwjiiPAjxFO/LiBR4RYNATO.iiiM.
waste is injected directly into the plasma. Solid waste is
pretreated using thermal desorption to extract volatile
contaminants. The extracted vapors are then condensed and injected into the plasma as liquid waste.
Liquid waste is vaporized by heat transfer from the plasma. Organic compounds present in the waste
pyrolize. The products formed during pyrolysis pass through a reaction tube providing sufficient
residence time to ensure complete decomposition of the feed material. Gases exit the tube at a
temperature of about 1,500 °C and are rapidly cooled to less than 100 °C in a spray condenser using an
alkaline spray solution. The gases are further cooled and scrubbed of any remaining acid gases in a
packed tower. Off-gases, which contain mainly carbon monoxide and argon, are then thermally oxidized
to convert carbon monoxide to carbon dioxide (Ref. 33).
BCD Technologies Private Limited in Brisbane, Australia, purchased a PLASCON™ plant to treat PCB-
contaminated wastes. This firm used a thermal desorption system in conjunction with PLASCON™ to
treat a range of solid and semi-solid waste streams (Ref. 46). Performance data for this system are not
available in the information sources used to prepare this report.
PLASCON™ has been used at full scale to treat various organic contaminants. SRL Plasma Pty. Ltd., an
Australian company, is the patent holder of this technology.
3.4.1.2 Plasma Arc Centrifugal Treatment
PACT is an ex situ technology that can be used to treat low- and high-strength wastes containing POP
contamination.
PACT uses heat generated by a plasma torch to melt and vitrify contaminated feed material. Primary
treatment occurs inside a centrifuge tank housing the plasma torch. Centrifugal force produced by the
rotating tank pushes the waste material away from the center and into the plasma torch's field of
influence. The plasma torch heats waste material within its field of influence to a temperature of about
1,650 °C (Ref. 10). At the end of primary treatment, the tank stops rotating and the molten waste exits the
tank through a chute at the center of the tank. Molten waste is collected in molds and cooled to form
vitreous solids. Volatilized contaminants pass from the centrifuge tank to a natural gas-fueled secondary
treatment tank. Secondary treatment of gaseous contaminants occurs at a temperature of about 1,000 °C.
This part of the process ensures destruction of products of incomplete combustion such as dioxins and
furans. Exhaust gases are discharged to an off-gas treatment system that cools the exhaust and scrubs it to
remove acid gases (Ref. 43).
PACT has been used at a pilot scale to treat waste contaminated with HCB and has been used at full scale
to treat contaminants other than POPs. Waste containing HCB was treated in a PACT demonstration
plant in 1991 (Ref. 43). The vendor, Retech Systems LLC, plans to ship a PACT system to Russia in
2005 for treatment of capacitors contaminated with PCBs (Ref. 43).
PACT is a full-scale treatment technology that is manufactured and marketed in the United States by
Retech Systems LLC.
3.4.1.3 Plasma Converter System
PCS is an ex situ technology that can be used to treat soil, liquid, and gaseous waste streams. It is
potentially applicable to both low- and high-strength wastes containing POP contamination.
29
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
PCS uses plasma generated by a torch inside a cylindrical reaction chamber. Mixed waste fed into the
reaction chamber passes through the plasma as the waste moves from one end of the chamber to the other.
The arc inside the plasma can reach a temperature as high as 16,000 °C. Contaminants dissociate into
their constituent elements within the plasma. The elements recombine outside the plasma to form gaseous
and molten products. Molten material formed in the reaction chamber is removed from the bottom of the
chamber and cooled to form inert solids. These solids can include metals and inert silicate stones.
Exhaust gases from the reaction chamber pass through an off-gas treatment system and are then
discharged. The off-gas treatment system includes a cyclonic separator for removal of particulate matter,
cartridge filters for dust removal, a catalytic converter for reduction of oxides of nitrogen, and a scrubber
for removal of acid gases. The recovered gas may be used to produce polymers or fuel gas (Refs. 10 and
47).
The PCS is a full-scale technology that is manufactured and marketed in the United States by
STARTECH Environmental Corp. The plasma converter vessel is available in several sizes with
treatment capacities ranging from 5 to 100 tons per day (Ref. 47). The technology vendor, STARTECH
Environmental Corp., has stated that the PCS could be tailored to treat PCBs and HCB.
3.4.2 Supercritical Water Oxidation
SCWO is an ex situ technology that has been used to treat solid and liquid wastes. It is potentially
applicable to both low- and high-strength wastes containing POP contamination. Current SCWO systems
are non transportable.
SCWO occurs in an enclosed system at a temperature
and pressure above the critical point of water (374 °C
and 22.1x10 Pascal). Under these conditions, the
,..,, , , . • ... j ... IITTP://W WW. 1H PA. 1N FO/IJ R V'N ATO. H TM.
gas-liquid phase boundary ceases to exist and water
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
exists in a fluid state that is neither liquid nor gas.
Organic compounds have a higher solubility in supercritical water. An added oxidant such as oxygen or
hydrogen peroxide reacts with dissolved organic contaminants in the supercritical water to form carbon
dioxide, water, inorganic acids, and salts (Refs. 17 and 35).
The specifics of SCWO system design and operation vary. In general, currently available SCWO systems
operate continuously, use corrosion-resistant materials in their reactors and process only fluid influents.
One such system marketed by Turbosystems Engineering Inc. blends a contaminated aqueous stream with
an oxidant from a storage tank. The blended stream is pressurized, preheated, and passed into the SCWO
reactor. Contaminants are destroyed inside the reactor, and the effluent is cooled, depressurized,
separated into liquid and gas streams, and discharged. SCWO technology is also available from General
Atomies' Advanced Process Systems division (Ref. 25).
The Assembled Chemical Weapons Assessment (ACWA) Program was established in 1997 to test and
demonstrate at least two alternative technologies to the baseline incineration process for the
demilitarization of assembled chemical weapons (Ref. 5). In 2003, the Bechtel Parsons Blue Grass Team
was awarded a contract to design, construct, test, operate, and close the Blue Grass Army Depot
Destruction Pilot Plant using SCWO. The SCWO system is currently in the design phase. SCWO was
also selected for use at the Newport Army Depot to destroy 1,269 tons of liquid agent VX. Existing
SCWO systems are limited to the treating of liquids and solids with a particle size of less than 200
microns suspended in a liquid. The process is best suited to wastes with less than 20 percent organic
content (Ref. 33). SCWO treatment of solid wastes after they have been ground into a fine slurry has
30
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
been demonstrated using feed materials containing up to 25 percent suspended solids (Refs. 5, 28, 33, 35
and 58).
In the United States, SCWO technology is available from General Atomies' Advanced Process Systems
division (Ref. 25). Although General Atomics primarily markets this technology to government clients,
the firm has also designed and fabricated SCWO systems for commercial entities (Refs. 25 and 35). The
SCWO process developed by General Atomics was selected for use as an Assembled Chemical Weapons
Assessment technology to treat non-POPs such as GB, VX, H, HD, and TNT. Turbosystems Engineering
Inc. also designs and markets SCWO systems in the United States (Ref. 55). Turbosystems Engineering
Inc. claims that its system can treat DDT and HCB. No performance data substantiating this claim are
available in the information sources used to prepare this report.
31
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
4.0 INFORMATION SOURCES
The following web based information sources were used during the preparation of this report. Additional
information on POPs can be obtained from the web sites identified below as well as from the references
listed in Section 6.0.
Stockholm Convention
http://www.pops.int/
International HCH and Pesticides Association
http://www.ihpa.info/libraryNATO.httn
Science and Technology Advisory Panel of the Global Environmental Facility
http://www.uncp.org/stapgcffliomc/indcx.httn
U.S. Environmental Protection Agency
http://www.clu-in.org/POPs
http://www.clu-in.org/acwaatap
http://www.epa.gov/oppfod01/international/pops.htm
United Nations
http://www.clicm.uncp.ch/pops/
j)rgM
http://www.gpa.uncp.org/pollutc/organic.httn
http://www.w'ho.int/iomc/groups/pop/cn/
Other Sources
http://www.africastockpiles.org/
http://www.fao.org/ag/AGP/AGPP/Pcsticid/Disposal/indcx_cn.htm
httpj//wj¥wjjdj^
http://ipen.ecn.cz/
http://europa.eu. int/comm/environnient/pops/index_en.htm
http://lnwebl8.worldbank.org/ESSP/envext.nsty50ByPocName/WhatArePOPs
_cL^
32
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
5.0
Full-Scale Technologies for Treatment of
POPs
Anaerobic Bioremediation Using Blood Meal
for Treatment of Toxaphene in Soil and
Sediment
Mr. Harry L. Allen III, Ph.D.
EPA Environmental Response Team
MS-101, Building 18
2890 Woodbridge Avenue
Edison, NJ 08837
Telephone: (732) 321-6747
Fax: (732)321-6724
Email: allen.harryffiepa.gov
DARAMEND®
Dr. Alan G. Seech or Mr. David Raymond
Adventus Remediation Technologies, Inc.
1345 Fewster Drive
Mississauga, Ontario, Canada L4W 2A5
Telephone: (905) 273-5374, Extension 221
Mobile: (416)917-0099
Fax: (905)273-4367
Email: InfoSijdyjOTte
Web site: http://www.advcntusrcmcdiation.com
Gas-Phase Chemical Reduction (GPCR™)
Bennett Environmental Inc.
1540 Cornwall Road, Suite 208
Oakville, Ontario, Canada L6J 7W5
Telephone: (905) 339-1540
Fax: (905)339-0016
Email: mfo@bcnncttcnv._com
Web site: http://www.bennettenv.com
GeoMelt™
Mr. Kevin Finucane
AMEC Earth and Environmental, Inc.
309 Bradely Boulevard, Suite 115
Richland, WA 99352
Telephone: (509) 942-1292
Fax: (509)942-1293
Email: kcvin.finucanc@amcc.com
Web site: wj¥w.geojiielt±goni
VENDOR CONTACTS
In Situ Thermal Desorption (ISTD)
Mr. Ralph Baker
TerraTherm, Inc.
356 Broad Street
Fitchburg, MA 01420
Telephone: (978) 343-0300
Fax: (978)343-2727
Email:
Web site: www.tcrratlicrm.com
Mechanochemical Dehalogenation (MCD™)
Mr. Bryan Black
Environmental Decontamination Ltd.
P.O. Box 58-609
Greenmount
Aukland, New Zealand
Telephone: (649) 274-9862
Fax: (649)274-7393
Email: bryanirt^nanca.canz
Web site: http://edl.net.nz
Mr. Volker Birke
Tribochem
Georgstrasse 14
D-31515 Wunstdrof
Germany
Telephone: 495031 67393
Fax: 495031 8807
Email: bJrke^tribochem_.coiTi
Web site: W7w7w7.tribochem.com
Xenorem
Mr. Michael Klerkin
Technology Transfer Corporation
University of Delaware
Newark, DE 19716
Telephone: (302)831-4230
Web site: http://www.udcl.cdu/
33
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
Pilot-Scale Technologies for Treatment of
POPs
Base Catalyzed Decomposition
Mr. Terrence Lyons
EPA National Risk Management Research
Laboratory
26 West Martin Luther King Drive
Cincinnati, OH 45268
Telephone: (513)569-7589
Fax: (513)569-7676
Mr. Charles Rogers
BCD Group Inc.
Cincinnati, OH
Telephone: (513)385-4459
CerOx™
Mr. Matt van Steenwyk or Mr. Norvell Nelson
CerOx Corporation
2602 Airpark Drive
Santa Maria, CA 93455
Telephone: (805)925-8111
Fax: (805)925-8218
Email: mattvs@ccrox.com/njnclson@ccrox.com
Web site: www.ccrox.com
Sonic Technology
Mr. Paul Austin
Sonic Environmental Solutions Inc.
1066 West Hastings Street, Suite 2100
Vancouver, British Columbia, Canada
V6E 3X2
Telephone: (604) 736-2552
Fax: (604)736-2558
Email: paustin@sesi.ca
Web site: www.soniccnvironmcntal.com
Bench-Scale Technologies for Treatment of
POPs
Self-Propagating High-Temperature
Dehalogenation
Dr. Ing. Giacomo Cao Centra Studi Sulle
Reazioni Autopropaganti Dipartimento di
Ingegneria Chimica e Material! Piazza d'armi
09123 Cagilari Italy
Telephone: 39-070-6755058
Fax: 39-070-6755057
Email: cao(rt}visnu.dicm.unica.it
TDR-3R™
Mr. Edward Someus
Terra Humana Clean Technology Engineering
Ltd.
1222 Budapest, Szechenyi 59
Hungary
Telephone: (36-20)2017557
Fax: (36-1)4240224
Email: cdward@tcrrcnum.nct
Web site:
Full-Scale Technologies with Potential to
Treat POPs
Plasma Arc Centrifugal Treatment
Mr. Leroy Leland
RETECH Systems
100 Henry Station Road
Ukiah, CA 95482
Telephone: (707) 467-1724
Fax: (707)462-4103
Email: LcioiiJ^landK^^
Web site: www.rctcchsvstcmsllc.com
PLASCON™
Mr. Rex Williams or Mr. Martin Krynen
BCD Technologies Pty. Ltd.
Narangba, Queensland, Australia 4504
Telephone: 61 732033400
Fax: 61 7 3203 3450
E-mail: niariu s@gil . com . au
Plasma Converter System
Startech Environmental Corp.
15OldDanburyRoad
Wilton, CT. 06897-2525
Telephone: (203) 762-2499
Toll Free: (888) 807-9443
Fax: (203)761-0839
Email: starmail@startccli.nct
Supercritical Water Oxidation
General Atomics
P.O. Box
San Diego, CA 92186-5608
Telephone: (858) 455-3000
Fax: (858)455-3621
Turbosystems Engineering Inc.
Telephone: (707) 529-7477
Fax: (707)581-1749
34
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
6.0 REFERENCES
1. Adventus Remediation Technologies, Inc. DARAMEND® project summaries. Online Address:
http://www.adventusremediation.com.
2. Allen, Harry L., and others. 2002. "Anaerobic Bioremediation of Toxaphene Contaminated Soil -
A Practical Solution." 17th World Congress of Soil Science, Symposium No. 42, Paper No. 1509.
Thailand. August 14 through 21.
3. Allen, Harry L., EPA Environmental Response Team. 2005. Email to Younus Burhan, Tetra Tech
EM Inc., Regarding EPA Comments on Draft Blood Meal Fact Sheet. January 25.
4. American Chemical Society. 2000. "Herbicide and Pesticide Destruction." Symposium on
Emerging Technologies: Waste Management in the 21st Century. San Francisco, California. May.
5. Assembled Chemical Weapons Alternative. Program Summary. Online Address:
http://www.pmacwa.army.mil/about/index.htm.
6. Baker, Ralph, and Myron Kuhlman. 2002. "A Description of the Mechanisms of In-Situ Thermal
Destruction (ISTD) Reactions." Second International Conference on Oxidation and Reduction
Technologies for Soil and Groundwater (ORTs-2). Toronto, Ontario, Canada. November 17
through 21.
7. Baker, Ralph, TerraTherm, Inc. 2004. Emails to Chitranjan Christian, Tetra Tech EM Inc.
October 27 and November 8, 15, 24, and 29.
8. Birke, Volker. 2002. "Reductive Dehalogenation of Recalcitrant Polyhalogenated Pollutants Using
Ball Milling." Proceedings of the Third International Conference on Remediation of Chlorinated
and Recalcitrant Compounds. Monterey, California.
9. CerOx™ Corporation. 2005. Process Technology Overview. Online Address:
http://www.cerox.com/systems_process.html.
10. CMPS&F - Environment Australia. 1997. "Appropriate Technologies for the Treatment of
Scheduled Wastes." Review Report Number 4. November. Online Address:
http://www.oztoxics.org/research/3000 hcbweb/library/gov fed/appteck/plasma.html#pact.
11. Donnelly, Paul K., Hedge, Ramesh, S., and Fletcher, John S. (1994) "Growth of PCB-Degrading
Bacteria on Compounds from Photosynthetic Plants." Chemosphere. Volume 28, Number 5. Pages
981-988.
12. Eco Logic. 2002. "Contaminated Soil and Sediment Treatment Using the GPCRTM/TORBED®
Combination." October. Online Address: http://www.torftech.com/start.htm.
13. U.S. Environmental Protection Agency (EPA). 1996. "Cost and Performance Summary Report,
Bioremediation at the Stauffer Management Company Superfund Site, Tampa, Florida." Office of
Solid Waste and Emergency Response.
14. EPA. 1994. "Eco Logic International Gas-Phase Chemical Reduction Process-The Thermal
Desorption Unit." Superfund Innovative Technology Evaluation Program. EPA/540/AR-94/504.
September. Online Address: http://\vw\v.epa.gov/ORD/SITE/reports/540ar945()4/54()ar945()4.pdf
15. EPA. 1996. Site Technology Capsule: "GRACE Bioremediation Technologies DARAMEND®
Bioremediation Technology." Superfund Innovative Technology Evaluation Program.
EPA/540/R-95/536.
35
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
16. EPA. 2000. "Cost and Performance Summary Report, Bioremediation at the Stauffer Management
Company Superfund Site, Tampa, Florida." Office of Superfund Remediation and Technology
Innovation. September.
17. EPA. 2000. "Potential Applicability of Assembled Chemical Weapons Assessment Technologies
to RCRA Waste Streams and Contaminated Media." Office of Solid Waste and Emergency
Response, Technology Innovation Office. August. EPA-R-00-004. Online Address:
http://www.cpa.gov/tio/download/rcmcd/acwatcclircport.pdf
18. EPA. 2002. "Persistent Organic Pollutants, A Global Issue, A Global Response." Office of
International Affairs. EPA160-F-02-001.
19. EPA. 2004. "Cost and Performance Summary Report, The Legacy of the Navajo Vats Superfund
Site, Arizona and New Mexico." Office of Superfund Remediation and Technology Innovation.
October.
20. EPA. 2004. "Field Evaluation of TerraTherm In Situ Thermal Destruction (ISTD) Treatment of
Hexachlorocyclopentadiene." Office of Research and Development, Superfund Innovative
Technology Evaluation Program. EPA/540/R-05/007. July. Online Address:
OT/O^
21. EPA. 2004. "In Situ Thermal Treatment of Chlorinated Solvents: Fundamentals and Field
Applications." EPA 542-R-04-010. March.
22. EPA. 2004. T.H. Agricultural & Nutrition Company Site Information and Source Data. Online
Address: http ://www .epareachit.org .
23. EPA. 2005. Web Site on Persistent Organic Pollutants (POP). Office of Pesticide Programs.
Information Downloaded on January 5. Online Address:
http : //www .epa. gov/oppfodO 1 /international/pops .htm .
24. Finucane, Kevin, Geomelt. 2005. Emails to Ellen Rubin, EPA, Office of Superfund Remediation
Technology Innovation, Regarding Geomelt ICV Process Description and Photo, and Results for
WCS Rock Flats and WCS Commercial TSCA Cleanup. May 23.
25. General Atomics. 2005. Website of Advanced Process Systems Division. Online Address:
http://demil.ga.com/.
26. GeoMelt® Technologies/AMEC Earth and Environmental, Inc., Richland, Washington. 2005.
Web Page on GeoMelt® Technology Description. Online Address:
http://www.geomelt.com/technologies/.
27. Gilbert, Eric S. and David E. Crowley. 1997. "Plant Compounds that Induce Polychlorinated
Biphenyl Biodegradation by Anthrobacter sp. Strain BIB ." Applied and Environmental
Microbiology. Volume 63, Number 5. Pages 1933-1938.
28. Global Security. 2005. Weapons of Mass Destruction. Army Facilities. Web Page on Newport
Chemical Depot (NECD), Newport, Indiana. Online Address:
http://www.globalsecuritv.org/wmd/facilitv/newport.htm.
29. Gray, N.C.C., AstraZeneca Group PLC. 2004. Telephone Conversation with Younus Burhan,
Tetra Tech EM Inc. December 15 .
30. Gray, N.C.C., P.R Cline, A.L. Gray, B. Byod, G.P. Moser, H.A. Guiler, and D.J. Gannon. 2002.
"Bioremediation of a Pesticide Formulation Plant." Proceedings of the Third International
Conference on Remediation of Chlorinated and Recalcitrant Compounds. Monterey, California.
3 1 . Hurt, K. 2005 . "Successful Full Scale Phytoremediation of PCB and TPH Contaminated Soil,"
The Third International Phytotechnologies Conference, Atlanta, Georgia. April 19-22.
36
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
32. Ing, Giacomo Cao, Centra Studi sulle Reazioni Autopropaganti. 2004. Email to Younus Burhan,
Tetra Tech EM Inc. December 12.
33. International HCH and Pesticides Association. NATO/CCMS Pilot Study Fellowship Report.
Evaluation of Demonstrated and Emerging Remedial Action Technologies for the Treatment of
Contaminated Land and Groundwater (Phase III). Online Address:
http://www.ihpa.info/libraryNATO.htm.
34. Interstate Technology Regulatory Council. 2003. "Technology Overview Using Case Studies of
Alternative Landfill Technologies and Associated Regulatory Topics."
35. Johnson, Lou, General Atomics. 2005. Telephone Conversation with Chitranjan Christian, Tetra
Tech EM Inc. February 15.
36. Leigh, M., Fletcher, J., Nagle, D.P., Prouzova P., Mackova, M. and Macek, T. 2003.
"Rhizoremediation of PCBs: Mechanistic and Field Investigations." Proceedings of the
International Applied Phytotechnologies Conference. Chicago, Illinois.
37. Lyons, Terry, EPA National Risk Management Research Laboratory. 2005. Email to Younus
Burhan, Tetra Tech EM Inc. January 19 and August 10.
38. Moklyachuk, L., Sorochinky, B. and Kulakow, P.A. 2005. "Phytotechnologies for Management of
Radionucleide and Obsolete Pesticide Contaminated Soil in Ukraine," The Third International
Phytotechnologies Conference, Atlanta, Georgia. April 19 - 22.
39. Nurzhanova, A., Kulakow, P., Rubin, E., Rakhimbaev, I., Sedlovsky, A., Zhambakin, K., Kalygin,
S., Kalmykov, E. L. and Erickson. L. 2005. "Monitoring Plant Species Growth in Pesticide
Contaminated Soil," The Third International Phytotechnologies Conference, Atlanta, Georgia.
April 19-22.
40. Pan, Danny, Bennett Environmental Inc. 2005. Telephone Conversation with Younus Burhan,
Tetra Tech EM Inc. January 18.
41. Phillips, T., G. Bell, D. Raymond, K. Shaw, and A. Seech. 2001. 6th International HCH and
Pesticides Forum, Poznan, Poland. "DARAMEND® Technology for In Situ Bioremediation of Soil
Containing Organochlorine Pesticides." March 20 - 22.
42. Raymond, David, Adventus Remediation Technologies, Inc. 2004. Telephone Conversation with
Younus Burhan, Tetra Tech EM Inc. August 25.
43. Retech Systems LLC. 2005. Web Page on Plasma Arc Centrifugal Treatment (PACT) Systems.
Online Address: http://www.retechsystemsllc.com/PACT%20webpagesC/index.htm.
44. Rogers, Charles, BCD Group Inc. 2005. Email correspondence with Younus Burhan, Tetra Tech
EM Inc. December 9 and 13.
45. Sonic Environmental Solutions Inc.2005. Sonic Technology Treatment Process, Online Address:
http://www.sesi.ca/.
46. SRL Plasma Pty. Ltd. 2005. Web Page on "PLASCON™ Electric-Arc Plasma Hazardous Waste
Destruction Process." Online Address: http://www.srlplasma.com.au/srlpages/srlframe.html.
47. STARTECH Environmental Corp. 2005. Process Description. Web Page on Plasma Converter
System. Online Address: http://www.startech.net/plasma.html.
48. Stegemeier, G.L., and Vinegar, H.J. 2001. "Thermal Conduction Heating for In-Situ Thermal
Desorption of Soils," Chapter 4.6, pages 1-37. Chang H. Oh (ed.), Hazardous and Radioactive
Waste Treatment Technologies Handbook, CRC Press, Boca Raton, FL.
37
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Stockpiles and Soil
49. Stockholm Convention on Persistent Organic Pollutants (POPS). 2005. Web Site for the
Stockholm Convention. Online Address: http://www.pops.int/
50. TerraTherm Environmental Services. 1999. "Naval Facility Centerville Beach, Technology
Demonstration Report, In-Situ Thermal Desorption." November.
51. TerraTherm, Inc. 2005. Web Page on Technology Process Description (ISTD). Online Address:
http://www.terratherm.com/default.htm.
52. Thermal Desorption Technology Group LLC of North America. 2005. Website of Terra Humana
Clean Technology Engineering Ltd. Online Address: http : //www .terrenum .net/index.htm .
53. Thermal Desorption Technology Group, Terra Humana Clean Technology Engineering Ltd. 2004.
"Summary Report of the TDT-3R Treatment - Latest Five Years - Projects 2000-2004." December
10.
54. Thiess Services NSW. 2004. "Proof of Performance Report, FCC Remediation, Mapua, New
Zealand." June.
55. Turbosystems Engineering Inc. 2005. Web Page on Supercritical Water Oxidation Technology.
Online Address: http://www.turbosynthesis.com/summitresearch/sumhome.htm.
56. U.S. Department of Health and Human Services. 2005. Toxicological Profile Information Sheet.
Agency for Toxic Substances and Disease Registry (ATSDR). Online Address:
http : //www . atsdr .cdc . gov/toxpro2 .html .
57. United Nations Environment Programme (UNEP). 2003. Science and Technology Advisory Panel
(STAP) of the Global Environmental Facility. "Report of the STAP/GEF POPs Workshop on Non-
Combustion Technologies for the Destruction of POPs Stockpiles." October. Online Address:
lJ!^
58. UNEP. 2004. STAP of the GEF. "Review of Emerging, Innovative Technologies for the
Destruction and Decontamination of POPs and the Identification of Promising Technologies for
Use in Developing Countries." GF/8000-02-02-2205. January. Online Address:
http://www.unep.org/stapgef/home/index.htm.
59. UNEP. 2005. "Technical Guidelines for the Environmentally Sound Management of Persistent
Organic Pollutant Wastes." UNEP/POPS/COP.1/11. May. Online Address:
http://www.pops.int/documents/meetings/cop 1/meetingdocs/en/copl 1 I/COP 1 1 1 .pdf
60. UNEP. 2005. Web Site of the Secretariat of the Basel Convention. Online Address:
http://www.basel.int/
61. White, J. C., Martina, M. I., Eitzer, B. D., Isleyen, M., Parrish, Z. D. and Gent, M. P.N. 2005.
"Enhancing the Uptake of Weathered Persistent Organic Pollutants by Cucurbita pepo," The Third
International Phytotechnologies Conference, Atlanta, Georgia. April 19-22.
62. Zeeb, B., Whitfield, M. and Reimer, K. J. 2005. "In situ Phytoextraction of PCBs from Soil: Field
Study," The Third International Phytotechnologies Conference, Atlanta, Georgia. April 19 - 22.
38
-------
APPENDIX A
Anaerobic Bioremediation Using Blood Meal for the
Treatment of Toxaphene in Soil and Sediment
-------
Anaerobic Bioremediation Using Blood Meal for
Treatment of Toxaphene in Soil and Sediment
POPS-WASTES APPLICABILITY (REFS. 1 AND 5):
Anaerobic Bioremediation Using Blood Meal was able to rapidly degrade toxaphene in soil to achieve
cleanup goals in bench- and pilot-scale tests. Bench-scale tests have indicated that the technology is
also effective in treating dichlorodiphenyltrichloroethane (DDT). Full-scale implementations have
successfully treated several toxaphene-contaminated sites. The quantity of soil treated at these sites
ranged from 250 to 8,000 cubic yards. This technology does not typically achieve greater than 90
percent contaminant reduction.
POPs Treated: Toxaphene and DDT
Other Contaminants Treated: None
Application: Ex-situ
TECHNOLOGY DESCRIPTION (REFS. 1 AND 5):
OVERVIEW
This technology uses biostimulation to accelerate the degradation of toxaphene in soil or sediment. It
involves the addition of biological amendments, including blood meal (nutrient) and phosphates (pH
buffer), to stimulate native anaerobic microorganisms. Blood meal is a black powdery fertilizer made
from animal blood. The typical dosage of blood meal and sodium phosphate is one percent by weight
of contaminated soil. This is sometimes augmented with one percent by weight of starch to rapidly
establish anaerobic conditions. The standard recipe uses monobasic and dibasic phosphate salts in
equal proportions (monobasic:dibasic-1:1) to maintain soil pH around 6.7. The low phosphate/starch
recipe uses three times more dibasic than monobasic phosphates (monobasic:dibasic - 1:3) and
maintains soil pH around 7.8.
The soil to be treated is mixed with amendments and water. Mixing methods including blending in a
dump truck, mechanical mixing in a pit, and mixing in a pug mill have been used to produce
homogeneous soil-amendment mixtures. The mixture is transferred to a cell with a plastic liner, and
excess water is added to provide up to a foot of cover above the settled solids. The water provides a
barrier that minimizes the transfer of atmospheric oxygen to microorganisms in the slurry, which helps
maintain anaerobic conditions. The lined cell is covered with a plastic sheet to isolate the cell from the
environment, and the slurry is incubated for several months. The slurry may be sampled periodically to
measure treatment progress. Once treatment goals have been met, the cell is drained. The slurry is
usually left in place, but it may be dried and used as fill material on site. The slurry also serve as a
source of acclimated microorganisms for use at another toxaphene-contaminated site.
Anaerobic degradation of toxaphene usually results in the production of intermediates such as less
chlorinated congeners of toxaphene. Further degradation of intermediates results in the production of
carbon dioxide, methane, water, inorganic chlorides, and cell mass.
STATUS AND AVAILABILITY (REFS. 2 AND 6):
The technology has been implemented at full scale to treat toxaphene-contaminated sites. Four such
sites are:
(1) The Laahty Family Dip Vat (LDV) site (253 cubic yards in one cell)
(2) The Henry O Dip Vat (HDV) site (660 cubic yards in two cells)
(3) The Gila River Indian Community (GRIG 1) site (3,500 cubic yards in four cells)
(4) The GRIG 2 site (8,000 cubic yards in five cells)
A-l
-------
Anaerobic Bioremediation Using Blood Meal for
Treatment of Toxaphene in Soil and Sediment
EPA's Environmental Response Team (ERT) is the developer of the technology. The technology is
unlicensed and is available through the ERT. The biological amendments (blood meal, and monobasic
and dibasic phosphates) are inexpensive and commercially available.
Design (Refs 1, 5):
Factors that need to be considered when designing an anaerobic bioremediation process using blood
meal include:
• The presence of active toxaphene-degrading bacteria
• Soil characteristics
• Volume of soil to be treated
• Concentration of toxaphene in contaminated soil
• Cleanup goal
• Availability of space on site for the construction of treatment cells
• Odor mitigation requirements as determined by surrounding land use and the proximity of
residences
• Need for agreements with landowners and community leaders
• Climate
• Security issues
• Availability of water
THROUGHPUT (REFS. 1 AND 5):
Throughput of a technology that does not operate like a batch processing plant is hard to define.
Remediation involves a series of steps including construction, mix preparation, and treatment.
Treatment is usually the slowest step. Factors that can influence treatment time include, the type of
microbial communities present, amendment dosage, contaminant concentration, treatment goals, and
the presence of inhibitors (such as very cold environments). In general, treatment time can vary from
five weeks to two years.
WASTES/RESIDUALS (REFS 2,3 AND 6):
Products of toxaphene degradation include lower-chlorinated chlorobornane congeners, chloride ions,
cell mass, carbon dioxide, and methane. Chlorobornane congeners have been shown to degrade
completely during treatment. However, treated soil can contain low concentrations (below cleanup
goals) of unutilized toxaphene and lower-chlorinated chlorobornane congeners.
Gaseous wastes produced can include methane and hydrogen sulfide. Therefore, odor concerns
should be considered. If treatment cells are not left in place at the end of remediation, solid wastes can
include debris from the demolition of treatment cells and associated temporary facilities. Debris
potentially contaminated with toxaphene will require testing to determine its hazardous nature in
compliance with local, State, and Federal requirements prior to disposal.
MAINTENANCE (REFS. 2 AND 6):
• Periodic addition of water to treatment cells to maintain water level
• Maintaining treatment cells to prevent leaks
• Maintaining cover integrity
• Monitoring for gas buildup
• Monitoring for fugitive odors
• Soil sampling to monitor remedial progress
LIMITATIONS (REFS. 2 AND 6):
• The anaerobic process is affected by temperature. Spring and summer are the best periods
for operation. This technology cannot be used in extremely cold climates.
• This technology requires a bench scale test to determine applicability at a given site, and to
estimate treatment duration.
• At a minimum, five weeks are required for treatment.
A-2
-------
Anaerobic Bioremediation Using Blood Meal for
Treatment of Toxaphene in Soil and Sediment
This technology typically does not achieve greater than 90 percent contaminant destruction.
Blood meal accelerates the rate of reductive dechlorination of toxaphene, but does not affect
the extent of dechlorination.
Unfavorable soil chemistry can inhibit the process. Unfavorable soil chemistry may result from
the presence of bioavailable heavy metals including mercury, arsenic, and chromium; solvents;
and pesticides (including toxaphene).
Level C personal protective equipment is required when working with blood meal.
FULL-SCALE TREATMENT EXAMPLES (REFS. 1,2,5 AND 6):
Anaerobic bioremediation using blood meal and phosphate amendments has been implemented at a
full scale at twenty two (22) Dip Vat sites in the Navajo Nation. Other sites where this technology has
been applied at a full scale to remediate toxaphene-contaminated soil include:
(1) The Ojo Caliente Dip Vat site
(2) The Laahty Family Dip Vat site
(3) The Henry O Dip Vat site
(4) The Acoma Reservation at Sky City
(5) The Gila River Indian Community (GRIG 1) crop duster site
(6) The GRIG 2 crop duster site
The resources used for this fact sheet contain performance data on nine applications of this
technology. Performance data for each of these sites is presented in Table 1 at the end of this fact
sheet. Three of these sites are discussed below in greater detail. The unit cost of implementation at
these sites in USD ranged from $98 to $296 per cubic yard.
Laahty Family Dip Vat (LDV) site
The LDV site is located in The Zuni Nation, New Mexico. Soil at the site was contaminated with
toxaphene at an average concentration of 29 milligrams per kilogram (mg/kg). A total of 253 cubic
yards (cy) of soil was excavated and stockpiled on site. A cell with dimensions, 73 feet (ft) by 30 ft by 4
ft (deep) was constructed and lined with a plastic liner. Contaminated soil was placed in a concrete
mixer and mixed with biological amendments and water. Blood meal and monobasic phosphate were
added, each at a dosage rate of 10 grams per kilogram (g/kg) of contaminated soil. Dibasic phosphate
salts were also added at a dosage rate of 3.3 g/kg soil. The nutrient-amended soil slurry was then
placed in the lined cell. Water was added to provide one foot of cover above the solids in the cell. The
cell was then covered with a plastic sheet and incubated. Samples were collected periodically to
monitor progress. The toxaphene concentration decreased in the anaerobic cell from an initial
concentration of 29 mg/kg to 4 mg/kg in 31 days. This corresponded to an overall reduction of 86
percent. The post-treatment concentrations were below the 17 mg/kg action level established for the
site. In 2004, the total cost of treatment in USD was $75,000. Consequently, the unit cost of treatment
at this site was $296 per cubic yard.
Henry O Dip Vat (HDV) Site
The HDV site is located in The Zuni Nation, New Mexico. Approximately 660 cy of soil at this site was
contaminated with toxaphene at an average concentration of 23 mg/kg. Two cells were constructed for
soil treatment:
• The north cell (Cell 1) was 75 ft by 35 ft by 5 ft (deep).
• The south cell (Cell 2) was 65 ft by 30 ft by 5 ft (deep).
Both cells were lined with plastic liners. Blood meal and sodium phosphate were added to
contaminated soil and placed in a mixing pit using a backhoe. The dosage rate of blood meal was 5
g/kg of contaminated soil, while that of monobasic phosphate was 10 g/kg of contaminated soil.
A-3
-------
Anaerobic Bioremediation Using Blood Meal for
Treatment of Toxaphene in Soil and Sediment
Dibasic phosphate salts were also added at a dosage rate of 3.3 g/kg. Water was added to the soil in
the mixing pit, and the resulting soil slurry was extensively mixed. Once mixed, the soil slurry was
transferred to anaerobic cells 1 and 2. Water was added to provide one foot of additional cover above
the solids in each cell. Each cell was then covered with a plastic sheet and incubated for 61 to 76
days. Samples were collected on day 1 and day 61 from Cell 1 and on day 1 and 76 from Cell 2.
Analysis of the samples indicated that the average toxaphene concentration was reduced from 23
mg/kg to 8 mg/kg. This corresponds to a percent removal of approximately 67 percent removal in 68
days. The post-treatment concentrations were below the 17 mg/kg action level established for the site.
In 2004, the total cost of treatment in USD was $65,000. Consequently, the unit cost of treatment at
this site was$98 per cubic yard.
Gila River Indian Community Site
The Gila River Indian Community (GRIG) site is located in Chandler, Arizona. Approximately 3,500 cy
of toxaphene-contaminated soil required treatment at this site. Four lined cells were constructed with
dimensions of 178 ft by 43 ft by 7 ft (deep). This dosage rate was lower than for other sites to reduce
costs. The dosage rate of blood meal, sodium phosphate, and dibasic phosphates was 5 g/kg of
contaminated soil. Blood meal and phosphates were first mixed in a pit, and then blended with
contaminated soil using a pug mill (100-300 cy/hr throughput). The mixture was then transferred to
cells filled with water to 25 percent capacity. Additional water was then added to the cells to provide
one foot of cover above the solids. Each cell was then covered with a plastic sheet. Samples were
collected from the cells after initial setup and at the end of 3 months, 6 months, and 9 months. The
removal of toxaphene in GRIG site soil took longer than usual due to the reduced amendment dosage
rates. The average toxaphene concentration at the end of 180 days ranged between 4 mg/kg and 5
mg/kg demonstrating 83 to 88 percent toxaphene removal. The samples collected at day 272 showed
residual levels of 2 to 4 mg/kg corresponding to a percent removal between 87 and 98 percent. The
post-treatment concentrations were below the 17 mg/kg action level established for the site. In 2004,
the total cost of treatment in USD was $793,000. Consequently, the unit cost of treatment at this site
was $226 per cubic yard.
A-4
-------
Anaerobic Bioremediation Using Blood Meal for
Treatment of Toxaphene in Soil and Sediment
Table 1
Performance Data for Anaerobic Bioremediation of Toxaphene Using Blood Meal at Selected
Sites
Site Name
Untreated
Concentration
(mg/kg)
Treated
Concentration
(mg/kg)
Period
(Days)
Percent
Reduction
Volume
Treated
(cy)
Navajo Vats Chapter
Nazlini
Whippoorwill
Blue Canyon Road
Jeddito Island
Poverty Tank
Ojo Caliente
Laahty Family Dip
Vat
Henry O Dip Vat
291
40
100
22
33
14
29
23
71
17
17
3
8
4
4
8
108
110
106
76
345
14
31
68
76
58
83
77
76
71
86
67
NA
NA
NA
NA
NA
200
253
660
Gila River Indian Community
Gila River Indian
Community (Cell 1)
Gila River Indian
Community (Cell 2)
Gila River Indian
Community (Cell 3)
Gila River Indian
Community (Cell 4)
59
31
29
211
4
4
2
3
272
272
272
272
94
87
94
98
3,500
Note:
mg/kg: Milligrams per kilogram
NA: Not available
Source: Refs. 1 , 2 and 6
A-5
-------
Anaerobic Bioremediation Using Blood Meal for
Treatment of Toxaphene in Soil and Sediment
U.S. EPA CONTACT:
U.S. EPA Environmental
Response Team
Harry L.Allen III, Ph.D.
Phone: (732)321-6747
Email: allen.harry@epa.gov
LAAHTY FAMILY AND HENRY O DIP
VAT SITES:
Bureau of Indian Affairs
Southwest Region
Zuni Nation
Phone: (505)563-3106
Gila River Indian Community
CONTACT:
GRIG Department of
Environmental Quality
Hazardous Waste Program
Manager
Dan Marsin
Email: hazmat@gilnet.net
Phone: (520)562-2234
PATENT NOTICE:
This technology has not been patented.
REFERENCES:
1. Allen L, Harry and others. 2002. Anaerobic bioremediation of toxaphene-contaminated soil -
a practical solution. 17th WCCS, Symposium No. 42, Paper No. 1509, Thailand. August 14 -
21.
2. Allen L., Harry, EPA Environmental Response Team. 2005. Email to Younus Burhan, Tetra
Tech EM Inc., Regarding Comments from Harry L. Allen on Draft (January 5, 2005) Blood Meal
Fact Sheet. January 25.
3. Allen L., Harry, EPA Environmental Response Team. 2005. Memo to Ellen Rubin, EPA Office
of Superfund Remediation and Technology Innovation. Response to Questions on Toxaphene
Fact Sheet. February 24.
4. U.S. Environmental Protection Agency (EPA). Office of Superfund Remediation and
Technology Innovation. 2004. Cost and Performance Summary Report. The Legacy of the
Navajo Vats Superfund Site, Arizona and New Mexico. October.
5. EPA. 2000. Fact Sheet - Gila River Indian Community Toxaphene Site. October.
6. Rubin, Ellen, EPA Environmental Response Team. 2005. Email to Younus Burhan, Tetra
Tech EM Inc., Regarding Comments from Dr. T. Ferrell Miller on Draft (January 5, 2005) Blood
Meal Fact Sheet. February 7.
A-6
-------
APPENDIX B
Bioremediation Using DARAMEND® for Treatment of
POPs in Soils and Sediments
-------
Bioremediation Using DARAMEND for
Treatment of POPs in Soils and Sediments
POPs - WASTES APPLICABILITY (REFS. 1,6, AND 10):
DARAMEND® is a bioremediation technology that has been used to treat soils and sediments
containing low concentrations of pesticides such as toxaphene and DDT as well as other contaminants.
POPs Treated:
Other Contaminants Treated:
Toxaphene and DDT
ODD, DDE, RDX, HMX, DNT, and TNT
TECHNOLOGY DESCRIPTION (REFS. 4,5 AND 10):
OVERVIEW
DARAMEND® is an amendment-enhanced
bioremediation technology for the treatment of
POPs that involves the creation of sequential
anoxic and oxic conditions. The treatment
process involves the following:
1. Addition of solid phase DARAMEND®
organic soil amendment of specific
particle size distribution and nutrient
profile, zero valent iron, and water to
produce anoxic conditions.
2. Periodic tilling of the soil to promote oxic
conditions.
3. Repetition of the anoxic-oxic cycle until
the desired cleanup goals are achieved.
DARAMEND® particle colonization as
viewed throuqh an electron-microscope
The addition of DARAMEND organic
amendment, zero valent iron, and water stimulates the biological depletion of oxygen generating strong
reducing (anoxic) conditions within the soil matrix. The diffusion of replacement oxygen into the soil
matrix is prevented by near saturation of the soil pores with water. The depletion of oxygen creates a
very low redox potential, which promotes dechlorination of organochlorine compounds. A cover may
be used to control the moisture content, increase the temperature of the soil matrix and eliminate run-
on/run off. The soil matrix consisting of contaminated soil and the amendments is left undisturbed for
the duration of the anoxic phase of treatment cycle (typically 1- 2 weeks).
In the oxic phase of each cycle, periodic tilling of the soil increases diffusion of oxygen to microsites
and distribution of irrigation water in the soil. The dechlorination products formed during the anoxic
degradation process are subsequently removed trough aerobic (oxic) biodegradation processes,
initiated by the passive air drying and tilling of the soil to promote aerobic conditions.
Addition of DARAMEND® and the anoxic-
oxic cycle continues until the desired
cleanup goals are achieved. The
frequency of irrigation is determined by
weekly monitoring of soil moisture
conditions. Soil moisture is maintained
within a specific range below its water
holding capacity. Maintenance of soil
moisture content within a specified range
facilitates rapid growth of an active
microbial population and prevents the
generation of leachate. The amount of
DARAMEND® added in the second and
subsequent treatment cycles is generally
less than the amount added during the first
cycle.
B-l
-------
Bioremediation Using DARAMEND for
Treatment of POPs in Soils and Sediments
DARAMEND technology can be implemented using land farming practices either ex situ or in situ. In
both cases, the treatment layer is 2 feet (ft) deep, the typical depth reached by tilling equipment.
However, the technology can be implementation in 2-ft sequential lifts. In the ex situ process, the
contaminated soil is excavated and sometimes mechanically screened in order to remove debris that
may interfere with the distribution of the organic amendment. The screened soil is transported to the
treatment unit, which is typically an earthen or concrete cell lined with a high-density polyethylene liner.
In situ, the soil may be screened to a depth of 2-ft using equipment such as subsurface combs and
agricultural rock pickers.
STATUS AND AVAILABILITY (REF. 1):
DARAMEND® is a proprietary technology and is available only through one vendor - Adventus
Remediation Technologies (ART), Mississauga, Ontario, Canada. In the U.S., the technology is
provided by ART'S sister company, Adventus Americas Inc., Bloomingdale, IL. The technology has
been used for the treatment of POPs (toxaphene and DDT) since 2001. Table 1 lists performance data
for DARAMEND® technology application at selected sites. Through 2005, DARAMEND® has been
implemented at two POPs contaminated sites.
Table 1: Performance Data of DARAMEND at Selected Sites
Site Name
Scale
Quantity
Treated
(tons)
No. of
treatment
cycles
Duration
of each
cycle
Cost
per
ton*
Performance
Contaminant
Untreated
Concen-
tration
(mg/kg)
Treated
Concen-
tration
(mg/kg)
POPs Contaminated Sites
T.H. Agricultural &
Nutrition (THAN)
Superfund Site,
Montgomery,
Alabama
W.R. Grace,
Charleston, South
Carolina
Full
Pilot
4,500
250
15
8
10 days
1 month
$55
$95
Toxaphene
DDT
DDE
ODD
Toxaphene
DDT
See Table 2 for
performance data
239
89.7
5.1
16.5
Non-POPs Contaminated Sites
Naval Weapons
Station, Yorkt own,
Virginia
Iowa Army
Ammunition Plant,
Burlington, Iowa
Confidential Site,
Northwest U.S.A.
(applied in multiple
2-ft lifts)
Full
Full
Full
4,800
8,000
6,000
12
5
Aerobic
treatment
7-10
days
7-10
days
N/A
$90
$150
$37
TNT
RDX
DNT
RDX
HMX
TNT
PCP
PCP
15,359
1,090
1,002
1 ,530,
1,112,
95.8
359
760
14
1.6
13
16.2
84.5
8
8
31
Source: Ref. 1
* Treatment costs are as reported by vendor. The vendor did not specify what was included in this cost.
B-2
-------
Bioremediation Using DARAMEND for
Treatment of POPs in Soils and Sediments
DESIGN (REF. 5):
The major design factor for the implementation of this technology is the amount and type of soil
amendments required for bioremediation. This is dependent on site conditions and the physical
(textural variation, percent organic matter, and moisture content) and chemical (soil pH, macro and
micronutrients, metals, concentration and nature of contaminants of concern) properties of the target
soil. The duration of the treatment cycle is based on soil chemistry, concentration of contaminants of
concern and soil temperature. The number of treatment cycles is based on the required cleanup levels
of the contaminant.
THROUGHPUT (REF. 4):
For ex situ treatment, the amount of POPs contaminated soil/sediment that can be treated is
dependent on the available surface area to spread contaminated soil. The technology can also be
applied ex-situ in windrows. For in-situ application, the tillage equipment limits the depth (2-ft) to which
the soil can be remediated. However, the technology can be used in-situ at depth greater than 2-ft
using alternative soil mixing equipment or injection techniques.
WASTES/RESIDUALS (REF. 4):
The primary wastes generated are debris, stone, and construction material that are removed in the
pretreatment process. No leachate is generated if a treatment area cover is used. If no cover is used,
precipitation in the treatment area may generate leachate or storm water run-off.
Sampling and monitoring activities of the treatment pile will generate personal protective equipment
(PPE) and contaminated water from decontamination activities.
MAINTENANCE:
Implementation
the upkeep of tilling, soil moisture control, and other industrial equipment. Because the specific
amendments and application rate of DA
will vary by site and type of soil treated.
Implementation of the DARAMEND® technology to treat POPs requires limited maintenance such as
her
amendments and application rate of DARAMEND® are site and soil-specific, the ongoing maintenance
LIMITATIONS (REFS. 4 AND 9):
DARAMEND® technology may become technically or economically infeasible when treating soils with
excessively high contaminant concentration. The technology has not been used for the treatment of
other POPs such as PCBs, dioxins, orfurans. ART, the developer of the technology, indicated that it
has been only marginally successful in bench scale treatment of PCB-contaminated soil. Bench scale
or pilot scale studies are typically conducted before field application of this technology; the type and
amount of soil amendments required are then based on the results of these studies.
In situ application of this technology using tilling equipment is limited to a depth of 2-ft. However, the
technology can be used in situ at depths greater than 2-ft using alternative soil mixing equipment or
injection techniques. This technology requires that the treatment area be free of surface and
subsurface obstructions that would interfere with the soil tilling. Ex situ application of this technology
requires a large surface area to treat large quantities of the contaminated soil. Implementation of this
technology in 2-ft sequential lifts would increase the total time required to treat the contaminated soil.
The technology can also be applied ex situ in windrows.
Application of this technology requires a source of water (either city, surface, or subsurface).
This technology cannot be applied to sites that are prone to seasonal flooding or have a water table
that fluctuates to within 3-ft of the site surface. These conditions make it difficult to maintain the
appropriate range of soil moisture required for effective bioremediation, and may redistribute
contamination across the site.
B-3
-------
Bioremediation Using DARAMEND for
Treatment of POPs in Soils and Sediments
Volatile organic compound emissions may increase during soil tilling. Other factors that could interfere
with the process would be large amounts of debris in the soil, which would interfere with the
incorporation of organic amendments and reduce the effectiveness of tilling. Presence of other toxic
compounds (heavy metals) may be detrimental to soil microbes. Soils with high humic content may
slow down the cleanup through increased organic adsorption and oxygen demand.
FULL-SCALE TREATMENT EXAMPLES (REF. 3):
Bioremediation of pesticides-impacted soil/sediment, T.H. Agriculture and Nutrition (THAN) Superfund
Site, Montgomery, Alabama.
The THAN site is located on the west side of Montgomery, Alabama, about 2 miles south of the
Alabama River. The site is approximately 16 acres in area. Previous site operations involved the
formulation, packing and distribution of pesticides, herbicides, and other industrial/waste treatment
chemicals. The site was listed on the National Priorities List (NPL) on August 30, 1990. In 1991, EPA
entered into a consent agreement with Elf Atochem North America Inc., the Potentially Responsible
Party (PRP) for the site, to conduct a remedial investigation/feasibility study for the site. The final
Record of Decision (ROD) for the site was signed on September 28, 1998, and bioremediation was
selected as the remedy for treating the contaminated soils and sediments. DARAMEND® was selected
as the bioremediation technology.
The contaminated soil and excavated sediments (approximately 4,500 tons) were treated using
anaerobic/aerobic bioremedi
involved the following steps:
anaerobic/aerobic bioremediation cycle using DARAMEND®. Implementation of the technology
1 . DARAMEND® amendment and powdered iron application and incorporation
2. Determination of water holding capacity (first cycle only)
3. Determination of treatment matrix moisture content
4. Irrigation
5. Measurement of soil redox potential
6. Soil allowed to stand undisturbed for anoxic phase (approximately 7 days)
7. Soil tilled daily to generate oxic condition (approximately 4 days)
8. Steps 1 , and 3 to 7 were repeated for each subsequent cycle. Fifteen treatment cycles were
implemented in some treatment areas on site.
Two agricultural tractors (Model: Massey-Ferguson 394 H) mounted with deep rotary tillers were used
for amendment application and tilling the treatment area. The target soil moisture content at the
beginning of each cycle was approximately 33% (dry wt. basis) or 90% of the soil's water holding
capacity. The optimal pH range (6.6 to 8.5) of the treatment area was maintained by adding hydrated
lime at a rate of 1 ,000 mg/kg during the oxic phase of the third, sixth, and twelfth cycle. Following the
application of each treatment cycle, samples were collected from the treatment area. The treatment
area was divided into 12 sampling zones and one composite sample (composite of four grab samples)
was collected from each zone. The samples were collected from the full 2-ft soil profile of treatment
area. Fifteen treatment cycles were applied to some areas of the site. Table 2 lists the initial and final
concentration of the samples collected from these 12 zones.
Based on the final sampling event DARAMEND® reduced the concentration of all the contaminants of
concern to less than the specified performance standards. The average treatment cost in USD at the
THAN site was $55 per ton. The vendor did not specify what was included in this cost.
B-4
-------
Bioremediation Using DARAMEND for
Treatment of POPs in Soils and Sediments
Table 2: DARAMEND18' performance at the THAN Site
Sampling
Zone
1
2
3
4
5
6
7
8
9
10
11
12
Toxaphene
(29 mg/kg) 1
Initial A
Cone.
(mg/kg)
77
260
340
45
230
90
100
13
330
48
20
720
Final J
Cone.
(mg/kg)
<20
<21
<21
<21
<21
<21
<20
<20
<21
<20
<20
<21
DDT
(94 mg/kg)1
Initial A
Cone.
(mg/kg)
126
227
33.2
55.1
216
13.3
151
9.1
45
44.4
12.6
78
Final J
Cone.
(mg/kg)
10.2
15
4.5
14.7
16.1
2.2
15.3
5.2
5.7
5.7
2.9
6.3
DDD
(94 mg/kg)1
Initial A
Cone.
(mg/kg)
52
133
500
34
93
130
85
44
312
146
46
590
Final J
Cone.
(mg/kg)
26.4
73
89
37
53
59
38
24.3
85
25.5
25.1
87
DDE
(133 mg/kg)1
Initial A
Cone.
(mg/kg)
33
35.3
49
15.8
22.4
17
25.2
6.9
28.2
20.1
6.9
59.6
Final J
Cone.
(mg/kg)
6
8.4
7.8
7.2
6.8
5.7
6.3
2.8
7.2
4.2
3.0
8.6
Notes:
1 . Performance Standard as specified in the Record of Decision, Summary of Remedial
Alternatives Selection, THAN Site.
2. Initial concentration reported from samples collected by responsible party.
3. Final concentration reported from splits samples collected by EPA.
U.S. EPA RPM FOR THAN SITE:
Brian Farrier
EPA Region 4
Telephone: 404-562-8952
Fax: 404-562-8955
Email: fjrnerbrairKgega^goy
VENDOR CONTACT DETAILS:
David Raymond
Adventus Remediation Technologies, Inc.
1 345 Fewster Drive
Mississauga, Ontario L4W2A5
Telephone: 905-273-5374, Extension 224
Mobile: 416-818-0328
Fax: 905-273-4367
Email: info@adventusremediation.com
Web Site: http://www.adventusremediation.com
PATENT NOTICE:
DARAMEND® is a patented technology with U.S. Patent No. 5,618,427.
B-5
-------
Bioremediation Using DARAMEND for
Treatment of POPs in Soils and Sediments
REFERENCES:
1. Adventus Remediation Technologies, Inc. DARAMEND project summaries. Online Address:
http://www.adventusremediation.com.
2. Adventus Remediation Technologies, Inc. March 2002. Draft Final Report, Ex-Situ
DARAMEND Bioremediation of Soil Containing Organic Explosive Compounds, Iowa Army
Ammunition Plant, Middletown, Iowa.
3. Adventus Remediation Technologies, Inc. November 2003. Final Report, Bioremediation of
Soil and Sediment Containing Chlorinated Organic Pesticides, THAN Superfund Site,
Montgomery, Alabama.
4. EPA. 1996. Site Technology Capsule, GRACE Bioremediation Technologies DARAMEND®
Bioremediation technology. Superfund Innovative Technology Evaluation. EPA/540/R-95/536.
5. EPA. 1997. Site Technology Capsule, GRACE Bioremediation Technologies DARAMEND®
Bioremediation technology. Superfund Innovative Technology Evaluation. EPA/540/R-
95/536a.
6. EPA. 2002. Technology News and Trends, Full-Scale Bioremediation of Organic Explosive
contaminated soil. EPA 542-N-02-003. July.
7. EPA. 2004. TH Agricultural & Nutrition Company Site Information and Source Data. Online
Address: http://www.epareachit.org.
8. EPA. 2004. TH Agricultural & Nutrition Company Site, RODS Abstract information, Superfund
Information Systems. Online Address: http://www.epa.gov/superfund.
9. Farrier, Brian, EPA Region 4. 2004. Telephone Conversation with Younus Burhan, Tetra Tech
EM Inc. August 31 and October 19.
10. Phillips, T., Bell, G., Raymond, D., Shaw, K., and Seech, A. 2001. "DARAMEND® technology
for in situ bioremediation of soil containing organochlorine pesticides."
11. Raymond, David, Adventus Remediation Technologies, Inc. 2004. Telephone Conversation
with Younus Burhan, Tetra Tech EM Inc. August 25.
B-6
-------
APPENDIX C
In Situ Thermal Desorption for Treatment of POPs in
Soils and Sediments
-------
In Situ Thermal Desorption for
Treatment of POPs in Soils and Sediments
POPS-WASTES APPLICABILITY (REFS. 4 AND 16):
ISTD is a thermally enhanced in-situ treatment technology that uses conductive heating elements to
directly transfer heat to environmental media. ISTD can heat soil or sediment in situ to average
temperatures of 1,000 degrees Fahrenheit (°F), and as a result has been used to treat compounds with
relatively high boiling points. Some of these include semivolatile organic contaminants (SVOCs) such
as polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), pesticides, and
herbicides. Pilot- and full-scale applications have been performed where ISTD has been used to
remove PCBs, and where dioxins and furans were trace contaminants. TerraTherm is the sole vendor
for ISTD. According to TerraTherm, laboratory-scale work and extrapolation techniques have
suggested the potential applicability of ISTD to POPs other than PCBs, dioxins, and furans (including
aldrin, dieldrin, endrin, chlordane, heptachlor, DDT, mirex, hexachlorobenzene, and toxaphene);
however, these contaminants have not yet been treated using ISTD on a full- or pilot-scale basis. ISTD
has been used to treat contaminants in most hydrogeologic settings, including beneath structures.
POPs Treated:
Other Contaminants Treated:
PCBs, dioxins, and furans, aldrin, chlordane, dieldrin, and endrin
Hexachlorocyclopentadiene, isodrin, VOCs, SVOCs, oils, creosotes,
coal tar PAHs, gasoline and diesel range organics, and MTBE
Well-field
TECHNOLOGY DESCRIPTION (REFS. 2,4,13 AND 16):
OVERVIEW
ISTD involves simultaneous application of heat and vacuum to subsurface soils. There are three basic
elements in an ISTD process: (1) application of heat to contaminated media; (2) collection of desorbed
contaminants through vapor extraction; and (3) treatment of collected vapors. Figure 1 presents a
typical ISTD system.
Figure 1
Typical ISTD System
ISTD has been used at full scale
to treat PCBs, PAHs, dioxins,
and chlorinated volatile organic
compounds (CVOC). At the
temperatures achieved by the
ISTD process, volatiles metals
such as mercury may also be
recovered.
In-Situ Heating
ISTD uses surface or buried
electrically powered heaters to heat contaminated media. The most common setup uses a vertical
array of heaters placed inside wells drilled into the remediation zone. A less common setup uses the
same type of heaters installed horizontally on the surface of the contaminated zone. This method of
heating (often called blanket heating) is typically used when contamination is shallow (usually 1 to 3
feet below ground surface (bgs)). Figure 2 illustrates the two different methods of heating.
ISTD heaters can attain temperatures as high as 1,600 degrees °F, and can produce average media
temperatures exceeding 1,000 °F. Heat originates from a heating element and is transferred to the
subsurface largely via thermal conduction and radiant heat transport, which dominates near the heat
sources. There is also a contribution through convective heat transfer that occurs during the formation
of steam from pore water present in the soil or sediment.
The thermal conductivity values of a wide range of soil types (e.g., clay, silt, sand, gravel) vary only by
a factor of approximately four. Therefore, the rate of heat transfer from the linear heaters to the
surrounding media is radially uniform. When heating commences, the temperature profile in the
remediation zone is characterized by large gradients, and temperatures decrease sharply with distance
from the source. Overtime, superposition of heat from adjacent heaters tends to even out these
differences.
Source: TerraTherm™ Inc.
C-l
-------
In Situ Thermal Desorption for
Treatment of POPs in Soils and Sediments
Figure 2
Blanket and Thermal Well Heating
ffirSrti lS'-:» ^i.'^"'-.',}.1;-? Sp
-1
Source: TerraTherm™ Inc.
Vapor Extraction
As the matrix is heated, adsorbed and liquid-
phase contaminants begin to vaporize. A
significant portion of organic contaminants
either oxidize (if sufficient air is present) or
pyrolize once high soil temperatures are
achieved. Desorbed contaminants are
recovered through a network of vapor-
extraction wells.
Vapor extraction wells are also heated to
prevent condensation of contaminants inside
the well. A vacuum is applied to these wells to
induce air flow through the contaminated
media creating a zone of capture.
Contaminant vapors captured by the
extraction wells are conveyed to an offgas
treatment system for treatment prior to
discharge to the atmosphere.
Offgas Treatment (Ref. 2)
TerraTherm offers two different methods of
vapor treatment. One treats extracted vapor
without phase separation (Figure 1), and the
other cools heated vapor, separates the resulting phases, and manages each phase separately.
The vapor treatment option depicted by Figure 1 uses a thermal oxidizerto break down organic vapors
to primarily carbon dioxide and water. Stack sampling has demonstrated that toxic pollutants in offgas,
including dioxins, are substantially below regulatory standards. When influent vapors contain
chlorinated compounds, hydrogen chloride (HCI) gas is produced. In such cases, the exhaust from the
thermal oxidizer is passed through an acid gas scrubber to capture HCI gas.
The other vapor treatment option uses a heat exchanger to cool extracted vapors. The resulting liquid
phase is then separated into aqueous and nonaqueous phases. The nonaqueous phase liquid (NAPL)
is usually disposed of at a licensed treatment storage and disposal facility. The aqueous phase is
passed through liquid-phase activated carbon adsorption units and then released into the environment.
Cooled, uncondensed vapor is passed through vapor-phase activated carbon adsorption units and then
vented to atmosphere.
Although setup varies from site to site, several components of the remediation system including
heaters, blowers, and offgas treatment equipment are either standard or adaptable to new situations,
with equipment reused from site to site. Downhole wells may not be salvageable and may be plugged
and abandoned in place.
STATUS AND AVAILABILITY (REFS. 4 AND 5):
ISTD is a patented technology originally developed by Shell Oil. While U.S. Patent rights were donated
to the University of Texas (UT), patent rights outside the U.S. were retained by Shell. TerraTherm
holds the exclusive license to this technology from both UT and Shell, and is currently the only vendor.
ISTD has been commercial for several years. Its ability to remove PCBs from contaminated soil was
first demonstrated more than 6 years ago. As shown on Table 1, ISTD has been used at six POP-
contaminated sites. Implementation at four of these sites was full scale, and the other two were pilot
scale.
C-2
-------
In Situ Thermal Desorption for
Treatment of POPs in Soils and Sediments
Table 1
Performance of ISTD at POPs Contaminated Sites (Refs. 2, 4 and 7)
Site Name
Former South
Glens Falls
Dragstrip,
Moreau, New
York
Tanapag
Village, Saipan,
NMI
Centerville
Beach,
Ferndale, CA
Missouri
Electric Works,
Cape
Girardeau, MO
Former Mare
Island Naval
Shipyard,
Vallejo, CA
Former Wood
Treatment
Area,
Alhambra, CA
Year
1996
1997-
1998
1998-
1999
1997
1997
2002-
2005
Scale
Full
Full
Full
Pilot
Pilot
Full
Contaminant
PCB
1248/1254
PCB
1254/1260
PCB 1254
Dioxins and
Furans
PCB 1260
PCB
1254/1260
Dioxins
Concentration
Initial
5,000
(Max)
10,000
(Max)
860
(Max)
3.2 (Max)
20,000
(Max)
2,200
(Max)
18
(Mean)
Final
<0.8
<1
<0.17
0.006 '
< 0.033
< 0.033
0.01
Goal
2
10
1
1
2
1
1
Units
mg/kg
mg/kg
mg/kg
ug/kg
TCDD
mg/kg
mg/kg
ug/kg
Note:
Avg Average concentration
Max Maximum concentration
mg/kg Milligrams per kilogram (or parts per million)
NMI Northern Mariana Islands
ND Below detection limit
TCDD Tetrachlorodibenzodioxin equivalents
ug/kg Micrograms per kilogram (or parts per billion)
1 Final concentration presented as average of residual concentrations in treatment area.
DESIGN (REF. 12):
Key design factors for ISTD include the number and depth of heater wells and vacuum wells, as well as
the requirements for electrical power and treatment of off gasses. These factors are affected by the
type of contaminants present, concentration of the contaminants, extent of contamination, soil type,
hydraulic conductivity, permeability, thermal properties, location of the water table, availability of site
facilities such as electrical power supply, and regulatory issues.
C-3
-------
In Situ Thermal Desorption for
Treatment of POPs in Soils and Sediments
THROUGHPUT (REF. 5):
ISTD has been used to treat volumes as low as a few hundred cubic yards to greater than 20,000 cubic
yards in 6 to 9 months. Factors affecting cleanup durations can include type of contaminants,
cleanup/remedial goals, and site geology.
WASTES/RESIDUALS (REFS. 3 AND 5):
Wastes produced by ISTD are likely to result from the treatment of extracted vapors, and vary
according to the type of treatment they are subjected to. Offgas treatment options that employ phase
separation techniques could produce process wastes such as NAPL, spent liquid- and vapor-phase
activated carbon, and inorganic salts as waste products. For example, the treatment of chlorinated
vapors in a thermal oxidizer results in the production of HCL gas. A wet or dry acid gas scrubber used
to neutralize HCI gas will produce inorganic salts as a waste product.
NAPL is typically transported off site for disposal at a licensed facility. Spent activated carbon may
either be disposed of, or regenerated at a licensed facility. Inorganic salts produced from neutralization
processes are typically considered nonhazardous and are consequently disposed of as nonhazardous
waste.
MAINTENANCE (REF. 4):
Maintenance associated with ISTD includes the occasional replacement of heater elements. ISTD
operation is typically characterized by less than 5% downtime. Other maintenance needs include
treatment media replacement and thermal oxidizer refueling.
LIMITATIONS (REF. 4):
The following are some of the limitations of this technology:
• ISTD cannot address contaminants that do not volatilize with in the temperature range of
approximately 15-1000°C.
• As long as liquid water remains within the remediation zone, the temperature that can be
attained is limited to the boiling point of water (212 °F). Once the water is boiled off, higher
temperatures can be attained. A continuing source of water influx into the treatment zone will
undermine the ability of this technology to produce temperatures necessary for the removal of
POPs. For this reason, formation dewatering and implementation of water control measures
are needed prior to the implementation of ISTD in high-permeability, water-saturated zones.
• Though not always the case, cost can be a limiting factor. Unit costs for treatment are
influenced by several factors including scale of the project, depth of the treatment zone, depth
to water table, air emission controls, cost of labor and cost of power. However, in general, unit
costs in USD range from $200 to $600 per cubic yard corresponding to treatment volumes
ranging from less than 5,000 to approximately 15,000 cubic yards for POP-type contaminants.
Larger volumes may have lower unit costs. Treatment costs for VOC contaminants are lower.
FULL-SCALE TREATMENT EXAMPLES:
Centerville Beach (Refs. 6, 8,10 and 14)
The Centerville Beach Naval Facility is a 30-acre site in Ferndale, California that was used for
oceanographic research and undersea surveillance. The site was decommissioned in 1993.
Operations at the site lead to contamination of a particular area with PCBs. The PCB of concern was
Aroclor 1254 which was present in concentrations ranging from 0.15 to 860 milligrams per kilogram
(mg/kg). Dioxins and furans were also present at a maximum concentration of 3.2 micrograms per
kilogram (ug/kg) as 2,3,7,8-tetrachlorodibenzodioxin (TCDD) equivalents. The contaminated medium
was primarily silty clay. Groundwater was encountered below the contaminated zone at depths
exceeding 60 feet bgs.
C-4
-------
In Situ Thermal Desorption for
Treatment of POPs in Soils and Sediments
From September 1998 through February 1999, approximately 1,000 cubic yards of PCB-contaminated
soil was treated using ISTD. Heater and vapor extraction wells were installed in a zone measuring 40
feet long, 30 feet wide, and 15 feet deep. The wells were installed 6 feet apart. Two sealed vacuum
blowers were used in parallel for vapor extraction. Offgas was treated using a flameless thermal
oxidizer (with greater than 99.99% demonstrated treatment efficiency), and two granular activated
carbon units configured in series. The total cost of the implementation in USD was approximately
$650,000.
The treatment goal was 1 mg/kg for PCBs and 1 ug/kg TCDD equivalent for dioxins and furans.
Remediation took place between September 1998 and February 1999. Treatment goals were met in
the bulk of the treatment area; however, one portion (178 cubic yards) still contained elevated
concentrations of PCBs. This was found to be caused by a previously undiscovered bank of PCB-
containing electrical conduits emanating from outside the treatment zone and passed into the treatment
area. Excavation and disposal was subsequently used to remove this area of contaminated soil and
the associated conduits.
Alhambra (Refs. 3, 9, 17 and 18)
Southern California Edison's (SCE) Alhambra Combined Facility occupies approximately 33 acres and
is currently used for storage, maintenance, and employee training. SCE carried out wood treatment
operations in SCE's 2-acre former wood treatment area between 1921 and 1957. The total volume of
contaminated soil was estimated to be 16,200 cubic yards of soil. The contaminated zone included a
variety of buried features including treatment tanks, the structural remains of the former boiler house
and tank farm, and various buried utilities. The contaminants of concern were PAHs,
pentachlorophenol (PCP), and dioxins. Total PAHs were present in site soils at a maximum
concentration of 35,000 mg/kg and an average concentration of 2,306 mg/kg. PCP was present at a
maximum concentration of 58 mg/kg and an average concentration of less than 1 mg/kg. Dioxins were
present at a maximum concentration of 0.194 mg/kg and an average concentration of 0.018 mg/kg
(expressed as 2,3,7,8-tetrachloro-dibenzodioxin [TCDD] Toxic Equivalency Quotient [TEQ]). The soil in
the remediation zone was composed of silty sands, inter-bedded with sands, silts, and clays. The
average thermal treatment depth was approximately 20 feet bgs and extended to 100 feet bgs in some
areas. The depth to the water table was greater than 240 feet bgs. The treatment goals were 0.065
mg/kg (expressed as benzo(a)pyrene [B(a)P] toxic equivalents) for PAHs; 2.5 mg/kg for PCP, and
0.001 mg/kg for dioxins (expressed as TEQ).
Remedial action at the site was conducted in two phases. Each phase addressed a different area of
the site. The overall ISTD system for the two phases consisted of 785 thermal wells (131 heater-
vacuum and 654 heater-only wells) at a
7.0-ft spacing between thermal wells, as
well as an insulated surface seal, thermal
oxidizer, heat exchanger, and granular
activated carbon for off-gas treatment.
The ISTD began cleanup operations for
Phase I of the remediation of Area of
Concern (AOC)-2 in February 2003.
Confirmation soil samples were submitted
to DTSC in July 2004 which confirmed that
the cleanup goals for Phase I of AOC-2
had been achieved. Phase 2 of the
cleanup began in July 2004 and was
scheduled for completion by October 2004.
Figure 3
Phase-1 Soil Sampling Results
m.
78-T1DD TIQi
C--51
>J'e- i «sa!rrsri Inlenn
Satnpiing Period
Source: TerraTherm™ Inc.
C-5
-------
In Situ Thermal Desorption for
Treatment of POPs in Soils and Sediments
However, a previously undiscovered volume of free product made it necessary to reduce in-situ
temperatures in order to control organic contaminant concentrations in the offgas treatment system
influent. This resulted in an anticipated 10-month increase in the cleanup duration. Phase 2 of the
cleanup is expected to end in August 2005. The total cost of the implementation in USD was
approximately $10 million.
Rocky Mountain Arsenal Hex Pit (Ref. 15)
The Hex Pit was a former disposal pit at the U.S. Department of Army's Rocky Mountain Arsenal
(RMA). Shell Oil Company leased a portion of the RMA from 1952 to 1982 to manufacture pesticides.
The pit was used from 1947 to 1975 to dispose of residues from distillation and other processes used in
the production of hexachlorocyclopentadiene (hex), an ingredient in the manufacture of pesticides.
The main part of the Hex Pit measured approximately 94 ft by 45 ft, and varied from 8 to 10 ft deep.
The pit contained a total of 2,005 cubic yards of waste-contaminated materials, of which 833 cubic
yards was estimated to be waste.
The Hex Pit consisted primarily of soil and waste material originally disposed of in the pit. The
impacted soil (silty sand) was stained dark brown, rust orange, or black, and at times included granules
or globules of hex. Black, tar-like, relatively pure hex residue occurred in distinct solid layers of waste
(approximately 1-foot thick). Hex was not detected in groundwaterdowngradient of the Hex Pit
boundaries.
The contaminants of concern were hex, aldrin, chlordane, dieldrin, endrin, and isodrin. Only hex,
chlordane, and dieldrin had treatment goals. The treatment goals were 760 mg/kg, 67 mg/kg and 335
mg/kg respectively. Laboratory tests indicated that Hex Pit wastes could be effectively treated by the
ISTD process.
ISTD at the Hex Pit was designed to heat a treatment soil volume of 3,198 cubic yards, extending from
0 to 12 ft bgs and 5 ft laterally beyond the boundaries of the Hex Pit. Thermal wells on 6-foot centers
were installed in a hexagonal arrangement. A total of 266 wells were installed, of which 210 were
heater-only and 56 were heater-vacuum wells.
The target treatment temperature based on the boiling point of COCs was 325 °C. All heater-only wells
reached their operating temperatures in early March 2002. Treatment was expected to last 85 days
and end in May 2002. However, twelve days after commencement, corrosion was observed in some of
the well manifolds. Subsequent investigation and assessment determined that unforeseen
concentration of HCL gas and production of HCL (liquid) in the vapor conveyance system, resulting
from the highly concentrated wastes in the Hex Pit, had caused corrosion. Corrosion damage to the
ISTD system was significant. A determination was made that replacements with necessary corrosion
resisting matrices was cost prohibitive. Wastes were excavated and capped.
STATE CONTACT (CENTERVILLE
BEACH):
California EPA
Dept. of Toxic Substances
Control (DTSC)
Ms. Christine Parent
Phone: (916)255-3707
Email: CParent@dtsc.ca.gov
STATE CONTACT (ALHAMBRA):
California EPA
DTSC
Mr. Tedd E. Yargeau
Phone: (818)551-2864
Email: tyargeau@dtsc.ca.gov
VENDOR CONTACT:
Mr. Ralph Baker
TerraTherm™, Inc.
Tel: (978)343-0300
Email: rbaker@terratherm.com
C-6
-------
In Situ Thermal Desorption for
Treatment of POPs in Soils and Sediments
PATENT NOTICE:
ISTD is covered by a total of 22 U.S. patents, with 6 patents pending. TerraTherm is the exclusive
licensee through the University of Texas and Shell.
REFERENCES:
1. Baker, Ralph and Kuhlman, Myron. 2002. 2nd International Conf. on Oxidation and Reduction
Technologies for Soil and Groundwater, ORTs-2, Toronto, Ontario, Canada. A Description of
the Mechanisms of In-Situ Thermal Destruction (ISTD) Reactions. Nov. 17-21
2. Baker, Ralph, TerraTherm, Inc. 2004. Email to Chitranjan Christian, Tetra Tech EM Inc.,
Regarding Questions on ISTD. October27, Novembers, 15, 24 and 29.
3. Baker, Ralph, TerraTherm, Inc. 2004. Telephone Conversation with Chitranjan Christian,
Tetra Tech EM Inc., Regarding Questions on ISTD. October 29.
4. Heron, Gorm, TerraTherm, Inc. 2004. Email to Chitranjan Christian, Tetra Tech EM Inc.,
Regarding Questions on ISTD. October 15.
5. Heron, Gorm, TerraTherm, Inc. 2004. Telephone Conversation with Chitranjan Christian,
Tetra Tech EM Inc., Regarding Questions on ISTD. October 15.
6. Parent, Christine, California EPA, DTSC. 2004. Telephone Conversation with Chitranjan
Christian, Tetra Tech EM Inc., Regarding Questions on ISTD implementation at Centerville
Beach. November 2.
7. Stegemeier, G.L., and Vinegar, H.J. 2001. "Thermal Conduction Heating for In-Situ Thermal
Desorption of Soils," Chapter 4.6, pages 1-37. Chang H. Oh (ed.), Hazardous and Radioactive
Waste Treatment Technologies Handbook, CRC Press, Boca Raton, FL.
8. TerraTherm Environmental Services. 1999. Naval Facility Centerville Beach, Technology
Demonstration Report, In-Situ Thermal Desorption. November.
9. TerraTherm Inc. Case Study-Alhambra. Online Address:
http://www.terratherm.com/CaseStudies/WS%20Final%20Alhambra%20Sheet.pdf.
10. TerraTherm Inc. Case Study - Centerville Beach Naval Facility. Online Address:
http://www.terratherm.com/CaseStudies/WS%20Centrvll-Tesi.pdf.
11. TerraTherm Inc. Case Study- Former Mare Island Naval Shipyard. Online Address:
http://www.terratherm.com/CaseStudies/WS%20BADCAT.pdf.
12. TerraTherm Inc. Feasibility Screening. Online Address:
http://www.terratherm.com/default.htm.
13. TerraTherm Inc. ISTD Process Description. Online Address:
http://www.terratherm.com/default.htm.
14. Tetra Tech EM Inc. 2000. Draft Final Closeout Report. Naval Facility Centerville Beach,
Ferndale, California. February.
15. Todd, Levi. Year. Publication or Report. Lessons Learned from the Application of In Situ
Thermal Destruction of Hexachlorocyclopentadiene Waste at the Rocky Mountain Arsenal.
Month.
16. U.S. Environmental Protection Agency. 2004. In Situ Thermal Treatment of Chlorinated
Solvents Fundamentals and Field Applications. EPA 542-R-04-010. March.
17. Yargeau, Tedd, California EPA, DTSC. 2004. Email to Chitranjan Christian, Tetra Tech EM
Inc., Regarding Questions on ISTD implementation at Alhambra. December 22.
18. Yargeau, Tedd, California EPA, DTSC. 2004. Telephone Conversation with Chitranjan
Christian, Tetra Tech EM Inc. Response to Questions on ISTD implementation at Alhambra.
November 2.
C-7
-------
------- |