Sh<
Reference Guide to Non-combustio
Technologies for Remediation of
Persistent Organic Pollutants in Soil,
Second Edition - 2010
w
•v
High
Long-ran
oceanic
transport
Reow/sl
j*/ mobility
s»© -r
£•***,•.*
Low latitudes.
Deposition > evaporal
^
-g^
I If'r',
-------
Solid Waste EPA 542-R-09-007
and Emergency Response September 2010
(5203P) www.clu-in.org/POPs
Reference Guide to Non-combustion Technologies for Remediation
of Persistent Organic Pollutants in Soil,
Second Edition - 2010
Internet Address (URL) http://www.epa.gov
Recycled/Recyclable. Printed with Vegetable Oil Based Inks on Process Chlorine Free Recycled Paper (minimum 50% Post consumer)
-------
CONTENTS
Section Page
ACRONYMS AND ABBREVIATIONS iii
NOTICE AND DISCLAIMER vi
EXECUTIVE SUMMARY vii
1.0 INTRODUCTION 1
1.1 Purpose of Report 4
1.2 Methodology 5
1.3 Report Organization 6
2.0 BACKGROUND 7
2.1 Stockholm Convention on POPs 7
2.2 Basel Convention 7
2.3 Convention on Long-Range Transboundary Air Pollution (LRTAP) - Protocol on POPs. 8
2.4 Sources of POPs 8
2.5 Characteristics and Health Effects of POPs 9
2.6 Review of Chemical Characteristics of POPs Listed and Under Review for the 2009
Stockholm Convention 13
2.7 Treatment of POPs 15
2.8 Related Documents 15
3.0 NON-COMBUSTION TECHNOLOGIES 18
3.1 Full-Scale Technologies for Treatment of POPs 18
3. .1 Anaerobic Bioremediation Using Blood Meal 25
3. .2 Base-Catalyzed Decomposition 26
3. .3 DARAMEND® 27
3. .4 Gas-Phase Chemical Reduction 30
3. .5 Gene Expression Factor 31
3. .6 GeoMelt™ 32
3. .7 Mechanochemical Dehalogenation 35
3. .8 Plasma Arc 38
3. .9 Radicalplanet® Technology 39
3. .10 Solvated Electron Technology 40
3. .11 Sonic Technology 41
3. .12 Thermal Desorption 42
3.2 Pilot-Scale Technologies for Treatment of POPs 45
3.2.1 Phytotechnology 45
3.2.2 Reductive Heating and Sodium Dispersion 47
3.2.3 Subcritical Water Oxidation 48
3.3 Bench-Scale Technologies for Treatment of POPs 49
3.3.1 Self-Propagating High-Temperature Dehalogenation 49
3.3.2 TDT-3R™ 49
4.0 INFORMATION SOURCES 51
5.0 VENDOR CONTACTS 52
6.0 REFERENCES 55
-------
Appendix
A Chemical Structures, Uses and Effects of POPs listed under the Stockholm Convention and
LRTAP
B Fact Sheet on Anaerobic Bioremediation Using Blood Meal for the Treatment of Toxaphene in
Soil and Sediment
C Fact Sheet on Bioremediation Using DARAMEND® for Treatment of POPs in Soils and
Sediments
D Fact Sheet on In Situ Thermal Desorption for Treatment of POPs in Soils and Sediments
E Additional Technologies Identified but Not Commercially Available
LIST OF TABLES
Table Page
1-1 POPs Identified by the Stockholm Convention and Long-Range Transboundary Air Pollution
Convention 3
2-1 Toxicology and Chemical Properties of POPs Listed and Under Review by the Stockholm
Convention and LRTAP 10
3-1 Summary of Full-Scale Non-combustion Technologies for Remediation of Persistent Organic
Pollutants 19
3-2 Performance of Pilot/Bench-Scale Non-combustion Technologies for Remediation of POPs 22
3-3 Performance of Non-combustion Technologies for Remediation of POPs 23
3-4 Performance of Anaerobic Bioremediation Using Blood Meal for Toxaphene Treatment 26
3-5 Performance of DARAMEND® Technology 29
3-6 Performance of GPCR™ Technology 30
3-7 Performance of Gene Expression Factor 32
3-8 Performance of GeoMelt™Technology 34
3-9 Soil Acceptance Criteria for the Mapua Site 36
3-10 Performance of MCD™ Technology at the Mapua Site 37
3-11 Performance of RadicalplanetR Technology at Various Japanese Sites 40
3-12 Performance of ISTD Technology 44
3-13 Results of Plant Uptake from the Royal Military College Study 46
-------
ACRONYMS AND ABBREVIATIONS
ART Adventus Remediation Technologies, Inc.
ATSDR Agency for Toxic Substances and Disease Registry
BCD Base-catalyzed decomposition
BDE Bromodiphenyl ether
BHC Hexachlorobenzene
BFR Brominated flame retardants
CaO Calcium oxide
CB Chlorobenzene
CCMS Committee on the Challenges of Modern Society
CD Catalytic dechlorination
CFC Chlorofluorocarbon
CHD Catalytic hydrodechlorination
CLU-IN Clean-Up Information
COP Conference of the Parties
cy Cubic yard
ODD Dichlorodiphenyldichloroethane
DDE Dichlorodiphenyldichloroethylene
DDT Dichlorodiphenyltrichloroethane
DDX Total Dichlorodiphenyldichloroethane, Dichlorodiphenyldichloroethylene, and
Dichlorodiphenyltrichloroethane
Dioxins Polychlorinated dibenzo-p-dioxins
DNT Di-nitro toluene
DRE Destruction and removal efficiency
EDL Environmental Decontamination Ltd.
US EPA U.S. Environmental Protection Agency
ERT Environmental Response Team
FAO Food and Agricultural Organization
FRTR Federal Remediation Technologies Roundtable
ft Foot
Furans Polychlorinated dibenzo-p-furans
GEF Global Environmental Facility
GPCR Gas-phase chemical reduction
gpd Gallon per day
GRB Gila River Boundary
GRIC Gila River Indian Community
HBCDD Hexabromocyclododecane
HCB Hexachlorobenzene
HCBD Hexachlorobutadiene
HCH Hexachlorocyclohexane
HEPA High-efficiency particulate air
HMX High melting explosive, octahydro-l,3,5,7-tetranitro-l,3,5,7 tetrazocine
HTTD High temperature thermal desorption
ICV In Container Vitrification
IHPA International HCH and Pesticides Association
ISTD In situ thermal desorption
ISV In situ vitrification
JESCO Japan Environmental Safety Corporation
kg Kilogram
LRTAP Long-Range Transboundary Air Pollution
in
-------
LTR Liquid tank reactor
LTTD Low temperature thermal desorption
M Meter
MCD Mechanochemical dehalogenation
MDL Method detection limit
MTBE Methyl tert-butyl ether
|lg/kg Microgram per kilogram
mg/kg Milligram per kilogram
mm Millimeter
ng-TEQ/g Nanogram Toxic Equivalent of Dioxins per gram
NA Not available
NAPL Nonaqueous-phase liquid
NATO North Atlantic Treaty Organization
ND Not detected (indicating concentration below detection limit)
NIP National Implementation Plan
OSRTI Office of Superfund Remediation and Technology Innovation
Pa Pascal
PACT Plasma Arc Centrifugal Treatment
PAH Polycyclic aromatic hydrocarbons
PCB Polychlorinated biphenyl
PCD Photochemical dechlorination
PCN Polychlorinated naphthalenes
PCNB Pentachloronitrobenzene
PCP Pentachlorophenol
PCS Plasma Converter System
PFOS Perfluorooctane
pg-TEQ/g Picogram Toxic Equivalent of Dioxins per gram
POP Persistent organic pollutant
POPRC Persistent Organic Pollutants Review Committee
ppb Part per billion
ppm Part per million
ppt Part per trillion
PVC Polyvinyl chloride
RCRA Resource Conservation and Recovery Act
REACHIT Remediation and Characterization Innovative Technologies
rpm Revolutions per minute
SCCP Short-chained chlorinated paraffins
SCWO Supercritical water oxidation
SITE Superfund Innovative Technology Evaluation
SOx Sulfur oxide
SP Sodium Powder Dispersion Dechlorination Process
SPHTD Self-propagating high-temperature dehalogenation
SPV Subsurface Planar Vitrification
SR Sodium reduction
STAP Science and Technology Advisory Panel
SVOC Semivolatile organic compound
t-BuOK Potassium tert-butoxide
TCDD Tetrachlorodibenzodioxin
TCLP Toxicity Characteristic Leaching Procedure
TSCA Toxic Substance Control Act
TNT Trinitrotoluene
IV
-------
UNECE United Nations Economic Commission for Europe
UNEP United Nations Environment Programme
UNR University of Nevada at Reno
USD United States Dollar
VOC Volatile organic compound
WCS Wasatch Chemical Superfund
-------
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 the 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 U.S. Environmental Protection Agency (US EPA) and external review by
experts in the field. However, information in this report is derived from many references (including
personal communications with experts in the field), some of which have not been peer-reviewed.
This report was prepared by the US EPA Office of Superfund Remediation and Technology Innovation
(OSRTI), with support provided under Contract Numbers 68-W-02-034 and EP-W-07-078. For further
information about this report, please contact Michele Mahoney at US EPA's Office of Superfund
Remediation and Technology Innovation, at (703) 603-9057, or by e-mail at mahoney.michele@epa.gov.
A PDF version of "Reference Guide to Non-combustion Technologies for Remediation of Persistent
Organic Pollutants in Soil, Second Edition-2010" is available for viewing or downloading at the
Hazardous Waste Cleanup Information System website at http://www.du-m.org/POPs. A limited number
of printed copies of the report are available free of charge and may be ordered via the website, by mail, or
by fax from the following source:
US EPA/National Service Center for Environmental Publications
P.O. Box 42419 USEPA
Cincinnati, OH 45242-2419
Telephone: 800-490-9198
Fax: 301-604-3408
Website: www.epa.gov/nscep
VI
-------
EXECUTIVE SUMMARY
This report is the second edition of the U.S. Environmental Protection Agency's (US EPA's) 2005 report
and 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 soil. POPs are
chemicals that are demonstrated to be toxic, persist in the environment for long periods of time, and
bioaccumulate and biomagnify as they move through the food chain. POPs are linked to adverse effects
on humans 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, largely located outside the United
States (US). 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. Since the
publication of this report in 2005, nine (9) additional chemicals have been listed in the Stockholm
Convention; this brings the total number of chemicals currently listed as POPs under the Stockholm
Convention to twenty-one (21)1. In addition, three (3) POPs are currently under consideration.
Historically, POP-contaminated soil has been widely treated by combustion systems using high
temperature incineration to destroy the contaminants. Incineration is widely used because high-
temperature incinerators can address large volumes of contaminated material and can treat most POPs
contaminants. Modern incinerators operating with highly controlled combustion environments can
achieve a high destruction and removal efficiency (DRE) for POP contaminants. In the US, DREs as high
as 99.9999% are achievable for incinerators treating non-liquid polychlorinated biphenyl compounds
(PCBs). The US EPA has approved the use of incinerators to treat PCB-contaminated material with PCB
concentrations greater than 50 parts per million (ppm). However, US EPA requires that incinerators meet
stringent operating conditions. For example, incinerators treating liquids contaminated with PCBs are
required to meet either (1) a 2-second residence time for the liquid waste at a temperature of 1200 °C and
with 3 percent excess oxygen in the stack gases or (2) a 1.5-second residence time at 1200 °C, with 2
percent excess oxygen.
Though incinerators can be used to treat POPs, they have several technology limitations, which are
addressed in the body of this report. Also, many interested parties have expressed concern about potential
environmental and health effects associated with this type of treatment technology (Ref 8). The
combustion of POPs can create by-products such as polychlorinated dibenzo-p-dioxins (i.e., dioxins) and
polychlorinated dibenzo-p-furans (i.e., furans) - two known human carcinogens. Due to concerns about
their safety, incinerators also can face negative public opinion and attract public opposition. However,
because alternative treatment approaches have been limited to date, incineration continues to be most
commonly used technology for the treatment of POPs (including in developing countries). Additional
information about incineration and other combustion technologies can be obtained from the US EPA's
Federal Remediation Technologies Roundtable (FRTR) website
(http://www.frtr.gov/matrix2/section3/3_6.html).
As a result of widespread interest in alternate technologies, numerous international organizations have
developed reports that identify and discuss non-combustion technologies for POPs, including:
• Evaluation of Demonstrated and Emerging Remedial Action Technologies for the Treatment of
Contaminated Land and Groundwater (Phase III), 2002. IHPA.
1 http://chm.pops.int/Convention/ThePOPs/tabid/673/language/en-US/Default.aspx
vn
-------
http://www.ihpa.info/resources/library
• Review of Emerging, Innovative Technologies for the Destruction and Decontamination of POPs
and the Identification of Promising Technologies for Use in Developing Countries, 2004. UNEP.
http://www.basel.int/techmatters/re view_pop_feb04.pdf
• Destruction and Decontamination Technologies for PCBs and Other POPs Wastes (Part III
Annexes) A Training Manual for Hazardous Waste Project Managers, Volume C, 2005. Basel
Convention. http://www.basel.int/meetings/sbc/workdoc/TM-A.pdf
• Non-Combustion Technologies for POPs Destruction - Review and Evaluation, 2007.
International Centre for Science and High Technology, http://www.ics.trieste.it
• Updated general technical guidelines for the environmentally sound management of wastes
consisting of, containing or contaminated with persistent organic pollutants (POPs). 2007. Basel
Convention. http://www.basel.int/pub/techguid/tg-PCBs.pdf
• Disposal Technology Options Study - review and update of technology Annex C: Review and
Update of Technology, 2008. Africa Stockpiles, http://www.africastockpiles.net
Some of the technologies discussed in these documents have progressed from the development stage to a
commercial stage; other technologies presented as commercial stage are no longer being developed. In
addition, promising destruction technologies for POPs continue to be developed. This Reference Guide
to Non-combustion Technologies for Remediation of POPs in Soil is intended to summarize and update
the First Edition prepared by US EPA in 2005, and build on these more recent studies. Updated
information for this document was obtained primarily by (1) reviewing various websites and documents,
(2) contacting technology vendors and experts in the field, and (3) working closely with the International
Hexachlorocyclohexane (HCH) and Pesticides Association, IHPA (John Vijgen), which has published
several factsheets that are used as references for this report.
This Second Edition Report also provides new performance data of the non-combustion technologies.
Tables 3-1 and 3-2 summarize full-scale and pilot/bench-scale technologies and provide information on
waste strength treated, ex situ or in situ treatment applicability, contaminants treated, available cost
information, pretreatment requirements, power requirements, configuration needs, and links to individual
fact sheets. Fact sheets prepared by US EPA are provided as appendices to this report. Additional fact
sheets for the various technologies are available through the IHPA website. Technologies identified in
the first edition (2005) of this report that are not currently commercially available are described in
Appendix E. This document is not intended as a roadmap for technology selection; however it is intended
to present the current state of knowledge for non-combustion technologies for treatment of POPs in soils.
Vlll
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
1.0 INTRODUCTION
Persistent organic pollutants (POPs) are toxic chemicals that are chemically stable, do not easily degrade
in the environment, and tend to bioaccumulate and biomagnify as they move through the food chain.
Serious human health problems are associated with exposure to POPs, including cancer, neurological
damage, birth defects, sterility, and immune system suppression. Restrictions and bans on the use of
POPs chemicals 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 waste/releases associated with past production and use of POPs have resulted in
contamination of soils around the world. The Programme on the Prevention and Disposal of Obsolete
Pesticides by the Food and Agricultural Organization (FAO) of the United Nations is creating an
inventory of obsolete pesticides stockpiled around the
world. Information about pesticides inventories by country II FURTHER INFORMATION ABOUT THE
can be obtained from FAO of the United Nations at LOCATION OF STOCKPILES is
http://www.fao.org/ag/AGP/AGPP/Pesticid/Disposal/en/492
74/index.html. Because of their chemical stability, tendency
to bioaccumulate, adverse health effects, and widespread
distribution and presence, remediation technologies are
needed to treat these pollutants.
AVALABLE AT
http://www.fao.org/ag/AGP/AGPP/P
esticid/Disposal/en/49274/index.html
The international community has responded to the health concerns posed by these unusable stockpiles of
POPs by developing various treaties and organizations to address POPs chemicals and waste. Under the
Stockholm Convention on POPs (Stockholm Convention), which was adopted in 2001 and enacted in
2004, parties committed to reduce or eliminate the production, use, and release of the 12 POPs of greatest
concern to the global community. The US is a signatory to the Stockholm Convention on POPs - but has
not yet ratified the Convention. The initial list of 12 POPs was identified by the Intergovernmental Forum
on Chemical Safety and the International Programme on Chemical Safety. Another treaty regulating
POPs internationally is the Basel Convention on the Control of Transboundary Movements of Hazardous
Wastes and their Disposal (Basel Convention). The Basel Convention was adopted on March 22, 1989 by
the Conference of Plenipotentiaries convened at Basel, Switzerland and entered into force in 1992. In
response to Stockholm Convention provisions requiring coordination with the Basel Convention on POPs
waste issues, the Basel convention developed guidance on the environmentally sound management of
POPs waste. In 2004, the Basel Convention invited signatories of the Stockholm Convention to consider
its recommendations on environmentally sound
management for POPs wastes (Refs. 69 and 70). The US
FURTHER INFORMATION ABOUT THE Convention on POPs - but has
STOCKHOLM CONVENTION ON POPs is & .J , . _,
pROViDEDAThttp://chm.pops.mt/ not yet ratified the Convention.
The Stockholm Convention's subsidiary body - the POPs
Review Committee (POPRC2) - includes environmental experts that review proposals to add new
chemicals to the Convention. The POPRC uses criteria set forth in the Convention3 to review a chemical's
characteristics as well as human health and environment effects. If the chemical meets the Convention's
screening criteria in Annex D to the Convention, then the POPRC develops a risk profile for the chemical
(according to Annex E of the Convention) and, if warranted, prepares risk management evaluation
Additional information about POPRC meeting can be found at:
http ://www.pops. int/documents/meetings/poprc/poprc. htm
3 See Article 8 and Annexes D, E, and F of the Stockholm Convention.
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
FURTHER INFORMATION ABOUT THE
CONVENTION ON LONG-RANGE TRANSBOUNDRY
AIR POLLUTION IS PROVIDED AT
http: //www .unece. org/env/lrtap/welcome .html
(according to Annex F of the Convention). Upon
completion of the risk management evaluation,
the POPRC makes the recommendation to the
Conference of the Parties (COP) whether or not to
add the chemical to one (or more) of the
Convention's Annexes (i.e., Annexes A, B, and/or
C). In addition, part of the listing process is to aid in creating a plan to reduce the chemical from current
and future environmental applications or uses (Ref 61).
In October 2008, the POPRC held its fourth meeting (POPRC-4) and an outcome of that meeting was that
it recommended to the May 2009 COP that nine (9) additional chemicals be added to the Stockholm
Convention (Ref. 27). In October 20094 at POPRC-5 meeting, several chemicals underwent a review
process by the Committee. However, no new chemicals were recommended by the POPRC to the COP
for listing. Future COP and POPRC meetings in 2010 and 2011 will continue to review chemicals and
possibly add new chemicals to the Stockholm Convention.
In addition to the (global) Stockholm Convention, the Convention on Long-Range Transboundary Air
Pollution (LRTAP) is a regional international treaty that addresses environmental issues of the United
Nations Economic Commission for Europe (UNECE) with a primary focus on air emissions. The US is a
Party to the LRTAP Convention (i.e., the US has signed and ratified the LRTAP Convention). The
LRTAP Convention has been extended by eight (8) Protocols that include specific requirements for
countries to reduce air pollution including long-range air pollution. In 1998, the LRTAP Convention
adopted a Protocol on POPs to regulate the production and use of 16 chemicals that were singled out
according to agreed risk criteria. The US is a signatory to the LRTAP's Protocol on POPs - but has not
yet ratified the Protocol and, therefore, not yet a Party to the LRTAP's Protocol on POPs. The LRTAP
POPs Protocol originally listed the following 16 chemicals when it was adopted in 1998: aldrin,
chlordane, chlordecone, dichlorodiphenyltrichloroethane (DDT), dieldrin, dioxins/furans, endrin,
heptachlor, hexabromobiphenyl, hexachlorobenzene (HCB), lindane (i.e., gamma-HCH), mirex,
polychlorinated biphenyls (PCB), poly cyclic aromatic hydrocarbons (PAHs), and toxaphene. On
December 18, 20095, the parties to the LRTAP POPs Protocol adopted amendments to the protocol to
include seven (7) additional chemicals, which are: octabromodiphenyl ether, pentabromodiphenyl ether,
pentachlorobenzene, perfluorooctane sulfonate (PFOS), short-chained chlorinated paraffins (SCCP),
polychlorinated naphthalenes (PCN) and hexachlorobutadiene (HCBD). PCN and HCBD are the only two
chemicals listed in the LRTAP's Protocol on POPs that are not already listed (or under review for listing)
by the Stockholm Convention.
Table 1-1 lists all of the 26 chemicals identified under the Stockholm Convention on POPs and the
LRTAP's Protocol on POPs - both currently listed and under review.
4 The final report from the POPRC-5 meeting can be found at: http://chm.pops.int/
5 The final report from the LRTAP's Executive Body meeting can be found at:
http://www.unece.org/env/lrtap/ExecutiveBodv/welcome.27.html
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
Table 1-1. POPs Identified by the Stockholm Convention and Long-Range
Transboundary Air Pollution Convention
POP
Stockholm Convention
Currently
Listed
Under
Review
(2009)
Long-Range
Transboundary Air
Pollution
Convention
Pesticides
Aldrin
Alpha-hexachlorocyclohexane
Beta-hexachlorocyclohexane
Chlordane
Chlordecone
Dichlorodiphenyltrichloroethane (DDT)
Dieldrin
Endosulfan
Endrin
Heptachlor
Hexachlorobenzene (HCB)
Lindane
Mirex
Toxaphene
v'
•/
v'
s
v'
s
•/
v'
S
v'
•/
v'
S
•/
S
•/
S
s
s
s
•/
s
s
s
•/
s
s
Industrial Chemicals or By-Products
Dioxins
Furans
Hexabromobiphenyl
Hexabromocyclododecane (HBCDD)
Hexachlorobutadiene (HCBD)
Octabromodiphenyl ether
Pentabromodiphenyl ether (penta-BDE)
Pentachlorobenzene
Perfluorooctane sulfonate (PFOS)
Polychlorinated biphenyls (PCB)
Polychlorinated naphthalenes (PCN)
Short-chained chlorinated paraffins
(SCCP)
v'
s
v'
s
s
s
•/
s
S
s
s
s
s
•/
s
s
s
s
•/
s
s
s
Sources: Refs. 27, 6land 68
Note: Nine additional chemicals that were recently listed by the Stockholm Convention in May 2009 are shown in
bold.
Historically, POP-contaminated soil and stockpiles have been widely treated using combustion systems
using high temperature incineration to destroy the contaminants. Incineration is widely used because
high-temperature incinerators can address large volumes of contaminated material and can treat most
contaminants. Modern incinerators operating with highly controlled combustion environments can
achieve a high destruction and removal efficiency (DRE) for POP contaminants. In the US, DREs as high
as 99.9999% are achievable for incinerators treating non-liquid PCBs. US EPA has approved the use of
incinerators to treat PCB-contaminated material with PCB concentrations greater than 50 parts per million
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
(ppm). The US EPA requires that incinerators meet stringent operating conditions. For example,
incinerators treating liquids contaminated with PCBs are required to meet a either: (1) a 2-second
residence time for the liquid waste at a temperature of 1200°C and with 3 percent excess oxygen in the
stack gases or (2) a 1.5-second residence time at 1200°C, with 2 percent excess oxygen (40 C.F.R.
§ 761.70). Because of its capabilities, incineration is a viable option for the treatment of materials
containing POPs.
There are several limitations in the reliance on incineration as the sole alternative for POPs waste
treatment. For example, incinerators cannot destroy inorganic constituents (metals) in waste streams, and
these maybe released in air emissions or retained in solid residues; therefore, waste containing POPs and
certain metals may not be suitable for incineration in some cases. Some heavy metals (including lead,
cadmium, mercury, and arsenic) may partially vaporize and leave the combustion unit of the incinerator
with the flue gases; this can require additional off-gas treatment systems for removal of these gaseous
combustion products. Incinerators treating waste streams contaminated with heavy metals can also
produce a bottom ash with high concentrations of metals. These bottom ashes then require
characterization to determine whether they are Resource Conservation and Recovery Act (RCRA)
hazardous waste, may require stabilization, and must be disposed of appropriately. Also, combustion
technologies that have historically been used for the destruction of POPs may fail to meet the stringent
environmental standards or DRE requirements established for POPs if the incinerator is not operated
under stringent technical requirements.
In addition, 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. One concern arises because combustion technologies can create polychlorinated dibenzo-p-dioxins
(dioxins) and polychlorinated dibenzo-p-furans (furans). Dioxins and furans have been characterized by
US EPA as "possible" human carcinogens and are associated with serious human health problems
(http://www.atsdr.cdc.gov/toxprofiles/phsl04.html).
Most of the POPs-containing stockpiles are located in developing countries whose incinerators do not, in
general, provide high DREs. Therefore, these developing countries must ship obsolete POPs stockpiles to
developed countries for treatment and disposal. International regulations on transporting contaminated
material are strict and transporting obsolete POPs from developing countries to developed countries can
be cost prohibitive. Due to human health and environmental concerns associated with waste incineration,
some countries (e.g., Australia and the Philippines) have non-incineration policies. Based on limitations
associated with combustion technology, concerns with incineration, 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 71).
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 soil. The report provides
short descriptions of these technologies and presents them based on the POPs treated, media treated,
pretreatment requirements, performance and cost. Case studies are provided to illustrate various
considerations associated with selecting a non-combustion technology. However, the report is not
intended as a step-wise, or complete guide to selecting remediation technologies for POPs. This report is
a second edition of a report initially published by US EPA in 2005 (EPA-542-R-05-006).
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
Because of international interest in POP waste management using alternate technologies, several
organizations have published documents on this topic. Additional information on non-combustion
technologies for the remediation of POPs waste is available in documents presented in Section 2.8 of this
report. Some of the technologies discussed in these documents have progressed from the development
stage to a commercial stage; other commercial technologies discussed in these reports are no longer being
developed. Also, additional promising destruction technologies for POPs have been developed since the
first edition of this report and other POPs treatment technology reports were prepared. The purpose of this
US EPA report is to summarize and update the older reports in a reader's guide format, with links to
sources of further information.
1.2 Methodology
In developing the 2005 report, US EPA identified non-combustion technologies for remediation of POPs
in soil by reviewing technical literature, US EPA reports, and US EPA databases such as the Federal
Remediation Technologies Roundtable (FRTR) (www.frtr.gov) (Ref 18) and the Remediation and
Characterization Innovative Technologies (REACHIT) system, and by contacting technology vendors and
experts in the field. For this edition of the report, US EPA contacted technology vendors listed in the
2005 report for technology updates. Additional research was conducted to locate new technologies for
the treatment of all 26 POPs identified by the Stockholm Convention and LRTAP. The US EPA
REACHIT system could not be searched since its use was discontinued in 2008. Limited but concise data
about remediation technologies is located in US EPA's Clean-Up Information (CLU-IN) (http://www.clu-
in.org/vendor/vendorinfo/). In addition, a key source of information for this report was communications
with John Vijgen of the IHPA. While this report has been reviewed by experts in the field, some of the
information sources cited have not been peer-reviewed.
From this research, non-combustion technologies for POPs were identified. For each technology, the
following information was identified: 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. This report discusses technologies
that have treated one or more of the 26 POPs presented in Table 1-1. Some technologies previously
discussed in other sources are no longer commercially available or have not been used to treat POPs;
therefore, these technologies are not included. Technologies identified in the first edition (2005) of this
report that are not currently commercially available are described in Appendix E.
Based on the available information,
US 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 were provided. US EPA did not perform independent evaluations of technology
performance to support this report. However, where feasible, data gaps were addressed by contacting
specific vendors, technology users, and representatives of the IHPA.
INTERNATIONAL HCH AND PESTICIDES ASSOCIATION
PUBLISHED 15 FACT SHEETS ABOUT EMERGING NON-
COMBUSTION ALTERNATIVES FOR THE ECONOMICAL
DESTRUCTION OF POPS
(http://www.ihpa.info/resources/library/). THESE FACT
SHEETS WERE USED AS A KEY INFORMATION SOURCE DURING
DEVELOPMENT OF THIS REPORT.
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
1.3 Report Organization
This report includes six sections and several appendices.
• Section 1.0 is an introduction discussing the purpose, methodology, and organization of the
report.
• Section 2.0 provides background information about international treaties and organizations that
address POPs issues and about the sources, characteristics, and health effects of POPs, including
chemical structures and toxicology profiles.
• Section 3.0 presents technology overviews; more detailed information for some technologies is
then provided in technology-specific fact sheets in the appendices to this report. Seventeen
technologies for POP treatment are described in Section 3.0, organized into three subsections
based on the scale of application. Section 3.1 contains descriptions of full-scale technologies that
have treated POPs. Section 3.2 and Section 3.3 contain descriptions of pilot-scale and bench-
scale technologies, respectively, that have been tested on POPs.
• Section 4.0 lists web-based information sources used to prepare this report.
• Section 5.0 contains contact details for technology vendors.
• Section 6.0 lists references used in the preparation of this report.
• Appendix A provides chemical structures, uses and effects of POPs listed under the Stockholm
Convention and LRTAP.
• Appendices B, C, and D provide fact sheets
prepared by US EPA for anaerobic bioremediation
using blood meal for the treatment of toxaphene in
soil, DARAMEND®, and in situ thermal desorption REMEDIATION OF POPs is PROVIDED AT
, _ , . . ... . . . -. . www.clu-in.org/POPs.
(ISTD), respectively, which were modeled after the a
FURTHER INFORMATION ABOUT NON-
COMBUSTION TECHNOLOGIES FOR
fact sheets prepared by IHPA and are described
below. Fact sheets for 10 other POP treatment technologies presented 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 IHPA in 2002. US EPA reviewed the 10 technologies as part of work for this report,
as well as three additional technologies for which fact sheets were prepared by IHPA (see list in
Section 2.8). Technologies identified in the first edition (2005) of this report that are not
currently commercially available are provided in Appendix E. This review was implemented to
evaluate whether additional, more recent information was available for these technologies.
Through 2008, four additional fact sheets for other POP treatment technologies were prepared by
IHPA. In addition, other technologies in this report were updated with site-specific performance
data and included in their respective sections, as appropriate.
Appendix E provides technologies identified in the first edition (2005) of this report that are not
currently commercially available.
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
2.0 BACKGROUND
This section provides background information about the Stockholm Convention, Basel Convention and
LRTAP. It also provides information about the sources, characteristics, and health effects of POPs. It
also identifies technology categories and documents that address the treatment of POPs.
2.1 Stockholm Convention on POPs
The Stockholm Convention is a global treaty intended to protect human health and the environment from
POPs. As of July 2010, 184 countries and one regional economic integration organization (i.e., the
European Union) are Parties to the Convention. The US signed the Stockholm Convention on May 23,
2001 but as of July 2010 has not yet ratified the Convention (Ref. 61).
The Stockholm Convention has had a large impact on various countries around the world. For example,
the Stockholm Convention designates the Global Environmental Facility (GEF) as the principal entity
entrusted with the operations of the financial mechanism of the Convention. The GEF was originally
established in 1991 and is the largest funder of projects to improve the global environment6. Currently, it
unites 182 member governments — in partnership with international institutions, nongovernmental
organizations, and the private sector — to address global environmental issues.
The Stockholm Convention's COP has established guidance for the GEF financial mechanism that
emphasizes capacity building and establishes the country-specific National Implementation Plan (NIP) as
the main driver for implementation activities. Specifically, the COP recommended that resources should
be allocated to activities "that are in conformity with, and supportive of, the priorities identified in
[Parties'] respective NIPs. This guidance has been reaffirmed and updated at subsequent COP meetings.
In sum, the GEF has distributed grants to Parties to the Convention to support their development of their
NIP. The NIP will:
(1) Include an initial inventory of POP stockpiles (including their location),
(2) Provide a framework for developing national laws on POPs, and
(3) Provide an action plan that details how to prioritize POPs, monitor the POPs inventory, and design a
plan to eliminate POPs (short term and long-term plans).
2.2 Basel Convention
The Basel Convention is a global environmental agreement that focuses on the international
transportation and disposal of hazardous waste. The convention, by means of a treaty, was first put into
effect in May 1992. In 2004, the Basel Convention invited signatories of the Stockholm Convention to
consider the development of information on best available techniques and environmental practices with
respect to POPs (Refs. 69 and 70). As of June 2010, 173 parties have either signed, or signed and ratified
the treaty. The US signed the treaty on March 22, 1990, but, like the Stockholm Convention, as of June
2010 has not ratified it (Ref. 12).
6 More on the GEF can be found at: http://www.thegef.org/gef/
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
2.3 Convention on Long-Range Transboundary Air Pollution (LRTAP) - Protocol on POPs
The Convention on Long-Range Transboundary Air Pollution (LRTAP 7) was signed in 1979 by 34
governments and the European Community to address issues with air pollution on a regional basis.
LRTAP entered into force in 1983 and has been implemented through eight (8) Protocols that provide
specific requirements for countries to reduce air emissions and pollution. In 1998, the LRTAP adopted
the Protocol on POPs that focuses on a list of 16 compounds that have been singled out according to
agreed risk criteria. The US is a Party to the LRTAP Convention but has not yet ratified the POPs
Protocol. The compounds consist of eleven pesticides, two industrial chemicals and three by-
products/contaminants. The ultimate objective is to eliminate any discharges, emissions and losses of
POPs. As of April 2010, 51 parties had ratified LRTAP. The US is a signatory to the LRTAP's Protocol
on POPs - but has not yet ratified the Protocol.
2.4 Sources of POPs
Most POPs originate from man-made sources associated with the production, use, and disposal of certain
organic chemicals. Some POPs are intentionally produced, while others are unintentional by-products of
industrial processes or result from the combustion of organic chemicals. The 24 POPs currently within
the scope of the Stockholm Convention (or under review) include 14 pesticides and 10 industrial
chemicals or by-products (Ref 24). Table 1-1 lists these POPs.
The 14 pesticides targeted by the Stockholm Convention were produced intentionally and used on
agricultural crops or for public health vector control. Over time, significant human health and
environmental impacts were identified for these pesticides. By the late 1970s, these pesticides had been
banned or subjected to severe use restrictions in many countries. However, some of these 14 pesticides
are still used in parts of the world where they are considered essential for protecting public health (Ref.
24).
The 10 industrial chemicals and by-product POPs within the scope of the Stockholm Convention include
PCBs, dioxins, furans, brominated flame retardants (BFRs), PFOS and pentachlorobenzene.
PCBs were produced intentionally but typically have been 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 US after
1979 usually does not contain PCBs. However, older equipment containing PCBs is still in use. Most
capacitors manufactured in the US before 1979 also contained 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. 24).
7 More on LRTAP can be found at: http://www.unece.org/env/lrtap/
-------
FURTHER INFORMATION ABOUT
THE TOXICOLOGICAL AND
CHEMICAL PROPERTIES OF POPS
IS AVAILABLE AT
HTTP://WWW.ATSDR.CDC.GOV/
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
2.5 Characteristics and Health Effects of POPs
POPs are synthetic chemicals with the following properties (Ref. 24):
• 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 (possessing an affinity for fats) and easily soluble in fat.
• They accumulate and biomagnify as they move through the food chain.
• They move over long distances in nature and can be found in regions far from their points of
manufacture, use, or disposal.
POPs are associated with serious human health problems, including cancer, neurological damage, birth
defects, sterility, and immune system defects. US EPA has
classified certain chemicals as "probable" human
carcinogens8, including aldrin, alpha- and beta-HCH, dieldrin,
chlordane, DDT, heptachlor, HCB, toxaphene, chlordecone,
lindane (i.e., gamma-HCH), dioxins and furans, HCBD and
PCBs. Laboratory studies have shown that low doses of
certain 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 certain POPs are listed below (Refs. 16 and 24):
• 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 various 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. 24).
Table 2-1 provides toxicological and chemical properties of the POPs listed and under review by the
Stockholm Convention and LRTAP. Appendix A provides chemical structures, uses and effects of
chemicals listed under the Stockholm Convention and LRTAP.
Based on the 1986 USEPA 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 Soil, Second Edition - 2010
Table 2-1. Toxicology and Chemical Properties of POPs Listed and Under Review by the Stockholm Convention and LRTAP
POPs
Molecular
Formula
LD50
(mg/kg)
Half Life
Water
Solubility
(mg/L)
Solubility in other Solvents
LogKoW
Vapor
Pressure®
25°C (mm Hg)
Pesticides
Aldrin
Alpha-
Hexachlorocyclo-
hexane (HCH)
Beta-HCH
Chlordane
Chlordecone
Dichlorodiphenyl
Trichloroethane
(DDT)
Dieldrin
Endosulfan
Endrin
Heptachlor
Hexachlorobenzene
(HCB)
C12H8Cl
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 2-1. Toxicology and Chemical Properties of POPs Listed and Under Review by the Stockholm Convention and LRTAP
POPs
Lindane (Gamma -
HCH)
Mirex
Toxaphene
Molecular
Formula
C12H4Br<>
Ci0Cl12
CioHioCl8
LD50
(mg/kg)
900-
1,000
365-740
80-293
Half Life
3-6 years
62.1-107
days
10 days
Water
Solubility
(mg/L)
0.01
17.00
0.60
Solubility in other Solvents
Soluble in ether and benzene
Soluble in dioxane, xylene,
benzene, methyl ethyl ketone
Freely soluble in aromatic
hydrocarbons, readily soluble
in organic solvents including
petroleum oils
LogKoW
5.73
3.72
5.28
Vapor
Pressure®
25°C (mm Hg)
1.09xlO'5@
20°C
4.20xlO-5@20°C
S.OOxlO'7
Industrial Chemicals or By-Products
Polychlorinated
biphenyls (PCB)
Dioxins (numerical
data for tetrachloro-
dibenzo-p-dioxin)
Furans
Hexabromobiphenyl
Octabromodiphenyl
ether
Pentabromodiphenyl
ether
Pentachlorobenzene
Perfluorooctane
sulfonate (PFOS)
Hexachlorobutadiene
(HCBD)
Hexabromocyclo-
dodecane (HBCDD)
Ci2Hio-xClx
C12HXC1X02
C4H40
Ci2LL;Br6
C12H2Br80
C12H5Br50
C6HC15
C8F17S03
C4C16
C12H18Br6
1,010-
4,250
0.022-
0.045
0.916
65-149
65-149
65-149
33-330
199-318
200-580
500-
1,000
9 years
7-12 years
2.6 days
>6 months
76 days2
150 days
260-7300
days
>41
years
1.6 years5
66-101
days4
0.42
0.001
0.010
0.011
0.0005
0.013
0.56
519-680
2.00-2.55 @
20°C
0.066
Very soluble in organic
solvents
Soluble in dichlorobenzene,
chlorobenzene, benzene,
chloroform and n-octanol
Soluble in toluene
Soluble in acetone and
benzene
Soluble in acetone, methanol
and benzene
Soluble in methanol, miscible
in toluene
Low solubility in water
Soluble in ethanol and
methanol
Soluble in ethanol and ether
Low water solubility
5.60
7.02-8.70
4.00-5.00
6.39
6.29
6.64-6.97
4.88-6.12
NA
4.78
5.62
4.00x1 0'4
7.50X10'9
No data
5. 20x1 0'8
6.59xlO-6@
21°C
2.20x1 0'7-
S.SOxlO'7
1.65X10'2
2.40xlO'6
0.15
4.70x1 0'6
LogKoe
6.08
3.57
3.76
NA
NA
NA
3.33-3.87
NA
4.89-5.10
6.08
2.57
3.67
NA
Henry's Law
Constant
(dimensionless)
5.8xlO'4
3. 50x1 0'6
5.16xlO'4@22°C
2.90xlO'4
1.61xlO-5-1.02xlO-4
NA
3.90xlO'6
10.6
1.20xlO'5
S.SxlO'4
3. 09x1 0'9
0.001-0.026
NA
11
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 2-1. Toxicology and Chemical Properties of POPs Listed and Under Review by the Stockholm Convention and LRTAP
POPs
Polychlorinated
Naphthalenes (PCN)
Short-chained
chlorinated paraffins
(SCCP)
Molecular
Formula
CioHio-nCln
Q(H(2x-y+2)Cly
LD50
(mg/kg)
530-710
0.34
Half Life
2-12 days
>1 year
Water
Solubility
(mg/L)
31.7
0.003-0.994
Solubility in other Solvents
Soluble in benzene, alcohol,
ether and acetone
Soluble in chlorinated
solvents, aromatic
hydrocarbons, ketones, esters,
ethers, mineral oils and some
cutting oils
LogKoW
3.29-3.37
4.48-8.69
Vapor
Pressure®
25°C (mm Hg)
0.087
2.10X10'9-
l.SSxlO'2
LogKoe
2.97-
3.27
NA
Henry's Law
Constant
(dimensionless)
4.6xlO'4
0.10-18.0
Notes:
1: Data and definitions used in this table are derived from the Agency for Toxic Substances and Disease Registry (ATSDR) website at http://www.atsdr.cdc.gov
and the Stockholm Convention on Persistent Organic Pollutants website at http://chm.pops.int/.
2: Half life for Octabromodiphenyl ether in air.
3: Half life for Perfluorooctane sulfonate in water.
4: Half life for Hexabromocyclododecane in sediments
5: Half life for Hexachlorobutadiene in air.
mg/kg = milligram per kilogram
LD50= Lethal Dose 50% is the dose of a substance required to kill 50% of the exposed test subjects.
Half Life = The rate at which a chemical breaks down is usually defined by how long it takes for half of the chemical to break down.
Log Kow = The octanol/water partition coefficient is used as a measurement of a compound's bioaccumulation potential.
mm Hg = millimeters of mercury (unit for standard air pressure)
mg/L = milligram per liter
Log Koc = The organic carbon partition coefficient is used as a measurement of soil adsorption potential.
Henry's Law Constant = A measurement that is used to estimate the tendency of a chemical to partition between its vapor phase and water.
NA = Not available
12
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
2.6 Review of Chemical Characteristics of POPs Listed and Under Review for the 2009
Stockholm Convention
To determine if the POPs listed and under review in the Stockholm Convention of 2009 would be
amenable to treatment using similar non-combustion technologies identified for the POPs listed by the
2001 Stockholm Convention, these new POPs were grouped and compared. For classification purposes,
physical organic chemistry principles and "structure-activity relationships" (which is a major tool for new
drug development) are used in this analysis. Both fields of analysis are based on types of constituents,
structures, and reaction rates (Ref. 14 and 49).
Chemicals Added at the May 2009 Stockholm Convention Conference of Parties (COP) meeting
Hexachlorocvclohexane (HCH) isomers: Lindane (i.e., Gamma-HCH),, Alpha-HCH,, and Beta-
HCH
Based on the types of chemical constituents, structures, and reaction rates, Lindane (i.e., gamma-HCH)
and 2 other HCH isomers (i.e., alpha-HCH and beta-HCH) will react with other chemicals and produce
combustion products much like toxaphene (Ref. 14 and 49). Complete combustion products are expected
to include the usual organic compound products (carbon dioxide and water) and hydrochloric acid.
Incomplete combustion products include carbon monoxide, acrolein, phosgene, chlorinated dioxins and
chlorinated furans. The products of non-combustion chemical technologies will depend on proprietary
chemicals and their reactions under the specific treatment conditions of the technology.
Chlordecone
Chlordecone (commonly know as its tradename Kepone®) is an isomer of mirex. Based on the types of
chemical constituents, structures, and reaction rates, chlordecone will react essentially identically to mirex
(Ref. 14 and 49). Complete combustion products are expected to include the usual organic compound
products (carbon dioxide and water) and hydrochloric acid. Incomplete combustion products include
carbon monoxide, acrolein, phosgene, chlorinated dioxins and chlorinated furans. The products of non-
combustion chemical technologies will depend on proprietary chemicals and their reactions under the
specific treatment conditions of the technology.
Brominated compounds (octabromodiphenyl ether, penta-BDE, and hexabromobiphenyl)
Based on the types of chemical constituents, structures, and reaction rates, these three brominated
compounds will react similarly to PCBs (Ref. 14 and 49). However, these brominated compounds will
probably be more reactive (less time/energy required for given amount of reaction) since bromine is a
belter "leaving group" than chlorine. A "leaving group" is the atom or functional group that breaks its
bond with a carbon atom during the reaction. Complete combustion products are expected to include the
usual organic compound products (carbon dioxide and water) and hydrobromic acid. Incomplete
combustion products include carbon monoxide, carbonyl bromide, and brominated dioxins and furans.
The products of non-combustion chemical technologies will depend on proprietary chemicals and their
reactions under the specific treatment conditions of the technology.
Pentachlorobenzene
Based on the types of chemical constituents, structures, and reaction rates, pentachlorobenzene will be
very similar to HCB (Ref. 14 and 49). Complete combustion products are expected to include the usual
organic compound products (carbon dioxide and water) and hydrochloric acid. Incomplete combustion
products include carbon monoxide, acrolein, phosgene, chlorinated dioxins and chlorinated furans. The
13
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
products of non-combustion chemical technologies will depend on proprietary chemicals and their
reactions under the specific treatment conditions of the technology.
Perfluorooctane sulfonate (PFOS)
PFOS is the only new POP with no close similarity to any of the previously listed POPs. Based on the
types of chemical constituents, structures, and reaction rates, it would undergo the same reactions as
chlordane, lindane, toxaphene, and other aliphatic chlorinated compounds, but will be considerably less
reactive (more time/energy required for a given amount of reaction), since fluorine is a very poor "leaving
group" (Ref. 14 and 49). There is also one special case: PFOS is relatively water-soluble, especially in
alkaline environments. Therefore a base-catalyzed reaction in aqueous media may proceed relatively
rapidly because the PFOS is more available to the other reactants. In contrast, other non-combustion
chemical technologies will be much less effective with PFOS than with previously discussed POPs.
Complete combustion products are expected to include the usual organic compound products (carbon
dioxide and water), hydrofluoric and sulfuric acids. Incomplete combustion products include carbon
monoxide, carbonyl difluoride, sulfur oxides (SOX) and fluorinated dioxins and furans.
Chemicals under Review at the May 2009 Stockholm Convention Conference of Parties (COP) meeting
Endosulfan
Based on the types of chemical constituents, structures, and reaction rates, endosulfan will be similar to
aldrin/dieldrin (Ref. 14 and 49). It includes a sulfur atom, but that will be relatively labile; therefore, the
sulfur atom should have no real effect on the properties that affect decomposition to a less toxic
compound. Complete combustion products are expected to include the usual organic compound products
(carbon dioxide and water), hydrochloric and sulfuric acids. Incomplete combustion products include
carbon monoxide, sulfur oxides (SOX), phosgene, and chlorinated dioxins and furans. The products of
non-combustion chemical technologies will depend on proprietary chemicals and their reactions under the
specific treatment conditions of the technology.
Hexabromocyclododecane (HBCDD)
Based on the types of chemical constituents, structures, and reaction rates, hexabromocyclododecane
(HBCDD) will be like PCB, but probably a bit easier to break down, similar to the other brominated
compounds (Ref. 14 and 49). Complete combustion products are expected to include the usual organic
compound products (carbon dioxide and water) and hydrochloric acid. Incomplete combustion products
include carbon monoxide, carbonyl dibromide, and brominated dioxins and furans. The products of non-
combustion chemical technologies will depend on proprietary chemicals and their reactions under the
specific treatment conditions of the technology.
Short-Chained Chlorinated Paraffins (SCCP)
Based on the types of chemical constituents, structures, and reaction rates, the chlorinated paraffins will
be most like toxaphene, with similarity depending on factors such as the ratio of chlorine to carbon atoms
and the overall size of the molecule (Ref. 14 and 49). Complete combustion products are expected to
include the usual organic compound products (carbon dioxide and water) and hydrochloric acid.
Incomplete combustion products include carbon monoxide, phosgene, and chlorinated dioxins and furans.
The products of non-combustion chemical technologies will depend on proprietary chemicals and their
reactions under the specific treatment conditions of the technology.
14
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
2.7
Treatment of POPs
As mentioned before, POP-contaminated soil has been widely treated using combustion systems
employing high temperature incineration to destroy the contaminants. Incineration is widely used
because high-temperature incinerators can address large volumes of contaminated material and can treat
most contaminants. Though incineration can be used to treat POPs, there are several limitations
associated with this technology, as discussed in Section 1.0. Other technology categories that can be used
to treat POPs include: (1) thermal desorption and degradation, (2) chemical degradation, (3) physical-
chemical degradation, (4) thermal-chemical degradation, (5) biodegradation, and (6) phytoremediation.
Technologies under these categories are discussed further in Section 3.0.
2.8
Related Documents
Three organizations, UNEP, Africa Stockpiles Programme and HPA, have developed summary/overview
reports and fact sheets about non-combustion technologies for POPs treatment. These documents are
provided below, with a list of the technologies addressed by each report.
• 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://www.ihpa.info/resources/library/.
This report (Ref 44) describes emerging non-combustion alternatives for the destruction of POPs.
Mr. John Vijgen of IHPA gathered the technology data and prepared the report and the fact sheets
for the 12 technologies listed below:
1. Base-catalyzed decomposition
(BCD)
2. CerOx™
3. Gas-phase chemical reduction
process (GPCR)
4. GeoMelt™
5. In situ thermal destruction
6. Mechanochemical
dehalogenation (MCD™)
7. Plasma arc (PLASCONR)
8. Self-propagating high-
temperature dehalogenation
(SPHTD)
9. Silverll™
10. Solvated electron technology
11. Supercritical Water Oxidation
(SCWO)
12. TDT-3R™
IHPA, 2009. Provisional Fact Sheets prepared by IHPA (POPs Technology Specification and
Data Sheets) for the Secretariat of the Basel Convention. IHPA prepared and updated six fact
sheets describing non-combustion technologies in 2009. The six technologies are listed below:
1. Catalytic hydrodechlorination
(CHD)
2. Potassium tert-butoxide (t-
BuOK) method
3. GeoMelt™
4. Supercritical water oxidation
(SCWO)
5. Radicalplanet Technology
(Mechanochemical Principle)
6. Waste to gas conversion
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.basel.int/techmatters/review_pop_feb04.pdf This report (Ref. 72) provides a
15
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
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
soil. The report was a background document for the STAP-GEF workshop held in Washington,
DC, in October 2003 and was based on work by the International Centre for Sustainability
Engineering and Science, Faculty of Engineering, at the University of Auckland, New Zealand.
The report contains overviews of the following 27 non-combustion technologies:
1. BCD 14. Molten metal
2. Bioremediation/Fenton reaction 15. Molten salt oxidation
3. Catalytic hydrogenation 16. Molten slag process
4. DARAMEND® bioremediation 17. Ozonation/electrical discharge
5. Enzyme degradation destruction
6. Fe (III) photocatalyst 18. Photochemically enhanced
degradation microbial degradation
7. GPCR 19. Phytoremediation
8. GeoMelt™ process 20. Plasma arc (PLASCON™)
9. In situ bioremediation of soils 21. Pyrolysis
10. MCD 22. SPHTD
11. Mediated electrochemical 23. Sodium reduction (SR)
oxidation (AEA Silver II) 24. Solvated electron technology
12. Mediated electrochemical 25. SCWO
oxidation (CerOx™) 26. TiO2 - based V2O5/WO3
13. MnOx/TiO2 - A12O3 catalyst catalysis
degradation 27. White rot fungi bioremediation
• The International Centre for Science and High Technology - United Nations Industrial
Development Organization, 2007. "Non-Combustion Technologies for POPs Destruction -
Review and Evaluation." Trieste, Italy. March. Online Address: www.ics.trieste.it. This report
(Ref 42) provides information about alternative non-combustion technologies for the treatment of
POPs. The report contains summaries for the following 15 technologies:
1. Ball Milling - MCD and DMCR 9. PLASCONR
2. BCD 10. PWC™
3. Cerox™ 11. SCWO
4. Geomelt™ 12. SET™
5. GPCR™ 13. Silver II™
6. HydroDec™ 14. SPHTD
7. MSO 15. SR
8. PACT™
• Africa Stockpiles Programme, 2008. "Review and Update of Technology." Online Address:
http://www.africastockpiles.net/ This report provides an overview of various non-combustion
technologies and includes fact sheets for the seven technologies listed below:
1. BCD 5. GeoMelt™
2. GPCR 6. Ball Milling (Radical Planet)
3. Plasma arc (PLASCONR) 7. Thermopower (Thermal Retorting)
4. SCWO Process
« Japan Environmental Safety Corporation (JESCO), 2005. JESCO is a primary technology
provider for the treatment of PCB contaminated wastes. Dr. Noma of National Institute for
16
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
Environmental Studies developed fact sheets for the following six technologies; the fact sheets
are available at http://www.ihpa.info/resources/library/
1. Radicalplanet" (Mechanochemical
Principle)
2. SP process (Sodium Powder
Dispersion Dechlorination Process)
3. Sub-critical water oxidation
4. Supercritical Water Oxidation of
Organo Corporation
5. Supercritical Water Oxidation of
Kurita Industries
6. Vacuum Heating Decomposition
Basel Convention, 2005. "Destruction and Decontamination Technologies for PCBs and Other
POPs Wastes (Part III Annexes) A Training Manual for Hazardous Waste Project Managers,
Volume C." Online address: http://www.basel.int/meetings/sbc/workdoc/TM-A.pdf. This report
contains seven fact sheets prepared by IHPA (listed as POP Technology Specification and Data
Sheets) for the Secretariat of Basel Convention. Four of these published fact sheets, listed below,
pertain to non-combustion technologies for the treatment of POPs:
1. Alkali metal reduction
2. Base-catalyzed decomposition
(BCD)
3. Gas-phase chemical reduction
(GPCR)
4. Plasma Arc (PLASCON)
Basel Convention, 2007. "Updated general technical guidelines for the environmentally sound
management of wastes consisting of, containing or contaminated with persistent organic
pollutants (POPs)" Online address: http://www.basel.int/pub/techguid/tg-POPs.pdf This report
contains summaries for the following technologies for the treatment of POPs.
1. Alkali metal reduction
2. Base-catalysed decomposition
(BCD)
3. Catalytic hydrodechlorination
(CHD)
4. Photochemical dechlorination
(PCD) and catalytic
dechlorination (CD) reaction
5. Gas-phase chemical reduction
(GPCR)
6. Plasma arc
7. Potassium tert-butoxide (t-
BuOK) method
8. Supercritical water oxidation
(SCWO) and subcritical water
oxidation
9. Waste to gas conversion
17
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
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 26
chemicals listed or under review in the Stockholm Convention on POPs and/or the LRTAP's Protocol on
POPs. 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 through which contaminant destruction occurs. Pretreatment is defined as any process that
precedes the primary treatment technology to prepare the contaminated material for treatment, typically
via transfer of contaminants from one media/phase to another (e.g., solid to liquid phase).
Tables 3-1 and 3-2 list the technologies addressed in this report and summarize available technology-
specific information, including: capability to handle waste strength, whether treatment is ex situ or in situ,
scale, contaminant treated, cost, pre-treatment needs, power requirements, technology configuration, and
location of any fact sheets available for the technology. Waste strength refers to high- and low-strength
wastes. High-strength waste includes soil contaminated with high concentrations of POPs. Low-strength
waste includes soil contaminated with low concentrations of POPs. Table 3-1 provides information about
full-scale9 technologies and Table 3-2 provides information about pilot-scale10 and bench-scale11
technologies for treatment of POPs. Table 3-3 presents performance data for the technologies. The
performance data include site location, contaminants treated, untreated and treated contaminant
concentrations, and percent reduction of the contaminants (as available). Section 5.0 contains contact
information for vendors of these various technologies.
3.1 Full-Scale Technologies for Treatment of POPs
This section presents 12 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 US EPA and IHPA provide additional
details for some of these technologies and their applications. Appendix B, C, and D of this report provide
fact sheets prepared by US EPA for anaerobic bioremediation using blood meal for the treatment of
toxaphene in soil, DARAMEND®, and in situ thermal desorption (ISTD), respectively. Links to the IHPA
fact sheets are included in the appropriate subsections of this report.
9 A full-scale project involves use of a commercially available technology to treat industrial waste and to remediate
an entire area of contamination.
10 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.
11 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.
18
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 3-1. Summary of Full-Scale Non-combustion Technologies for Remediation of Persistent Organic Pollutants *
Technology
Commercial
Availability
Waste
Strength 2
Ex/In
situ3
Contaminant(s) Treated
POPs
Pesticide(s) "
PCBs
Dioxin/ Furans
Non-POPs5
Cost
Pre-
Treatment
Power
Requirement
Configuration
Fact Sheet
Full-Scale Technologies
Anaerobic
bioremediation
using blood meal
for the treatment
of toxaphene in
soil and
sediment
Base Catalyzed
Decomposition
(BCD)
DARAMEND®
Gas Phase
Chemical
Reduction
(GPCR™)
Yes
Yes
Yes
No6
Low
Low/High
Low
High
Ex
situ
Ex
situ
Ex/In
situ
Ex
situ
Toxaphene,
DDT
Chlordane,
Heptachlor,
DDT, HCB,
Lindane, HCH
Toxaphene,
DDT, HCB,
Dieldrin, a-HCH,
B-HCH, Lindane
DDT, HCB,
Dieldrin,
Lindane, Aldrin
None
Yes
None
Yes
None
Yes
None
Yes
None
PCP, herbicides,
pesticides,
insecticides
ODD, DDE,
RDX, HMX,
DNT, TNT, 2,4-
D; 2,4,5-T
Metoachlor,
Atrizine
PAH,
chlorobenzene
$130 to $271 per cubic
yard (in 2007)
1,400-1,700 Euros/ton
(in 2004)
$500,000 to $2 million
for one reactor
(physical plant facility
only)
$55 per ton (ex situ),
$12.50 per cubic yard
(in situ), $30,000 per
acre (in situ full-scale)
(in 2005)
Capital cost estimate
for two-Thermal
Reduction Batch
Procesor plants (solid
feed): $10.8M for full-
scale, $5M for semi-
mobile, and one
estimate for one TRBP
plant (liquid/gaseous
feed): $10.3M for full-
scale, $4.75M for
semi-mobile
Minimum set-up costs:
$10.5M for full-scale,
$5M for semi-mobile
None
Thermal
desorption
Debris
removal
pHor
moisture
content
adjustment
None
Thermal
desorption
None
Low- High
None
Low- High
Transportable
Transportable
and fixed
Transportable
Fixed and
transportable
Appendix
B
http://www
.ihpa.info/r
esources/li
brarv/
Appendix
C
http://www
.ihpa.info/r
esources/li
brarv/
19
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 3-1. Summary of Full-Scale Non-combustion Technologies for Remediation of Persistent Organic Pollutants *
Technology
Gene Expression
Factor®
(bioremediation)
GeoMelt™
Mechanochemic-
al
Dehalogenation
(MCD™)
Plasma Arc
(PLASCON™)
(8
Radicalplanet
Technology
Solvated
Electron
Technology™
Sonic
Technology
Commercial
Availability
Yes
Yes
Yes7
Yes8
Yes9
Yes
Yes
Waste
Strength 2
Low
Low/High
Low/High
Low/High
Low/High
Low/High
Low/High
Ex/In
situ3
In/Ex
situ
Ex
situ
Ex
situ
Ex
situ
Ex
situ
Ex
situ
Contaminant(s) Treated
POPs
Pesticide(s) "
DDT, Chlordane,
Dieldrin,
Heptachlor,
HCB
Aldrin, Dieldrin
DDT, Lindane
DDT, Chlordane,
Endosulfan,
Aldrin, HCB,
Dieldrin,
Lindane
Chlordane, DDT,
Endrin, HCH,
Lindane
NA
DDT
PCBs
Yes
Yes
Yes
Yes
Yes
Yes
Dioxin/ Furans
Yes
No
Yes
Yes
Yes
Yes
Non-POPs5
DDE
Metals and
radioactive waste
ODD, DDE,
HCH, PCP,
PAHs, organic
pesticides,
hydrocarbons
NA
PCP, PCNB,
PVC (Asbestos)
Explosives,
CFC, Halons
PAH, VOCs,
Pesticides
Cost
Initial cost for bench-
scale study was
$30,000.
$30 to $60 per ton of
contaminated soil
depending on site
conditions
NA
NA
$1M for standard 150
kW plant
2.8 million Euros for
E-200 (one machine
with 105 tons/y)
3 .3 million Euros for
E-500 (one machine
with 210 tons/y)
NA
NA
Pre-
Treatment
None
De watering
/drying
maybe
required
Grinding,
drying
Thermal
desorption
None
Shredding/
grinding,
dewatering/
drying
Mixing
with
solvent to
produce a
slurry
Power
Requirement
None
High
High
Low/High
Low
Moderate
75 kW
Configuration
Fixed and
transportable
Fixed and
transportable
NA
Fixed and
transportable
Fixed and
Transportable
Fixed and
transportable
Transportable
Fact Sheet
None
http://www
.ihpa.info/r
esources/li
brarv/
http://www
.ihpa.info/d
ocs/librarv/
librarvNAT
O.php
http://www
.ihpa.info/r
esources/li
brarv/
http://www
.ihpa.info/r
esources/li
brarv/
http://www
.ihpa.info/d
ocs/librarv/
librarvNAT
O.php
None
20
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 3-1. Summary of Full-Scale Non-combustion Technologies for Remediation of Persistent Organic Pollutants *
Technology
Thermal
In Situ Thermal
Desorption
(ISTD)
Commercial
Availability
Yes
Waste
Strength 2
Low/High
Ex/In
situ3
In
situ
Contaminant(s) Treated
POPs
Pesticide(s) "
NA10
PCBs
Yes
Dioxin/ Furans
Yes
Non-POPs5
VOCs, SVOCs,
oils, creosote,
coal tar,
gasoline, MTBE,
volatile metals
Cost
$200 to $600 per cubic
yard (data from 1996
to 2005)
Pre-
Treatment
De watering
maybe
required
Power
Requirement
High
Configuration
Transportable
Fact Sheet
Appendix
D
Notes:
1: Data in these tables are derived from various documents, vendor information, and other sources - both peer reviewed and not, provided in the later technology-specific
sections.
2: 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 13 pesticides addressed within the scope of the Stockholm Convention and LRTAP.
5: Non-POPs include contaminants outside the scope of Stockholm Convention and LRTAP.
6: Technology is not commercially available and is currently being modifying to improve its cost effectiveness
7: Technology is commercially available from EDL in Auckland, New Zealand and Tribochem in Wunstrof, Germany. No technology vendor is available in the US
8: SRL Plasma Pty. Ltd., an Australian company, is the patent holder of this technology. Technology commercially used in Japan.
9: Technology is commercially available only in Japan
10: 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, but these contaminants have not yet been treated using ISTD at full or pilot scale.
HCB: Hexachlorobenzene
HCH: Hexachlorocyclohexane
BFRs: Bromated Flame Retardants - Octabromobiphenyl ether,
Pentabromodiphenyl ether, Hexabromobiphenyl &
Hexabromocyclododecane (HBCDD)
ODD: Dichlorodiphenyldichloroethane
DDE: Dichlorodiphenyldichloroethylene
DDT: Dichlorodiphenyltrichloroethane
DNT: Di-nitro toluene
HMX: High melting explosive, octahydro-l,3,5,7-tetranitro-l,3,5,7 tetrazocine
PCB: Poly chlorinated biphenyls
PCP: Pentachlorophenol
PVC: Poly vinyl chloride
CFC: Chlorofluorocarbon
TNT: 2,4,6-Trinitrotoluene
MTBE: Methyl tert-butyl ether
NA: Not available
PAH: Polycyclic aromatic hydrocarbons
Penta-CB: Pentachlorobenzene
PCNB: Pentachloronitrobenzene
PCNs: Polychlorinated napthalenes
SCCPs: Short-chained chlorinated paraffins
SVOC: Semivolatile organic compound
VOC: Volatile organic compound
21
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 3-2. Summary of Pilot/Bench-Scale Non-combustion Technologies for Remediation of Persistent Organic Pollutants *
Technology
Waste
Strength 2
Ex/In
situ3
Pilot-Scale Technologies
Phytoremediation
Reductive Heating
and Sodium
Dispersion
Sub-critical Water
Oxidation
Low
Low/High
NA
In/Ex
situ
Ex
situ
Ex
situ
Contaminant(s) Treated
POPs
Pesticide(s) "
PCBs
Dioxin/ Furans
Non-POPs 5
Cost
Pre-Treatment
Power
Requirement
Configuration
Fact Sheet
DDT, Chlordane
DDT, Chlordane,
Aldrin, B-HCH
Aldrin, Dieldrin,
Chlordane
Yes
Yes
Yes
No
Yes
Yes
DDE
PCNB
BHC
NA
NA
NA
None
None
Extraction into a
solvent
None
NA
NA
Transportable
Transportable
Fixed and
transportable
None
None
http://www.ih
pa.info/resour
ces/librarv/
Bench-Scale Technologies
Self Propagating
High Temperature
Dehalogenation
TDR-3R™
High
High
Ex
situ
Ex
situ
HCB
HCB
No
No
No
No
None
PAH, VOCs,
SVOCs
NA
NA
None
Thermal
desorption
NA
High
NA
NA
http://www.ih
pa.info/docs/li
brarv/librarvN
ATO.php
http://www.ih
pa.info/docs/li
brary/libraryN
ATO.php
Notes:
1: Data in these tables are derived from various documents, vendor information, and other sources - both peer reviewed and not, provided in the later technology-specific
sections.
2: 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 13 pesticides addressed within the scope of the Stockholm Convention and LRTAP.
5: Non-POPs include contaminants outside the scope of Stockholm Convention and LRTAP.
B-HCH: beta- hexachlorocyclohexane
BHC: Hexa-Chloro Benzene (BHC/Lindane)
DDE: Dichlorodiphenyldichloroethylene
DDT: Dichlorodiphenyltrichloroethane
HCB: Hexachlorobenzene
NA: Not available
PAH: Polycyclic aromatic hydrocarbons
PCNB: Pentachloronitrobenzene
SVOC: Semi volatile organic compound
VOC: Volatile organic compound
22
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 3-3. 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)3
Treated
Concentration
(mg/kg)
Percent Reduction
Full-Scale Applications
Anaerobic bioremediation using blood
meal for the treatment of toxaphene in
soil and sediment
DARAMEND®
Gene Expression Factor
GeoMelt™
Mechanochemical Dehalogenation
(MCD™)
Radicalplanet® Technology
Solvated Electron Technology
Sonic Technology
Gila River Indian Community, Arizona
Gila River Boundary, Arizona
T.H. Agricultural and Nutrition Superfund Site,
Montgomery, Alabama
Former North American Transformer South Yard
Area, Milpitas, California
Borello Property, Morgan Hill, California
Mantegani Property, South San Francisco,
California
Parsons Chemical Works, Inc. Superfund Site,
Grand Ledge, Michigan
TSCA Spokane, Spokane, Washington
Wasatch Chemical, Salt Lake City, Utah
WCS-Commercial TSCA cleanup, Andrews,
Texas
Fruitgrowers Chemical Company Site, Mapua,
New Zealand
Ibraki, Japan
Ibraki, Japan (with Geo-Environmental Protection
Center)
Pennsylvania Air National Guard Site, Harrisburg
International Airport, Harrisburg, Pennsylvania
Juker Holdings Site, Vancouver, British Columbia
Toxaphene
Toxaphene
Toxaphene
DDT
PCBs
Dieldrin
Toxaphene
DDT
Dieldrin
DDT
Chlordane
Dieldrin
PCBs
Dioxins
DDT
Chlordane
PCBs
Aldrin +Dieldrin+ Lindane
(ADL)
DDX (total DDT, ODD, and
DDE)
PCBs
PCBs
PCBs
PCBs (from soil)
PCB (concentrate in kerosene)
29-34
23-110
189 (Mean)
81 (Mean)
156 (Max)
0.48
6.2
9.0 (Max)
1.0 (Max)
340 (Max)
89 (Max)
87 (Max)
17,860
38 (Max)
1.091 (Max)
535 (Max)
496
73.245 (Mean)
717 (Mean)
42,800
75,000 ng-TEQ
17-560
400-1,600
46,000 (Max)
4-5
5-20
10 (Mean)
9 (Mean)
<1
0.00354 (Mean)
0.130
<0.5
0.5
O.016
<0.08
<0.016
ND
ND
ND
ND
ND
20.6 12 (Mean)
64.8 (Mean)
0.01
0.1 3 ng-TEQ
<1
<25
<3
86-93 %
66-82%
89%
90%
99.38%
99.12%
97.9%
94.5%
50%
99%
99%
99%
NA
NA
NA
NA
NA
71.86%
90.96%
99.99%
99.9999%
99.99%
98.43%
99.99%
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in Soil, Second Edition - 2010
Table 3-3. Performance of Non-combustion Technologies for Remediation of Persistent Organic Pollutants *
Technology
In Situ Thermal Desorption (ISTD)
Examples of Treatment Performance2
Site Name or Location
Tanapag Village, Saipan, Northern Mariana
Islands
Former South Glens Falls Dragstrip, Moreau, New
York
Centerville Beach, Ferndale, California
Alhambra "Wood Treater", Alhambra, California
Contaminant
PCBs
PCBs
PCBs
Dioxin/Furans
Dioxins
Untreated
Concentration
(mg/kg)3
10,000 (Max)
5,000 (Max)
.15-860
0.0032 (Max)
.0194
Treated
Concentration
(mg/kg)
<10
0.8
<0.17
0.00006
<.001
Percent Reduction
99.9%
99.9%
99.98%
99.81%
94.85%
Pilot-Scale Applications
Base Catalyzed Decomposition (BCD)
DARAMEND®
In Situ Thermal Desorption (ISTD)
Warren County Landfill, Warren County, North
Carolina
PCX Superfund Site, Statesville, North Carolina
Former Agricultural Site, Florida
Hot-Spot Treatment, Former Manufacturing
Facility, Southeastern US
Missouri Electric Works, Cape Girardeau,
Missouri
Former Mare Island Naval Shipyard, Vallejo,
California
PCBs
Heptachlor
Chlordane
Dieldrin
Toxaphene
PCBs
PCBs
81,100
0.648
.02
.046 (Mean)
127.7 (Mean)
20,000 (Max)
2,200 (Max)
<5
ND2
ND2
.015
8.7 (Mean)
O.033
O.033
99.99%
NA
NA
67.39%
93.19%
99.99%
99.99%
Bench-Scale Applications
DARAMEND®
TDT-3R™
Former obsolete pesticide warehouse, Moldova
Gare Site, Hungary
Lindane
HCB
17 (Mean)
1,215
10 (Mean)
0.1
41.18%
99.99%
Notes:
1: Data in this table are derived from various document, vendor information, and other sources, cited in the later technology-specific sections.
2: Treatment examples were selected to illustrate the types of treatment performance data available.
3: The concentrations are maximum concentrations unless otherwise indicated in parenthesis.
4: The specific limits for the MDL and ND were not provided in the source document.
5: Full-scale data are present in this table but available pilot-scale data can be found in Section 3 under each specific technology.
ODD: Dichlorodiphenyldichloroethane
HCB: Hexachlorobenzene
Max: Maximum Concentration
mg/kg: Milligram per kilogram
NA: Not available
DDE: Dichlorodiphenyldichloroethylene DDT: Dichlorodiphenyltrichloroethane
PCBs: Polychlorinated biphenyls ND: Not detected (concentration below method detection limit)
Mean: Mean Concentration MDL: Method detection limit
ng-TEQ/g = Nanogram Toxic Equivalent of Dioxins per gram
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
3.1.1 Anaerobic Bioremediation Using Blood Meal
This technology claims to use biostimulation with amendments to promote degradation of toxaphene in
soil or sediment by native anaerobic microorganisms. For treatment, 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 are added to the contaminated material (Ref. 3). In some applications, starch is also
used. The contaminated soil is mixed with the amendments and water. The technology can use several
methods to produce soil-amendment mixtures, including blending in a dump truck, mechanical mixing in
a pit, and mixing in a pug mill. The soil 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 is
intended to minimize the transfer of atmospheric oxygen to the soil amendment mixture 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 is then sampled periodically to measure
contaminant concentration. The process continues until II THE FACT SHEET PREPARED BY US EPA
., . . . , , , . , . ,.. ., „ | IS INCLUDED IN APPENDIX B.
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.
,^^^^^^^^^^^^^^^^^^^^^^^^—, Anaerobic bioremediation using blood meal has been used
to treat low-strength waste contaminated with toxaphene.
Essential components such as mixing troughs are typically
POPs TREATED: TOXAPHENE constructed and left in place. Other components such as
MEDIUM: SOIL AND SEDIMENT mixing equipment and biological amendments have been
procured locally.
PRETREATMENT: NONE
TECHNOLOGY TYPE: BIODEGRADATION
RESIDUALS: Low CONCENTRATIONS OF
TOXAPHENE AND CAMPHENES WITH
VARYING DEGREES OF CHLORINATION
(COST IN 2007 USD)
FULL SCALE
EXSITU
The technology has been used to treat toxaphene at several
livestock dip vat sites and one site with a pesticide spill.
Dip vats are trenches with a pesticide formulation used to
COSTS: $130 TO $271 PER CUBIC YARD treat livestock infested with ticks. In 2007, cleanup costs in
US Dollar (USD) for full-scale implementation ranged from
$130 to $271 per cubic yard (Ref. 29). Performance data
from applications at nine dip vat sites and one pesticide site
are presented in Table 3-4.
Anaerobic bioremediation using blood meal was developed by US EPA's Environmental Response Team
(ERT). The technology has been used at sites with toxaphene contaminated soil and sediments. Bench
scale testing is recommended to determine if the technology will be effective at a particular site, as well
as to evaluate amendment types and quantities, possible removal, and whether degradation products are
formed and persist. Differences between unamended live, killed, and amended live units may also help to
evaluate treatment effectiveness. Bench testing should be conducted in gas tight units to reduce volatile
losses. Based on structural similarity of toxaphene to other POPs described in section 2.6 of this report,
this technology may potentially be used to treat other POPs. However, because of the specificity of
biochemical reactions, this technology may or may not be effective in treating other similar POPs. This
technology is publicly available and is currently not patented (Ref. 4). The most recent application was in
2004 at the Gila River Boundary (GRB) site in Laveen, Arizona. Further technology information can be
obtained by contacting the technology developer using the information provided in Section 5.0.
25
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
Table 3-4. Performance of Anaerobic Bioremediation Using Blood Meal for Toxaphene Treatment
Site
Location
Period
(Days)
Quantity
of Soil
Treated
Untreated
Concentration
(mg/kg)
Treated
Concentration
(mg/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 (Mean)
23 (Mean)
291
40
100
22
14
33
4
8
71
17
17
o
6
4
8
Gila River Boundary (GRB)
GRB (6 cells)
Laveen,
Arizona
180
8,000 cy
Full
23-110
5-20
NA = Not available
Sources: Refs. 3 and 29
Notes:
cy = Cubic yard
mg/kg = Milligram per kilogram
3.1.2 Base-Catalyzed Decomposition
Base-Catalyzed Decomposition (BCD) is an ex situ technology that has been used to treat high-strength
soil containing POP contamination. The technology is available in both transportable and fixed
configurations.
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
http://www.ihpa.info/resources/library/.
The use of BCD technology may require pre-
treatment using thermal desorption when
pollutants are in ppm rather than percent
concentrations in contaminated matrices.
Depending on the concentration of the
contaminants, a selected amount of an alkali such as sodium bicarbonate is mixed with the contaminated
soil in the pre-treatment stage of the process and the mixture is heated in a thermal desorption reactor to
temperatures ranging from 315 to 500°C. The heat separates the halogenated compounds from the soil by
evaporation. In the second stage of the pre-treatment process, the volatilized contaminants pass through a
condenser. The condensate is then sent to a BCD liquid tank reactor (LTR). Sodium hydroxide, a
proprietary catalyst, and carrier oil are added to the LTR, which is then heated to above 326°C for three to
six hours. The carrier oil serves both as a suspension medium and a hydrogen donor. The heated oil is
then cooled and sampled to determine whether it meets disposal criteria. If the oil does not meet the
disposal criteria, it is returned to the LTR, reagents are added, and the reactor is reheated (Ref 48). The
26
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
TECHNOLOGY TYPE: CHEMICAL
DEGRADATION
POPs TREATED: PCBs,
CHLORDANE, HEPTACHLOR, DDT,
HCB, HCH, LlNDANE, DIOXINS,
AND FURANS
PRETREATMENT: THERMAL
DESORPTION
MEDIUM: SOIL AND LIQUIDS
FULL SCALE
EXSITU
treated soil can be used as backfill on site. BCD was developed by
US EPA's National Risk Management Research Laboratory in
Cincinnati, Ohio. US EPA holds the patent rights to this
technology in the US. The foreign rights are held by BCD Group
Inc., Cincinnati, Ohio. The technology has been licensed by BCD
Group Inc., to environmental firms in Spain, Australia, Japan,
Czech Republic, and Mexico. Since its initial development in
1990, considerable technology advancements have been made
with the development of a new catalyst, which reduces the
reaction time in the BCD reactor (Ref 56). This second
generation technology has been applied in Australia, Mexico and
Spain to treat PCB-contaminated oil.
Several full-scale applications of BCD have addressed POP-
contaminated wastes. Two commercial facilities operated in
Australia and treated approximately 8,000 to 10,000 tons of PCB
contaminated waste, PCB-contaminated oil, 25 tons of pesticide
chemicals and pesticide wastes, and 15 tons of pesticide
concentrates generated and collected as a result of soil remediation. Another commercial facility has been
operating in Mexico since 1998 and has treated 1,400 tons of liquids and solids contaminated with PCBs.
In the Czech Republic, a full-scale BCD unit has been operating since 2006 and has treated 29,000 to
38,000 tons of soil and building debris contaminated with dioxins, furans, HCB, lindane, and HCH, as
well as nearly 200 tons of waste chemicals. In addition, 300 tons of concentrated contaminants from the
thermal desorption process have been treated using BCD. A system also operated between 2000 and
2002 in Spain to treat 3,500 tons of pure HCH waste. The performance data for these applications could
not be obtained from the technology vendor.
BCD is a non-combustion technology that uses sodium hydroxide, a proprietary catalyst, carrier oil and
heat to treat POPs contaminated soil and liquids. BCD has been used to treat PCBs, HCB, HCH, lindane,
dioxins and furans. Based on structural similarity of known POPs treated using BCD to other similar
POPs described in section 2.6 of this report, this technology can potentially be used to treat other POPs.
However, the potential of BCD technology to treat other POPs is dependent on the proprietary chemical
catalyst used and the specific reactions under the treatment conditions of this technology. BCD is
licensed by BCD Group Inc. and has been used at full-scale in various countries around the world
including Spain, Australia, Japan, Czech Republic and Mexico. The most recent application of this
technology was in 2006 at a site in the Czech Republic. The performance data for this technology were
provided by John Vijgen (IHPA). No performance data could be obtained directly from the technology
vendor. Currently, no full-scale applications of this technology exist in the US. Contact information for
the technology vendor is provided in Section 5.0.
3.1.3 DARAMEND®
DARAMEND® has been used to treat low-strength wastes contaminated with toxaphene and DDT. It is
an amendment-enhanced bioremediation technology that involves the creation of sequential anoxic and
oxic conditions (Ref. 54). 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 contaminated soil 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
27
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
The addition of the DARAMEND®
organic amendment, zero valent iron,
and water stimulates the biological and
chemical 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 reduction-
oxidation (redox) potential, which
promotes dechlorination of
organochlorine compounds. The soil
matrix (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 then removed
through aerobic (oxic) biodegradation processes, which are initiated and promoted by the air drying and
tilling of the soil. Addition of the DARAMEND® amendment and the anoxic-oxic cycle continue until
cleanup goals are achieved (Ref. 21).
Bioremediation using DARAMEND® process. Ref. 1
THE DARAMEND FACT SHEET
PREPARED BY US EPA IS INCLUDED IN
APPENDIX C.
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 the specialized deep-
tillage 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 for excessively high
contaminant concentrations in soils (Ref. 21).
DARAMEND® has been used to treat soil and
sediment containing low concentrations of pesticides
such as toxaphene, HCB, and DDT as well as other
contaminants. The technology has not been used for
treatment of other POPs such as PCBs, dioxins, or
furans.
DARAMEND® has been used to treat POPs at several
sites in the US, Canada, Europe and Brazil. In the US,
the technology has been implemented at the T.H.
Agriculture and Nutrition Superfund site in
Montgomery, Alabama, and the W.R. Grace site in
Charleston, South Carolina. Table 3-5 presents
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
and 55). According to the vendor, Adventus Group, costs for in situ treatment have ranged from
TECHNOLOGY TYPE: BIODEGRADATION
POPs TREATED: TOXAPHENE, HCB,
DIELDRIN, DDT, A-HCH, B-HCH AND
LINDANE
PRETREATMENT: NONE
MEDIUM: SOIL AND SLURRY
COSTS: $55 PER TON (Ex SITU, COST IN
2004 USD) AND $30,000 PER ACRE (IN
SITU, FULL-SCALE COST IN 2007)
FULL SCALE
EX SITU AND IN SITU
28
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
approximately $40,000 per acre for a pilot study to approximately $30,000 per acre for full-scale
applications (in 2007 USD). In addition, the vendor estimates that ex situ treatment costs approximately
$5 5 per ton of soil (Ref 2).
Table 3-5. Performance of DARAMEND® Technology
Site
T.H.
Agriculture
and Nutrition
Superfund site
W.R. Grace
site
Uniroyal
Chemical
Unknown
Future
Residential
Development
ATOFINA
Chemicals
Former
obsolete
pesticide
warehouse
Former
Agricultural
Site
Hot-Spot
Treatment,
Former
Manufacturing
Facility
Confidential
Client
Location
Montgomery,
Alabama
Charleston,
South Carolina
Ontario,
Canada
Canada
Kentucky
Moldova
Florida
Southeastern
US
Ontario,
Canada
Year
Implemented
2003
1995
NA
NA
NA
NA
2004
2003
2007
Period
(Months)
5
8
9
<1
<4
<2
<1
8
<1
POP
Toxaphene
DDT
Toxaphene
DDT
DDT
DDT
Dieldrin
HCB
a-HCH
b-HCH
Lindane
Lindane
Dieldrin
Toxaphene
DDT
Quantity of
Soil Treated
(Tons)
4,500
250
NA
2 acres
NA
NA
2,600
NA
147,000
Scale
Full
Pilot
NA
Pilot
NA
Bench
Pilot
Pilot
Full
Untreated
Concentration
(mg/kg)
189 (Mean)
81 (Mean)
239
89.7
53.5
2.0
.064
10.9
7,647
1,200
567
17 (Mean)
.046 (Mean)
127.7 (Mean)
2.2
Treated
Concentration
(mg/kg)
10 (Mean)
9 (Mean)
5.1
16.5
4.7
0.33
.040
1.3
446
373
14
10 (Mean)
.015
8.7 (Mean)
0.5
Source: Ref. 1
Notes:
DDT = Dichlorodiphenyltrichloroethane
HCB = Hexachlorobenzene
HCH = Hexachlorocyclohexane
mg/kg = Milligram per kilogram
NA = Not available
DARAMEND® is a proprietary technology provided by Adventus Remediation Technologies, Inc. (ART)
in Mississauga, Ontario, Canada. In the US, the technology is provided by ART's sister company,
Adventus Americas, Inc. in Bloomingdale, Illinois. Contact information for the technology vendor is
provided in Section 5.0.
The technology has been used to treat toxaphene, HCB, dieldrin, DDT, a-HCH, b-HCH and lindane
contaminated soil. Based on structural similarity of the POPs treated by DARAMEND* to other POPs
described in section 2.6 of this report, this technology can potentially be used to treat other POPs.
However, because of the specificity of biochemical reactions, this technology may or may not be effective
29
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
in treating similar POPs. The most recent application of this technology to treat POPs was in 2007 at a
confidential site in Ontario Canada.
3.1.4 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 has been operated in both fixed and transportable configurations.
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. At high temperature the organic compounds desorb from the solid matrix
and enter the gas phase. The treated soil is allowed to cool prior to its appropriate 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. 43 and 44).
GPCR™ has been implemented at both full and pilot
scales to treat solids and liquids contaminated with
POPs. The POPs treated include HCB, DDT, dieldrin,
aldrin, PCBs, dioxins, and furans. Table 3-6 presents
performance information for the technology. In 1992,
GPCR™ was field-tested by US 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. 19).
Table 3-6. Performance of GPCR™ Technology
TECHNOLOGY TYPE: THERMAL-
CHEMICAL DEGRADATION
POPs TREATED: HCB, DDT, DIELDRIN,
PCBS, ALDRIN, DIOXINS, AND FURANS
PRETREATMENT: THERMAL
DESORPTION
MEDIUM: SOIL, SEDIMENT, AND LIQUID
WASTE
FULL SCALE
EXSITU
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. 43
Notes:
DDT = Dichlorodiphenyltrichloroethane
HCB = Hexachlorobenzene
PCB = Polychlorinated biphenyl
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. 44 and 71).
30
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/.
GPCR is a thermal-chemical degradation technology
that combines high temperature and hydrogen gas to
treat POPs. Based on available information, the
technology has treated DDT, HCB, PCBs and dioxin
in contaminated soil, sediments, and liquids. Due to
the high temperature requirement of this technology, GPCR could potentially treat other POPs. This
technology was developed by Eco Logic International, Inc. of Ontario, Canada. Bennett Environmental
Inc. of Oakville, Ontario, acquired exclusive patent rights to the technology and is currently modifying
the technology to improve its cost effectiveness (Ref 53). The most recent application of this technology
was in 2000 to treat PCBs and DDT at a site in Australia. The performance data for this technology was
provided by John Vijgen (IHPA). No performance data, process details, or costs for this technology
could be obtained directly from the technology vendor. This technology has not been implemented at a
full-scale in the US and is currently not commercially available in the US. Contact information for the
technology vendor is provided in Section 5.0.
3.1.5 Gene Expression Factor
TECHNOLOGY TYPE: BIODEGRADATION
POPs TREATED: DIELDRIN, DDT,
TOXAPHENE, AND PCBS
PRETREATMENT: NONE
MEDIUM: SOIL AND SEDIMENTS
FULL SCALE
EX SITU AND IN SITU
Gene Expression Factor (or simply Factor) is a new
technology available to treat soils and sediments
contaminated with POPs. The vendor claims that
Factor is a site-specific protein that restores the initial
protein within the native bacteria species that was
either damaged or removed by site contamination.
The Factor enhanced bacteria then metabolically
transform chlorine attached to hydrocarbon molecules
into inert substances. The vendor claims that Factor is
non-hazardous and is applied with other soil
amendments, such as lime, organic matter (manure,
charcoal, etc.), and fertilizers. Once thoroughly
mixed, the amended soil is irrigated for approximately two months at least twice a day during warm days
and every other day during cooler days until confirmation sampling indicates that the chemicals of
concern have been removed. In theory, this treatment can be conducted either in situ or ex situ.
According to the vendor, BioTech Restorations, a bench-scale study must be performed on site-specific
soil collected from a potential bioremediation site prior to treatment. This study involves sending
approximately 3 gallons of soil to BioTech Restorations laboratory for analysis where detailed soil
chemistry, biological oxygen demand, biologically available carbon, indigenous bacteria survey and
contaminants are analyzed and identified before conducting the bench study. A variety of Factor proteins
are then applied to the soil to determine the most cost effective and efficient Factor for that site. The cost
for conducting a bench study is $30,000. Actual treatment costs for Factor range from $30 to $60 per ton
of contaminated soil, depending on access and site complexity (Ref. 32). Factor has been applied at
several sites in California; performance data are included in Table 3-7.
Gene Expression Factor is a bioremediation technology that has been used to treat PCBs, DDT, dieldrin
and toxaphene contaminated soil and sediments. Based on structural similarity of the POPs treated by this
technology to other POPs described in section 2.6 of this report, Gene Expression Factor may potentially
be used to treat other POPs. However, because of the specificity of biochemical reactions involved with
this technology, it may or may not be effective in treating similar POPs. This technology was most
recently implemented at the Mantegani Property, in South San Francisco, California and was completed
in 2007. A fact sheet is not available for this technology. Further technology information can be obtained
31
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
by contacting the vendor BioTech Restorations. Contact information for the vendor is provided in Section
5.0.
Table 3-7. Performance of Gene Expression Factor
Site, Location
Former North
American
Transformer
South Yard Area,
Milpitas, CA
Borello Property,
Morgan Hill, CA
Mantegani
Property, South
San Francisco,
CA
Period
Nov 2005
to
Oct 2006
June 2005
to
Aug 2005
May 2005
to Jan
2007
Type
Ex situ
In situ
In situ
Quantity
of Soil
Treated
(cy)
15,000
14,200
2,200
POP
PCBs
Dieldrin
Toxaphene
DDT
Dieldrin
Initial
Concentration
(mg/kg)
156 (Max)
0.48
6.2
9.0 (Max)
1.0 (Max)
Final
Concentration
(mg/kg)
<1
0.00354
(Mean)
0.130
<0.5
0.5
Source: Ref 32
Notes:
cy = cubic yard
DDT = Dichlorodiphenyltrichloroethane
3.1.6 GeoMelt™
Geomelt1MICV process. Ref. 30
mg/kg = milligrams/kilograms
PCB = Polychlorinated biphenyl
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 reduce
mobility of residual contaminants by
incorporating them into a vitrified end
product. GeoMelt™'s in situ process is
available in two primary configurations: (1)
In Situ Vitrification (ISV) and (2) 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 below the ground surface. SPV is suitable
for more shallow applications. GeoMelt™ also
provides a variation of SPV called Deep-SPV,
which can vitrify narrow treatment zones
deeper than 30 feet.
32
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
For treatment, an 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
a current through the soil, heating the 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 temperature increases,
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 discharge to the atmosphere. When the heating stops,
the medium cools to form a crystalline monolith vitrified end product, which encapsulates the nonorganic
contaminants that were not destroyed or volatilized (Ref 40).
TECHNOLOGY TYPE: HIGH TEMPERATURE
DEGRADATION
POPs TREATED: DIELDRIN, CHLORDANE,
HEPTACHLOR, DDT, HCB, PCBS, DIOXINS,
AND FURANS
PRETREATMENT: NONE
MEDIUM: SOIL AND SEDIMENTS
FULL SCALE
EX SITU AND IN SITU
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/.
GeoMelt™'s ex situ process, which is called In
Container Vitrification (ICV™), 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, a NOX (oxides of
nitrogen) scrubber, a 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 an appropriate landfill based on the results of
US EPA Toxicity Characteristic Leaching Procedure (TCLP) analysis.
GeoMelt™ is a full-scale thermal degradation technology that uses high temperature (up to 2,000°C) to
treat soil and sediments contaminated with POPs such as dieldrin, chlordane, heptachlor, DDT, HCB,
PCBs, dioxins, and furans (Ref. 40). GeoMelt™ has also been used to treat radioactive waste. Table 3-8
provides performance information for the technology. The use of high temperature destroys and
volatilizes the POPs found in contaminated media. The contaminants that are not destroyed are
encapsulated in the crystalline monolith vitrified end product. Due to the high temperature requirement of
this technology, other POPs could also be potentially treated using GeoMelt™. This technology was
originally commercially available from AMEC Earth and Environmental, the sole licensee of this
technology in the US. In 2009, IMPACT Services, Inc. (http: //www .impactservice sine .net/ ), a waste
processing facility located at the East Tennessee Technology Park, acquired all assets relating to the
GeoMelt™ business of AMEC Earth and Environmental. The most recent application of this technology
to treat POPs in the US was in 2005 at a Wasatch Chemical Superfund. However, GeoMelt™ has been
extensively used in Japan to treat POP contaminated soil, and it was most recently used to treat POPs in
2008 at MCK facility in Mie Prefecture, Japan. Further information about this technology can be
33
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
obtained by contacting the vendor (IMPACT Services, Inc.). Vendor contact information is provided in
Section 5.0.
Table 3-8. Performance of GeoMelt™ Technology
Site
Parsons
Chemical/ ETM
Enterprises
Superfund Site
TSCA Spokane
Wasatch
Chemical
WCS-
Commercial
TSCA cleanup
WCS-Rocky
Flats
POPs
Agricultural
Treatment
Project
Nose Dioxin
Contaminated
Waste
Treatment
Project
POPs
Agricultural
Treatment
Project
Dioxin
Contaminated
Sludge
Treatment
Location
Grand Ledge,
Michigan
Spokane,
Washington
Salt Lake
City, Utah
Andrews,
Texas
Andrews,
Texas
MCK, Mie
Prefecture,
Japan
MCK, Mie
Prefecture,
Japan
MCK, Mie
Prefecture,
Japan
Nose, Osaka
Prefecture,
Japan
Period
1993 to
1994
1994 to
1996
1995 to
1996
2005
2005
2006
2006
2007
2007
POP
DDT
Chlordane
Dieldrin
PCBs
Dioxins
DDT
Chlordane
HCB
PCBs
PCBs
Aldrin
HCH
DDT
Dieldrin
Endrin
Dioxins
Dioxin
Aldrin
HCH
DDT
Dieldrin
Endrin
Dioxins
Dioxins
Quantity
of Soil
Treated
4,350 tons
5,375 tons
5,440 tons
5 tons
1 1 tons
161 tons
5 1 tons
209 tons
5.4 tons
Scale
Full
Full
Full
Full
Pilot
9.5
tonne/
batch
9.5
tonne/
batch
9.5
tonne/
batch
1
tonne/
batch
Untreated
Concentration
(mg/kg)
340 (Max)
89 (Max)
87 (Max)
17,860
38 (Max)
1.091 (Max)
535 (Max)
17
496
130
26
4,000
1100
240
2
9.3 ng-TEQ/g
81 ng-TEQ/g
0.0047 mg/1
0.55 mg/1
0.094 mg/1
0.0005mg/l
0.04 mg/1
0.0086 ng-
TEQ/g
1.6 ng-TEQ/g
Treated
Concentration
(mg/kg)
O.016
0.08
O.016
ND
ND
ND
ND
0.08
ND
ND
O.0003 mg/1
0.0025 mg/1
O.0125 mg/1
0.0003 mg/1
O.005 mg/1
0.002 pg-
TEQ/g
0.019 pg-
TEQ/g
0.00000005
mg/1
0. 000007 mg/1
0.0000022
mg/1
O.0000002
mg/1
0.0000003
mg/1
0.00045 pg-
TEQ/g
0 pg-TEQ/g
34
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
Site
POPs
Agricultural
Treatment
Project
Location
MPK Mie
Prefecture,
Japan
Period
2008
POP
HCH
DDT
Quantity
of Soil
Treated
71 tons
Scale
o 5
tonne/
batch
Untreated
Concentration
(mg/kg)
210
130
Treated
Concentration
(mg/kg)
0.000089
0.00011
Source: Ref. 30 and 44
PCB = Polychlorinated biphenyl
pg-TEQ/g = Picogram Toxic Equivalent of
Dioxins per gram
TSCA = Toxic Substance Control Act
WCS = Wasatch Chemical Superfund
Notes:
DDT = Dichlorodiphenyltrichloroethane
HCB = Hexachlorobenzene
HCH = Hexachlorocyclohexane
mg/kg = Milligram per kilogram
ND = Below detection limit
ng-TEQ/g = Nanogram Toxic Equivalent of
Dioxins per gram
3.1.7 Mechanochemical Dehalogenation
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. Hydrogen donors include alcohols, ethers,
hydroxides, and hydrides. The process occurs ex situ in an enclosed ball mill, with a grinding medium to
provide mechanical energy and mixing. The
technology is applicable to soil, sediments, and mixed
solid-liquid phases. The by-products generated by the
process are reportedly nonhazardous organics and
metal salts (Ref. 66).
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/.
TECHNOLOGY TYPE: PHYSICAL-CHEMICAL
DEGRADATION
POPs TREATED: DDT, ALDRIN, DIELDRIN,
LINDANE AND PCBS
MEDIUM: SOIL, SEDIMENT AND LIQUID WASTES
PRETREATMENT: SOIL DRYING AND SCREENING
FULL SCALE
EXSITU
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 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 710,000
cubic feet of soil contaminated with DDT,
dichlorodiphenyldichloroethane (ODD),
^•l ^•n " —TM° P*H
MCD process at the Mapua Site. Ref.
66
35
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
dichlorodiphenyldichloroethylene (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 cleanup
standards for commercial land use. The cleanup criteria are listed in Table 3-9 and the proof of
performance testing results are listed in Table 3-10. The criteria are based on the concentration of DDX
(the sum of the concentrations of DDT, ODD, and DDE) and the sum of the concentrations of aldrin,
dieldrin, and lindane.
Table 3-9. Soil Acceptance Criteria for the Mapua Site
Land Use
Commercial
Depth
(meters)
0 to 0.5
Below 0.5
DDX (Total DDT, ODD, and DDE)
(mg/kg)
5
200
Aldrin + Dieldrin + Lindane
(mg/kg)
3
60
Source: Ref 66
Notes:
ODD = Dichlorodiphenyldichloroethane
DDE = Dichlorodiphenyldichloroethylene
DDT = Dichlorodiphenyltrichloroethane
DDX = Total ODD, DDE, and DDT
mg/kg = Milligram per kilogram
At the Mapua site, soil with greater than a 10-millimeter (mm) size has contaminant concentrations below
the soil acceptance criteria for the site and requires no treatment. EDL receives contaminated soil that is
less than 10 mm in size. The 10 mm size fraction is dried and 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, soil screening, and MCD processing
are described below.
Soil Drying: Contaminated soil with a size of 10 mm or less enters a temperature controlled, diesel-fired
rotary drum unit. As the soil passes through the dryer, the soil particles undergo size reduction. The
moisture content in soil exiting the dryer is typically less than 2 percent. Gaseous emissions from the
dryer are treated by an air quality control system consisting of cyclones, a baghouse, a scrubber and an
activated carbon filter.
Soil Screening: Soil exiting the dryer is passed through a rotary screen to separate soil particles by size.
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
(Ref. 66). The less than 2-mm size fraction and the fines from the cyclones and baghouse are fed into the
._ •-*—,1-v™
MCD reactor.
MCD™ Processing: Dried contaminated soil (the less than 2-mm fraction) and fines from the cyclones and
baghouse are fed into the MCD™ reactor and 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 with two
horizontally mounted cylinders containing a grinding medium. The grinding medium provides 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.
36
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
During proof of performance testing at the Fruitgrowers Chemical Company site in Mapua, New Zealand,
the MCD™ system treated a maximum of 139 cubic meters per week. Table 3-10 lists the initial and final
contaminant concentrations in the soil treated by the MCD™ reactor. The concentrations listed in Table 3-
10 are mean concentrations in samples collected. The treated soil met the cleanup criteria for soil taken
from a depth of over 0.5 meter (m) below ground surface, but did not meet the criteria for surface soil
taken from between 0 and 0.5 m below ground surface.
Table 3-10. Performance of MCD™ Technology at the Mapua Site
POP
DDX
Aldrin
Dieldrin
Lindane
Aldrin+Dieldrin
+Lindane
Untreated
Concentration
(mg/kg)
717 (Mean)
7.52 (Mean)
65.6 (Mean)
1.25 (Mean)
73.245 (Mean)
Treated
Concentration
(mg/kg)
64.8 (Mean)
0.798 (Mean)
19.8 (Mean)
0.145 (Mean)
20.612 (Mean)
Percent
Reduction
91%
89%
70%
88%
72%
Soil Acceptance Criteria (mg/kg)
by Depth Below Ground Surface
0 to 0.5 meters
5
NA
NA
NA
3
> 0.5 meters
200
NA
NA
NA
60
Source: Ref 66
Notes:
DDX = Total Dichlorodiphenyldichloroethane (ODD), Dichlorodiphenyldichloroethylene (DDE), and
Dichlorodiphenyltrichloroethane (DDT)
mg/kg = Milligram per kilogram
NA = Not available
Subsequent to the proof of performance testing, EDL began a full-scale application later in 2004. By
early December 2006, a total soil/sediment volume of 55,250 cubic meters was excavated, screened,
relocated, or treated. Of this volume, approximately 5,500 cubic meters were treated using MCD™.
Cleanup completion was scheduled for March 2007 with a total project cost of $8 million, including
construction and continuous operation for 2.5 years (Ref. 28).
EDL has conducted two treatability studies at Hunters Point Shipyard in San Francisco, California. The
initial study was conducted in 2006 to evaluate the feasibility of remediating PCB contaminated soils. A
supplemental study was also conducted from August to November 2007 to evaluate treatment of
additional on-site soils. Initial PCB concentrations of approximately 300 mg/kg were reduced to less than
1 mg/kg during the first and supplemental studies. The supplemental study also evaluated post-treatment
stabilization of soils to (1) stabilize heavy metals in the soil matrix and (2) restore the physical
characteristics of the treated soil converting it from a powdery form to a texture similar to garden soil.
Based on results from these studies, a full-scale MCD™ system with a capacity of 10 metric tons per hour
could be used at this site (Ref. 57). The performance data for this application could not be obtained from
the technology vendor.
MCD™ uses mechanical energy in combination with a base metal and a hydrogen donor to promote
dehalogenation of POPs. This technology has been used to treat DDT, aldrin, dieldrin and lindane. Based
on structural similarity of known POPs treated using MCD to other similar POPs described in section 2.6
of this report, this technology can potentially be used to treat other POPs. However, the potential of
MCD™ technology to treat other POPs is highly dependent on the base metals and hydrogen donors used
and the specific chemical reactions that occur under the treatment conditions. The most recent application
of this technology to treat POPs in the US was in 2005 at Hunters Point Shipyard in San Francisco,
California. The technology was also implemented in 2004 to treat POPs contaminated soil at the
Fruitgrowers Chemical Company site in Mapua, New Zealand. The MCD™ technology is available from
37
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
EDL in Auckland, New Zealand (http://www.edl-asia.com/home.html) and from Tribochem in Wunstrof,
Germany (http: //www .tribochem .com) (Ref. 13). Information for this section of the report was provided
by EDL. Contact information for EDL is provided in Section 5.0. Tribochem has not provided process
details, performance data, or costs for its technology. Currently, no vendor is available in the US for this
technology.
3.1.8 Plasma Arc
TECHNOLOGY TYPE: THERMAL
DEGRADATION
POPs TREATED: PCBs, CHLORDANE,
DDT, ENDOSULFAN, DIOXINS, AND FURANS
MEDIUM: SOLID AND LIQUID WASTES
PRETREATMENT: THERMAL DESORPTION
FULL SCALE
EXSITU
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).
This report focuses on PLASCON™, which has been used at full scale to treat POPs. PLASCON™ is an
ex situ technology that can treat both solid and liquid waste streams. It is potentially applicable to both
low- and high-strength wastes containing POP contamination. 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 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
i^^^^^^^^^^^^^^^^^^^^^^^^^^^^i 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. 44).
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/.
Several full-scale applications of this technology have been performed to treat POPs around the world.
At least nine commercial plants are in operation (four in Japan, four in Australia, and one in the United
Kingdom). One plant in Japan operated by the Mitsubishi Chemical Corporation treated more than 1,000
tons of PCB contaminated waste from May through July 2004 (Ref. 42). A facility in Brisbane, Australia
treats concentrated PCB solutions (>10 %) as well as a range of POP pesticides. Information about these
applications was provided by John Vijgen (IHPA). No performance data could be obtained directly from
the technology vendor.
PLASCON™ uses high temperatures and heated plasma to degrade POP contaminants found in soil and
liquid waste into their individual atomic elements. This technology has been used to treat various POPs
38
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
such as PCBs, DDT, chlordane, endosulfan, dioxins and furans. Due to the high temperature requirement
of this technology (temperature ranging from 1,600 to 20,000°C), other POPs could also be potentially
treated using PLASCON™. SRL Plasma Pty. Ltd., an Australian company, is the patent holder of this
technology. The most recent application of this technology to treat POPs was in 2004 in Japan. Currently,
no know vendors for this technology exist in the US. Contact information for SRL Plasma Pty. Ltd. is
provided in Section 5.0.
3.1.9 Radicalplanet * Technology
TECHNOLOGY TYPE: PHYSICAL-
CHEMICAL DEGRADATION
POPs TREATED: PCBs, CHLORDANE,
DDT, ENDRIN, DIOXINS, AND FURANS
MEDIUM: SOLID WASTE, SOIL, ASH
PRETREATMENT: NONE
FULL SCALE
EXSITU
Radicalplanet® technology is an ex situ process that uses
mechanochemical principle to treat POPs (Ref 51). It has been
used to treat PCBs, chlordane, DDT, endrin, dioxins, and furans.
This process transforms POPs molecules into their "radical"
state by use of the "planetary mill." The treatment occurs in a
reaction vessel where steel balls and a reagent chemical, such as
calcium oxide (CaO), are placed prior to the placement of the
wastes. The vessels are then sealed and placed on the
Radicalplanet® machine where the vessels are rotated (rotation
speed: 70 to 100 revolutions per minute [rpm]). As the steel
balls crash into each other, the bonds of the POPs are broken by
the mechanical energy. At a rotation speed of 100 rpm, the
dechlorination reaction is complete in about three to six hours.
The reaction vessel is cooled externally by circulating cooling water. The treatment technology does not
require pretreatment and does not require a high amount of power to operate. No effluent or off-gases are
generated from this treatment process. The reaction vessels are mobile and are available in two different
sizes; an E-200 Type reaction vessel that can hold up to 750 liters of contaminated material and an A-500
Type reaction vessel that can hold up to 1500 liters of contaminated material.
Radicalplanet* technology uses mechanical energy in the presence
of chemicals like CaO to promote dehalogenation of contaminants.
This technology has been used to treat BHC, DDT, endrin, HCH,
PCBs and Dioxin. Based on structural similarity of known POPs
treated using Radicalplanet® to other similar POPs described in
section 2.6 of this report, this technology can potentially be used to
treat other POPs. However, the potential of Radicalplanet®
technology to treat other POPs is highly dependent on the
chemicals used and the specific chemical reactions that occur
under the treatment conditions. According to the technology's
vendor, Radicalplanet® technology was evaluated and approved by
three Japanese Ministries of Government. Currently, this
technology is available only in Japan and further information can
be obtained from the technology's vendor, Radicalplanet®
Research Institute Co. Ltd. Performance data is provided in Table
3-11. Vendor contact information is provided in Section 5.0.
Radicalplanet89 Technology Ref. 51
39
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
Table 3-11. Performance of Radicalplanet® Technology at Various Japanese Sites
Contaminant(s) and
Medium
BHC (powder)
DDT (powder)
Endrin (powder)
HCH (powder)
PCB (soil)
PCB (soil)
Dioxin (ash)
Site Location
Ibraki, Japan
(with Institute
of
Environmental
Toxicology)
Ibraki, Japan
Ibraki, Japan
(with Geo-
Environmental
Protection
Center)
Untreated
Concentration
(mg/kg)
970,000
50,000
20,000
50,000
42,800
75,000 ng-TEQ
81,OOOng-TEQ
Treated
Concentration
(mg/kg)
0.16
0.001
0.01
0.01
0.01
0.13 ng-TEQ
0.15ng-TEQ
Percent
Reduction
99.9999%
99.9999%
99.9999%
99.9999%
99.9999%
99.9999%
99.9999%
Treated Dioxin
Toxic Equivalent
(pg-TEQ/g)
<1
<1
<1
<1
<1
<1
<1
Source: Ref. 58
Notes:
BHC = Hexachlorobenzene
DDT = Dichlorodiphenyltrichloroethane
HCH = Hexachlorocyclohexane
PCB = Polychlorinated biphenyl
3.1.10 Solvated Electron Technology
pg-TEQ/g = Picogram Toxic Equivalent of
Dioxins per gram
ng-TEQ/g = Nanogram Toxic Equivalent of
Dioxins per gram
mg/kg = Milligram per kilogram
Solvated Electron Technology (SET™) is a non-thermal chemical degradation treatment process that has
been used to treat PCB contaminated soil. The SET™ process occurs in a closed system and 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. The solvated electron solution is added to the
treatment cell containing the waste and ammonia solution.
A chemical reaction occurs in the treatment cell between
the solvated electrons and the contaminants instantly.
After the reaction is complete, hot water or steam is
circulated through the jacket of the treatment cell. The
warmed ammonia is then removed from the treatment cell
and recovered for reuse through the ammonia recovery
system. At the end of the reactions, the treated material
left behind in the treatment cell may have a high pH and is
adjusted using a dilute acid solution prior to disposal.
According to the vendor of this technology, the
technology does not produce regulated by-products such
as dioxins or furans or their precursors.
TECHNOLOGY TYPE: CHEMICAL
DEGRADATION
POPs TREATED: PCBs
MEDIUM: SOIL
PRETREATMENT: NONE
FULL SCALE
EXSITU
SET™ has been used to treat PCB contaminated oil, mixed waste and soil. It was used at full-scale to treat
PCB contaminated soil at the Pennsylvania Air National Guard Site in Harrisburg, Pennsylvania. The site
was contaminated with PCBs from an electrical transformer dielectric spill that occurred in 1979. PCB
40
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
concentrations in the soil ranged from 17 to 560 ppm. Approximately, 340 tons of soil was excavated
from the spill area and treated using the SET™ process from May 2000 to July 2001. Post treatment
sampling indicated that the PCB concentrations were less than 1 ppm and the treated soil was used to
backfill the excavated area (Ref 33).
SET™ is a chemical degradation process that uses solvated electron solutions to treat POP-contaminated
soils. Commodore Advanced Sciences, Inc., based in Washington State, developed and holds the patent
for this technology. This technology has been used to treat PCBs. Based on structural similarity of PCBs
to other similar POPs described in section 2.6 of this
report, this technology can potentially be used to treat
other POPs. However, the potential of SET™ to treat other
POPs is dependent on the solvated electron solution used
and the specific reactions that occur under the treatment
conditions of the technology. The most recent application
of this technology to treat POPs, PCB-contaminated soil,
was in 2001 at the Pennsylvania Air National Guard Site
in Harrisburg, Pennsylvania. No fact sheet is available for
this technology. Further information about this technology
can be obtained by contacting the vendor (Commodore
Advanced Sciences, Inc). Vendor contact information is
provided in Section 5.0.
3.1.11 Sonic Technology
Typical SET™ Plant
Sonic Technology is an ex situ process used to treat low- and high-strength soils containing PCB
contamination. Pretreatment is performed using the Terra-Kleen process, which involves mixing
contaminated soil with a solvent to produce a slurry. The solvent extracts the contaminants from the soil
and concentrates them in a residual waste stream, which is collected in a receiving tank. After the
extraction is completed, the waste stream with PCB concentrate is diluted, mixed with proprietary method
for creating a self-regenerated sodium dispersion chemical destruction and subjected to the sonic energy
generated by a proprietary low-frequency generator (Sonoprocess™). 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. 59).
TECHNOLOGY TYPE: PHYISCAL-
CHEMICAL DEGRADATION
POPs TREATED: PCBs
MEDIUM: SOIL
PRETREATMENT: TERRA-KLEEN
FULL SCALE
EXSITU
In 2006, the technology was implemented at full scale to
treat approximately 3,000 tons of PCB-contaminated soil at
the Juker Holdings site in Vancouver, British Columbia,
Canada. At this site, PCB concentrations in soil were
reduced from an initial range of 400 to 1,600 ppm to <25
ppm. The modified Terra-Kleen solvent extraction process
isolated the PCB fraction in an oil matrix. The final
concentration of the oil contained 46,000 ppm of PCB at the
start of the application of the sonic, low frequency sonicator
process. The process uses ordinary solid sodium ingots and
creates an in situ, self-generating sodium dispersion that is
much lower in cost and more effective than purchasing pre-
made sodium dispersions. The final treatment process treated approximately 11,000 gallons of PCB
concentrate to <3 mg/kg within two weeks. This project was completed in its entirety in 2007. The
equipment is skid-mounted and transportable.
41
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
Sonic Technology is a physical-chemical
degradation process that uses solvent extraction
process as a pre-treatment stage to extract the
contaminants in solution and uses low frequency
sonic energy to dehalogenate chlorinated
compounds. This technology has been used to
treat PCB-contaminated soil. The potential of
Sonic Technology to treat other POPs is
dependent on the proprietary solvent used to
extract the POPs in solution and the frequency of
sonic energy generated by the Sonoprocess™.
The most recent application of this technology to
treat POPs was in 2006 at Juker Holdings site in
Canada. Vendor contact information is provided
in Section 5.0.
Sonic Technology process. Ref. 59
3.1.12 Thermal Desorption
Thermal desorption is a physical separation process which heats wastes to volatilize water and organic
contaminants. A vacuum system or a carrier gas transports the volatilized organic contaminants to an off-
gas treatment system. In the off-gas treatment system, particulates, if present, are removed by
conventional particulate removal equipment (such as wet scrubbers or fabric filters) and contaminants are
removed either through condensation followed by carbon adsorption, or they are destroyed in a secondary
combustion chamber or a catalytic oxidizer. Three types of conventional mobile or fixed thermal
desorption units are available, including: direct fire, indirect fire, and indirect heat. In the direct fire type,
fire is applied directly upon the surface of contaminated media to desorb contaminants from the soil. In
the indirect fire type, a direct-fired rotary dryer heats an air stream which, by direct contact, desorbs water
and organic contaminants from the soil. In the
indirect heat type, an externally fired rotary
dryer volatilizes the water and organics from
the contaminated media into an inert carrier
gas stream. The carrier gas is later treated to
remove or recover the contaminants. Based
on the operating temperature of the desorber,
conventional thermal desorption processes can
be categorized into two groups: high
temperature thermal desorption (HTTD) and
low temperature thermal desorption (LTTD).
HTTD is a full-scale technology in which
wastes are heated to 320 to 560°C (600 to
1,000°F). In LTTD, wastes are heated to
between 90 and 320°C (200 to 600°F).
This report focuses on in situ thermal
desorption (ISTD), which has been used to
THE FACT SHEET PREPARED BY US EPA
IS INCLUDED IN APPENDIX D.
ISTD process at the Alhambra site. Ref. 63
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
42
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
heating to transfer heat directly to environmental media. Although there are other in-situ thermal
technologies commercially available, ISTD is the only in situ technology that can reach the elevated
temperatures (greater than 100°C) required for treatment of low volatility POPs such as dioxins and DDT.
ISTD, sometimes also known as "In Situ Thermal Destruction," is a patented technology developed by
Shell Oil Co., and the patent was donated to The University of Texas at Austin. TerraTherm holds the
exclusive license to the technology in the United States and is the only vendor. TerraTherm partners with
other companies abroad to apply the technology internationally.
The ISTD process includes three basic elements (Ref. 63):
1. Application of heat to contaminated media by thermal conduction
2. Collection of desorbed contaminants through vapor extraction
3. Treatment of collected vapors
In the most common setup, ISTD uses a vertical array of electrically powered heaters placed in wells
drilled into the remediation zone. The heaters reach temperatures in excess of 600°C and heat
contaminated media by thermal conduction. Surface heating blankets or in pile desorption units are less
commonly used. As the matrix is heated, adsorbed and liquid-phase contaminants begin to vaporize. For
treatment of POPs, after target soil temperatures (typically 335°C) are achieved, a portion of the organic
contaminants either oxidizes (if sufficient air is present) or pyrolizes. In order to reach the treatment
temperatures required for the least volatile POPs, the treatment must be above the water table or the influx
of water must be significantly reduced.
TECHNOLOGY TYPE: THERMAL REMEDIATION
POPs TREATED: PCBs, DIOXINS, AND FURANS
MEDIUM: SOIL AND SEDIMENT
PRETREATMENT: NONE
COSTS: $200 TO $600 PER CUBIC YARD (COST
IN USD, DATA FROM 1996 TO 2009)
FULL SCALE
INSITU
A network of vapor extraction wells is used to recover
volatilized contaminants. Contaminant vapors captured
by the extraction wells are conveyed to an off-gas
treatment system for treatment before 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 adsorption. 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. 10, 26 and 63).
Pilot- and full-scale applications of ISTD have been used to address 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 pilot or full scale. ISTD was field-
tested by US EPA's SITE Program to evaluate the performance of the technology at the Rocky Mountain
Arsenal site near Denver, Colorado. The site was contaminated with hexachlorocyclopentadiene, aldrin,
chlordane, dieldrin, endrin, and isodrin. After 12 days of operation, the ISTD system was shut down
because portions of the aboveground piping had been corroded by hydrochloric acid that was generated
during the heating of the contaminants. Shutdown of the system prevented the evaluation of the
43
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
effectiveness of the technology at this site (Ref 25). Thus, highly concentrated chlorinated wastes that
can decompose at the temperatures required for treatment may require expensive materials to reduce
corrosion.
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 cubic yard (cy). Projects involving
ISTD treatment of larger volumes of waste may have lower unit costs. Available performance
information for the technology is presented in Table 3-12.
Table 3-12. 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
September
2005
POP
PCBs
PCBs
PCBs
Dioxins
and
Furans
PCBs
Dioxins
and
Furans
PCBs
Dioxins
and
Furans
Quantity of
Soil Treated
(cy)
NA
1,000
667
NA
222
16,200
Scale
Full
Full
Full
Pilot
Pilot
Full
Untreated
Concentration
(mg/kg)
5,000 (Max)
500 (Mean)
0.15-860
3.2 ug/kg
(Max)
20,000 (Max)
6.5 ug/kg
2,200 (Max)
19.4 ug/kg
(Max)
Treated
Concentration
(mg/kg)
0.8
<10
0.17
0.006 ug/kg
0.033
.003 ug/kg
0.033
<. 11 ug/kg
Source: Refs. 9, 11, 38, 60, 62 and 63
Notes:
cy = Cubic yard
ug/kg = Microgram per kilogram
mg/kg = Milligram per kilogram
NA = Not available
PCB = Polychlorinated biphenyl
ISTD is a physical separation process that uses high temperatures to desorb and volatilize contaminants.
Some recovered contaminants may oxidize or pyrolize, during the process. The contaminant vapors are
then captured and treated using an off-gas treatment system. ISTD has been used to treat POPs such as
PCBs, dioxins and furans. Due to the high temperature requirement of this technology, other POPs could
also be potentially treated using ISTD. The most recent full-scale application of this technology to treat
POPs was at the Alhambra "Wood Treater" Site in California and was completed in 2005. In 2009,
TerraTherm and SheGoTec Japan completed a demonstration under the sponsorship of the Japan Ministry
of the Environment on dioxin-contaminated soils. The remedial goal of less than 1,000 pg-TEQ/g was
44
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
achieved while meeting all vapor emission standards in Japan. Further information about this technology
can be obtained by contacting the vendor (TerraTherm; http://www.terratherm.com/). Vendor contact
information is provided in Section 5.0.
3.2 Pilot-Scale Technologies for Treatment of POPs
This section describes technologies that have been implemented to treat POPs at the pilot 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 provide 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.
3.2.1 Phytotechnology
TECHNOLOGY TYPE:
PHYTOREMEDIATION
POPS: DDT, CHLORDANE, AND
PCBs
MEDIUM: SOIL AND SEDIMENT
PRETREATMENT: NONE
PILOT SCALE
EX SITU AND IN SITU
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:
• Enhanced rhizosphere biodegradation (degradation
in the soil immediately surrounding plant roots),
• 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),
• Hydraulic control (the use of trees to intercept and transpire large quantities of groundwater or
surface water for plume control), and
• Evapotranspiration (the use of the ability of plants to intercept rain to prevent infiltration and take
up and remove significant volumes of water after it has entered the subsurface to minimize the
percolation into the contained waste).
In general, more data are available for field studies that have been conducted using phytostabilization and
hydraulic control mechanisms. Other proven uses of phytotechnologies include use as 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 highly contaminated soil, since high concentrations of POPs
are toxic to plants, but it can be used as an appropriate polishing technology for residual contamination in
soils. Initial laboratory research identified enhanced degradation of PCBs in the rhizosphere (Refs. 17,
34, and 47). Other researchers are finding promising results for phytoextraction in the laboratory and at
the pilot scale. The Connecticut Agricultural Experimental Station's preliminary data have 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 73).
45
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
In 2002, the Royal Military College (RMC) of Canada
performed a three-part study to evaluate the treatment
of PCB contaminated soil by phytotechnology (Ref.
75). Initially, a Greenhouse Treatability Study was
conducted to determine the uptake of PCBs by
pumpkin (Cucurbita pepo cv. Howden), tall fescue
(Festuca Arundinaced) and Sedge. Initial PCBs
concentrations in soil used for the greenhouse study
ranged from 27.5 to 3050 ug/g. Plant uptake for the
treatability study is provided in Table 3.13. Based on
the success of the treatability study, a field study was
conducted using larger containers and no coverings.
The results of this study indicated an increased uptake
of PCBs by all three species. The results of the field
experiment showed that a significant amount of PCBs
were not released into the environment through
volatilization. In 2004, a full-scale application was
started at a site in Etobicoke, Ontario. The soil was
contaminated with PCBs at an average concentration
of 21 ppm. The PCB concentrations in the plant stem
and leaf in the second season were higher (11 and 8.9
ppm, respectively) than the concentrations in the first
season (5.7 and 3.9 ppm, respectively). Consistent
uptake has been observed, however, no difference was noticed in the soil PCB concentration before and
after the field study took place (Ref. 74).
Table 3-13. Results of Plant Uptake from the Royal Military College Study
Pumpkin
Fescue
Sedge
Greenhouse Treatability Study
Roots (jig/g)
730
440
1200
Shoots(jig/g)
16.8
6.2
470
Small Field Experiment
Roots(jig/g)
790
805
785
Shoots(jig/g)
370
580
410
Source: Ref. 75
Note: |lg/g = Microgram per gram
Research has also been conducted in Ukraine and Kazakhstan 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. 50). In Kazakhstan, native vegetation that can tolerate and accumulate pesticides
has been identified (Ref. 52). While research is still active and needed, field-scale projects are also being
implemented. A cleanup project was conducted at a 40-year-old scrap yard site with PCB contaminated
soils at 225 ppm. The site contamination was approximately 2 acres in area and 3 feet deep. The project
demonstrated that PCB concentrations decreased over 90% within 2 years, in the presence of red
mulberry trees and bermuda grasses (Ref. 39).
46
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
In 2001, phytotechnology was demonstrated by US EPA's SITE Program to evaluate the performance of
the technology at the Jones Island Confined Disposal Facility Site in Milwaukee, Wisconsin. In this
demonstration, four different treatments were evaluated for treating PCB contaminated soil. Three plant-
based (corn, willow and natural vegetation) and one microbe-based treatment were planted at the site. The
initial PCB soil concentrations in the test plots ranged from 2.0 to 3.6 mg/kg. At the end of the
demonstration in September 2002, the final results indicated that none of the treatments produced a final
mean concentration of total PCBs below the cleanup standard of 1 ppm. Further information about the
Jones Island Confined Disposal Facility Site can be found at
http://www.epa.gov/nrmrl/pubs/540r04508/540r04508.htm.
Furthermore, two US EPA Superfund sites have utilized phytotechnology as a treatment for POPs:
• Aberdeen Pesticides Dumps in North Carolina is using phytotechnology for residual
contaminants (dieldrin, DDT, HCB and HCH) (plantings of poplar trees and grasses over 7.5
acres). This technology was selected in 2003 and continues at this site. Updated information is
not available for this project.
• Fort Wainwright in Alaska used ex situ phytotechnology for aldrin, dieldrin and DDT with Felt
Leaf Willow trees. After treatment, the soil was deposited in the site landfill. This project was
completed in 2002.
FURTHER INFORMATION ABOUT
PHYTOTECHNOLOGY CAN BE FOUND AT
HTTP://WWW.CLU-
IN.ORG/TECHFOCUS/DEFAULT.FOCUS/SEC/
PHYTOTECHNOLOGIES/CAT/OVERVIEW/
In general, the science of using phytotechnologies to
remediate PCB soil has not had major advancements since
the previous edition of this report in 2005. Researchers are
still working with Cucurbita pepo species and looking at
ways such as fertilizer and manipulation of vegetation to
enhance the biomass of the plants.
3.2.2 Reductive Heating and Sodium Dispersion
Reductive heating and sodium dispersion is an ex situ thermo-
chemical technology for treating POPs. In the first part of the
process, POP-contaminated wastes are indirectly heated using
a reductive heating kiln at temperatures ranging from 350 to
600°C in an oxygen-controlled atmosphere, and POPs are
decomposed and evaporated from the wastes. The
decomposed and evaporated POPs are collected via the oil
scrubber, and at the same time evaporated water from the
wastes is also condensed. The decomposed and evaporated
POPs are dissolved in an oil phase, and the condensed water is
accumulated at the bottom of the scrubber. The scrubbing oil
containing dissolved POPs and their decomposed substance is
treated by a batch method using metallic sodium powder
dispersion at a temperature of about 90°C for one hour. After
the reaction, water is added to remove excess sodium and
settled to separate the treated oil and alkali solution. Separated, treated oil is recycled to serve as the
scrubbing oil (Ref 44).
TECHNOLOGY TYPE:
THERMAL-CHEMICAL
DEGRADATION
POPS: DDT, CHLORDANE,
ALDRIN, PCBS, B-HCH,
DIOXINS AND FURANS
MEDIUM: SOIL
PRETREATMENT: NONE
PILOT SCALE
EXSITU
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/
In a pilot-scale demonstration in Okinawa, Japan, a
mobile system was used to treat soil contaminated
with BHC and PCBs. The reductive heating kiln had a
diameter and length of 400 mm each. The system
operated at a maximum capacity of 500 kg/day and
47
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
each batch was heated at 600°C in an oxygen deficient atmosphere for 1 hour. The exhaust gas from the
kiln was passed through a scrubber. The POPs retained were condensed in oil and then treated using
sodium dispersion at 90°C for 1 hour. BHC was reduced from 10 mg/kg to less than 0.001 mg/kg in each
type of soil, and PCBs were reduced from 53 mg/kg to less than 0.5 ug/kg by reductive heating. The
treated soil was then tested for its use as a recycled planting material, and results confirmed its
applicability (Ref 45). Information about this application was provided by John Vijgen (JHPA).
Reductive heating and sodium dispersion combines thermal degradation with sodium dispersion to treat
POPs. The initial heating process removes POPs from the contaminated soil followed by the use of
metallic sodium to decompose the POP contaminant. This technology has been used at a pilot-scale to
treat BHC and PCBs. Due to the high temperature requirement of this technology in the reductive heating
process, other POPs could also be potentially treated using this technology. Powertech Labs Inc. from
British Columbia, Canada is the developer of this technology. Kobelco-Eco Solutions Co., Ltd. based in
Japan is the exclusive licensee for this technology. Currently, this technology is only available in Japan.
Powertech Labs Inc. indicated that that there are no plans at this time to license the technology in North
America. No information regarding process details, performance data, or costs could be obtained directly
from the technology vendor. Vendor contact information is provided in Section 5.0.
3.2.3 Subcritical Water Oxidation
Subcritical water oxidation is an ex situ process used to treat
POPs. For this process, POPs must be in a liquid form and may
require extraction into acetone prior to treatment. Within the
treatment system, preheated water and sodium hydroxide
solution, high-pressure oil and oxygen react in a reaction tower,
at specific temperature and pressure (to 370°C and 26.7
megapascal). Carbon dioxide generated by the oxidation of the
oil reacts with sodium hydroxide to produce sodium carbonate.
When the specified conditions are reached inside the reaction
tower, the contaminated waste stream to be treated replaces the
oil, and decomposition of the contaminants occurs. Processed
liquid that has completed the decomposition process is cooled
and after depressurization, the liquid and gas are separated. The
treated liquid is tested to confirm decomposition, while the gas
is passed through an activated carbon unit prior to discharge.
TECHNOLOGY TYPE:
THERMAL-CHEMICAL
DEGRADATION
POPs: ALDRIN, DIELDRIN,
CHLORDANE, PCBS, DIOXINS
AND FURANS
MEDIUM: SOLID WASTE
PRETREATMENT: EXTRACTION
INTO A SOLVENT
PILOT SCALE
EXSITU
A pilot plant in Japan has processed PCB contaminated waste streams for more than 3,500 hours without
^^^^^^^^^^^^^_^^^^^^^^^^^^^_i encountering difficulties. In 2005, a full-scale system
was being constructed in Japan with a capacity of 2
tons per day. However, the current status of this
system is not documented in the information identified
and reviewed for this report (Ref. 44).
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/
Subcritical water oxidation is a thermochemical technology that uses thermal degradation and sodium
hydroxide to treat POPs. A pre-treatment stage is needed for treating contaminated soil to extract the
contaminants in solution. This technology has been used at a pilot-scale to treat PCBs. Due to the high
temperature requirement of this technology, other POPs could also be potentially treated using Subcritical
water oxidation. The most recent application of this technology was in 2005 to treat a PCB-contaminated
waste stream in Japan. The information for this technology was provided by John Vijgen (IHPA). No
performance data, process details, or costs for this technology could be obtained directly from the
48
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
technology vendor. Currently, this technology is available only through the technology vendor
Mitsubishi Heavy Industries of Japan. Vendor contact information is provided in Section 5.0.
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 that has been tested
to treat soil containing HCB contamination.
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/.
For SPHTD to operate, HCB containing soil would be
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 mixture can reach a
temperature of 1,400°C, which creates thermochemical conditions that
convert HCB to calcium chloride, carbon, and hydrogen (Ref 71).
TECHNOLOGY TYPE:
THERMAL-CHEMICAL
DEGRADATION
POPs TREATED: HCB
MEDIUM: POP STOCKPILES
BENCH SCALE
EXSTTIT
SPHTD has been tested at bench scale using materials contaminated
with HCB, but no bench-scale test results were available in the
information identified and used for this report (Ref. 41). The
information sources identified and used to prepare this report also did
not provide information about application of the technology at the pilot
or full scale.
Self-propagating high-temperature dehalogenation is a thermal-
chemical degradation technology that has been used to treat HCB-contaminated soil at bench scale. The
SPHTD technology is being developed by Centra Studi Sulle Reazioni Autopropaganti, University of
Cagliari in Italy and is not currently commercially available. Further technology information can be
obtained by contacting the technology developer using the information provided in Section 5.0.
3.3.2 TDT-3R™
TDT-3R™ is an ex situ technology that has been tested for treatment of high- and low-strength soils
containing HCB contamination.
TECHNOLOGY TYPE: THERMAL
DEGRADATION
POPs TREATED: HCB
PRETREATMENT: THERMAL DESORPTION
MEDIUM: SOIL
BENCH SCALE
EXSITU
The TDT-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 (Pa). In some instances,
the kiln is heated to higher temperatures when POPs are
49
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
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 discharged. Process water from the scrubber is treated and discharged. Treated soil
exiting the kiln is cooled indirectly and removed (Refs. 44 and 64).
TDT-3R has been implemented at a bench scale in I THE FACT SHEET PREPARED BY IHPA is
Gare, Hungary, to treat 100 kilograms (kg) of soil I AVAILABLE AT
contaminated with HCB. Treatment occurred at a || HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/.
temperature of 450°C under a vacuum of 30 Pa. The
technology reduced the soil's HCB concentration from 1,215 to 0.1 mg/kg (Ref 65).
TDT-3R™ is a thermal degradation technology that uses continuous low-temperature desorption and a
thermal oxidizer to treat contaminated soil. The technology has been used at bench scale to treat HCB
contaminated soil. Due to the high temperature (temperature exceeding 1,250°C) requirement of this
technology, other POPs could also be potentially treated using TDT-3R™. TDT-3R™ is marketed by
Thermal Desorption Technology Group LLC in the US and its European subsidiaries. This firm has
developed pilot-scale kilns that operate with throughput of 0.1 tons per hour. A larger thermal desorption
technology kiln that would operate with a throughput of 4 m3/hour has been engineered and designed.
According to the vendor, a conceptual design has been developed for a kiln with a throughput of 70 tons
per hour (Ref. 64). Further technology information can be obtained by contacting the vendor using the
information provided in Section 5.0.
50
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
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 websites 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/resources/library/
Science and Technology Advisory Panel of the Global Environmental Facility
http://stapgef.unep.org/
U.S. Environmental Protection Agency
http://www.clu-in.org/POPs
http: //www. clu-in.org/acwaatap
http: //www. epa. gov/oppfodO 1 /international/pops .htm
United Nations
http://www.basel.int
http://www.chem.unep.ch/pops/
http: //www. gpa.unep.org/pollute/organic .htm
http://www.who.int/iomc/groups/pop/en/
http://www.unido.org/doc/29487
http://www.unece .org/env/lrtap/welcome .html
Other Sources
http://www.africastockpiles.org/
http://www.fao.org/ag/AGP/AGPP/Pesticid/Disposal/index en.htm
http://www.sdpi.org/research Programme/environment/Hazardous Waste Management.htm#2
http://www.ipen.org
51
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
5.0 VENDOR CONTACTS
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.
US EPA Environmental Response Team
MS-101, Building 18
2890 Woodbridge Avenue
Edison, NJ 08837
Telephone: (732) 321-6747
Fax: (732)321-6724
Email: alien .harry@epa.gov
Base Catalyzed Decomposition
Mr. Terrence Lyons
US 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
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: info@AdventusGroup.com
Website: http://www.adventusgroup.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: info@bennettenv.com
Website: http://www.bennettenv.com
Gene Expression Factor (bioremediation)
Christopher Young
GeoSolve, Inc.
137 Cross Center Road, #143
Denver, North Carolina 28037
Telephone: 704-489-6538
Email: cyoung2281@aol.com
GeoMelt™
Mr. Bret Campbell or Mr. Keith Witwer
IMPACT Services, Inc.
GeoMelt Division
1135 Jadwin Avenue
Richland,WA 99352
Telephone: (509)942-1114
Fax: (509)99942-1122
Email: Bret.Campbell@impactserviceinc.com
orKeith.Witwer@impactserviceinc.com
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: rbaker@terratherm.com
Website: www.terratherm.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: bryan@manco.co.nz
Website: http://edl.net.nz
Mr. Volker Birke
Tribochem
Georgstrasse 14, D-31515 Wunstdrof, Germany
Telephone: 495031 67393
Fax: 495031 8807
Email: birke@tribochem.com
Website: www.tribochem.com
52
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
SRL Plasma Pty Ltd
POBoxll9Narangba
Qld. 4504 Australia
Telephone: 61 732033400
Fax: +61 7 3203 3450
Email: nevillet@srlplasma.com.au
Website: http://www.plascon.com.au/
Radicalplanet® Technology
Head Office: 1-21-8 Sakae Naka-ku,
Nagoya City, Aichi 460-0008
Telephone: +81-52-222-8333
Fax:+81-52-702-6620
info@radicalplanet.co.jp
Solvated Electron Technology
Commodore Advanced Sciences, Inc
Jonathan Rogers
507 Knight Street
Suite B
Richland,WA 99352
Telephone: 865.483.9619
Fax: 509.943.2910
Email: jonrogers@commodore.com
Website: http: //www. commodore .com
Sonic Technology
Mr. Claudio Arato
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: carato@sonictsi.com
Website: www.sonicenvironmental.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@crs4.it
TDT-3R™
Mr. Edward Someus
Terra Humana Clean Technology Engineering
Ltd.
1222 Budapest, Szechenyi 59
Hungary
Telephone: (36-20)2017557
Fax: (36-1)4240224
Email: edward@terrenum.net
Website: http://www.terrenum.net
Technologies Identified in 2005 Report to
Treat POPs but Not Commercially Available
Xenorem™
Mr. Brad Yops
Technology Transfer Corporation
University of Delaware
Newark, DE 19716
Telephone: (302)831-0147
Website: http://www.udel.edu/
Pilot-Scale Technologies for Treatment of POPs
Reductive Heating and Sodium Dispersion
Keith Lee
Powertech Labs
12388 88th Ave, Surrey,
BC V3W 7R7, Canada
Telephone: 604-590-7438
Email: keith.lee@powertechlabs.com
Supercritical Water Oxidation
Dave Ordway
Telephone: 858-455-3568
Email: david.ordway@gat.com
Email: info@turbosvnthesis.com
53
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
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:
Alan G. Seech, Adventus Remediation Technologies, Inc.
Brad Yops, Technology Transfer Corporation, University of Delaware
Bryan Black, Environmental Decontamination Ltd.
Bret Campbell, IMPACT Services, Inc.
Carl V. Mackey, Washington Group International
Charles Rogers, BCD Group, Inc.
Christine Parent, California Department of Toxic Substances Control-
Christopher Young, BioTech Restorations
Claudio Arato, Sonic Environmental Solutions, Inc.
Edward Someus, Terra Humana Clean Technology Engineering Ltd.
Giacomo Cao, Centre Studi Sulle Reazioni Autopropaganti
John Fairweather, Thermal and Chemical Soil Remediation Ltd
John Vijgen, IHPA
Kevin Finucane, AMEC Earth and Environmental, Inc.
Jonathan Rogers, Commodore Advanced Sciences, Inc
Ralph Baker, TerraTherm, Inc.
Tedd E. Yargeau, California Department of Toxic Substances Control
Volker Birke, Tribochem
54
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
6.0 REFERENCES
1. Adventus Americas, Inc. 2009. "Representative DARAMEND® Project Summaries." Online
Address: http://www.adventusgroup.com/projects/proj daramend.shtml.
2. Adventus Americas, Inc. April 2009. "Bioremediation of Pesticides." Online Address:
http://www.adventusgroup.com/pdfs/tech bullet/DARAMEND%20Bioremediatoin%20of%20PES
TICIDES.pdf.
3. Allen, H.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.
4. Allen, H.L., US EPA Environmental Response Team. January 25, 2005. Email to Younus Burhan,
Tetra Tech EM Inc., Regarding US EPA Comments on Draft Blood Meal Fact Sheet.
5. American Chemical Society. May 2000. "Herbicide and Pesticide Destruction." Symposium on
Emerging Technologies: Waste Management in the 21st Century. San Francisco, California.
6. Assembled Chemical Weapons Alternative (ACWA). 2009. "About ACWA." Online Address:
http://www.pmacwa.army.mil/about/index.html.
7. Agency for Toxic Substances and Disease Registry (ATSDR). 2009. Website for ATSDR. Online
Address: http://www.atsdr.cdc.gov.
8. ATSDR. March 2002. "Public Health Reviews of Hazardous Waste Thermal Treatment
Technologies." Online Address: http://www.atsdr.cdc.gov/hac/thermal/thermall.html.
9. Baker, R., TerraTherm, Inc. October 27 and November 8, 15, 24, and 29, 2004. Emails to
Chitranjan Christian, Tetra Tech EM Inc.
10. Baker, R., and M. 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.
11. Baker, R.S., D. Tarmasiewicz, J.M. Bierschenk, J. King, T. Landler and D. Sheppard. 2007.
Completion of In Situ Thermal Remediation of PAHs, PCP and Dioxins at a Former Wood
Treatment Facility. 2007International Conference on Incineration and Thermal Treatment
Technologies (ITS), May 14-18, 2007, Phoenix, AZ. Air & Waste Management Association,
Pittsburgh, PA.
12. The Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their
Disposal. 2010. Website for the Basel Convention. Online Address: http://www.basel.int.
13. Birke, V. 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.
14. Boethling, R.S. and D. Mackay. 2000. "Handbook of Property Estimation Methods for
Chemicals." Environmental and Health Sciences. Boca Raton, Florida. Lewis Publishers
15. CerOx™ Corporation. 2005. Process Technology Overview. Online address is not available.
55
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
16. Donnelly, P.K., Hedge, R.S., and Fletcher, J.S. 1994. "Growth of PCB-Degrading Bacteria on
Compounds from Photo synthetic Plants." Chemosphere. Volume 28, Number 5. Pages 981-988.
17. The Federal Remediation Technologies Roundtable (FRTR). 2009. "Remediation Technologies
Screening Matrix and Reference Guide, Version 4." Online Address:
http: //www. frtr. gov/matrix2/top_page .html.
18. U.S. Department of Health and Human Services (DHHS). 2005. "Toxicological Profile
Information Sheet." Agency for Toxic Substances and Disease Registry (ATSDR). Online
Address: http://www.atsdr.cdc.gov/toxpro2.html.
19. US EPA. September 1994. "Eco Logic International Gas-Phase Chemical Reduction Process-The
Thermal Desorption Unit." Superfund Innovative Technology Evaluation Program. EPA/540/AR-
94/504. Online Address: http://www.epa.gov/nrmrl/lrpcd/site/reports/540ar93522/540ar93522.pdf
20. U.S. Environmental Protection Agency (US EPA). 1996. "Cost and Performance Summary
Report, Bioremediation at the Stauffer Management Company Superfund Site, Tampa, Florida."
Office of Solid Waste and Emergency Response.
21. US EPA. 1996. Site Technology Capsule: "GRACE Bioremediation Technologies
DARAMEND® Bioremediation Technology." Superfund Innovative Technology Evaluation
Program. EPA/540/R-95/536.
22. US EPA. September 2000. "Cost and Performance Summary Report, Bioremediation at the
Stauffer Management Company Superfund Site, Tampa, Florida." Office of Superfund
Remediation and Technology Innovation.
23. US EPA. August 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. EPA-R-00-004. Online Address:
http://www.epa.gov/tio/download/remed/acwatechreport.pdf.
24. US EPA. April 2002. "Persistent Organic Pollutants. A Global Issue. A Global Response." Office
of International Affairs. EPA160-F-02-001. Online Address:
http://www.epa.gov/oia/toxics/pop.pdf
25. US EPA. July 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. Online Address:
http://www.epa.gov/ORD/NRMRL/pubs/540r05007/540R05007.pdf.
26. US EPA. March 2004. "In Situ Thermal Treatment of Chlorinated Solvents: Fundamentals and
Field Applications." EPA 542-R-04-010. Online Address:
http://www.epa.gov/tio/download/remed/epa542r04010.pdf
27. US EPA. 2005. Website on Persistent Organic Pollutants (POP). Office of Pesticide Programs.
Information Downloaded on January 5. Online Address:
http: //www .epa. gov/international/toxics/pop .htm.
28. US EPA. January 2007. "Combined Mechanical/Chemical Process Removes POPs from Soil and
Sediment." Technology News and Trends. Issue 28. EPA 542-N-06-007. Online Address:
http://www.clu-in.org/products/newsltrs/tnandt/view.cfm?issue=0107.cfm.
29. US EPA. January 2007. "EPA Evaluates Cost and Performance of Blood Meal-Enhanced
Anaerobic Bioremediation of Toxaphene-Contaminated Soil." Technology News and Trends. EPA
542-N-06-007. Issue 28. Online Address:
http://www.du-m.org/products/newsltrs/tnandt/view.cfm?issue=0107.cfm.
56
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
30. Finucane, K., Geomelt. May 23, 2005. Emails to Ellen Rubin, US 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.
31. General Atomics. 2005. "Advanced Process Systems Division." Online Address:
http://www.ga.com/atg/aps.
32. GeoSolve, Inc. 2009. "Factor Description." Online Address: http://www.geosolve-
inc. com/biotech .html.
33. Getman, G.D. 2001. "Closure Report for SoLV Process Treatment of Soils Excavated from the
Pennsylvania Air National Guard Site At Harrisburg International Airport Harrisburg,
Pennsylvania."
34. Gilbert, E.S. and D.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.
35. Global Security. Weapons of Mass Destruction. Army Facilities. 2005. "Newport Chemical Depot
(NECD), Newport, Indiana." Online Address:
http: //www. globalsecurity .org/wmd/facility/ne wport.htm.
36. Gray, N.C.C., AstraZeneca Group PLC. December 15, 2004. Telephone Conversation with
Younus Burhan, Tetra Tech EM Inc.
37. 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.
38. Haley & Aldrich, 1997. Demonstration Test Report, Thermal Wells, In Situ Thermal Desorption
Technology, Missouri Electric Works Site, Cape Girardeau, Missouri, Nov. 1997, Rochester, New
York. p. 31 and Appendix B, p. 2.
39. Hurt, K. 2005. "Successful Full Scale Phytoremediation of PCB and TPH Contaminated Soil,"
The Third International Phytotechnologies Conference, Atlanta, Georgia. April 19 - 22.
40. Impact Services, Inc. 2005. "GeoMelt® Technology Description." Online Address:
http://www.impactservicesinc.com/divisions/geomelt.html.
41. Ing, G.C., Centra Studi sulle Reazioni Autopropaganti. December 12, 2004. Email to Younus
Burhan, Tetra Tech EM Inc.
42. International Centre for Science and High Technology. 2007. Website for International Centre for
Science and High Technology; United Nations Industrial Development Organization. Online
Address: http://www.ics.trieste.it.
43. International HCH and Pesticides Association (IHPA). June 2005. "Gas-Phase Chemical
Reduction." Online Address:
http://www.ihpa.info/docs/librarv/reports/Pops/FactSheet%20SBC GPCR%20 251105 DBF.pdf
44. IHPA. 2002. "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/docs/library/libraryNATO.php.
45. Ishii, Y., Kawai, T., Nobuaki, H., Takehara, H., Yara, H., and Y. Tokashiki. March 2007. "POPs
Contaminated Soil Treatment with 'Reductive Heating and Sodium Dispersion Method' and Its
Recycling for Material of Green Planting." Journal of Environmental Science for Sustainable
Society. Volume 1. Pages 11 through 14.
57
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
46. Johnson, L., General Atomics. February 15, 2005. Telephone Conversation with Chitranjan
Christian, Tetra Tech EM Inc.
47. 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.
48. Lyons, T., US EPA National Risk Management Research Laboratory. January 19 and August 10,
2005. Email to Younus Burhan, Tetra Tech EM Inc.
49. March, J. 1985. "Advanced Organic Chemistry. Reactions, Mechanisms, and Structure." Third
Edition. New York. John Wiley & Sons.
50. 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.
51. Noma, Y. 2009. Japanese Pesticides Treatment Fact Sheets, National Institute for Environmental
Studies, Research Center for Material Cycles and Waste Management, Ibaraki, Japan.
http://www.ihpa.info/docs/librarv/other/jp factsheet/Fact sheet%28Radicalplanet Technology%29
l.pdf.
52. 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.
53. Pan, D., Bennett Environmental Inc. January 18, 2005. Telephone Conversation with Younus
Burhan, Tetra Tech EM Inc.
54. Phillips, T., G. Bell, D. Raymond, K. Shaw, and A. Seech. 2001. "DARAMEND® Technology for
In Situ Bioremediation of Soil Containing Organochlorine Pesticides." 6th International HCH and
Pesticides Forum, Poznan, Poland. March 20 - 22.
55. Raymond, D., Adventus Remediation Technologies, Inc. August 25, 2004. Telephone
Conversation with Younus Burhan, Tetra Tech EM Inc.
56. Rogers, C., BCD Group Inc. December 9 and 13, 2005. Email correspondence with Younus
Burhan, Tetra Tech EM Inc.
57. Shaw Environmental Inc. and Environmental Decontamination Ltd. May 15, 2008.
"MechanoChemical Destruction Supplemental Treatability Study, PCB Hot Spot - Soil Stockpiles
12 and 15, Hunters Point Shipyard, San Francisco, California." Final Report.
58. Shimme, K., Radicalplanet Research Institute Co. Ltd. October 8, 2009. E-mail correspondence
with Younus Burhan, Tetra Tech EM Inc.
59. Sonic Environmental Solutions Inc. 2005. Website for Sonic Technology. Online Address:
http://www.sesi.ca.
60. 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.
61. Stockholm Convention on Persistent Organic Pollutants (POPs). 2009. Website for the Stockholm
Convention. Online Address: http://www.pops.int.
62. TerraTherm Environmental Services. November 1999. "Naval Facility Centerville Beach,
Technology Demonstration Report, In Situ Thermal Desorption."
58
-------
Reference Guide to Non-combustion Technologies for Remediation of Persistent Organic Pollutants in
Soil, Second Edition - 2010
63. TerraTherm, Inc. 2005. "Process Description In Situ Thermal Desorption (ISTD)." Online
Address: http://www.terratherm.com.
64. Thermal Desorption Technology Group LLC of North America. 2005. Website for Terra Humana
Clean Technology Engineering Ltd. Online Address: http://www.terrenum.net.
65. Thermal Desorption Technology Group, Terra Humana Clean Technology Engineering Ltd.
December 10, 2004. "Summary Report of the TDT-3R Treatment - Latest Five Years - Projects
2000-2004."
66. Thiess Services NSW. June 2004. "Proof of Performance Report, FCC Remediation, Mapua, New
Zealand."
67. Turbosystems Engineering Inc. 2005. Web Page for Supercritical Water Oxidation Technology.
Online Address: http://www.turbosynthesis.com/summitresearch/sumhome.htm.
68. United Nations Economic Commission for Europe (UNECE). 2009. Website for the United
Nations Economic Commission for Europe. Online Address: http://www.unece.org/env/lrtap.
69. United Nations Environment Programme (UNEP). 2005. Website for the Secretariat of the Basel
Convention. Online Address: http://www.basel.int.
70. UNEP. May 2005. "Technical Guidelines for the Environmentally Sound Management of
Persistent Organic Pollutant Wastes." UNEP/POPS/COP.1/11. Online Address:
http://www.pops.int/documents/meetings/cop 1/meetingdocs/en/cop 11 I/COP 1 11 .pdf
71. UNEP. January 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. Online Address:
http://www.basel.int/techmatters/review_pop feb04.pdf
72. UNEP. October 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." Online Address:
http://www.basel.int/techmatters/review_pop_feb04.pdf
73. White, J. C., Mattina, 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.
74. Whitfield, M., Rutter, A., Reimer, K. J., and Zeeb, B., 2008. "The Effects of Repeated Planting,
Planting Density, and Specific Transfer pathways on PCB uptake by Cucurbita pepo grown in field
conditions," Science of the Total Environment, September 10.
75. 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.
59
-------
APPENDIX A
Chemical Structures, Uses and Effects of POPs listed
under the Stockholm Convention and LRTAP
-------
Appendix A
Chemical Structures, Uses and Effects of POPs listed under the Stockholm Convention and LRTAP
PESTICIDES
Aldrin & Dieldrin
Aldrin and Dieldrin are chemical compounds that were once used as insecticides.
Aldrin and Dieldrin are persistent in the environment and resistant to
biodegradation and abiotic transformation. They both undergo bioaccumulation
and bio-magnify in terrestrial and aquatic ecosystems. Aldrin and Dieldrin are toxic
to humans and cause damage to the liver and immune system. They are also
carcinogenic to certain animals (Ref. 7).
Alpha-hexachlorocyclohexane & Beta-hexachlorocyclohexane
Alpha and beta-hexachlorocyclohexane (HCH) are by-products from the production of Lindane. Alpha
and beta-HCH are both persistent in the environment; however, beta-HCH is found to be more persistent
than alpha-HCH. Both HCHs bioaccumulate in aquatic and terrestrial ecosystems and can transport over
long ranges in the atmosphere. Alpha-HCH and beta-HCH are considered to be human carcinogens that
affect the human reproductive, neurological and immune systems (Ref. 7).
alpha-HCH
beta-HCH
Chlordane
Chlordane is an organochlorine compound that was once used as a pesticide. It is
extremely persistent in the environment and has the potential to bioaccumulate in
aquatic ecosystems. There is not sufficient evidence to consider chlordane as a
human carcinogen; however, chlordane is toxic to humans and affects the liver,
digestive and nervous systems (Ref. 7).
-cl
Chlordecone
Chlordecone is a manufactured chemical that is present in pesticides and
insecticides. Chlordecone is persistent in the environment, has a tendency to
bioaccumulative and bio-magnify in terrestrial and aquatic food chains, is
readily absorbed in soil and sediments, and has a high resistance to
biodegradation. Chlordecone is highly toxic to humans, as well as aquatic
organisms, and damages the musculoskeletal, liver, neurological and
immune systems. Chlordecone is considered as a human carcinogen (Ref. 7).
Dichlorodiphenyltrichloroethane (DDT)
Dichlorodiphenyltrichloroethane (DDT) was a widely used pesticide and
insecticide that controlled agricultural crop pests as well as insects that
carried human diseases. DDT is persistent in the environment, which
contributes to the bioaccumulation and bio-magnification effect that DDT
has on organisms in the environment. DDT also has the potential to undergo long-range global transport
A-l
-------
Appendix A
Chemical Structures, Uses and Effects of POPs listed under the Stockholm Convention and LRTAP
through the air. DDT is listed as a "probable" carcinogen to humans and can cause damage to the lungs
and respiratory system if inhaled (Ref. 7).
Endosulfan
•s=o
Endosulfan is a synthetic organochlorine compound that is widely used in
agricultural insecticides. It is persistent in the environment, bioaccumulative, and
has the potential for long-range environmental transport. Endosulfan is highly
toxic to all organisms and humans; it affects the neurological, reproductive and
developmental systems in humans (Ref. 7). Based on recent data and evaluations,
as of June 2010, EPA is taking action to eliminate all uses of endosulfan in the
US; additional information is available at
http://www.epa.gov/pesticides/reregistration/endosulfan/endosulfan-cancl-fs.html.
Endrin
Endrin was primarily used as an insecticide and a rodenticide. Endrin is
extremely persistent in the environment because it adsorbs strongly to soil
particles and is practically immobile, which contributes to endrin's high
bioaccumulation capabilities. Unlike other organochlorines, endrin has a
relatively low bio-magnification factor. Endrin affects the nervous system in
humans, but is not considered to be a human carcinogen (Ref. 7).
Heptachlor
Heptachlor is an organochlorine that has been used as an insecticide. Heptachlor is
persistent in the environment and adsorbs strongly to soil sediments, which
contributes to a high bioaccumulation factor. Heptachlor has a relatively low bio-
magnification factor. It is listed as a "possible" human carcinogen that affects the
liver, nervous and reproductive systems (Ref. 7).
Ck Cl
Hexachlorobenzene (HCB)
Hexachlorobenzene (HCB) is classified as a chlorinated hydrocarbon and was used as a
fungicide for agricultural seed treatment. HCB is one of the most persistent chemicals
found in the environment due to its chemical stability and high resistance to
degradation. HCB significantly bioaccumulates in both terrestrial and aquatic food
chains. For humans, HCB is considered a "probable" human carcinogen and is also an
animal carcinogen (Ref. 7).
Lindane
Lindane is an organochlorine that was used in agricultural insecticides and in the
pharmaceutical treatment of lice or scabies. Lindane is persistent in the environment
and has the potential to bioaccumulate and bio-magnify in terrestrial and aquatic
ecosystems. There is significant evidence for lindane to be considered as
carcinogenic but is currently listed as a "possible" human carcinogen (Ref. 7).
Mirex
Mirex is a chlorinated hydrocarbon that was used as an insecticide and is also found
in flame retardants. Mirex, like HCB, is very persistent in the environment due to its
high resistance to chemical and biological degradation. This contributes to high
A-2
-------
Appendix A
Chemical Structures, Uses and Effects of POPs listed under the Stockholm Convention and LRTAP
bioaccumulation and bio-magnification factors in terrestrial and aquatic ecosystems. Mirex is considered
to be an animal carcinogen and can affect the liver in humans (Ref 7).
Toxaphene
Toxaphene, a complex mixture of hundreds of organic compounds, was used as an
insecticide. It is persistent in the environment and has the potential to bioaccumulate
and bio-magnify in terrestrial and aquatic ecosystems. Toxaphene can be transported
over very long distances in the atmosphere. Toxaphene is a human carcinogen, which
affects the kidneys, lungs and nervous system (Ref. 7).
INDUSTRIAL CHEMICALS OR BY-PRODUCTS
Polychlorinated biphenyls (PCBs)
Polychlorinated biphenyls (PCBs) were one of the most widely manufactured
industrial chemicals in the US. PCBs are extremely persistent in the
environment, bioaccumulate significantly in terrestrial and aquatic
ecosystems, and have a very high resistance to environmental degradation. In
humans and animals, PCBs are considered to be a carcinogen and can affect
the liver and kidneys (Ref. 7).
Dioxins & Furans
Dioxins and furans are by-products associated with the production of organochlorides. Dioxins and furans
are persistent in the environment and are resistant to biodegradation. They also have a great potential to
bioaccumulate in terrestrial and aquatic ecosystems. Several different forms of dioxins and furans are
considered to be "possible" human carcinogens (Ref. 7).
Dioxin
H
H
0
Furan
Octabromodiphenyl ether, Pentabromodiphenyl ether (penta-BDE), Hexabromobiphenyl &
Hexabromocyclododecane (HBCDD)
Octabromodiphenyl ether, pentabromodiphenyl ether (penta-BDE), hexabromobiphenyl and
hexabromocyclododecane (HBCDD) are all classified as brominated flame retardants (BFRs). BFRs have
been used as industrial chemicals to produce foam for furniture and upholstery and casings for electronic
goods. BFRs are toxic and persistent in the environment.
Under the Stockholm Convention, the POPs review
committee provided experimental evidence that the
bioaccumulation of high blood level of BFRs in women of
childbearing age could potentially harm the women and their
unborn children.
Br
m
Brn
Pentachlorobenzene
Pentachlorobenzene is persistent, bioaccumulative, and toxic to humans and
aquatic organisms. Pentachlorobenzene also has a high bio-magnification
A-3
-------
Appendix A
Chemical Structures, Uses and Effects of POPs listed under the Stockholm Convention and LRTAP
potential and can undergo long-range transport in the air. In humans, pentachlorobenzene affects the
central nervous system, liver, kidneys and reproductive system (Ref. 7).
Perfluorooctane sulfonate (PFOS)
Perfluorooctane sulfonate (PFOS) is a widely used industrial chemical
that is found in paints, polishes, leathers and fire retardants in the form
of a fire fighting foam. PFOS is easily absorbed, bioaccumulative,
persistent in the environment and toxic to humans and wildlife. PFOS
also has the ability to transport over long distances in the environment (Ref. 7).
Hexachlorobutadiene (HCBD)
/ \
Hexachlorobutadiene (HCBD) is mainly used to make rubber compounds.
It is also used as a solvent, and to make lubricants, in gyroscopes, as a heat
transfer liquid, and as a hydraulic fluid. HCBD is also a by-product of
chemical processing. HCBD has the potential to transport over long
distances through water, soil or the atmosphere. Limited data is available
about the bioaccumulation and biomagnification abilities of HCBD but it
is predicted to bioaccumulate only in aquatic ecosystems. HCBD is
considered a "possible" human carcinogen (Ref. 7).
Polychlorinated naphthalenes (PCN)
Cl
Polychlorinated naphthalenes (PCNs) are chemical by-products that are created
when chlorine reacts with naphthalene. This may occur during the production
of coal tar. Limited data is available for PCNs, but available information
indicates that PCNs likely have a low potential for bioaccumulation and
biomagnification. PCNs are harmful to humans and affect the liver (Ref. 7).
Short-chained chlorinated paraffins (SCCP)
Short-chained chlorinated paraffins (SCCPs) are industrial chemicals
found in flame retardants, metal working fluids and in polyvinyl
chlorinated (PVC) plastics. SCCPs are persistent, toxic (particularly
to aquatic organisms), and undergo long-range transport in the
environment. In humans, SCCPs have the potential to harm a breast-
fed child through bioaccumulation (Ref. 7).
A-4
-------
APPENDIX B
Fact Sheet on
Anaerobic Bioremediation Using Blood Meal for the
Treatment of Toxaphene in Soil and Sediment
-------
Appendix B
Anaerobic Bioremediation Using Blood Meal for the 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 serves 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)
B-l
-------
Appendix B
Anaerobic Bioremediation Using Blood Meal for the Treatment of Toxaphene in Soil and Sediment
US 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.
• This technology typically does not achieve greater than 90 percent contaminant destruction.
B-2
-------
Appendix B
Anaerobic Bioremediation Using Blood Meal for the Treatment of Toxaphene in Soil and Sediment
• 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 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.
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
B-3
-------
Appendix B
Anaerobic Bioremediation Using Blood Meal for the Treatment of Toxaphene in Soil and Sediment
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.
B-4
-------
Appendix B
Anaerobic Bioremediation Using Blood Meal for the 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
B-5
-------
Appendix B
Anaerobic Bioremediation Using Blood Meal for the 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, US 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, US EPA Environmental Response Team. 2005. Memo to Ellen Rubin, US
EPA Office of Superfund Remediation and Technology Innovation. Response to Questions on
Toxaphene Fact Sheet. February 24.
4. U.S. Environmental Protection Agency (US 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. US EPA. 2000. Fact Sheet-Gila River Indian Community Toxaphene Site. October.
6. Rubin, Ellen, US 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.
B-6
-------
APPENDIX C
Fact Sheet on
g DARAMEN
POPs in Soils and Sediments
Bioremediation Using DARAMEND® for Treatment of
-------
Appendix C
Bioremediation Using DARAMEND9 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
DARAMEND® particle colonization as viewed
through an electron-microscope
Source: Adventus Americas, Inc.
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.
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
Application of DARAMEND at the T.H. Agricultural and
Nutrition Superfund Site (Source: Adventus Americas, Inc.).
C-l
-------
Appendix C
Bioremediation Using DARAMEND9 for Treatment of POPs in Soils and Sediments
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.
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
NA
$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.
C-2
-------
Appendix C
Bioremediation Using DARAMEND9 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 of the DARAMEND® technology to treat POPs requires limited maintenance such as
the upkeep of tilling, soil moisture control, and other industrial equipment. Because the specific
amendments and application rate of DARAMEND® are site and soil-specific, the ongoing maintenance
will vary by site and type of soil treated.
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.
Volatile organic compound emissions may increase during soil tilling. Other factors that could interfere
C-3
-------
Appendix C
Bioremediation Using DARAMEND9 for Treatment of POPs in Soils and Sediments
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, US
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.
C-4
-------
Appendix C
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 ^
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 z
Cone.
(mg/kg)
126
227
33.2
55.1
216
13.3
151
9.1
45
44.4
12.6
78
Final"
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 z
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 ^
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 US EPA.
U.S. EPA RPM FOR THAN SITE:
Brian Farrier
EPA Region 4
Telephone: 404-562-8952
Fax: 404-562-8955
Email: farrier.brian@epa.gov
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@AdventusGroup .com
Website: http://www.adventusgroup.com/
PATENT NOTICE:
DARAMEND® is a patented technology with U.S. Patent No. 5,618,427.
C-5
-------
Appendix C
Bioremediation Using DARAMEND9 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. US EPA. 1996. Site Technology Capsule, GRACE Bioremediation Technologies
DARAMEND® Bioremediation technology. Superfund Innovative Technology Eva
EPA/540/R-95/536.
5. US EPA. 1997. Site Technology Capsule, GRACE Bioremediation Technologies
DARAMEND® Biore
EPA/540/R-95/536a.
DARAMEND® Bioremediation technology. Superfund Innovative Technology Evaluation.
6. US EPA. 2002. Technology News and Trends, Full-Scale Bioremediation of Organic
Explosive contaminated soil. EPA 542-N-02-003. July.
7. US EPA. 2004. TH Agricultural & Nutrition Company Site Information and Source Data.
Online Address: http://www.epareachit.org.
8. US EPA. 2004. TH Agricultural & Nutrition Company Site, RODS Abstract information,
Superfund Information Systems. Online Address: http://www.epa.gov/superfund.
9. Farrier, Brian, US 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.
C-6
-------
APPENDIX D
Fact Sheet on
In Situ Thermal Desorption for Treatment of POPs in
Soils and Sediments
-------
Appendix D
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
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.
Vapor cap
Well-field
Source: TerraTherm™ Inc.
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°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.
D-l
-------
Appendix D
In Situ Thermal Desorption for Treatment of POPs in Soils and Sediments
Figure 2
Blanket and Thermal Well Heating
Thermal Well
Heating
Source: TerraTherm™ Inc.
separately.
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
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.
D-2
-------
Appendix D
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 and
Furans
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.
D-3
-------
Appendix D
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.
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
D-4
-------
Appendix D
In Situ Thermal Desorption for Treatment of POPs in Soils and Sediments
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 fordioxins 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 fordioxins
(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.
Figure 3
Phase-1 Soil Sampling Results
30.600
m
I
E
o
e
I
3
t>
Z9.000
J4.000
19.000
14.000
0.000-
4.UUO
DPAHs |B(a)P Equivalent]
Goal: 65
Dioxins (2.3.7.8-TSDD TEQ)
(5oai:
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.
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 was completed in August 2005. The
results showed a 99% decrease in contaminant concentration from 18 ug/kg initially to .01 ug/kg. In
February 2007, the Department of Toxic Substances Control (DTSC) issued a letter of closure to the
Source:
Pfe-Treatment Interim
Sampling Pcrud
TerraTherm™ Inc.
Pcst-Trealment
D-5
-------
Appendix D
In Situ Thermal Desorption for Treatment of POPs in Soils and Sediments
SCE Alhambra Combined Facility that states the site needed "No further action." 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. Shell
Oil Company leased a portion of the Rocky Mountain Arsenal 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 groundwater downgradient 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, 12 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
D-6
-------
Appendix D
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.
D-7
-------
Appendix E
Additional Technologies Identified but Not Commercially Available
APPENDIX E
Additional Technologies Identified but Not
Commercially Available
-------
Appendix E
Additional Technologies Identified but Not Commercially Available
This Appendix presents technologies that were identified in the first edition (2005) of this report that are
not currently commercially available.
E-l Xenorem™
TECHNOLOGY TYPE: BIODEGRADATION
POPs TREATED: CHLORDANE, DDT,
DIELDRIN, AND TOXAPHENE
MEDIUM: SOIL
PRETREATMENT: NONE
COSTS: $132 PER CUBIC YARD (COST IN
2000 USD)
FULL SCALE
EXSITU
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 37).
A self-propelled SCAT windrow incorporates the amendments
into the soil and provides aeration to create aerobic conditions.
High levels of available nutrients from the amendment
increase the metabolic activity in the amended soil and deplete
the oxygen content, creating anaerobic conditions. The
anaerobic conditions promote dechlorination of
organochlorine compounds. 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 for a full-scale cleanup at the Stauffer Management Company Superfund site
in Tampa, Florida. The site is a former pesticide manufacturing and distribution facility that operated
from 1951 to 1986 (Ref. 20). 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. 20). Table 3-13 presents the performance data for both batches. 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. 22).
The Xenorem™ technology also was applied to a third batch of contaminated site soil at the site. 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. US EPA is awaiting details of the modification proposal. US EPA will prepare an
Explanation of Significant Difference (ESD) fact sheet explaining the selection of a new remedy (Ref.
36).
E-l
-------
Appendix E
Additional Technologies Identified but Not Commercially Available
Table E-l. 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)
-------
Appendix E
Additional Technologies Identified but Not Commercially Available
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 31).
TECHNOLOGY TYPE: THERMAL-
CHEMICAL DEGRADATION
POPs TREATED: CHLORDANE, DDT,
PCBS, DIOXINS AND FURANS
PRETREATMENT: EXTRACTION/
GRINDING, DILUTION
MEDIUM: SOLID AND LIQUID WASTES
PILOT SCALE
EXSITU
The Assembled Chemical Weapons Assessment (ACWA)
Program was established by the Department of Defense
(DoD) in 1997 to test and demonstrate at least two
alternative technologies to the baseline incineration
process for the demilitarization of assembled chemical
weapons (Ref. 6). 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 being constructed. 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 treating 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. 44). SCWO treatment of solid
wastes after they have been ground into a fine slurry has been demonstrated using feed materials
containing up to 25 percent suspended solids (Refs. 6, 35, 44, 46 and 71).
Information regarding the SCWO technology is available from General Atomies' Advanced Process
Systems Division (General Atomics) (Refs. 31 and 46). The SCWO process developed by General
Atomics was selected for use as an ACWA technology to treat non-POPs such as GB, VX, H, HD, and
TNT. However, no further information regarding process details, performance data, or costs could be
obtained directly from General Atomics. Turbosystems Engineering Inc. also designs and markets
SCWO systems in the US (Ref. 67). Turbosystems Engineering Inc. claims that its system can treat DDT
and HCB; however, no performance data substantiating this claim are available in the information sources
identified and used to prepare this report.
Supercritical Water Oxidation is a thermal-chemical degradation process that uses both, high
temperatures and chemical additions to treat POP contaminated material. This technology has been
proven to treat certain pesticides and industrial chemicals that are listed as POPs. Due to the high
temperature requirement and the specific reactions under the treatment conditions of the technology, other
POPs could also be potentially treated using Supercritical Water Oxidation. A commercial SCWO system
developed by SRI International, USA and licensed to Mitsubishi Heavy Industries has been operational in
Japan since 2002. The system is treating PCBs and uses sodium carbonate as an oxidant, which allows
operation at a moderate temperature (380-420 °C) and mitigates potential corrosion problems. The most
recent application of Supercritical Water Oxidation occurred in 2003. Currently, no further information
regarding process details, performance data, or costs could be obtained directly from the technology
vendor. Further technology information can be obtained by contacting the vendor using the information
provided in Section 5.0.
E-3
-------
Appendix E
Additional Technologies Identified but Not Commercially Available
E-3 Vacuum Heating Decomposition
Vacuum heating decomposition is an ex situ technology for treating POP contaminated soil. This
treatment is based on a technology used to remove zinc from zinc-plated steel by vacuum heating. Pre-
treatment is not required for POPs prior to decomposition by vacuum heating. The wastes are heated
under vacuum conditions, where POPs are decomposed by pyrolysis and dechlorination reactions. The
heating is regulated so the pressure ranges from 0.5 to 2,000 Pascals (Pa). Gaseous emissions pass
through activated carbon prior to discharge.
POPs-related pesticides have been treated at one
commercial site in Japan since 2004; however, no
information is available for any full-scale projects
treating POPs in the information identified and used to
prepare this report (Ref 44).
Vacuum Heating Decomposition technology uses high
temperatures for thermal degradation under regulated
pressure conditions to treat POPs such as; HCBs, PCBs
and dioxins and furans. Due to the high temperature and
pressure requirement of this technology other POPs
could also be potentially treated using Vacuum Heating
Decomposition. The vendor of this technology is Hoei-
Shokai Co., Ltd. of Japan. This technology is not
commercially available in the US. Currently, no further information regarding process details,
performance data, or costs could be obtained directly
from the technology vendor. Technology information
can be obtained by contacting the vendor using the
information provided in Section 5.0.
TECHNOLOGY TYPE: THERMAL-
PHYSICAL DEGRADATION
POPs TREATED: CHLORDANE, ALDRIN,
DIELDRIN, ENDRIN, HCB, PCBS, DIOXINS
AND FURANS
MEDIUM: SOIL
PRETREATMENT: NONE
PILOT SCALE
EXSITU
THE FACT SHEET PREPARED BY IHPA IS
AVAILABLE AT
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/
E-4 CerOx™
CerOx™ is an ex situ electrochemical reaction technology
that has been used in pilot tests to treat low-strength liquids
containing POP
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
(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
POPs TREATED: CHLORDANE, DIOXINS,
ANDPCBS
PRETREATMENT: SOIL AND SEDIMENT
ARE MIXED WITH WATER TO PRODUCE A
FLUID INFLUENT
MEDIUM: LIQUIDS
PILOT SCALE
EXSITU
CerOx treatment system,
Source: Ref. 15
E-4
-------
Appendix E
Additional Technologies Identified but Not Commercially Available
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 (VOCs). 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. 15).
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 ^^^^^^^^^^^^^^^^^^^^^
fed to the system. The system is reported to have I THE FACT SHEET PREPARED BY IHPA is
achieved a chlordane destruction efficiency of 99.995 AVAILABLE AT
percent in the gaseous-phase reactor (Ref. 5).
Chlordane concentrations in the liquid effluent were
not reported.
HTTP://WWW.IHPA.INFO/RESOURCES/LIBRARY/
The vendor later performed additional tests of the UNR system to determine the ability of CerOx™ to
treat PCBs and dioxins (Ref. 71). 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. 15).
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. 15). This technology was included in the 2005 report; however, no information
about this vendor could be found for this report.
E-5
-------
Q_
O
.Q 3
Eu
S 3:
LJJ oo
T3
c
to
O g
C
O 0) ^
z E °
O QJ
4-> Q; (J
(L> i- c
o
o
o
^
(J
£P o
O p
4-> T3
C UJ
ST:
00 C
I 8
Q- oo
U
C
on
o
u
s
Q-
4J C
00 I —
"O o ^~
4J -^ O
o
NO
o
(N
U
Q
on
c
o
o
ro
•oo-
c c
------- |