Remediation Treatment Technologies: Reference Guide for Developing Countries Facing Persistent Organic Pollutants

by Loretta Li, Ph.D., P.Eng. Associate Professor Department of Civil Engineering The University of British Columbia 6250 Applied Science Lane Vancouver, B.C. V6T 1Z4

to Dr. Mohamed EISA, Chief of POPs Unit UNITED NATIONS INDUSTRIAL DEVELOPMENT ORGANIZATION (UNIDO) Vienna International Centre P.O. Box 300, A-14000 Vienna Austria

Table of Contents

Page List of Tables ..................................................................................................................... iii List of Figures .................................................................................................................... iv Acknowledgements..............................................................................................................v Disclaimer .......................................................................................................................... vi 1. 2. 3. 4. Introduction.................................................................................................................1 Methodology ...............................................................................................................2 Full Scale Technology Profiles...................................................................................2 Development of a Screening Matrix ...........................................................................3 4.1. 4.2. 5. 6. Logistics..........................................................................................................4 Grading System for the Developed Screening Matrix....................................8

The Potential for Improvement of Existing Remediation Techniques .......................9 Address the Potential Improvement of Incinerator.....................................................9 6.1. 6.2. 6.3. Methodology .................................................................................................10 Incineration of Hazardous Waste Materials/POPs........................................10 Conclusion ....................................................................................................15 Methodology .................................................................................................16 Landfilling: Engineered Landfill for Hazardous Waste Materials/POPs .....16 Conclusion ....................................................................................................19

7.

Address the Potential Improvement of Landfilling for POPs...................................15 7.1. 7.2. 7.3.

Appendix A Overviews of established, demonstrated and emerging technologies........21 A-1 A-2 A-3 A-4 Incineration ...................................................................................................22 Bioremediation (DARAMEND & XenoremTM) ........................................29 Solvent Extraction.........................................................................................41 Vitrification (PACT, PLASCONTM & GeoMeltTM) .....................................45

A-5 A-6 A-7 A-8 A-9

Solidification/Stabilization ...........................................................................50 Gas Phase Chemical Reduction ....................................................................56 Alkali Metal Reduction (Sodium Reduction) ...............................................61 Pyrolysis and Gasification ............................................................................64 Ball Milling/ Mechano-Chemical Dehalogenation (MCDTM) ......................70

A-10 Thermal Desorption ......................................................................................74 A-11 Supercritical Extraction (SCE) .....................................................................83 A-12 Soil Washing.................................................................................................92 A-13 Chemical Dehalogenation...........................................................................100 A-14 Phytoremediation ........................................................................................105 Appendix B Soil Effect on Cost of Technology ...........................................................111 Appendix C Treatment Technology Combinations ......................................................117 Appendix D Chemical abbreviations, synonyms and trade names of 12 POPs identified by UNIDO in the Stockholm Convection................................119 Bibliography ..................................................................................................................122

ii

List of Tables
Page Table 1 Table 2 Table 3 The list of reviewed technologies ......................................................................3 Proposed screening matrix system choosing an appropriate technology for a specific site in each developing country....................................................6 Grading System for screening matrix ................................................................8 1989; Evans 1990; USEPA 1991a; USEPA 1992b; USEPA 1994b; USEPA 1995b; USEPA 1997; USEPA 2004a; USEPA 2005) .....................113 Table B2 Critical Characteristics Affecting Cost Ranges for Technology Alternatives for Remediating POP- Contaminated Soil and Sediment (Dvila et al., 1993) .......................................................................................114 Table B3 Cost Summary of Each Technology and the Estimated Cost in 2007 U.S. Dollars using Construction Cost Index..................................................115 Table B4 Annual Construction Cost Index....................................................................116 Table B1 Soil Characteristics Affecting Cost of Remedial Technology ((USEPA

iii

List of Figures
Page Figure C1 Common combinations of treatment technologies applied in remedial actions (USEPA 2004b).................................................................................118

iv

ACKNOWLEDGEMENTS

Special acknowledgment is given to Dr. John R. Grace of the Department of Chemical and Biological Engineering at The University of British Columbia for his contributions to the section on combustion technology; Tamer Gorgy, my Ph.D. student, who performed a literature search and prepared a compilation of existing technologies; Dr. Raymond Li of CH2MHILL for his cooperation and thoughtful suggestions during the preparation of this report. I also express my special thanks to the United Nation Industrial Development Organization (UNIDO) for its financial support for this project.

DISCLAIMER

This report compiles information on a wide range of technologies for remediation of POPs in soil and stockpiles based on available published and unpublished information available to the author. In preparing this review, technical literature and reports from various organizations have been surveyed. Note that the evaluation is based on existing available information, some of which may not be complete or fully accurate. This report is provided as a reference guide, but it is not intended to provide guidance regarding selection of a specific technology or vendor. It also should not be construed in any manner as constituting endorsement, recommendation or discouragement for the use of any trade name or commercial product.

vi

1. Introduction
Persistent organic pollutants (POPs), originating from a variety of human activities (agricultural and industrial), are toxic chemical compounds that resist chemical and biological breakdown in the environment. POPs can be conveyed for thousands of miles through air or water currents, and may be found in remote ecosystems far from their source, even in locations where POPs have never been used (EUROPA 2007). Through bioaccumulation, animals, like humans, higher in the food chain, are more likely to have higher concentrations of these pollutants, often to the degree that the substances may cause cancer, as well as neurological and immune system disorders (USEPA 2007, OMoE 2005). The United Nations Environment Programme (UNEP) Stockholm Convention on Persistent organic Pollutants is a global agreement intended to protect human health and the environment from POPs. It was signed on May 23 2001 and entered into force on May 17 2004. Parties to the Stockholm Convention agree to the management and control of POPs (UNEP 2003). many developed countries. Because of their adverse health effects and associated Unfortunately, industrialization of many developing environmental hazards, remediation of POPs in stockpiles and soils has been underway in countries has resulted in extensive use of these chemicals, causing serious environmental pollution and resulting in serious negative social impacts. Many advanced soil remediation techniques have been commercialized and adopted in industrialized and developed countries. These include Gas Phase Chemical Reduction (GPCR), Mechanochemical dehalogentation (MCD), and Thermal Desorption. Some promising techniques such as Base Catalyzed Decomposition (BCD) and Sonic technology are still either at the laboratory stage or at the pilot study. However, due to the financial constraints, many advanced technologies are unlikely to be adopted by the developing countries. The success of finding suitable and affordable technologies is critical in solving problems in the developing countries.

The objective of this report is to review existing commercially available and sustainable techniques of remediating POPs and to explore the potential for adopting or improving existing remediation techniques for use in developing countries. Existing technologies are first summarized. A set of criteria is then provided as an aid to developing countries in identifying which technology is most suitable in each case based on country specific factors and site-specific conditions.

2. Methodology
Both well developed and commercialized combustion and non-combustion technologies for remediation of POPs in soil and stockpiles are summarized here, based on available information. In preparing this review, technical literature and reports from various organizations have been surveyed. Sources which are especially useful are: USEPA Reference Guide to Non-Combustion Technologies for Remediation of Persistent Organic Pollutions in Stockpiles and Soil (2005) UNEP, Science and Technology Advisory Panel (STAP) of the Global Environmental facilities (GEF) Review of Emerging, Innovative Technologies for the Destruction and Decontamination of POPs and the Identification of Promising Technologies for Use in Developing Countries (2004) 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) (2002)

3. Full Scale Technology Profiles

As listed in Table 1, Appendices 1 to 14 of this report provide overviews of established, demonstrated and emerging technologies for remediation of POPscontaminated soils and sediments. The information there includes process descriptions, 2

site requirements, estimated costs, by-products, and performance (covering where possible laboratory-, bench, pilot- and full-scale test results). The advantages and limitations of the various technology options, as well as their applicability in developing countries are also considered briefly.

Table 1. The list of reviewed technologies

Technology Established Incineration Bioremediation (DARAMEND & XenoremTM) Solvent Extraction Vitrification (PACT, PLASCONTM & GeoMeltTM) Solidification/Stabilization Gas Phase Chemical Reduction Alkali Metal Reduction (Sodium Reduction) Pyrolysis (STARTECH) Ball Milling/ Mechano-Chemical (MCDTM) Demonstrated Thermal Desorption Super Critical Extraction (SCE) Soil Washing Chemical Dehalogenation Emerging Phytoremediation

Appendix 1 2 3 4 5 6 7 8 Dehalogentaiotn 9

10 11 12 13 14

4. Development of a Screening Matrix

Screening Matrices are common tools for screening potentially applicable commercialized technologies for POPs remediation projects. A matrix allows the user to screen in-situ (with a few exceptions) technologies to treat POPs for countries at various stages of development. The US Federal Remediation Technologies Roundtable (FRTR 2007) has developed a similar screening matrix for remediation technologies.

In this report, three sets of criteria have been developed to form the screening matrix. The matrix provides a foundation for decision-making and for choosing an appropriate technology for a specific site in each developing country. The matrix can be readily expanded as more commercial technologies become available.

4.1.

Logistics The criteria for comparison are based on on-site technology (in-situ/ex-situ)

except for landfilling and incineration. All the criteria are grouped under three major headings: (a) technical considerations, (b) health and environmental considerations, and (c) economic considerations. These three subtitles are intended to encourage a wideranging evaluation of the technologies, not only including financial factors, but also taking into consideration technical and environmental criteria. Equal weight is applied here to each criterion, but weighting factors can be established to reflect the differing relative importance of different criteria in each jurisdiction. However each factor should at least be considered in all cases. Note that the evaluation is based on existing available information, some of which may not be complete or fully accurate.

(a)

Technical considerations Site Specific Requirements: Soil Temperature Dependence Soil Moisture Dependence Particle Size Distribution of Soil Permeability/Clay Content Organic matter (insufficient data and information to be included in the matrix) Space available Proximity of population or sensitive sites Pretreatment Power/energy/fuel Water quantity, quality and seasonal variations 4

Resource/Technical Requirements:

 (b) (c)

Chemicals Equipment Monitoring Skilled labour Transportation: roads, rail, canals, etc. Off-gas treatment Post-treatment Excavation

Health and Environmental Considerations Impact on the local, regional and global environment in all aspects, i.e. air, water, soil and sediments Hazardous by-product(s) Worker health and safety Odours, aesthetic factors Pretreatment cost Labour cost Monitoring cost Power/fuel cost Equipment cost Installation/decommissioning cost Operating and maintenance cost Disposal cost Transportation cost Water cost Intellectual property cost Post treatment cost Influence on regional economy

Economic considerations

Table 2 displays the proposed matrix system for considering these various factors. 5

Table 2. Proposed screening matrix system choosing an appropriate technology for a specific site in each developing country.

Combustion Incineration In/Ex situ On Site/Off site Efficient Estimate cost ($/m3) * Technical Consideration Site Specific Requirement Soil Temperature Dependence Soil Moisture Dependence Particle Size Permeability/clay content Space Requirement Resource Requirement Pretreatment Power Water Chemical/enemzy Monitoring Skill Labour Transportation Off Gas Treatment Post Treatment Excavation Sub total Ex On site 99.99% 140-360 Ex Off site 99.99% Thermal Desorption Super Critical Extraction

Non Combustion Solvent Phytoremediation Bioremediation GPCR Extraction In On Site 147-626 In/Ex On Site 60-80% 55-360 Ex On Site 99.99% 500-630 Ex On site 95-99% 125-400

Vitrification In/Ex On Site 99.99 500-8000

Pyrolysis Ex On Site 99.99 375-500

MCD Ex On Site 70-91% ??

Sanitary landfilling Ex Off Site 150

Ex/In Ex On Site On Site 93-99.8% 99.99% 350-450/350-700 122-154* partial cost

1 3 2 1 2

1 3 2 1 1

2 3 3 1 2

2 3 3 1 2

2 3 2 1 1

3 3 3 3 3

3 3 2 1 2

1 3 2 3 3

3 3 1 1 1

3 3 1 1 1

3 3 3 1 1

1 1 1 1 1

2 3 1 1 3 3 1 2 1 3 29

2 1 1 1 1 1 3 1 1 3 23

2 3 1 1 3 3 1 3 1 3 32

3 1 3 3 3 3 1 3 3 3 37

1 1 2 1 1 1 1 1 1 1 20

1 1 3 3 1 2 1 1 1 1 30

3 3 1 3 3 3 1 3 1 3 35

2 3 2 3 3 3 1 1 3 3 36

1 3 1 1 2 3 1 3 1 3 28

1 3 1 1 3 3 1 2 1 3 28

1 2 1 1 2 2 1 1 1 2 25

1 1 1 1 1 1 3 1 1 3 19

Table 2 (continued)
Combustion Incineration Health & Environmental Consideration Impact to Environment Bi-products Hazardous Sub total Financial Consideration Pretreatment Cost Labour cost Monitoring Cost Power/fuel Cost Equipment Cost Installation/Decommissioning Cost Operational & Maintenance Cost Chemical (or equivalent) Cost Disposal Cost Transportation Cost Water Cost Patent Cost Post Treatment Cost Sub total Rating Code : 1 - No/Low 2 - Average 3 - Yes/high * See Appendix A for detail information on cost Thermal Desorption Super Critical Extraction Non Combustion Solvent Phytoremediation Bioremediation GPCR Extraction

Vitrification

Pyrolysis

MCD

Sanitary landfilling

3 5

3 5

1 2

1 2

1 2

1 2

3 4

1 2

3 5

2 4

1 2

2 4

1 2 3 3 3 2 2 1 1 1 1 1 1 21

1 2 1 1 2 1 1 1 3 3 1 1 1 18

3 2 3 3 3 3 3 1 1 1 1 3 1 25

3 3 3 2 3 3 3 3 1 1 3 3 3 31

1 3 2 1 1 1 2 1 1 1 2 1 1 17

1 2 2 1 1 1 2 2 1 1 3 1 1 18

3 2 3 3 3 3 3 3 1 1 1 3 3 29

2 3 3 1 2 2 2 3 1 1 1 1 3 23

1 3 2 3 3 3 3 1 1 1 1 3 1 25

1 2 2 3 2 3 3 1 1 2 1 2 2 24

2 2 2 2 2 2 2 1 1 1 1 2 1 19

1 1 1 1 1 1 1 1 3 3 1 1 1 16

4.2.

Grading System for the Developed Screening Matrix The symbols used in the treatment technologies screening matrix are simple.

Table 3 provides an explanation of this grading system.

Table 3. Grading System for screening matrix Rating Code 1 - No/Low Explanation Low degree of intensity or not required - in cost, negative impact or skilled labour 2 - Average 3 - Yes/high Average degree of intensity - in cost, negative impact or skilled labour High degree of intensity or requirement - in cost, negative impact or skilled labour

In this matrix evaluation, the lower the score, the better the technology for a specific site. Completing the matrix is a valuable tool for the site owner, as well as for government agents who are responsible to determine which available technology is most suitable for managing POPs. Each criterion can be weighted by multiplication by weighting factors, accounting for the varying importance of different attributes. The sum of all scores, multiplied by the corresponding weighting factors results in a total qualification grade for comparing alternatives and selecting the best technology for the specific site subject to its own local and specific conditions. The weighting factor for each item can be adjusted upward or downward as circumstances change, depending on local factors. Note that there is no a priori methodology to assign the right weighting factors for the criteria in Table 2. It is up to site owners to assign the appropriate weighting factor for each criterion based on local priorities and regulatory requirements. For example, the cost of water and energy can vary radically between difference communities, so that their weighting factors are likely to differ. Also, the regulatory requirements for developing countries can differ greatly from those of developed countries. Therefore, again the corresponding weighting factors with respect to environmental impacts are likely to differ in such cases.

5. The Potential for Improvement of Existing Remediation Techniques

Many of the remediation technologies described in the previous sections are proprietary and protected by patents. Know-how needed to exploit existing technologies can also be proprietary to design firms or other private interests. Because of the competition between technologies for the existing market and differences in local conditions, there may well be potential for improvement of proprietary techniques, or for adaptations that would make them more suitable to local situations in developing countries. Incineration and landfilling are the two most common technologies which are unlikely to require consideration of patents. Although they have been in practice in many countries for many year, they are still have potential for improvement, e.g. those based on the directorate of the Stockholm Convention. The facilities must exist for safe and appropriate reuse and/or reformulation; they must present no additional unacceptable hazards, and they must benefit both people and the environment.

6. Address the Potential Improvement of Incinerator

Incineration is a combustion technology which if not designed or operating optimally, can create products of incomplete combustion such as polychlorinated dibenxo-p-dioxins (dioxins) and polychlorinated dibenzo-p-furans (furans). Note that dioxins and furans are often synthesized de novo, i.e. formed downstream, at an intermediate temperature range e.g. ~400C. According to Carroll (2003) the key to reduction of generation and emissions of dioxins and furans (PCDD/Fs) is proper design and operation of the combustor. The uniformity of conditions is significant because problems often occur when part of the stream by-passes the hot zone. Attention also needs to be paid to free radical reactions which can result in the synthesis of a wide variety of compounds, some of which are harmful. Specification and operation of pollution control equipment requires utilization of good combustion practices, often expressed as the "Three T's": Time in the combustion zone, Temperature of combustion and combustion gases, and strong Turbulence to ensure good mixing and favourable 9

contacting with oxygen. Successful governmental policy reflects these requirements as a condition for operation of incinerators, especially those burning toxic and other special wastes. With more research on combustion and careful attention to detail, incineration is one of the best and most economic technologies for POPs.

6.1.

Methodology

In preparing this section, I have relied on: Review of a number of recently published papers and unpublished material relating to incineration of POPs, PCBs and emissions of dioxins/furans. Input from a world-recognized process engineer and research scientist, with experience related to combustion of a wide range of materials, reactors, hightemperature processes, and air pollution control, including special waste incineration. Some available material with respect to the Canadian experiences at the Swan Hills, Alberta facility and the Sydney Tar Ponds, Nova Scotia facility are used for illustration purposes.

6.2.

Incineration of Hazardous Waste Materials/POPs Incineration of waste materials is commonly employed as a method for converting

waste carbonaceous materials into relatively harmless substances, mostly carbon dioxide, water and ash. The flue gas also includes oxides of nitrogen (NOx) and sulphur (mostly SO2), as for combustion of fossil fuels; when the combustible material contains chlorine, hydrogen chloride (HCl) is also a product. Control of these three gases is standard, practiced routinely, e.g. in furnaces, boilers and power generation. Inevitably small amounts of other undesirable products like carbon monoxide (CO) will also be present in the flue gas. Traces of highly undesirable products of combustion, in particular products of incomplete combustion, such as chlorinated dioxins and furans, also occur in combustion processes. The major objective in incineration is to keep the concentrations of these substances to extremely low and tolerable levels, while effectively destroying the waste materials fed to the incinerator.

10

The main challenges facing the designers and operators of an incinerator for destroying POPs are:

Effective destruction and removal efficient (DRE) for the waste material; Minimization of the production and emission of noxious pollutants, like
dioxins and furans, which can be formed in incineration systems.

Effective control of the emissions of heavy metals. Controlling the emissions of standard combustion pollutants like NOx, SO2,
CO and particulates. These will be considered in turn, followed by some general observations. (a) Destruction of POPs (e.g. PCBs) and Other Fed Waste Materials A rotary kiln is the most common type of hazardous waste incinerator. This type of high-temperature reactor is also often employed in cement-making, limestone calcination and pulp and paper operations. Waste liquid and/or solids are fed into one end of a slightly-inclined rotating cylinder which has been heated (by auxiliary fuel such as oil) to approximately 1200C or more. The temperature is maintained at that level by the calorific value of the waste stream, supplemented if needed by fossil fuel such as oil or natural gas. The wastes are lifted and dropped repeatedly by the revolving furnace, leading to effective contact with combustion air. Excess air is employed (i.e. more than required for stoichiometric combustion) in order to promote complete burning of the wastes. Typically 30 - 50% excess air is recommended. The standards required for the incinerator need to be fixed, but previous experience (Grace 2007) with rotary kiln furnaces has shown that they are capable of meeting usual incinerator standards of six nines (99.9999%) destruction of PCBs, and four nines (99.99%) destruction of polyaromatic hydrocarbons like naphthalene and anthracene. Well-designed and properly operating commercial incinerators exceed these values, frequently by a factor of 10 to 100. Operating conditions which are most important to achieve high DREs are the mean temperature level, temperature uniformity, sufficient excess oxygen concentration (e.g. >4% oxygen by volume in the flue gas), uniform feeding, and turbulence or other effective contacting mechanisms in the furnace. To further improve the combustion efficiency, the off-gases are fed to a secondary combustion chamber (often called an 11

afterburner), to assist in oxidizing any unburnt gases. In addition, downstream pollution control devices, such as scrubbers, filters and/or electrostatic precipitators, are added to capture fine particulates (fly ash) and gaseous component which would otherwise escape. A revolving fluidized bed incinerator has demonstrated destruction with at least six nines efficiency for coke wastes (tar containing a number of potentially harmful constituents, in particular polycyclic aromatic hydrocarbons (PAHs), PCBs, and heavy metals, as well as small amounts of volatile organic compounds). Tests by Jia et al. (2005) of Natural Resources Canada have also indicated that tar sludge can be efficiently destroyed in circulating fluidized bed combustors. These combustors operate at significantly lower mean temperatures (typically 850 - 900C, though with greater temperature uniformity than rotary kilns.) PCB wastes, with much higher concentrations than those of the tar sludge, are also routinely incinerated in the rotary kiln incinerators at Swan Hills in Alberta, Canada, with DREs well in excess of six nines. Rotary kiln incinerators in other countries have had similar success. When problems are encountered, these can often be related to materials handling in delivering the wastes to the incinerator, not to the incinerator itself. For example, with Sydney tar ponds wastes in Nova Scotia, Canada, incineration failed in tests carried out two decades ago due to problems in pumping the sludge material up hill to the level of the incinerator (Campbell 2002).

(b)

Minimization of Dioxins, Furans and Other Products of Incomplete Combustion Considerable work has been completed in a number of countries on the

mechanisms by which it is possible to form and emit noxious substances, in particular poly-chlorinated dioxins and furans, in combustion facilities. Some of the key factors needed to minimize their generation are the same as those cited above with respect to achieving high destruction and removal efficiencies, i.e. high and uniform temperatures, uniform feeding, sufficient excess oxygen, effective gas/waste contacting through turbulence, and proper downstream separation devices. In addition, it is very important that the cooling of the flue gases through the temperature interval from ~ 400 to 300C be as quick as possible to prevent de novo synthesis of dioxins and furans downstream of the 12

incineration chambers.

These stipulations are generally well-known to operators of

incinerators. If an experienced vendor is chosen, with a well designed and effectively operated and maintained incinerator, it should be possible to operate within normal hazardous waste limits. (c) Emissions of Heavy Metals Some wastes and by-products contain small amounts of heavy metals, which are present in the material fed to the incinerator. For instance, in coke tar, the metals of concern are likely to be arsenic, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, vanadium and zinc. It is important to minimize emissions of these metals. Mercury is the most volatile of these metals, and its control depends on effective capture of fly ash entrained by the flue gases, i.e. on efficient gas-solid separation in the off-gases. Standard separation techniques like scrubbers, bag filters and electrostatic filters are available to control such emissions. The less-volatile metals are likely to end up predominantly in the bottom ash. Careful controls can ensure that the heavy metals emissions satisfy the applicable codes, both in terms of emissions and levels at point of impingement. Residual (fly and bottom ashes) from the incinerator could be an issue and must be disposed of and handled properly. (d) Emissions of Standard Combustion Pollutants Incinerators must also meet standard emission limits for pollutants (e.g. acid gases like SO2 and NOx, as well as CO) commonly controlled in stationary combustion. There is a need to keep the oxygen concentration in the flue gas higher than about 4% to achieve uniform combustion with good burnout. If this is done, emissions of CO and unburnt hydrocarbons should be low. The need to control mercury and other heavy metals also requires effective capture of particulates, so that particulate emissions should be well controlled by filters, scrubber or precipitator. If opacity is controlled, this should also be readily achievable given the other controls. Given the oxidizing conditions, gases like hydrogen sulphide and ammonia will not be problematic.

13

(e)

Materials Handling Issues An incinerator is only as good as its auxiliaries, with continuous and uniform

feeding being of the utmost importance. This can sometimes be overlooked. Special attention to handling and feeding of the waste is needed. As noted above, an attempt to utilize incineration for Sydney Tar Ponds sludge failed because of materials handling issues. An accident at the Swan Hills facility in the 1990s was also attributed to materials handing problems.

(f)

Continuous Operation It is preferable for incinerators to maintain operation night-and-day once

incineration has been started up and to have scheduled shutdowns only in frequently, e.g. once per year, since steady state continuous operation facilitates trouble-free operation.

(g)

Pilot-Scale Testing Pilot scale testing of POPs burning may be required to prove the successfulness of

the design combustion conditions and operation for a given waste material. Some companies and government laboratories have pilot scale facilities that can be used for this purpose. Normally, the test results should be conservative in that a full-scale incinerator will have greater residence times than those in a pilot unit, and therefore if the pilot unit meets the requirements, the full-scale should also do so.

(h)

Operation and Maintenance The safety of any technology can be compromised by improper operation or

failure to provide proper maintenance. It is not only vital that proper equipment be chosen, designed, fabricated, installed and commissioned, but that the operations and maintenance be at the top level for the full period of operation. The role of government in assuring quality and continuity of operation is vital to the safety of incinerator facilities.

14

(i)

Monitoring and Emissions Testing Standard substances like oxygen, NOx, SO2, CO, unburnt hydrocarbons and HCl

should be monitored continuously. Their levels can provide a good overall indication that the incinerator is working properly, and upsets can be detected, e.g. through a sudden drop in oxygen level and increase in off-gas CO concentration. Testing for complex organics like dioxins/furans, PAHs and PCBs requires specialized stack testing. While this would normally be done annually, it is appropriate to conduct additional tests in the first year in addition to the initial testing required for acceptance of an incinerator.

6.3.

Conclusion Incineration is a widely-practised technique for destroying wastes, including those

containing POPs. Well designed, well constructed and well maintained incinerators with appropriate monitoring, downstream air pollution control and stack, can often be an appropriate technique for destruction of hazardous organic substances.

7. Address the Potential Improvement of Landfilling for POPs

Landfilling is a technique which can contain the migration of POPs. Since

landfilling does not normally destroy POPs, every effort has to be used to prevent the migration. Proper lining and monitoring are required to ensure that there is no leakage from the landfill containment system. The engineer/control landfill can be considered as a temporary measured until the destructive technologies for POPs become available for developing countries, which provide environmental sustainability and fall within economical affordability. Developing countries should follow the most up-to-date requirements and technologies to build landfills which are suitable to handle the disposal of POPs. Two types of liners can be used: flexible membrane and clay liners. Measurement of the liner compatibility is critical to success. Flexible membranes deteriorate over time, particular when they are chemically incompatible with the leachate. Flexible membranes contain pinholes and therefore cannot be made leak-free. Organic chemical solutions affect the

15

hydraulic conductivity of clay liners. Therefore, it is suggested that a flexible membrane, compatible with POPs, underlain by a clay liner, is the minimum requirement of a landfill for disposal of POPs. Although there is no universal method to test the compatibility, two test methods have been promoted (EPA 1992c). They are NSF (National Sanitation Foundation) Standard No. 54 and EPA Test Method 9090. Local soil materials or waste materials with high adsorptivity and low hydraulic conductivity could be explored for possible use as containment barrier materials. If appropriate for adoption, these materials can benefit the local economy and may possibly gain a global market for such a material for containment purpose.

7.1.

Methodology In preparing this section, I have relied on the following: Review of a number of recently published papers and some unpublished material relating to landfill, clay liner, properties of POPs and soil minerals. Personal experience with landfill liners, waste containment systems, soilcontaminant contaminants. Some available material with respect to experiences in different research and consulting projects related to remediation of contaminants in soils and landfill liner studies. interactions, mobility/immobility of contaminants, and remediation of contaminated sites, including those involving organic

7.2.

Landfilling: Engineered Landfill for Hazardous Waste Materials/POPs Landfilling is generally regarded as the most economical and practical method for

disposal of large volumes of municipal and industrial solid wastes. Land disposal has been in practice throughout human history. Traditionally waste was dumped in depressions (e.g. holes left after quarries and gravel were mined) or in open spaces without any lining system. This led to air, soil and water pollutions, and also to landfill fires. In developing countries where there is a lack of environmental awareness, economical means and technological infrastructure to use other treatment options, waste 16

will continue to be discarded onto land, whether or not it is regarded as an option for POPs. Many POPs are still being stored or disposed onto land, regardless of the development level of the country. Many environmental problems from landfill sites arise due to lack of understanding of science, including geology, hydrogeology, soil conditions, properties of contaminants and the resulting leachate. The legitimate environmental concern with respect to landfilling is whether pollutants contained in, or generated from, the wastes can be safely contained in landfills. Flexible membrane liner or clay liners (waste containment barriers) are frequently installed at waste disposal sites as a means of preventing pollutant migration and minimizing or eliminating the potential for groundwater contamination. In this section, I focus on the improvement of clay liners because many countries have access to clay minerals which may be suitable barrier materials. These include smectite/bentonite, vermiculate and illite. In using clays as a liner material in landfill construction, one relies on the effectiveness of the clay barrier to impede transport of contaminants due to the low permeability of the barrier. In addition, the ability of the clay barrier to adsorb (accumulate) contaminants (Li and Li 2001) can make a very useful contribution to the attenuating capability of the clay liner. Waste containment barriers are in the form of landfill liners and covers, lagoon liners, and slurry walls. However, the use of cay barriers below waste disposal sites to protect underlying groundwater resources has become a contentious issue following experimental and field evidence of failure due to clay-leachate incompatibility and other factors such as the mineralogical and physical properties (e.g. wetting/drying of clays that may cause cracking of the liner. Siting and construction of a landfill can be as important as selection and design of the liner system.

(a)

Landfill Siting Attention must be paid to the local geological and hydro-geological situation in

selecting a landfill site. Avoid: Flood-hazard areas and wetlands 17

Areas subject to heavy rainfall Highly permeable soil (i.e. silt, sand, gravel) Public water supply watersheds Groundwater aquifers, recharge areas, areas with high water tables Limestone bedrock Designated parks, forests, historic areas, and wildlife refuges Seismic-risk zones

Environmental impacts must be assessed for environmental impacts (i.e. air pollution, noise, water pollution, soil contamination and ecological risks); consider economic impacts also; then plan for preventive and mitigation measures.

(b)

Liner materials Local clay minerals (montmorillolite, vermiculite, illite and kaolinite) and soil

minerals (zeolite) should be explored as possible liner barrier materials for their adsorptivity, compatibility and hydraulic conductivity for POPs. The methodology and approach have been outlined by Li and Li 2001, Li and Denham 2000 and others (http://www.civil.ubc.ca/people/faculty/lli/li_personalpage.html). Clay is an inexpensive material, widely used as a barrier in containment systems because of its low hydraulic conductivity (k) and high adsorptivity. However, the surface of clay is hydrophilic because of the strongly hydrated metal ions (principally Na+ and Ca2+) occupying the cation exchange sites (Li and Denham 2000). Hydrophobic organic contaminants (HOCs) such as POPs are repelled by this environment and are therefore not adsorbed well by natural clay. Thus, HOCs in landfill leachate may pass through clay barriers and into ground or surface waters. It is possible to make clays more adsorptive to HOCs by using cationic surfactants (Li and Denham 2000). These surfactants consist of a cationic, hydrophilic moiety and a non-ionic, hydrophobic moiety. The cationic ends of the surfactant molecules using simple ion exchange reactions replace the native inorganic cations on the clay surface. The modified clay is called organoclay. Large portions of the organoclay surface are rendered hydrophobic due to the hydrophobic moieties of the surfactant molecules. Thus, organoclay adsorbs many HOCs very well. Clay/soil 18

minerals such as zeolite and bentonite can be modified and adsorb HOC. The inclusion of organoclay in a clay barrier can effectively immobilize hydrophobic organic chemicals. Organic matter is an important constituent of soils with very high cation exchange capacity and very high specific surface areas. It partitions organic contaminants onto its surface. Admixing organic matter into soil liners may increase the retention ability of contaminants because many surface functional groups are available on soil organics for forming complexes (Sparks 1995). There is a lack of studies addressing alternative materials or reuse waste materials that would improve POPs compatibility.

(c)

Construction and Design A landfill site needs to have a sound design with daily cover, and a leachate

collection and removal system. The construction must ensure a safe and secure landfill. Proper training of skilled workers is also needed.

(d)

No co-disposal of municipal or other wastes Most POPs are hydrophobic or have low solubility. However, in landfill situation

when these are interactions with other organic solvents or humic substance, POPs have been detected in landfill leachates.

(e)

Composite Landfill Liners Depending on the locally available material, landfill liners can be composite liners

or admixed with different materials which achieve the high retention capacity and low hydraulic conductivity with POPs. Detailed tests of materials need to be conducted before implementation to ensure that the environment is protected.

7.3.

Conclusion Lined/engineered landfill could be an option to temporary store POPs for

developing country. Hazardous waste landfill design criteria have been set by many developed countries such as Canada, Australia, USEPA, and EU, and can be adopted. Local natural materials should be explored for use as landfill liners. Understanding of the 19

POPs and soil interaction is needed. When other sustainable, effective and economical POPs remediation technologies have been developed which are widely available for poorer countries, the stored POPs could be excavated for permanent destruction.

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Appendix A Overviews of Established, Demonstrated and Emerging Technologies

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A-1 Incineration

Overview
Incineration treats POPs in solids and liquids by subjecting them to temperatures typically greater than 500oC in the presence of oxygen. These conditions cause volatilization, combustion, and destruction of the organic compounds. The technology can be scaled-down, with trailer-mounted versions of conventional rotary kiln and fluidized bed incinerators in existence. At large sites where the cleanup will require several years, it may be feasible to construct an incinerator onsite. Economic reasons are often the key factor in determining whether mobile, transportable, fixed, or off-site commercial incineration will be provided at a given site. In addition to the furnace, incinerator systems also include subsystems for waste preparation and feeding, combustion of feed, air pollution control (APC), and residue/ash handling (Oppelt 1987). The three major wastestreams generated by incineration are solids from the incinerator and the associated APC system, water from the APC system, and gaseous emissions from the incinerator (Freeman and Harris 1995). The applicability of incineration to the remediation of POP- contaminated soil or sediment may be limited by the types and concentrations of metals present in the waste to be treated. When soil or sediment containing metals is incinerated, some metals vaporize, reacting to form other metal species, while less volatile metals remain with the soil residuals. Metals in ash, scrubber sludge, or stack emissions, if improperly managed, can result in potential exposures and adverse health effects (USEPA 1992a). For example, lead, a metal commonly found associated with polychlorinated biphenyl (PCB)contamination, volatilizes at most incinerator operating temperatures and must be captured before process off-gases are released into the atmosphere (USEPA 1992a). It is therefore essential to adequately characterize the metal content of the soil or sediment when considering incineration systems for treatment of PCB and other POPs.

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Weber (2007) describes three mechanisms that affect the emissions of polychlorinated dibenzo-para-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) for high-temperature incinerators: (a) (b) (c) Formation of PCDDs/PCDFs within the high-temperature zone due to free radical reactions. Emission of PCDD/PCDF precursors from high temperature processes and formation of PCDDs/PCDFs in the cooling zone. Formation of PCDDs/PCDFs via degradation of products of incomplete thermal destruction (soot, polyaromatic hydrocarbons (PAHs), etc.) in the cooling zone. If POPs waste and its associated thermal decomposition products are exposed to elevated temperatures for sufficient residence times, the POP components can be virtually completely destroyed. For combustion, the times required for destruction are typically only milli-seconds for gaseous compounds in the active flame zones. On the other hand, combustion times of the order of seconds may be required for complete destruction of small solid particles. A combustion temperature of 850oC and residence time of 2s, respectively, are generally believed sufficient to destroy all chlorinated organic molecules including PCBs and PCDDs/PCDFs (Weber 2007). However, this relies on all waste elements travelling through the hot zones something that is difficult to achieve.

For sufficient safety margins state-of-the-art hazardous waste incinerators are required to operate at temperatures above 1100oC and with a residence time in excess of 2s (Weber 2007). Conditions in cement kilns are even more severe (temperature >1400oC and several second residence time). Therefore for such facilities, bypassing around the hot zone has the greatest potential impact on total PCDD/PCDF formation (if stable operation is maintained) (Weber 2007). This is probably similar for other high temperature technologies, which can operate steadily at appropriate high temperatures and sufficient residence time. In addition, all high temperature technologies will face the challenges of PCDD/PCDF formation during cooling (so-called de novo synthesis), posing the additional challenge of investigating, minimizing and documenting these 23

formations, while also ensuring that off-gas streams cool rapidly through the temperature range of ~250 - 500C (Weber 2007).

Treatment Process
The primary stages in the incineration process are waste preparation, waste feed, combustion, and off-gas treatment. Waste preparation includes excavation and/or transporting the waste to the incinerator. Depending on the requirements of the incinerator, various equipment is used to remove oversized particles and obtain the necessary feed size for soil and sediments (USEPA 1997). Blending of the soil or sediment and size reduction are sometimes required to achieve uniformity of feed size, moisture content, temperature, and contaminant concentrations (USEPA 1989). The waste feed mechanism, which varies with the type of incinerator, must introduce the waste smoothly and continuously into the combustion system. The feed mechanism sets the requirements for waste preparation. Bulk solids are usually shredded; contaminated media are usually ram or gravity fed (USEPA 1992a). The combustion reactor usually consists of one of three major systems: rotary kiln, infrared furnace, or circulating fluidized bed. The primary factors affecting the design and performance of the system are the uniformity of feeding, the temperature at which the furnace is operated, the time during which the combustible material is subjected to the high temperature (residence time and time distribution), and the turbulence required to control (APC) equipment to remove particulates and capture and neutralize acid gases. APC equipment includes cyclones, venturi scrubbers, wet electrostatic precipitators, bag-houses, and packed scrubbers. Rotary kilns and infrared processing systems may require both external particulate control and acid gas scrubbing systems. Circulating fluidized beds do not require scrubbing systems because limestone can be added directly into the combustor loop; however, they are likely to require a downstream system to remove particulates such as cyclones, bag filters or electrostatic precipitators (USEPA 1992a; USEPA 1997).

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Site Requirements
The site should be accessible by truck or rail, and a graded or gravel area is required for setup of onsite mobile systems (USEPA 1997). Concrete pads are required for some equipment (e.g., rotary kiln). For a typical commercial-scale unit, 2 to 5 acres are required for the overall system site including ancillary support. A stack of height exceeding that of local buildings and trees should be available or provided as part of the project. Standard high-voltage, three-phase electrical service is generally needed. A continuous water supply must be available at the site. Various ancillary equipment may also be required, such as liquid or sludge transfer and feed pumps, ash collection and solids handling equipment, personnel and maintenance facilities, and process-generated waste treatment equipment. In addition, a feed-materials staging area, decontamination trailer, ash handling area, water treatment facilities, and a parking area may be required (USEPA 1992a). Special handling measures should be provided to hold any process residual streams until they have been tested to determine their acceptability for disposal or release. Depending on the site and the nature of the waste, a method to store waste that has been prepared for treatment may also be necessary. Storage capacity depends on waste volume and equipment feed rates (USEPA 1992a).

Cost
The cost of incineration includes the relatively fixed costs of site preparation, permitting, and mobilization/demobilization; and variable operational costs, such as labour, utilities, and auxiliary fuel. Average costs of the treatment system were said to range from $140- $360/m3 (1989 dollars) (USEPA 1997).

By-products
Three major waste streams generated by incineration are solid ash from the incinerator and any solids captured by the APC system, water from the APC system, and gaseous emissions from the incinerator. 25

Ash is commonly either air-cooled or quenched with water after discharge from the combustion chamber. Dewatering or solidification/stabilization of the ash may also have to be applied since the ash could contain leachable metals at concentrations above regulatory limits. The alkalinity of the matrix may influence the leachability of the ash (USEPA 1989). The flue gases from the incinerator should treated by an APC system such as an electrostatic precipitator, scrubber or filter before discharge through a stack. A high- or low-pH liquid waste may be generated by the APC system, specifically by a scrubber or wet precipitator. This liquid waste may contain high concentrations of chlorides, volatile metals, trace organics, metal particulates, and other inorganic particulates. Wastewater requiring treatment may be subjected to neutralization, chemical precipitation, reverse osmosis, settling, evaporation, filtration, or carbon adsorption before discharge (USEPA 1997).

Performance
Incineration technologies were selected as the remedial action at 65 U.S. Superfund sites with VOC and SVOC- contaminated soil or sediment (USEPA 1991a; USEPA 1993). Incinerator performance is most often measured by comparing initial PCB concentrations in feed materials with both final concentrations in the ash and concentrations present in off-gas emissions. In all the reported pilot and field scale studies, removal efficiencies exceeded 99.99% (USEPA 1997).

Advantages and Limitations

A well designed incinerator will have the following advantages: Capability of the highest overall degree of destruction and control for the broadest range of hazardous waste streams. The technology has effectively treated soils, sludges, sediments, and liquids containing all organic contaminants found at wood 26

preserving sites, such as PCDDs/PCDFs, PCP, PAHs, and other halogenated and nonhalogenated VOCs and SVOCs (Oppelt 1987; USEPA 1997). Treatment can achieve stringent cleanup levels. Broad application capability, for example with respect to different POP-contaminated soils. The limitations of this treatment technology are: The inorganic components of hazardous wastes are not destroyed by the process, mostly reporting to the bottom ash, and thus requiring either further treatment or disposal under stringent regulatory procedures. Continuous perfectly stable operation of a man-made facility operated by humans with heterogeneous or variable feed streams is unattainable. Technical defects, fatigue of construction materials and sensors, mistakes of operators, problems in power supply etc. sometimes lead to unstable operation. This may lead to some PCDD/PCDF/POPs emission (Weber 2007). Performance can be limited by the physical properties and chemical content of the waste stream, if not accounted for in the system design. Oversized particles (e.g., stones, debris) can hinder processing and can cause high particle loading from fines carried through the process. Feeds with high moisture content increase feed handling and energy requirements.

Applicability to Developing Countries

Incineration is a viable treatment method since many countries possess the infrastructure of incineration systems for municipal solid waste disposal and cement kilns. These facilities can use the contaminated soil as part of the fuel source, if the system is upgraded to include APC systems, and maintain proper ash treatment or disposal methods. Where there are high precipitation rates or where contaminated site is in a flood hazard plain, there may be problems with incineration, since the soil has to be predried to 27

provide the desired outcome, with minimal dioxin/furan emissions. Also high moisture content soils require more energy needs to achieve dryness.

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A-2 Bioremediation (DARAMEND & XenoremTM)

Overview
Bioremediation usually refers to the use of microorganisms to break down complex organic contaminants into simpler compounds. The technology usually involves enhancing natural biodegradation processes by adding nutrients, oxygen (if the process is aerobic), and in some cases, microorganisms to stimulate the biodegradation of contaminants. Anaerobic processes utilize microorganisms that are capable of degrading contaminants in the absence of oxygen. Bioremediation is typically performed by adding essential nutrients, adjusting moisture levels, and controlling the concentration of oxygen in the treatment area or vessel. Microorganisms already present in the soil may be biodegraders, or additional strains may be introduced. Solid-phase bioremediation uses conventional soil management practices, such as tilling, fertilizing, and irrigating, to accelerate microbial degradation of contaminants in above-ground treatment systems. If necessary, highly contaminated soils can be diluted with clean soils in order to reduce the contaminants to levels conducive to biodegradation. Composting uses bulking agents, such as straw or wood chips, to increase the porosity of contaminated soils or sediments. Additional components may be added to increase nutrients and readily available degradable organic matter. These additives include manure, yard wastes, and food-processing wastes. The resulting mixture often favours the growth of thermophilic microorganisms which are capable of degrading the organic contaminants of concern (USEPA 1997). In-situ bioremediation is accomplished by providing electron acceptors (e.g., oxygen and nitrate), nutrients, moisture, or other amendments to soils or sediments, without disturbing or displacing the contaminated media. In-situ bioremediation is often 29

used in conjunction with traditional pump-and-treat and soil flushing groundwater systems, in which the treated water is amended, as required, to stimulate microbial activity. It is then re-injected into the zone of contamination. An example of that is bioventing, where vacuum extraction wells, air injection wells, or both are installed and operated at relatively low flow rates, providing increased oxygen to the microorganisms in the soil (NRC 1993). There are several commercialized bioremediation bio-amendment substances that are in use. These include: using blood meal, DARAMEND and XenoremTM.

Treatment Processes
Bioremediation can occur under anaerobic or aerobic conditions. These will be presented separately in the following paragraphs.

Anaerobic Bioremediation In anaerobic bioremediation, bacteria replace chlorine substituents with electrondonating hydrogen (from H2) on the organic molecule. Under anaerobic conditions, PCB, PCDD and PCDF reduction is known to occur as a co-metabolic process, where these compounds are transformed during the metabolism of another compound. However, PCDDs and PCDF have shown resistance to breakdown. There are 2 known dechlorinating organisms for PCBs, o-17 and DF-1 which depend on 2,3,5,6 tetrachlorobiphenyl (tetraCB) for growth and require acetate to survive (Cutter et al., 2001). Anaerobic bioremediation can involve two major remedial actions: biostimulation and bio-augmentation. Bio-stimulation involves addition of a primer to galvanize a targeted dechlorinating population. Primers include FeSO4, which provides free sulfate, consumed by sulfate reducers. The bioenergetics favour sulfate reducers over methanogens. This process is favourable for in-situ applications because it is cheap and environmentally benign (Bedard et al., 1996). 30 In addition, the procedure can

introduce halogenated organics to prime processes which are recalcitrant to degradation (Abraham et al., 2002). Bio-augmentation, involves enriching a contaminated site with organisms capable of degrading the targeted compound. Anaerobic degradation of POPs is generally faster than aerobic degradation. Anaerobic degradation usually involves dechlorination, which has little effect on the total mass of the target contaminant, but can reduce toxicity by targeting highly chlorinated congeners (Mondello 2002). Hence dechlorination is sometimes used prior to aerobic remediation to decrease the reluctance of contaminants to undergo biodegradation. Usually a sequential of anaerobic and aerobic processes yields better overall degradation results. No practical and effective universal systems for bioremediation of PCBs, Dioxins and furans in soil have been developed for several reasons. PCBs, PCDD/Fs are mixtures of congeners having different physical and chemical properties. Microorganisms cannot use PCBs, PCDD/Fs as source of carbon and energy growth. Thus they have no selective advantage by which they expend energy to perform these reactions (Wiegel and Wu 2000; Smidt and de Vos 2004). It is also difficult to promote successful cometabolic biotransformation. The available data are limited, and major differences between lab-scale and site conditions often exist (Zhang and Bennett 2005). Contaminants can be more bioavailable in the laboratory than on site. In addition, discrepancies are also common in reported results due to volatilization, redistribution of congeners, and partitioning to equipment in lab studies (Mondello 2002; Wu et al., 2002; Zhang and Bennett 2005). In laboratory-scale studies, bacteria are commonly made more competitive or conditions are adjusted to their favour (Mondello 2002; Wu et al., 2002; Zhang and Bennett 2005).

Aerobic Bioremediation Aerobic degradation of POPs can be carried out by a variety of aerobes acting synergistically. The degradation usually attacks lightly-chlorinated congeners (e.g. in PCBs 5 or fewer) (Bedard et al., 1996; Abraham et al., 2002). 31

Studies have shown that a broad range of gram-negative and gram-positive bacteria can breakdown PCBs. The range is narrower for PCDD/Fs. Extensive research found strains of PCB-degrading-bacteria, especially in contaminated soils: Enterobacter sp. SA-2, Ralstonia sp. SA-4, and Pseudomonas sp. SA-6. e.g., Achromobacter sp., Alcaligenes, sp., Acinetobacter sp., Corynebacterium sp., Rhodococcus sp., Burkholderia sp. and Pseudomonas sp. that can metabolize PCBs or, in the case of congeners containing one or two chlorines, use them as a sole source of carbon and energy (Adebusoye et al., 2007). Burkholderia xenovorans LB400 and Rhodococcus sp. strain RHA1 are two of the more promising strains for application in the aerobic stage of a PCB biotreatment process because of their abilities to degrade a wide range of PCB congeners (Rodrigues et al., 2006). However, like other PCB-degrading microorganisms, they have only limited ability to grow on PCBs, so repeated addition (bio-augmentation) would be required for bio-treatment (Rodrigues et al., 2006). In-situ bioremediation takes place in the vadose zone of soils and in the top few millimetres of sediments, ensuring aerobic conditions. This often leads to the production of chlorobenzoic acid (CBA) due to enzymatic degradation of the ring resulting in fewer attached chlorine atoms, with release of the second ring as CBA. If accumulated, CBA itself can be toxic (Abraham et al., 2002). Rodrigues et al (2006) reported that PCB degraders cannot catalyze degradation CBA, with the consequence being a buildup of the metabolite.

Performance
Aerobic Studies Bench, Laboratory and Pilot Scale Studies Laboratory scale studies commonly experience greater effectiveness than field treatment because they are conducted under more controlled, uniform and favourable conditions than in the field (NRC 1993). Laboratory studies can provide upper limit results, but caution must be exercised when forecasting results expected in full scale and field bioremediation. Most reported studies have been done on PCB bioremediation in 32

particular on Aroclor, including 1221,1242 and 1254 incubated in aerated sludge reactors. The mono- and dichlorinated PCBs rapidly degraded and the rate decreased as percent chlorine of Aroclors increased (Mondello 2002). Studies on high-density PCB-degrading bacteria suspended in buffer solution with a PCB mixture revealed that degradation occurred, except to Aroclor 1254 (Furukawa et al., 1983). In bioreactor studies, PCB reduction was up to 80% in bench scale systems (Mondello 2002). Degradation of Aroclor 1248, 1254 and 1260 has been studied in 8 different types of agricultural and forest soils (Mondello 2002). Results showed degradation rates up to 80%. The least degraded mixtures were those containing highlychlorinated congeners like 1254 and 1260.

Field Studies Field studies results show less degradation than in laboratory investigations. The following provides some examples of recorded field studies: (a) Glenn Falls, NY (Mondello, 2002) The site consisted mainly of sandy soil contaminated with Aroclor 1242, at levels of 50-500 mg/kg. Many di- and trichlorobiphenyls were degraded. The study attempted to stimulate the process by adding Pseudomonas strain LB400 (which is known to degrade a wide variety of PCBs). Laboratory scale test, showed 85% degradation. In the field study the strain was repeatedly dosed over a designated area for a period of 4 months. Only 20% of the PCBs degraded. In an adjacent plot, which was repeatedly dosed with nutrient solution and no bacteria introduction relying only on native microorganisms, there were negligible degradation.

33

(b) Hudson River NY (Harkness et al., 1993) This site was contaminated with Aroclor 1242. Bioremediation used naturally occurring anaerobic bacteria, which had previously extensively dechlorinated PCBs in 6 in-situ bioreactors. Treatment operated with varying nutrients, aerobic PCB organisms, oxygen content and mixing, for 73 days. The initial PCB concentration varied between 6 and 50 mg/kg. After the test period the process yielded 60% PCB degradation. Laboratory-scale experiments again yielded higher degradation rates.

(c) French Limited, Tx (Mondello 2002) Pilot and full scale bioremediation were tested. The contaminants were PAHs and PCBs, less than 600 mg/kg. The treatment process included slurry phase bioremediation with aeration and mixing. Results showed that PCBs levels were reduced by at most 60%. Aeration could have contributed to improved degradation or helped in volatilization.

Anaerobic Studies Bench, Lab and Pilot Scale Studies (a) Anaerobic Bioremediation of Toxaphene using Blood Meal (USEPA 2005) Bench and pilot scale results show the toxaphene and DDT can degrade rapidly.

Field Studies (a) Wood Pond, MA(Bedard et al., 1986; Bedard et al., 1996) In a field study PCB dechlorination was stimulated in sediments contaminated with Aroclor 1260. The treatment used 2,6 brominated biphenyl as an alternative electron acceptor whose dechlorination to biphenyls induces or enriches the activation of the indigenous anaerobic bacteria. 34

After 373 days, hexa- to nona-CBs decreased from 68% to 26%. However, TriCB increased. Overall there was no net reduction in total PCB concentration.

(b) Anaerobic Bioremediation of Toxaphene using Blood Meal (USEPA 2005) This method uses blood meal as a nutrient to the native anaerobic bacteria. The contaminated soil was treated for toxaphene by bio-stimulation. The soil was mixed with blood meal and saturated with water (0.3 m above the soil). In ex-situ systems, the soil was placed on lined cells, covered and incubated for several months. The by-products from this process were lower chlorinated chlorobenzenes, chloride ions and cell mass, in addition to H2S and methane. An attempt to treat chlorobenzenes by blood meal under aerobic conditions achieved 90% dechlorination.

Anaerobic-Aerobic Remediation Aerobic bacteria do not degrade highly chlorinated compounds such as PCBs. Coupled systems of anaerobic and aerobic phases may be implemented, where highly chlorinated compounds are dechlorinated, to enhance aerobic degradation. DARAMEND and XenoremTM coupled system. DARAMEND (USEPA 2005) The process includes addition of DARAMEND (which contains nutrients and zerovalent iron) with water to produce an anoxic phase causing bio-stimulation. Periodic tilling of the soil is performed to promote oxic conditions. Watering and tilling are performed several times to achieve effective treatment. The technology can be implemented using land-farming techniques for ex-situ or insitu conditions: o Ex-situ requires excavated soil to be placed on lined cells after removal of debris. are commercialized technologies utilized in this

35

o In-situ is only applicable for surface soil or soil within reach of tilling equipment. The soil must be screened to remove large debris. By-products of concern are the leachate produced, if cells are not covered on top to prevent exposure to rainfall. This technology is generally not feasible for highly contaminated soils.

XenoremTM This is a patented technology developed by Stauffer Management Company, a subsidiary of AstraZeneca Group PLC of Mississauga, Ontario, Canada. Recently, this technology was sold to the University of Delaware (USEPA 2005). It is an exsitu bioremediation technology utilizing aerobic and anaerobic cycles with enhanced composting (USEPA 2005). The anaerobic conditions promote dechlorination of organochlorine compounds. The duration of the anaerobic phase is determined by bench-scale studies. At the end of the anaerobic phase, the amended soil is mixed again creating aerobic conditions (USEPA 2005; Rubin and Burhan 2006). XenoremTM treats low-strength wastes containing chlordane, dichlorodiphenyltrichloroethane (DDT), dieldrin and toxaphene. Organic amendments such as manure and wood chips are added to the contaminated soil. This can increase the final amended soil volume by as much as 40% (Rubin and Burhan 2006). The metabolic activity is increased due to the presence of high levels of nutrients from the amendment, depleting the oxygen content and creating anaerobic conditions (USEPA 2005; Rubin and Burhan 2006). The anaerobic and aerobic cycles are repeated until the desired contaminant reductions are achieved (USEPA 2005; Rubin and Burhan 2006). The organic amendments are reportedly spent after 14 weeks (USEPA 2005; Rubin and Burhan 2006). This technology was applied in a full-scale cleanup at the Stauffer Management Company Superfund site in Tampa, Florida (Jackson and Gray 2001). o The site is the location of a pesticide manufacturing and distribution facility that operated from 1951 to 1986 (Jackson and Gray 2001). 36

o Soil was contaminated with chlordane, dichlorodiphenyldichloroethane (DDD), dichlorodiphenyldichloroethylene (DDE), DDT, dieldrin, molinate, and toxaphene. o The technology was applied to two batches of soil. o DDD, DDE, DDT and toxaphene were reduced by 65%, 68 %, 88 %, and 94 %, respectively; however, neither batch achieved the site cleanup goals for DDT and toxaphene (USEPA 2005; Rubin and Burhan 2006).

Site Requirements
Space requirements depend on the specific technology employed. In general, insitu applications do not require large areas. Installation of infiltration galleries and wells to circulate amendment-laden water, however, requires from several hundred to several thousand square meters of clear surface area (Mondello 2002; USEPA 2004b; USEPA 2005). During ex situ applications, more open space is typically required to accommodate equipment.

Cost
Cost varies from $55 to $360/m3 (2005 dollars) (USEPA 2005) . Costs at the higher end mainly apply to ex-situ, and mechanical bioremediation. technologies. Vendor-related technologies, such as DARAMEND and XeonremTM, incur high costs if exported.

By-products
Offensive odours from anaerobic degradation. More soluble chlorinated compounds, needing further treatment. Chloride ions.

37

Leachates generated from uncovered systems. Biomass from microorganisms. Minerals and salts from completely degraded compounds.

Advantages and Limitations

Advantages of bioremediation are: Both in-situ and ex-situ bioremediation technologies have been shown to be successful in treating both water-soluble and relatively insoluble compounds. Organic compounds that are highly soluble in water may biodegrade rapidly, particularly in slurry-phase systems. In general, the rate of biodegradation of a given compound is proportional to the solubility of that compound in water. Slurry-phase bioremediation also has the advantage of allowing more precise control of operating conditions (e.g., temperature, mixing regimes) than solid-phase or in situ applications. Slurry-phase systems utilizing tanks can be operated under anaerobic or aerobic conditions, either sequentially in the same tanks, or in series with multiple vessels. Slurry-phase bio-remediation allows improved contaminant monitoring due to increased homogeneity of the contaminated media. Solid-phase bioremediation and composting offer several advantages common to slurry-phase operations and other ex-situ treatment technologies: better process control, increased homogeneity, and improved contaminant monitoring. In addition, treatment units can be built to accommodate large quantities of media. Composting also enriches the treated soil, providing nutrients for revegetation (Petkewich 2001). In situ bioremediation minimizes the need for excavation and transport of contaminated soils, sediments, or sludges. Energy costs required for bioremediation treatment are typically less than for alterative remedial approaches.

38

Limitations include: Many factors affect the success of bioremediation. The physical form, amount, location, and distribution of contaminants have major impacts on the degree to which contaminants are degraded (Downwy et al., 2004). Biodegradable contaminants may undergo mineralization (complete degradation to inorganic constituents); however, incomplete degradation (ending with the formation of organic intermediates) is also possible. Soil characteristics, including particle size distribution, moisture content, and permeability, also affect the success of bioremediation. Soil and contaminant characteristics affect bioavailability (the extent to which contaminants can be degraded by microorganisms). The contaminated soil must not exceed 10 % by volume of the treated soil (Bedard et al. 1996). Bioavailability of contaminants in soil can decrease with time, as the contaminants age and become more strongly sorbed to soil particles. Bioremediation is slower than many other technologies and may require frequent monitoring during startup. Monitoring and sampling will also be necessary to determine when prescribed cleanup levels have been achieved. Temperature, moisture content and pH values below or above the optimal range for the microorganisms retard or halt bioremediation. In some cases, excessive biomass growth may impede further remediation. Bioremediation has not proven to be effective on PCDDs/PCDFs. Breakdown of contaminants may generate more toxic by-products or contaminants which are mobile. Chlorinated compounds used as bioaugmentation, may cause increased contamination by chlorinated compounds at the site. Ex-situ remediation practices require large surface areas to treat large quantities of contaminated soil. This is a disadvantage for heavily populated countries where land is very expensive. Aerobic remediation is not applicable to sites prone to flooding, because water logging leads to anaerobic conditions. 39

In addition to these general limitations, in situ and, to a lesser extent, solid-phase bioremediation present potential difficulties in determining the performance of the treatment. Contaminant spatial heterogeneity, fate and transport, and sorption dynamics all lead to variability in results across the site and over time. Sorption dynamics are particularly important for composting, since contaminants may bind strongly to the added organic matter, reducing bioavailability. Degradation rates, therefore, may be limited by desorption kinetics rather than microbial activity. Especially when recalcitrant contaminants such as PCBs are present. PCBs are often tightly bound to soil particles, resisting enzymes of dechlorination and making it difficult to establish and stimulate PCB organisms in remediation sites (Abraham et al., 2002).

Applicability to Developing Countries

Many bioremediation options are affordable. If contaminated land is expensive, then time-consuming technologies are likely to be infeasible. Countries with extreme weather conditions require more controlled treatment environments since bioremediation technologies are sensitive to moisture content and temperature. Many developing countries are subject to high precipitation and to flooding conditions. In this case, aerobic remediation is only feasible if conducted in protected sites or ex-situ locations. Ex-situ bioremediation involving soil spreading requires large surface areas, especially when large quantities of soil are contaminated. For highly populated countries suffering from lack of free land, ex-situ remediation tends to be very expensive. In-situ bioremediation technology can be promising for areas with relatively moderate climates. Technologies involving farming equipment are feasible, since such equipment is often already present in such areas.

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A-3

Solvent Extraction

Overview
Solvent extraction is an ex-situ process in which contaminants are separated from soils, sludges, and sediments, thereby reducing the volume of waste that must be treated. In the process, the contaminated soil or waste material is brought into contact with a fluid that selectively dissolves the contaminants.

Treatment Process
The primary stages of the solvent extraction technology are media preparation, contaminant extraction, solvent/media separation, contaminant collection, and solvent recycling. Waste preparation includes excavation or moving the waste material to the process where it is normally screened to remove debris and large objects. Depending upon the process vendor and whether the process is semi-batch or continuous, the waste may need to be made mobile (pumpable) by the addition of a solvent or water. In the extractor, the soil or sediment and solvent are contacted with each other, and the organic contaminant dissolves into the solvent. The extraction behaviour exhibited by this technology is usually similar to other mass-transfer-controlled processes, like liquid-liquid extraction, although equilibrium considerations often become limiting factors when the time of contacting is long. It is important to conduct a laboratory-scale treatability test to determine whether mass transfer or equilibrium is likely to be the controlling factor, since the controlling factor is critical to the design of the unit and to the determination of whether solvent extraction technology is appropriate for treatment of the particular waste.

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After a predetermined extraction time, the solid and the fluid are separated, and the target contaminants are concentrated in the extraction fluid. The number and length of the extraction stages are selected based on the remediation criteria, i.e. to achieve the required degree of extraction. The extracted organics are removed from the extractor with the solvent and go to a separator, where the pressure and/or temperature is changed, causing the organic contaminants to separate from the solvent by forming different phases (Rowe 1987). The solvent is then recycled to the extractor, and the concentrated contaminants are removed from the separator (Rowe 1987). Soil properties affect the efficiency of the treatment method. Optimal soil

conditions for treatment include less than 15% clay in the soil and less than 20% moisture in the soil (USEPA 1995b). Higher moisture contents require drying of the soil and /or solvent distillation to reduce accumulation of water in the solvent. Soils containing more than 20% moisture must be dried prior to treatment. Excess water dilutes the solvent, reducing contaminant solubilization and transport efficiency (USEPA 1995b). Water buildup in the stock solvent requires the addition of a distillation step to maintain solvent integrity. Excessive clay concentrations require additional wash cycles and physical handling to reduce clay aggregate size (USEPA 1995b).

Site Requirements
Typical commercial-scale units (50 to 70 tons per day) may require a total treatment area of 930 m2 and a power supply (USEPA 1995b). Water must also be available at the site (USEPA 1995b).

Cost
One time start-up (including capital) cost is estimated at $175,000 for a commercial unit. 42

Average treatment cost range between $125-$400/m3 (in 1995 dollars) (USEPA 1995b)

By-products
There are three main by-product streams generated by this technology: The extract containing concentrated contaminants, after the organic contaminants being separated from the solvent, which requires further treatment. The treated soil or sludge may need to be dewatered before being returned to the site. Water involved in the process. The volume of the water depends on the inherent dewatering capability of the liquid-solid separation process, the specific water requirement for feed slurrying, and the initial water content of the soil or sediment (USEPA 1997).

Performance
Solvent extraction technologies have been selected as the remedial action at several U.S. Superfund sites. This section briefly summarizes pilot and full-scale studies.

Laboratory, Bench and Pilot Scale Studies Treatability pilot studies on different PCB contaminated soils of different soil properties have been conducted, with varying number of wash cycles. The process resulted in a removal efficiency of 95-99%, with better removal as the number of wash cycles increased (USEPA 1995b).

Full Scale Studies Removal efficiency at 4 U.S. Superfund sites contaminated with PCBs was 99% (USEPA 1997). A full scale study of solvent extraction on DDT-contaminated soil resulted in a 98.8% contaminant reduction (USEPA 1995b).

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Advantages and Limitations

The primary advantage of solvent extraction is that it can be capable of efficiently removing many different organic contaminants from a variety of soils, sediments, and sludges. This is partially due to the flexibility of solvent extraction processes. The solvent can be selected based on the target contaminants, whereas the number and duration of the extraction stages are selected based on the remediation criteria. The disadvantages of solvent extraction are: It produces a concentrated organic extract that is likely to require further treatment or disposal unless the contaminants can be used, recycled or incinerated after being extracted from the soil. In addition to the organic contaminants, the concentrated extract may also contain organically-bound metals (which can co-extract with the organic contaminants) and traces of the extraction solvent. Soils with high moisture content need to be dried to achieve high removal rates. High clay content soils experience reduced treatment efficiencies.

Applicability to Developing Countries

Treatment of extracts is needed before disposal. Thus additional treatment methods are needed, increasing the overall cost of the treatment process. Solvent extraction can be used on a wide variety of POPs. Thus different sites can be cleaned using the same treatment facility. Storage and disposal of solvents need special handling, with strict regulations. Appropriate facilities and regulations may not be available. Countries having high precipitation rates are unlikely to benefit from the technology, since high moisture content soils need to be pre-dried before high removal rates can be achieved.

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A-4 Vitrification (PACT, PLASCONTM & GeoMeltTM)

Overview
Vitrification can be used to treat soil and sediment containing organic, inorganic, and radioactive contaminants. This technology uses heat to melt the contaminated soil or sediment. It then forms a rigid, glassy product when it cools, causing a reduction in the volume of the treated soil. Organic contaminants, including PCBs, are destroyed as a result of the high temperatures used during vitrification. The destruction mechanism is either pyrolysis (in an oxygen-poor environment) or oxidation (when oxygen is present) (USEPA 1995). Vitrification can either be performed in situ or ex situ. There are conflicting reports on the whether this technology should be considered under development or well-established (Rahuman et al., 2000; McDowall et al., 2004; USEPA 2005).

Treatment Process
In situ vitrification (ISV) typically uses a square array of four electrodes up to 5 m apart. The electrodes are inserted or gravity fed into the ground to the desired treatment depth. An electric current flows then between the electrodes generating heat, melting first a starter path and then the surrounding soil, which typically melts at 1100 to 1400oC (USEPA 1995). The molten mass continues to grow downward and outward until the melt zone reaches the desired depth and width. The process can typically produce individual melts of up to 1,000 tons, which solidify into vitrified monoliths upon cooling (USEPA 1995). Multiple melts can be combined to remediate an entire site. Off-gas collection systems such as tents or hoods are generally necessary.

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There are a number of ex situ vitrification systems commercially available, distinguished from one another primarily by the heating method employed, such as a plasma arc (Rahuman et al., 2000; McDowall et al., 2004; USEPA 2005). Ex-situ processes typically heat the contaminated media to temperatures between 1000 and 5000oC. In thermal heating, the heat for vitrifying of the contaminated material is generated by the combustion of an external fuel source. In the other heating methods, the heat is generated electrically. Ex-situ vitrification by plasma heating relies on the conversion of a gas such as argon into a plasma using an electrical arc. In microwave heating, the contaminated material is heated by electromagnetic radiation. Various patented and commercial plasma reactors have been developed for the thermal destruction of hazardous waste. For example: PACT (Plasma Arc Centrifugal Treatment) (AEW 1997): o Vitrifies soils by a plasma torch at 1100oC. o Organic components are decomposed vaporized and ionized by the air used as the plasma gas. o Gas emissions are treated by an air pollution control (APC) process. o Destruction and removal efficiency is unknown. o Treated soil is said to be converted to ash, and can be backfilled. o This technology is commercially available. PLASCONTM (In-Flight Plasma Arc System) (AEW 1997): o Soil has to be introduced as a slurry. o The slurry is mixed with argon gas. o Organic chemicals in the waste disassociate into elemental ions and atoms at 3000oC, recombining in the cooler area of the reaction zone. o End products are gases and an aqueous solution of inorganic sodium salts. o This technology is again commercially available.

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GeoMeltTM o Used for in-situ and ex-situ treatments. o In-situ process available as ISV and subsurface planar vitrification (SPVTM) for treating soil at depths >3 m and shallow soils respectively (USEPA 2005). o SPV can be modified to accommodate treatment zones of depths greater than 9 m (USEPA 2005). o Electrodes are inserted in the contaminated zone of the soil with graphite and glass frit to conduct the electricity through the soil. When melting begins the path becomes conductive. o Operating temperature range from 1400 to 2000oC. o The contaminants start to volatilize and are thermally destroyed. o The by-products include CO2, water vapour and HCl gas. o There is usually a gas collection system for the gaseous reaction products. o The ex-situ model of Geomelt, In Container Vitrification (ICVTM), involves heating contaminated material in a refractory-lined container, with a hood cover to collect the off-gases. o Operating temperatures are the same as for the ISV. o The off gas treatment unit has baghouse particulate filter, a NOx scrubber, a hydrosonic scrubber, a mist eliminator and a heater (USEPA 2005).

Site Requirements
There are very few site requirements for offsite ex situ vitrification, since the only onsite activity is excavation. Access to the site must be available for the excavation equipment. For ISV systems, areas must be cleared for heavy equipment requiring access roads, automobile and truck parking lots, the ISV equipment, setup areas, and equipment sheds (AEW 1997). The ISV system also requires electricity, which can be supplied by a utility distribution system or generated onsite by a diesel generator (McDowall et al., 2004).

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Cost
This technology is characterized by very high capital and operating costs. The treatment cost ranges between US$500 and $8000/m3 in 1997 dollars value (AEW 1997; McDowall et al., 2004). This cost includes mobilization, demobilzation, site preparation, operation and maintenance (O/M) and waste disposal.

By-products
By-products from vitrification are mainly: Vitrified soil, which cannot be reused, however, in some cases the treated soil is converted in ash, which can be returned to site (AEW 1997). Scrubber water. Trace of Dioxins can be produced if the emitted organic products are not completely combusted (AEW 1997). HCl, a waste residual from dry and wet scrubbers used in treating off-gas emissions. CO2 NOx

Performance
Both in-situ and ex-situ vitrification technologies have been commercially available and employed in several contaminated sites in the U.S.A, Europe and Australia to treat pesticide and PCB-contaminated soils. Destruction and removal efficiencies for both technologies are said to be 99.999 for all POPs (AEW 1997; Rahuman et al., 2000; McDowall et al., 2004; USEPA 2005).

Advantages and Limitations

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There are two main advantages of vitrification: Very high destruction and removal efficiencies are achieved for all types of POPs. The treated soil can be reused.

Limitations and disadvantages include: High cost. The process can produce trace of dioxins. The process is time-consuming and energy intensive. Requires treatment of gas emissions.

Applicability to Developing Countries

Although this technology achieves high destruction efficiencies, the high capital and operating costs make it unsuitable for less developed countries. The technology also requires high energy, again likely to make it unattractive for many countries.

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A-5 Solidification/Stabilization

Overview
Solidification and stabilization (S/S) are both immobilization technologies, since they remediate soils and other contaminated materials by reducing the mobility of contaminants. In S/S processes, the contaminated materials are combined with various additives that reduce contaminant mobility. Solidification treatment techniques typically produce a solid block of waste material with high structural integrity and low permeability. The contaminants are mechanically encapsulated within the solid matrix, which may also chemically react with certain reagents used in the solidification process such as Portland cement (Yilmaz et al., 2003). Stabilization treatment techniques chemically limit the solubility or mobility of waste contaminants, but may not change the physical characteristics of the waste. Stabilization is often applied to wastes containing a high fraction of non-volatile organics, such as sludges. Solidification and stabilization are often combined, i.e. employed together. The organic compounds are generally encapsulated in the pores of the binding material, and their leachability depends on their solubility in water and their diffusivity through the waste matrix (Paria and Yuet 2006). In S/S processes, immobilization of contaminants, depending on their nature, occurs by one of three main mechanisms: Chemical fixation of contaminants by interactions between the hydration products of cement and the contaminants; Physical adsorption of contaminants on the surface of cement hydration products, or Physical encapsulation of contaminated waste or soil.

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Solidification/stabilization processes can be applied using several different schemes (Paria and Yuet 2006): In-drum processing - In this process, S/S binders are added to the waste contained in a drum or other container. The waste-binder matrix is normally disposed of in the drum after mixing and setting. In-plant processing - A plant and/or process is specifically designed to solidify and stabilize bulk waste materials. The process may be used to manage wastes from an internal industrial operation, or a plant may be specifically built and operated to solidify and stabilize wastes from external sources. Mobile plant (ex situ) processing -In this scheme, the processing equipment, which is either mobile or can be easily transported, is set up on a site, and subsequently moved to other sites. In-situ processing -Binders or solidifying/stabilizing materials are injected directly into a lagoon or soil subsurface to promote the solidification/stabilization of the contaminated sludge or soil.

Treatment Process
The term solidification/stabilization refers to a general category of processes that are used to treat a wide variety of wastes, including solids and liquids. However, solidification and stabilization are actually distinct technologies, as described below (USEPA 2000): Solidification - refers to processes that encapsulate a waste to form a solid material and to restrict contaminant migration by decreasing the surface area exposed to leaching and/or by coating the waste with low-permeability materials. Solidification can be accomplished by a chemical reaction between a waste and binding (solidifying) reagents or by mechanical processes. container of waste is referred to as macroencapsulation. Stabilization - refers to processes that involve chemical reactions that reduce the leachability of a waste. Stabilization chemically immobilizes hazardous materials or 51 Solidification of fine waste particles is referred to as microencapsulation, while solidification of a large block or

reduces their solubility through a chemical reaction. The physical nature of the waste may or may not be changed by this process. There are several types of binder materials used for S/S including inorganic binders, organic binders, and combinations of organic and inorganic binders. Many binders include one or more proprietary additives. Examples of inorganic binders include cement, fly ash, lime, soluble silicates, and sulfur-based binders. Organic binders include asphalt, epoxide, polyesters, polyethylene, granular activated carbon and organophillic clay. Cement, organophillic clay and granular activated carbon are most commonly utilized in many S/S treatment processes. Cement-based S/S treatment of organic contaminants can be classified into three categories: (i) direct immobilization of organic contaminants, (ii) immobilization of organic contaminants after adsorption, and (iii) immobilization of organic contaminants using oxidizing/reducing agents. In direct immobilization of organic contaminants, organic compounds tend to have a detrimental effect on the properties of cementitious materials (Pollard et al., 1991), and they may leach out after the curing process (Sora et al., 2002). Bates et al. (2002) reported the results of S/S treatment of various organic contaminants, including dioxins, pentachlorophenol (PCP), and creosote, using cement formulations containing activated carbon and other proprietary reagents. The results showed that the immobilization was successful in reducing the concentration of organics to a target level in the leachate (Bates et al., 2002). Yilmaz et al. (2003) investigated a Portland cement-based S/S treatment of adsorbable organic halogens (AOX) and polychlorinated biphenyl (PCB) contaminated soil. They found that the S/S process reduced the AOX mobility by 85%. The efficiency did not increase significantly when the cement proportion was increased from 30% to 50% (Yilmaz et al., 2003). The efficiency of S/S treatment of organic contaminants may be improved using adsorbents for the organic components. These adsorbents can be incorporated as 52

additives in the cement mix, or they can be used for pretreatment prior to conventional cement-based solidification. Several potential adsorbent materials have been investigated for organics in solidification/stabilization treatment. These include metal oxides, clays, natural materials (e.g. zeolites), fly ash, organic polymers and activated carbon. Most current research efforts in this area focus on organophilic clays. These are formed by exchanging naturally occurring cations, such as Na+, K+, Ca2+, and Mg2+, in bentonite or montmorillonite clays with organic cations. This results in enhanced adsorption of organic contaminants, including benzene, ethylbenzene, toluene, xylene (BTEX), phenols and chlorinated phenols due to the hydrophobicity of the alkyl chains (Sora et al. 2005). A S/S study on PCB-contaminated soil using an organophilic bentonite clay showed that, for lightly contaminated soils (83 mg PCB/kg), the leachate PCB concentrations were below the detection limit (0.1 g/L), whereas for highly PCBcontaminated soils (5628 mg/kg), the leachate PCB concentrations were as high as 98 g/L (USEPA 1997). (Conditions regarding temperature, time etc. were not specified.)

Cost
Average estimated costs for S/S treatment (including equipment, O/M, permitting, mobilization, demobilization, labour, excavation and utilities) are between $50 and $250/m3(1992 dollars) (USEPA 2000). Costs are highly variable due to variations in site, soil, and contaminant characteristics that affect the performance of the S/S processes.

By-products
Neither ex-situ nor in-situ S/S technologies generate significant quantities of contaminated liquid or solid waste. However, some S/S projects require treatment of the off-gas. Pre-screening collects debris and materials too large for subsequent treatment; this material may also have to be further treated. 53

Performance
S/S is an established technology that has been used for at least 20 years to treat a variety of wastes, for example at Superfund remedial sites throughout the U.S. (USEPA 2000). In fact, S/S has been one of the top five source control treatment technologies used at Superfund remedial sites (USEPA 2000).

Advantages and Limitations

Advantages of the S/S technology are: S/S processes are relatively inexpensive and can be designed to immobilize both organic and inorganic contaminants. The technology can be employed either in situ or ex situ. S/S is a well established (mature) technology.

The limitations are: S/S processes increase the volume of the material being treated (since reagents are added and not consumed). The technology is not appropriate for wastes containing significant quantities of volatile contaminants. If volatile organic compounds (VOCs) are present, they may be released during S/S treatment if they are not captured separately. Formulations developed to reduce the leachability of one contaminant group may not be effective for other contaminants.

Applicability to Developing Countries

S/S is commonly a relatively affordable technology, since the reagents (e.g. concrete) are similar to those used in construction. Thus S/S has widespread potential for many countries.

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By-products are very limited and relatively harmless, thus eliminating the need for more preventative steps for proper disposal.

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A-6 Gas Phase Chemical Reduction

Overview
This process is mainly known by its commercialized product, Eco Logic, developed in Canada. It is an alternative to incineration. Hydrogen reacts with chlorinated organic compounds, such as PCBs, at high temperatures (850C) and low pressure yielding primarily methane and hydrogen chloride accompanied by minor amounts of other low molecular weight (MW) hydrocarbons, such as benzene.

Treatment Process
The process is non-discriminatory; that is organic molecules such as PCBs, PAHs, chlorophenols, dioxins, chlorobenzenes, pesticides, herbicides and insecticides are quantitatively converted to methane. Approximately 40% of the methane produced can be subsequently converted to hydrogen, with the remaining portion is used as a fuel (AEW 1997). Thus, once steady state is achieved, the process can operate without an external supply of hydrogen. For highly concentrated wastes the process produces excess methane (McDowall et al. 2004). Organic liquid waste streams are pumped into the reactor. Recirculating product gas (PG) is used to atomize the liquid waste. The mixture of gases and vaporized liquids are then heated. The reactions come to completion before the gases reach the scrubber where water, heat, acid and carbon dioxide are removed. A caustic scrubbing agent is added, if required, to maintain the scrubber water pH between 6 and 9. The temperature of the exit gas is maintained near 350oC. The dirty scrubber water, after filtration, returns to the scrubber through a drop-tube which extends well below the water surface.

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The gas leaving the scrubber, consists of a clean dry mixture of hydrogen, methane, carbon monoxide and other light hydrocarbons. In order to maintain the required concentration of hydrocarbons in the reactor, some of the gas may be recirculated to a catalytic steam reformer to convert methane (CH4), carbon monoxide (CO), and steam to hydrogen (H2) and carbon dioxide (CO2). Side-streams may also go to a Thermal Reduction Mill (TRM) and Sequencing Batch Vaporiser (SBV) as a sweep gas (USEPA 2005). Excess gas is directed to the compressor and product gas stage tank, where the gas is stored temporarily and analyzed on a continuous basis. The compressed product gas may then be used to fuel the boiler, steam reformer, SBV or TRM (USEPA 2005). Solid wastes such as soil or decanted sediment may be decontaminated using a thermal reduction mill (TRM) with the vaporized contaminants directed to the reactor. The TRM is proprietary technology. It is designed to heat solids gradually while mechanically dispersing them into a fine mixture (USEPA 2005). The efficiency of the thermal desorption unit (SBV or TRM) and its ability to completely desorb organic contaminants in the desorption time available can be expected to be important in controlling the efficiency of waste treatment. This in turn can be expected to depend on both physical processes (heat, residence time, desegregation, and mixing) as well as the chemical reaction process.

Site Requirements
According to Eco Logic, the supplying vendor, the system requires a relatively level area, and approximately 40 m x 50 m, for the processing and auxiliary equipment, for a capacity of 150 tons of contaminated soil per month (USEPA 1994a) Utility tanks require level surfaces or supports. The reactor system equipment sits on two mobile trailers; a separate trailer transports the TDU, solid feed hopper, and quench system (USEPA 1994a).

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Cold-weather operations may inhibit efficient destruction because of the incremental amount of energy required to heat the reactor and the TDU molten metal bath. In addition, feedstock liquids may require melting prior to treatment; liquid residuals could freeze in unheated storage tanks (USEPA 1994a).

Cost
The cost is reported to be $500-$630/m3 (USEPA 1994a). The treatment capacity corresponding to this cost range was not specified.

By-products
It is expected that the system will produce: HCl Light hydrocarbons including benzene (which can be reused as a fuel source or flared.) Dioxins (It is not specified what happens to these.)

Performance
Lab, Bench and Pilot Scale Performance The gas phase reduction technology developed by Eco Logic International has been successfully demonstrated on a pilot plant scale in both Canada and the USA, processing oils containing PCBs and PCB/dioxin-contaminated soil. The test work demonstrated the capability of the technology to process soils contaminated with PCBs, hexachlorobenzene (HCB) and dioxins, achieving 99.999% destruction efficiency (EPA, 1993).

Field Scale Projects In Australia, a gas phase reduction plant processing PCB-containing material 58

achieved 99.999% destruction efficiencies (AEW 1997). In commercial-scale performance tests in Canada, the gas-phase reduction process achieved destruction and removal efficiencies (DREs) for high-strength PCB-containing oils and chlorobenzenes (USEPA 2005). Dioxins present as contaminants in the PCBcontaining oil were destroyed with efficiencies ranging from 99.999 to 99.9999% (USEPA 2005).

Advantages and Limitations

Advantages include: Since this is a hydrogenation process, adding hydrogen atoms to any incompletely hydrogenated organic molecule, dechlorinates the molecules and breaks down aromatic rings. The method is therefore indiscriminate in its treatment of organic substances. For this reason, it can be expected to treat pentachlorophenol (PCPs) with similar effectiveness to PCBs, hexachlorobenzene (HCB) and dioxins, and it can also be extended to other non-halogenated compounds such as PAHs. The process requires water in its operation and therefore can process wastes with a relatively high water content. This may prove to be an advantage over other thermally based processes where high water content is problematic. Under a reducing atmosphere the formation of dioxins is less likely to occur.

This process has several limitations: The process has to be preceded by a thermal desorption unit when treating solid wastes. The thermal desorber will operate under a reducing hydrogen atmosphere, offering simultaneous destruction. Application of the thermal desorption unit to irregular solids such as concrete (containing reinforcing materials) is uncertain; however, the sequencing batch vaporizer has been used to treat concrete slabs. Material handling considerations for such wastes may limit the application of the process.

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Applicability to Developing Countries

This technology can be challenging due to extra treatment processes for the gas emissions and the thermal desorption unit required for contaminated soils. Countries with high population densities will find this technology expensive given the space requirements needed to accommodate the treatment facility. Strict regulations must be at hand for the storage of sodium hydroxide or other chemicals needed for the caustic scrubber.

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A-7 Alkali Metal Reduction (Sodium Reduction)

Overview
Alkali metal reduction treatment processes use metallic alkali, such as sodium, to react with chlorine in the halogenated non-aqueous waste to produce salt and nonhalogenated waste. This process is an ex-situ technology and is only used to treat contaminated oils, with no mention of it being utilized to remediate contaminated soils.

Process
Process operates (Vijgen and McDowall 2004): o At atmospheric pressure (sometimes up to 4 atmospheres). o At temperatures between 90 and 165oC. o Oil generated from the process by dielectric generation is reused as transformer fluid. Thus higher temperatures are not possible as higher temperatures would prevent the oil from being preserved and recovered. The most commonly used reducing agent is metallic sodium. However, other agents such as potassium have also been used. Prior to treatment, the oil must be dewatered to prevent explosive reactions with the metallic reducing agent.

Site Requirements
The site must have: o A power supply. o Fuel storage area for oil heating. o A water supply. The building must be weather-tight to prevent water from contacting the reagents. 61

Cost
The cost for transformer oil with low PCB concentration is estimated to be $0.15/L, rising to $0.70/kg for oil with higher PCB concentrations or more impurities (Vijgen and McDowall 2004).

By-products
Salt solution containing some oil and biphenyl polymer. High pH due to the presence of NaCl or NaOH. Air emissions include nitrogen and hydrogen gas. Emissions of organic compounds are expected to be relatively minor. PCDDs can be formed from chlorophenols under alkaline conditions at temperatures as low as 150C (Weber 2007).

Performance
The treatment technology has been applied commercially in several countries since 1995, including Canada, USA, Japan, France and England (Vijgen and McDowall 2004). Vijgen and McDowall (2004) have reported destruction efficiencies as high as 99.999% from several treatment projects, in the countries mentioned above.

Advantages and Limitations

The advantages of alkali metal reduction include: Oil produced by the process can be reused.

The limitations of this technology are: The alkali metals need special handling, as well as strict segregation from moisture.

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There is a risk of producing dioxins from chlorophenols under alkaline conditions at temperatures as low as 150C (Weber 2007). By-products need special handling due to their high values of pH. The contaminated oil needs to be stripped of any water content, thus using more energy.

Applicability to Developing Countries

Special buildings are needed to provide water tight conditions, increasing the cost of treatment. The use of power and fuel is a limitation in developing countries, since these resources are expensive. Special storage, disposal and treatment measures must be implemented for the reagents and by-products.

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A-8 Pyrolysis and Gasification

Overview
In this ex-situ process, organic contaminants are decomposed chemically by heat in an oxygen-starved environment. In practice, it is not possible to achieve a completely oxygen-free atmosphere; actual pyrolytic systems are operated with less than stoichiometric quantities of oxygen. The pyrolysis process degrades waste to produce char (or ash), pyrolysis oil and synthetic gas (called syngas). The gasification process then breaks down the hydrocarbons left into a syngas using a controlled amount of oxygen (FOE 2002). Because some oxygen is present in any pyrolytic system, nominal oxidation will occur. If volatile or semi-volatile materials are present in the waste, thermal desorption also occurs. Pyrolysis is capable of destroying dioxins by decomposition and volatilization (Hu et al., 2007). The compounds are transformed into gaseous components and a solid residue (coke) containing fixed carbon and ash. Dioxins are known to evaporate over a temperature range of 315C to 537C. Addink and Olie (1995) have shown that oxygen plays a crucial role in the reactions of PCDD/Fs during thermal oxidation. Therefore, in addition to removal, pyrolysis may also prevent further dioxin formation, particularly of PCDDs and PCDFs in the residual material, due to the reducing atmosphere (Ferreira et al., 2003; Hu et al., 2007). However, Weber (2007) argued that the formation of PCDDs/PCDFs does not require the presence of oxygen. Gasification involves using a sub-stoiciometric (typically 20-40% of

stoichiometric) amount of oxygen, whereas pyrolysis uses none. Both produce a synthetic gas (often called a syngas) made up mainly of carbon monoxide and hydrogen (85 per cent), with smaller amounts of carbon dioxide and methane. This gas has a calorific value, so it can be used as a fuel to generate electricity or steam, or used as a basic 64

chemical in the petrochemical and refining industries. Other by-products include liquids (mainly water but may also include some tars) and solid residues ash, or char.

Treatment Process
Most gasification and pyrolysis processes have four stages (FOE 2002): Pre-treating the waste, which usually involves sterilizing it and separating out some of the recyclables, especially glass, grit and metal (which have no calorific value). Heating the remaining waste, mainly organic pulp, to produce gas, oils and char (ash). Scrubbing the gas to remove some of the particulates, hydrocarbons and soluble matter. Using the scrubbed gas to generate electricity and, in some cases, heat (through combined heat and power CHP). Pyrolysis transforms hazardous organic materials into gaseous components, small quantities of liquid, and a solid residue (coke) containing fixed carbon and ash. Conventional thermal treatment methods, such as rotary kilns, rotary hearth furnaces, and fluidized bed reactors, are used for waste Pyrolysis (Deuren et al., 2002). Kilns and furnaces are similar to those used in incineration, but they operate at lower temperatures and with less air (Deuren et al., 2002). Molten salt process may also be used for waste pyrolysis. A more advanced method delivering higher temperature environments (3000 5000oC) is the Plasma torch method, commercially known as STARTECH, another form of Pyrolysis (McDowall et al., 2004). These processes are described below: Rotary Kiln: The rotary kiln is a refractory-lined, slightly-inclined, rotating cylinder that serves as a heating chamber (Deuren et al., 2002). Material is fed at the higher end of an inclined by cylindrical chamber, which rotates around its axis. It is then lifted by flights in the long cylinder and gradually travels to the lower end where it leaves the furnace.

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Fluidized Bed Furnace:

Fluidized bed pyrolysers can either be bubbling beds

(relatively low superficial gas velocity), or circulating fluidized beds. The circulating fluidized bed uses high-velocity air to circulate and suspend the waste particles in a heating loop and operates at temperatures up to 430 C (Deuren et al., 2002) or higher. Molten Salt Destruction (Deuren et al., 2002) : In molten-salt destruction, a molten salt incinerator uses a molten, turbulent bed of salt, such as sodium carbonate, as a heat transfer and reaction/scrubbing medium to destroy hazardous materials. Shredded solid waste is injected with air under the surface of the molten salt. Hot gases composed primarily of carbon dioxide, stream, and unreacted air components rise through the molten salt bath, pass through a secondary reaction zone, and through an off-gas cleanup system, before being discharged to the atmosphere. Other pyrolysis by-products react with the alkaline molten salt to form inorganic products that are retained in the melt. Spent molten salt containing ash is tapped from the reactor, cooled and placed in a landfill. STARTECH (Plasma-electric waste converter) (AEW 1997; McDowall et al., 2004): o This is a patented commercialized technology developed in the US by the Startech Environmental Corporation. o Gas is ionized into a plasma at 3000 - 5000oC forming free radicals. o Soil introduced with the plasma heats extremely rapidly, causing the organic contaminants to dissociate into their elemental atomic components. They then recombine, mostly into CO, H2O, CH4 and H2. o Molten solids are removed from the bottom of the chamber and can also be reinjected.

Site Requirements
Little information is reported on site requirements. However, since pyrolysis has many similarities to incineration, site requirements are similar.

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Cost
Pyrolysis technology is reported to cost between $375 and $500/m3, with no information on what is included in this cost (AEW 1997; Deuren et al., 2002).

By-products
Pyrolysis of organic materials produces combustible gases, including carbon monoxide, hydrogen and methane, and other hydrocarbons (Deuren et al., 2002; McDowall et al., 2004). Cooled off-gases form liquids which include an oil/tar residue and contaminated water (Deuren et al., 2002; McDowall et al., 2004). The pyrolysis gases require further treatment. Because of this extreme temperatures and unpredictability of free radical reactions, plasma reactors may form traces of a very wide variety of organic by-products, including some that are hazardous. The off-gases may be treated in a secondary combustion chamber, flared, and partially condensed (Deuren et al., 2002; McDowall et al., 2004).

Performance
According to AEW (1997), this technology has been commercially available in USA and Canada. PCB and dioxins contaminated soils from different sites in the USA have been treated using Pyrolysis, with reported destruction and removal efficiencies of 99.999% (Deuren et al., 2002).

Advantages and Limitations

The advantages of this system include:

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Applicability to a wide range of organic contaminants achieving high destruction and removal efficiencies. Some technologies such as STARTECH do not require prescreening of soil. Wastes may be converted into recoverable commodities by-products (McDowall et al., 2004). Pyrolysis uses less O2 and thus air emissions tend to be lower than for incineration (FOE 2002)

Limitations and disadvantages include: Some Pyrolysis technologies such as rotary kiln, fluidized bed, and molten salt require specific limits of particulate feed size and material handling (Deuren et al., 2002). These technologies may require pre-drying of soil to achieve low moisture content and to decrease treatment costs. Highly abrasive feed can potentially damage the treatment units due to wear caused by the moving particles (Deuren et al., 2002). There is potential production of dioxins, furans and other hazardous compounds, especially in units that operate at very high temperature (Weber 2007). Treated media containing heavy metals require stabilization (Deuren et al., 2002). Energy costs, especially for plasma reactors, are substantial.

Applicability to Developing Countries

Transportation of contaminated soil to treatment facilities must be under strict regulations, and must include minimizing risk of human exposure. This can be challenging in countries where road accessibility is limited and population density is high. The system requires addition treatment units to treat off-gases, and thus cost will increase.

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In countries where flooding and high precipitation is an issue, the need to dry the soil increases treatment costs. Interruptions in electrical power can cause severe operational problems. The capability of pyrolysis to treat a wide range of organic contaminants tends to be offset by the complexity of the equipment and high energy costs.

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A-9 Ball Milling/ Mechano-Chemical Dehalogenation (MCD

TM

Overview
Ball milling technology, commercially known as MCDTM, treats high-strength waste containing POPs, using mechanical energy to promote reductive dehalogenation of the contaminants (USEPA 2005). The MCDTM process was developed by Environmental Decontamination Ltd. Little information is available on its use in full scale projects. However, it has been reported that it has been utilized in New Zealand (USEPA 2005).

Treatment Process
MCDTM uses mechanical energy to initiate chemical reactions. High energy input is needed, necessitating the use vibratory or planetary balls mills where mechanochemical reactions occur through a number of mechanisms (Deuren et al., 2002). Intense mixing occurs in a ball mill, where the reactants are brought into intimate contact with each other (Deuren et al., 2002). At the point of contact between two grinding balls during a collision event, a highly localized triboplasma is formed providing energy for chemical reactions to occur locally (Deuren et al., 2002). The grinding reduces the particle size and exposing new surface area for reaction (Deuren et al., 2002). New reactive surfaces are exposed during particle fracture, and the introduction of dislocations increases the surface reactivity. Milling also tends to create free radicals, which can then go on to react with neighbouring compounds (Deuren et al., 2002). In the early 1990s, researchers at the University of Western Australia (UWA) discovered that DDT could be destroyed by milling with calcium oxide (AEW 1997). Most of the chlorine reacts with calcium to form calcium chloride and the carbon forms a black graphitic residue containing the remainder of the chlorine. While the destruction of DDT and other organic chemicals by milling with calcium oxide was successful, long 70

milling times were required, making the process uneconomical on an industrial scale. As a result, the focus of UWA shifted elsewhere. To get the CaO, it must need a calciner (CaCO3 CaO + CO2). CaO is highly hygroscopic (CaO + H2O Ca(OH)2), picking up water rapidly from the atmosphere. Hence the calciner would need to be on site or next door. Prior to treatment contaminated soils are dried using a temperature-controlled, rotary drum unit, as well as undergo size reduction (USEPA 2005). Soil is also screened, and only particles less than 2 mm in size are fed forward to the process (USEPA 2005).

Site Requirements
No information has been published. Electrical power or diesel units are needed to run the mechanical units.

Cost
Unknown due to limited reporting on this technology.

By-products
According to Dueren et al. (2002), by-products likely include graphite, calcium chloride, as well as CaCO3.

Performance
Although this technology is reported to be a full-scale treatment method, only one project documented as proof-of-performance is available (USEPA 2005). This project included the treatment of soils contaminated with DDT, aldrin, dieldrin and lindane, in

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New Zealand using MCDTM, where the percent reductions for these contaminants were reported to be 91%, 89%, 70%, and 88%, respectively (USEPA 2005).

Advantages and Limitations

A number of potential advantages were claimed by AEW (1997): Reduced release of contaminants due to low energy. The process can be readily shutdown in a short period of time, further reducing the potential for release in case of an emergency or power failure. Low temperature operation increases safety, reducing energy consumption and reducing the potential for formation of dioxins and other toxic organics. Well-established mineral processing equipment and principles are used. The high degree of mixing of wastes tends to break up agglomerated material. No gaseous emissions are produced. The process is likely to readily treat wastes containing a range of organic contaminants, or mixtures of organic contaminants in one step, reducing waste handling and associated risks. Although limitations have not reported explicitly, this technology clearly has several significant disadvantages: Soil needs to be dried to reach a moisture content of 2% at most. Prescreening may be needed to meet the size limitations. Although limited information is present on performance, the destruction efficiency is relatively lower than for other treatment technologies, indicating that the method is unsuitable for highly contaminated soils. The milling inevitably causes generation of fine particulates, a potential source of dust. The balls used in the milling will also undergo wear, further adding to the dust. The equipment is extremely noisy.

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Applicability to Developing Countries

Affordability in developing countries cannot be determined due to lack of information on the cost of this treatment. Developing countries with a well established mineral processing industry may make use of this process as an add-on for wastes of limited toxicity. The relatively low energy requirement is advantageous to developing countries. Countries with flooding and high precipitation will incur more cost for drying the contaminated soil prior to treatment.

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A-10 Thermal Desorption

Overview
Thermal desorption is primarily an ex-situ treatment technology that uses direct or indirect heat. Most thermal treatment technologies involve a two-step process. In step 1, heat is applied to a contaminated soil or sediment to vaporize the contaminants into a gas stream. In step 2, the gas stream from Step 1 is collected, condensed or destroyed. Several gas treatment technologies may be used to meet regulatory requirements prior to discharge such as particulate removal systems, air pollution control systems (APCs) and scrubbers. Thermal desorption is capable of treating various materials, including soil, sediment and sludge, contaminated with a wide range of organic contaminants. Semivolatile organic compounds (SVOCs), pesticides, and other compounds with boiling points up to about 300C are typically processed through direct- or indirect-contact thermal desorption units. Contaminants with boiling points above 300C, such as PCBs, dioxins, and furans, may be treatable with higher-temperature systems (Depercin 1995). It is cost-effective to implement thermal desorption on wastes containing up to 10 percent organics and a minimum of 20 percent solids (USEPA 1991b).

Treatment Process
The primary stages of a thermal desorption system are: materials handling, desorption, particulate removal, and off-gas treatment. Materials handling requires excavation of the contaminated soil or sediment. Large contaminated media or sizable boulders may not be directly treatable, due to possible nonuniform or inadequate heat transfer or potential jamming of feed systems and material conveyors. Instead, pretreatment screening and/or size reduction would be required. For many types of 74

thermal desorption systems, the approximate maximum particle feed size is about 50 mm, because larger particles may not allow the core to be heated sufficiently to volatilize the organic contaminants (USEPA 1991b). As the contaminants are desorbed, they volatilize and are transferred to the gas stream. An inert gas, such as nitrogen, may be injected as a sweep stream to prevent contaminant combustion and to aid in volatilizing and removing the contaminants (Depercin 1995). Other systems simply direct the hot gas stream from the desorption unit to the off-gas treatment system (Depercin 1995). Off-gas from desorption is typically processed to remove particulates that remain in the gas-contaminated stream after the desorption step. Organics in the off-gas may be treated onsite, collected on activated carbon, or recovered in condensation equipment. The selection of the gas treatment system will depend on the concentrations and types of contaminants, air emission standards, and the economics of the off-gas treatment system(s) employed. Methods most commonly used to remove the particulates from the gas stream are cyclones, wet scrubbers, and bag-houses. There are different thermal desorption systems differentiated from each other by the methods used to transfer heat to the contaminated materials, and by the gas treatment system for treating the off-gases. Heat may be directly applied by radiation from a combustion flame and/or by convection from direct contact with the combustion gases. Systems employing this type of heat transfer are referred to as direct-contact or directfired thermal desorption systems. Heat may also be applied indirectly by transferring the heat from the source (e.g., combustion or hot oil) through a physical barrier that separates the heat source from the contaminated materials, such as a steel wall. Systems employing this type of heat transfer are referred to as indirect-contact or indirect-fired thermal desorption systems (USEPA 1991b). Thermal desorption systems can be further divided into two broad categories: continuous-feed and batch systems. Continuous-feed systems are ex-situ processes, meaning that the contaminated material must be excavated from its original location, 75

followed by some degree of material handling, and then fed continuously to the treatment unit. Continuous-feed thermal desorption systems can use direct-contact (direct-fired) equipment or indirect-contact (indirect-fired) equipment, as described above. Direct-contact thermal desorptionrotary dryer. Indirect-contact thermal desorptionrotary dryer and thermal screw conveyor. Batch systems can be either ex-situ or in-situ, the latter meaning that the material is treated in place, without the need for, and expense of, excavating or dredging it before treatment. As with all thermal desorption systems, the off-gases from in-situ systems must be treated prior to discharge to the atmosphere. The following are representative types of batch thermal desorption technologies: Ex-situ: heated oven and hot-air vapor extraction (HAVE). In-situ: thermal blanket, thermal well, enhanced soil vapour extraction. Direct-contact thermal desorption systems are intended to treat of high-boilingpoint, chlorinated contaminants and pesticides. Materials are usually heated to between 260C and 650C in a rotary dryer, and the off-gas is subsequently oxidized in an afterburner at temperatures in the range of 760C to 980C, sometimes as high as 1100C. The off-gas is then cooled, or quenched, and passed through the bag-house as in a second-generation system. At the end of the treatment train, however, acid gas neutralization is included to control emissions of hydrochloric acid (HCl) to the atmosphere. A wet gas scrubber utilizing caustic-enriched water sprays is the most common acid gas control system. The addition of a wet scrubber adds a significant degree of complexity to the thermal desorption system and the project because it involves water make-up, wastewater discharge flows, and monitoring and control of water chemistry. In addition to neutralizing the acid gas, the wet scrubber provides some degree of particulate collection. The collected particulates become sludge in the wastewater treatment system and must be removed and managed prior to discharge. The following are representative types of continuous-feed thermal desorption technologies:

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In Batch Systems - Heated Oven, the heated oven thermal desorption system is a batch-type, ex situ design. It was improved upon by the technology owner, TerraChem (NFESC 1998). The desorption chamber is an oven where a small quantity of contaminated material, typically 4 to 15 m3, is heated for a given period of time, generally 1 to 4 hours under vacuum (NFESC 1998). The number of chambers can be optimized to fit the project in terms of the total quantity of material to be treated, the timeframe to complete the project, the actual time required per batch for the particular material and contaminant, the physical space available, and other variables. Normally, four or more chambers are utilized (NFESC 1998). The technology licensor has sought to adapt the system equipment to higher boiling-point contaminants, such as PCBs, by modifying the design to maintain higher levels of vacuum. In doing so, the boiling point temperature of the contaminated media is effectively reduced, because the operating pressure is maintained significantly below atmospheric pressure (NFESC 1998). Although most thermal desorption methods are ex-situ, there are selective in-situ treatment technologies, such as thermal blanket/well system and enhanced soil vapour extraction (ESVE). The thermal blanket and thermal well types of thermal desorption technology are in situ thermal treatment technologies. They are proprietary technologies of Terratherm Environmental Services, an affiliate of Shell Oil Company (NFESC 1998). They represent one of the few in-situ forms of thermal desorption technology that has been demonstrated to work effectively on a commercial scale. The thermal blanket system utilizes modularized electric heating blankets about 2.5 x 6.0 m, placed on top of the contaminated ground surface (NFESC 1998). The blankets can be heated to 1000C and, by thermal conduction from direct contact with the contaminated material. They are able to vaporize most contaminants down to a depth of about 0.9 m (NFESC 1998). The blanket module is covered with an impermeable membrane having a vacuum-exhaust port. Several modules can be treated simultaneously by connecting the exhaust ports to a common manifold leading to an induced-draft 77

blower. As the contaminants are volatized from the materials, they are drawn out of the material by the vacuum caused by the induced-draft blower. Once the contaminants are in the vapour stream, they are oxidized at high temperature in a thermal oxidizer near the treatment area (NFESC 1998). The gas stream is then cooled to protect the downstream induced-draft blower and passed through an activated carbon bed to collect any trace levels of organics not oxidized prior to release to the atmosphere (NFESC 1998). The thermal well system involves an arrangement of electrical immersion heating elements placed deep in the ground about 2 to 3 m apart (NFESC 1998). The wells are intended to remediate contaminated material from about 0.9 m below grade to at least the water-table elevation, if necessary (NFESC 1998). The heating element temperatures are raised to more than 1000C, thereby, heating the surrounding material (NFESC 1998). Similar to the thermal blanket system, heat transfer for the thermal well system is via conduction only. The wells are installed with an outer perforated sleeve or screen. The top outlets of all of the wells in a particular application are connected to a common manifold. As for the blanket modules, the manifold is exposed to a vacuum so that as the contaminants are desorbed from the material, they are evacuated through the well sleeve/manifold network and destroyed. ESVE or in-situ thermal desorption (ISTD) utilizes a series of wells installed in the contaminated areas. One series of wells injects hot air or steam into the ground to heat the materials and contaminants. The other wells are subjected to a vacuum to extract the volatized contaminants from the materials. The gases drawn from the wells can be treated in the same manner as for other thermal desorption technologies, i.e. via condensation, collection on activated carbon, or combustion. ISTD can heat soil or sediment in situ to average temperatures of ~500C. As a result, it has been used to treat compounds with relatively high boiling points, including semi-volatile organic contaminants (SVOCs) such as PCBs, PAHs, pesticides and herbicides (USEPA 2004a). Pilot- and full-scale applications have been reported where ISTD was used to remove 78

PCBs, with dioxins and furans as trace contaminants. Laboratory-scale work and extrapolation have suggested that ISTD may be applicable also to POPs other than PCBs, dioxins, and furans (including aldrin, dieldrin, endrin, chlordane, heptachlor, DDT, mirex, hexachlorobenzene, and toxaphene). However, these contaminants have not apparently been treated using ISTD on a full- or pilot-scale basis (USEPA 2004a). ISTD has been used to treat contaminants in most hydrogeologic settings, including beneath structures. Three basic factors control the effectiveness of enhanced SVE: (1) The physical and chemical properties of the contaminants to be removed; (2) The in-place air permeability of the materials to be treated; and (3) The homogeneity of the materials. Because this technology is well established and documented in various reports and design documents, it will not be addressed in any further detail.

Site Requirements
The system requires at least a 50 m by 50 m space for installation. Components such as the desorber, particulate control and gas treatment units are usually transported on modified flat-bed semi-trailers (NFESC 1998).

Cost
Costs for onsite thermal treatment vary widely depending on conditions specific to the site. Unit costs at some recent cleanups have ranged from $350 to $450/m3 for exsitu systems and from $350 to $700/m3 for in-situ systems (1990 dollar value) (USEPA 1991b; Depercin 1995).

By-products
Operation of thermal desorption systems may lead to the generated of treated medium, oversized medium and debris rejects, condensed contaminants, process water, 79

particulate control system dust, clean off-gas, spent carbon, and aqueous-phase activated carbon. Treated medium, debris, and oversized rejects may be suitable for replacement onsite, or may require offsite disposal. The vaporized organic contaminants can be captured by condensation or passing the off-gas through a carbon adsorption bed or other treatment system. Condensed contaminants must then be destroyed by another technology. Organic compounds may also be destroyed by an off-gas combustion chamber or catalytic oxidation unit integrated into the thermal desorption system. When an off-gas is condensed, the resulting water stream may contain significant contamination, depending on the boiling points and solubilities of the contaminants, and may also require treatment (such as activated carbon adsorption). If the condensed water is relatively clean, it may be used to suppress the dust from the treated medium. If carbon adsorption is used to remove contaminants from the off-gas or condensed water, spent carbon is generated. Off-gas from a thermal desorption unit contains entrained particulates from the medium, vapourized organic contaminants, and water vapour. Particulates are removed by conventional equipment such as cyclones, fabric filters, and wet scrubbers.

Performance
Treatment efficiencies of TCE and PCE contaminated soils were 93-99.98% at temperatures near 250C (Brusseau et al., 2001). Thermal desorption of PCBs required much higher temperatures, approximately 450C. The remediation standards adopted for this work were 400 ppb for TCE and 1000 ppb for PCE (Brusseau et al., 2001). Offgases are thermally treated at about 1000C to ensure that dioxins and furans are not discharged.

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In 1998 silt clay at a naval facility in Ferndale California was contaminated with PCB at 0.15 to 860 mg/kg, and PCDD/Fs at 3.2 mg/kg. ISTD yielded 99.99% removal efficiency from this clay (USEPA 2004a). In June 1991, an EPA SITE demonstration was performed at the Outboard Marine Corporation Superfund site in Waukegan Harbour, Illinois. This site was primarily contaminated with PCBs, together with VOCs, SVOCs and metals. The technology vendors system used a combination of thermal desorption and chemical dehalogenation. Approximately 253 tons of contaminated soil were treated. The average PCB concentration in the feed soil was 9,173 mg/kg compared with the average final concentration of 2 mg/kg, corresponding to a 99.98 percent removal efficiency. The concentration of PCBs in the stack gas was reduced by 99.9999%. The pH of the soil rose from 8.59 in the contaminated soil to 11.35 as a result of the treatment, likely due to the addition of sodium bicarbonate to reduce PCB emissions (USEPA 1997).

Advantages and Limitations

The advantages of thermal desorption (TD) are: Separating the organic contaminant from the medium to an off-gas stream where the vapours are treated directly or condensed before treatment. Thermal desorption has the added advantage of separating SVOCs The total volume of material requiring subsequent treatment is typically small in comparison to the volume of the contaminated medium at any given site. TD may be viewed as a step in a sequence of remediation steps where isolating and concentrating the contaminants are useful. Groups of organic contaminants can be selectively removed from the medium by careful control of the treatment temperature.

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Limitations include: Most thermal desorption systems require excavation and transport of the contaminated medium, use of materials handling/segregation equipment, and feeding of the material into the desorption unit. The contaminated medium must contain at least 20 percent solids to facilitate placement of the waste material into the desorption equipment. Materials handling of soils that are tightly aggregated or largely clay can result in poor processing performance due to caking. A very high moisture content may result in low contaminant volatilization, a need to recycle the soil through the desorber, or a need to dewater the material prior to treatment to reduce the energy required to volatilize the water. Since TD does not destroy contaminants, subsequent treatment of residuals is required. TD units have the potential to produce PCDDs/PCDFs when treating chlorinated compounds. Careful monitoring of operating conditions and feed rates must be performed. Treated material may need to be tested for PCDDs/PCDFs, even if those compounds were not detected in the feed.

Applicability to Developing Countries

Countries suffering from high precipitation rates will incur high cost in treating the wet soil to attain the optimum moisture content. Excavation and transportation of soil to thermal desorption increase the risk of air pollution by POP-contaminated particulate matter, if transportation is not under strict containment regulations. For ESVE, developing countries will have to issue a contract to the firm owning the patent for the technology. This could lead to high costs.

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A-11 Supercritical Extraction (SCE)

Overview
SCE is based on the supercritical fluid (SCF) extraction of organic compounds from different solid matrices for analytical purposes. Early efforts focused on extracting harmful organic chemical from spiked soils/sediments using supercritical carbon dioxide (SCCD) were followed by later tests on contaminated soils and sediments from different sites (Reutergardh et al., 1998). SCE has been under study in pilot scale studies, but it has apparently not yet been commercialized. The SCF is chosen such that it has a higher affinity for contaminants than for the bulk material of the solid matrix. Most SCE processes use SCCD (critical temperature 31oC; critical pressure 74 bar) individually or mixed with co-solvents (entrainers; modifiers) the most common being methanol (critical temperature 239oC; critical pressure 81 bar) (Anitescu and Tavlarides 2006). SCE uses the SCF properties (i.e. liquid-like density, low viscosity, high diffusivity, and no surface tension) to extract contaminants at optimum temperature, pressure, and flow rate conditions (Anitescu and Tavlarides 2006). Rather than destroying in-situ pollutants at relatively low concentrations with significant energy and/or for materials to be absorbed by the bulk matrix, the SCE process is the first step of a two-step or multi-step remedial technology. SCE does not destroy either contaminants or the soil/sediment. Instead, the extracted pollutants are highly concentrated and subsequently destroyed more cost effectively. All SCE processes for remediation purposes employ similar unit operations including feed preparation, extraction, separation of solids and solvent, and recovery of the solvent. The following is a brief description of the treatment process and the factors affecting extraction.

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Treatment Process
Pre-treatment A pre-treatment step is frequently required for SCE systems. It consists of soil/sediment preparation for an optimal SCE process. Rocks, roots, and other debris are removed and the water content adjusted appropriately. Other characteristics of the soils/sediments may also be adjusted (e.g. pH, chemical composition).

Treatment Environmental SCE removes the organics from contaminated solids followed by solutesolvent separation and solvent recycle (Tavlarides et al., 2000). In the SCE step, excavated solids are placed in a pressure vessel and extracted with a recirculated stream of SCFs, which are intimately mixed with the contaminated matrix to allow contaminants to transfer to the solvent (Tavlarides et al., 2000). The clean matrix, the solvent, and the solute(s) are then separated by physical methods. Following extraction and separation, organic contaminants are subjected to a suitable destruction technology while the clean solvent is recycled to the extraction stage (Tavlarides et al., 2000). The soils/sediments are not significantly affected by a SCE process and can be returned to the natural site (Tavlarides et al., 2000; Anitescu and Tavlarides 2006).

Post-treatment SCE is not a stand-alone technology (Zhou, 2004). The concentrated contaminants and any separated co-solvent and water are typically subjected to further specific treatment and disposal techniques, as appropriate, to complete the cleanup (Zhou, 2004). Side streams generated during treatment, such as spent solvent/co-solvent, spent activated carbon, air emissions, etc., must also be treated. However, SCE systems are contained and designed to operate without air emissions (Zhou, 2004).

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Factors Affecting Extraction Efficiency The effects on PCB desorption efficiencies of pressure, temperature, co-solvent, soil moisture content, and initial concentration have been investigated. Thermodynamic conditions of temperature and pressure (SCF density) are the main factors affecting the success of the SCE process (Tavlarides et al., 2000; Anitescu and Tavlarides 2006). Temperature affects SCE recovery by changing both the thermodynamic and kinetics of the process. Increasing the temperature also decreases the fluid density and hence, the solute recovery on the one hand, and increases solute solubility through its vapour pressure, on the other hand. In one example, screening studies of PCB desorption from soils/sediments were conducted in a laboratory scale SCE apparatus to provide basic information (Chen et al., 1997b). The effects of temperature, pressure, co-solvent, water content, and soil/sediment type on PCB desorption were studied. The results showed that the effectiveness of SCE as a technology for the cleanup of PCB-contaminated soils and river sediments after 30 min of extraction at 40oC and 101 bar was more than 90% (Chen et al., 1997b). The extraction of PCBs from spiked samples showed higher efficiencies. The effects of temperature and pressure on recovery of SCE were studied by Hartonen et al. (1997). SCE conditions using SCCD at 40150oC were developed to allow sequential extraction of PCBs associated with rapidly, moderately, slowly, and very slowly desorbing sites on polluted sediments and soils (Bjorklund et al., 2000). The results demonstrated that the sample matrix, rather than the PCB identity, was most important factor controlling desorption behaviour. Increasing SCF temperatures for extracting spiked and native PCDDs, and PAH extraction from different environmental samples at constant fluid density and flow rate of the SCF is an effective way to increase SCE rates (Langenfeld et al., 1995). Class-selective aqueous extractions of polar (e.g. chlorinated phenols), lowpolarity (e.g. PAHs), and non-polar (e.g. alkanes) organics can be achieved by decreasing the polarity of the water by sequentially raising the temperature to 400oC to provide Supercritical water (SCW), (P > 221 bar) (Hawthorne and Miller 1994).

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It has been reported that co-solvent and soil moisture are the two most important factors affecting PCB extraction efficiencies. Significant differences between spike samples and native samples are found because of the heterogeneous nature of environmental samples. The partitioning may be controlled by solute solubility in the SCF, kinetic limitations, and/or the ability of the SCF to interrupt matrixsolute interactions (Anitescu and Tavlarides 2006). Data suggest that having a co-solvent (up to 15%) can enhance SCE recovery for specific solutes (Anitescu and Tavlarides 2006). The most important property of a co-solvent is its polarity. The modifier effects were dependent on the sample matrix and modifier identity when environmental samples were extracted with SCCD alone and modified with 10 vol.% MeOH, diethylamine, or toluene (Yang et al., 1995). The recovery benefits of high temperature and modifier were additive, indicating that temperature and modifiers have different mechanisms of improving solute recoveries. SCE recoveries for in situ pollutants including PCBs from sediment and PAHs from a petroleum waste sludge and railroad bed soil were compared using supercritical CHClF2 , N2O, and CO2 (Hawthorne et al., 1992). While SCE with SCCD yielded the lowest recoveries for each sample, CHClF2 consistently yielded the highest extraction efficiencies because of its high dipole moment. MeOH-modified CO2 also yielded acceptable recoveries of PCBs from the sediment (<90%). In one case, PCB concentrations in real-world sediments were reduced from 2200 to <10 ppm in 25 min of extraction time in the presence of 5 mol% MeOH in SCCD (Chen et al., 1997b). The presence of MeOH increased PCB desorption rates and reduced final PCB residual concentrations in sediments. Sequential SCE was applied to extract chlorinated and brominated organic pollutants from nine sediments (Hartonen et al., 1997). Of the total SCE recovery, 8095% was obtained with SCCD alone, and further recovery was achieved with the addition of a modifier. The recovery varied with the sediment, indicating that the usefulness of the modifier depends on the sample matrix. Water has a significant influence on the SCE of organics from solid matrices, even if there is a low natural water content (Chen et al., 1997b; Smyth et al., 1999). The water content of the samples and the presence of co-solvent were the most important factors affecting desorption of PCBs from sediments (Chen et al., 1997b). These solutes 86

are more tightly bound in real-world than in spiked samples. Although the role and the mechanism of water effects on SCE are still controversial, the reported data indicate that a small amount of water, <5%, may increase the rate of SCE. Water contents <10% showed no signs of significant mass transfer limitations. However, at >20% water, mass transfer was <10 times slower than at water contents of <10%. The effects of various water contents on thermodynamic and kinetic parameters of the SCE process were measured using different matrices. The reported results for a naphthalene-contaminated loamy sand (Smyth et al., 1999) showed that SCCD easily extracted naphthalene from soil when the water content was below 10%. At low water contents, mass transfer is rapid and the equilibrium partition coefficient is independent of the water content of the soil. However, the overall mass transfer coefficient decreased by a factor of <200 when the water content increased from 10 to 20%.

Green Technology Using green supercritical water solvent instead of organic solvents in a wide variety of chemical processes offers environmental advantages and may prevent pollution. Supercritical water oxidation (SCWO) of organic compounds is the most popular technology, taking advantage of the complete miscibility of organic compounds and oxygen with supercritical water (SCW), and thereby eliminating the slow mass transfer which often occurs in multiphase systems (Tavlarides et al., 2000). Moreover, essentially complete conversion of organic carbon to carbon dioxide occurs in a few minutes. Tavlarides et al. (2000) demonstrated the feasibility for SCWO destruction of environmentally harmful chemicals including PCBs. However, there is a gap in available data to determine the feasibility of SCWO for PCBs/PAHs in general, and in particular for PCBs/PAHs dissolved in solutions extracted from soils. Moreover, no kinetic studies have been reported on PCB oxidation in SCW to determine reactor optimum conditions and the nature and concentrations of reaction by-products. In most cases, small-scale SCE data do not translate to reliable designs for commercial applications. Instead, scale-up experiments are crucial. However, follow-up experiments conducted with a 2 L fixed bed bench scale unit confirmed the laboratory 87

scale findings for the extraction and destruction of PCBs from contaminated sediments (Tavlarides et al., 2000; Anitescu and Tavlarides 2006). Results of laboratory- and bench-scale investigations indicated that SCCD5% MeOH is an effective SCF, and conditions were defined to achieve less than 5 ppm PCB residual concentration in 4560 min for 99.8% removal. Comprehensive data on PCB solubilities in SCCD/MeOH, partition equilibrium, and desorption provided a firm basis to scale-up the extraction step of these processes. Further, the SCW oxidation (SCWO) stage, coupled to the SCE process with three possible configurations provided clean effluent materials. The ultimate products of the proposed technology were mainly clean soil/sediments and inorganic species such as H2O, CO2 , and small amounts of chlorides. The SCWO studies indicated that 5245 ppm Aroclor 1248 in methanol-simulated soil extracted solutions can be oxidized to 99.95% conversion in less than 1 min at 550oC. A two-step process using SCE with SCCD and wet air oxidation of the extracted contaminants in solid matrices has also been investigated (Tavlarides et al., 2000; Anitescu and Tavlarides 2006). SCE tests have been conducted over wide ranges of temperature, pressure, and CO2 /contaminant ratios with PAH polluted soils. The addition of methanol as a modifier has also studied. A skid-mounted field test unit based on the laboratory bench-scale test results was constructed which allowed on-site testing of the integrated supercritical extraction/liquid phase oxidation process with contaminated soils. At comparable CO2 to contaminant ratios and extraction conditions of 48oC and 139 bar, the total PAHs removed from three soils were 76.997.9% with CO2 alone and 88.498.6% with methanol added.

Performance
Lab, Bench and Pilot Scale Studies Bench-scale study results from SCE of soil polluted with naphthalene and 1,2,4-trimethylbenzene as a function of the SCCD flow rate and density have been reported by Montero et al. (1996). Data were used to perform a basic economic analysis of the process and to develop scale-up methodology from laboratory-scale SCE devices to 88

industrially useful equipment.

Laboratory scale data such as mass transfer

coefficients can affect the sizing and the control of process units since high mass transfer rates allow smaller vessels. This study also included experimental data collection and analysis to support the application of SCE and to provide design and operational processes required to construct a pilot plant. A preliminary economic analysis using these results indicated that the proposed SCE process is feasible. Soil polluted with hydrocarbons from a petrochemical plant was treated to reduce the pollution level below legal limits by a pilot-scale SCE unit (Cocero et al., 2000; Alonso et al., 2002). This pilot plant for soil remediation with SCCD and subsequent adsorption of pollutants on activated carbon have been used to study scale-up procedures for SCE processes. Operational parameters (e.g. extraction temperature, solid particle size, solvent ratio) were optimized, and the results showed optimal conditions to be an extraction temperature of 40oC, particle size of 0.425 mm, and solvent ratio of 15.8 kg CO2 /kg soil. Increasing the temperature improved initial extraction rates and total recovery. Pollutant solubility in the SCF did not limit SCE. Diffusion into the SCCD phase was the extraction rate-limiting step. The effect of particle size was particularly strong for spiked soil in the laboratory with brief exposure time. The data have also been used to obtain the mass transfer coefficients and the equilibrium parameters using a desorption model. From the pilot results, the design of a mobile full-scale plant has been developed and the following data were obtained: soil treatment capacity of 250 kg/h under 260 bar and 40oC extraction conditions; adsorption conditions of 260 bar and 50oC; soil concentration of 14,500 ppm; SCCD flow of 452 kg/h; extraction of 270 L (three extractors in series of 90 L per extractor and an additional extractor for semi-continuous operation); extraction time of 84 min per shift. Results of bench scale SCE of diesel, PCB, and bis(2-ethylhexyl)phthalate polluted soil and the process implications for scale-up were also reported (Anitescu and Tavlarides 2006). Extractions at 69413 bar at 2560C and different solvent to feed ratios were tested. For 50 g samples, extraction efficiencies were >99% for soil containing 45 g/kg-diesel at 76 bar and 23oC; 87% for soil containing 34 mg/kg PCBs

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at 96 bar and 24oC; and 95% for soil containing 15 g/kg at 90 bar and 24oC. Extractions at 60oC and 413 bar of a 500 g sample reduced the same pollutant levels by >99% for diesel-polluted soil, and 97% for the PCB- and bis(2ethylhexyl)phthalate polluted soils.

By-products
Extracted organic contaminants requiring further treatment or disposal. Side stream of spent solvents. Air emissions.

Advantages and Limitations

This technique has several benefits: High extraction efficiency (up to 99.99%). Cleaning process can be completed in a few minutes. No second-hand pollution. Soil structure is left intact.

However, there are several limitations: SCE is not a stand-alone technology. It is machine-intensive, requiring further treatment method of the extracts. High pressures require special pressure vessels and other components. Soil excavation is required, increasing the risk of atmospheric contamination. Very specific equipment is needed, limiting the applicability to developing countries.

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Cost
Equipment and excavation contribute to the main cost of the treatment technology. The cost was said to range between $122 and 154 $/m3 (Montero et al., 1996).

Applicability to Developing Countries

This type of technology is machine intensive. For example, it requires a pressure vessel, a compressor and heating. Therefore to apply this technology, special equipment would need to be imported, and thus the cost of treatment is likely to be unachievable. Another factor is likely to be the cost of foreign-trained labour to train local personnel to operate and maintain the equipment. This is an ex situ technology, requiring the excavated soil to be safely transported to the treatment facility, under strict regulations, which may be lacking in developing countries. Hence, risk of pollution from soil transportation is of great concern.

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A-12 Soil Washing

Overview
Soil washing is a process that uses physical and/or chemical techniques to separate contaminants from soil and sediments. Contaminants are concentrated into a much smaller volume of contaminated residue, which is either recycled or disposed. Wash water can consist of water only, or it can include additives such as acids, bases, surfactants, solvents, chelating or sequestering agents which are utilized to enhance the separation of contaminants from the soils or sediments. recycled for reuse within the system. The process is often utilized for pretreatment in conjunction with other technologies when treating wood preserving wastes. Soil washing processes may be either continuous or batch processes. Typical applications do not decontaminate, destroy, or significantly alter contaminants, but they reduce contaminant concentrations in soils by three mechanisms: particle size separation, phase transfer, and physical removal (Ehsan et al., 2007). When appropriately utilized, a substantial portion of the washed soil will be amenable to further treatment or can either be backfilled onsite or beneficially reused/recycled in some other way. The spent wash water is then treated to concentrate the contaminants and fine particles in a residual waste stream. The waste stream can then be treated to reduce contamination level, and to separate any solids for safe disposal. There are many factors that should be considered in the selection of soil washing as a remedy for contaminated soil. The following are general screening factors: Soil Washing is considered feasible for the treatment of a wide range of inorganic and organic contaminants including heavy metals, radionuclides, cyanides, polynuclear aromatic compounds, pesticides and PCBs. Soil washing is most appropriate when soils contain of at least 50 to 70% sand. 92 Process water is typically

Soil washing is unlikely to be cost-effective for soils with fines (silt/clay) content in excess of 30 to 50%. Typically, onsite treatment of soils using soil washing will not be cost-effective unless the site contains at least 5000 tons of contaminated soil. Surfactants are particularly attractive for such applications as they potentially

have low toxicity and favourable biodegradability in the environment relative to organicsolvent-based systems. Yet, there is no comprehensive guidance in selecting surfactants for ex situ soil washing (Deshpande et al., 1999). Surfactants (e.g., nonionic and There are three possible cationic) may adsorb efficiently onto certain soil minerals, likely due to their high polarities and large molecular weights (Lee et al., 2004). mechanisms whereby surfactants sorb onto soils: ion exchange, adsorption and surfactant partitioning to soil organic matter (SOM) (Lee et al., 2004). For nonionic surfactants, the adsorption usually occurs due to hydrogen bonding or van der Waals forces. For cationic surfactants, ionic bonding is the main mechanism because soils often contain negative charges on the surface. Surfactants may also partition into the SOM to an extent, influenced by the properties of the surfactant and the SOM (Lee et al., 2004). The adsorption of anionic surfactants is similar to that for nonionic surfactants, but the repulsive charge on the soil surface tends to weaken the adsorption. Surfactant micelles offer a good hydrophobic environment to which organic solutes can partition. This is because a solute with a relatively low water solubility tends to have a relatively high affinity with the hydrophobic surfactant group.

Treatment Process
The primary stages in soil washing are soil preparation, washing, soil and water separation, wastewater treatment, and vapour treatment when required. Soil preparation begins with the excavation or moving of contaminated soil to the process, where it is normally screened to remove debris and large objects. Depending on the technology and

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whether the process is semi-batch or continuous, the soil may be made pumpable by the addition of water. The contaminated soil is mixed with wash-water and possibly surfactants to remove contaminants from soil and transfer them to the extraction fluid. The soil and wash-water are next separated, and the soil is rinsed with clean water. The clean soil is then removed from the process as a product. Suspended soil particles are recovered, as sludge, directly from the spent wash-water using gravity separation and, when necessary, flocculation with a polymer or other chemical. Sand particles larger than 50 to 80 m can be easily separated because of their relatively high settling velocity; equipment such as settling chambers are often used. Coarse-soil particles are generally separated by screening. The separated smaller particles will most likely be of lower quantity, but these tend to carry higher levels of contamination than the original soil and, therefore, should be targeted for either further treatment or secure disposal. The water from the soil washing process is treated by conventional wastewater treatment processes to enable it to be recycled for further use. Residual solids may require post-treatment to ensure safe disposal or release. Vapour treatment may be needed to control air emissions from excavation, feed preparation, and extraction processes; these emissions are collected and treated, normally by carbon adsorption or incineration, before being released to the atmosphere (USACE 2003). The effectiveness of soil washing technology is limited by several factors: (a) The percentage of soil fines (silt/clay, less than 63-74 microns) affects soil washing technology in several ways (Lee et al., 2004; Ehsan et al., 2007). If soil moisture content is low, fines can cause physical handling problems such as clogging of feed equipment. Most contaminants concentrate in the fines fraction of soils. At or near the end of most soil washing processes, fine materials containing the contaminants of concern are separated from the larger particle size soil fractions. Depending on the particular soil washing process, the contaminated fines may be disposed or undergo further treatment to remove the contaminants. Depending on the technology, there will be a point at which the percentage of fines becomes a limiting 94

factor. Soil washing is generally not cost-effective for soils with silt/clay content in excess of 30 to 50%. For specific sites, such factors as contaminant type and concentration, together with physical characteristics of the soils, determine whether or not soil washing is appropriate. It is important to emphasize that a high percentage of fines in soils does not preclude soil washing, but rather this is a factor influencing the cost of treatment. Soils with a high concentration of fines can be effectively treated using soil washing, but the treatment is likely to be relatively costly compared to treatment of soils with lower fines content. The specific information relevant to a site and treatment efficiency should be obtained from a treatability study performed prior to system design and implementation. (b) Hydrophobic compounds such as PCBs, PCDD/Fs and pesticides can be difficult to separate from the soil matrix. Contaminants with high partitioning coefficients may require addition of surfactants or other additives to the soil washing system. When additives are used, there is generally an increase in water volume and additional treatment steps are required to remove or recycle the additive. (c) Complex mixtures of contaminants in the soil such as SVOCs make design of soil washing treatment systems more difficult. Variations in contaminant concentrations may make wash fluid and operational settings more critical, and they may also require the use of additional techniques, such as blending of feed soils, to provide a more consistent feedstock. (d) The presence of soils with high humic content can also make the separation of contaminants from soils more difficult. This occurs because humic matter has additional binding sites for organics (Lee et al., 2004; Ehsan et al., 2007).

Site Requirements
Typically, mobile soil washing systems are located onsite and may occupy up to 16 000 m2 for a 20 ton-per-hour unit; the exact area depends on the vendor system selected, the amount of soil storage space required, and the number of tanks or ponds needed for wash-water preparation and wastewater treatment (USEPA 1997; USACE 95

2003). Typical utilities required are water, electricity, steam, and compressed air. The quantity of local water required for soil washing, including water cleanup and recirculation, is estimated to be between 600 and 4000 litres per cubic meter of soil (USEPA 1997; USACE 2003).

Cost
The cost of soil washing depends on several site- and contaminant- specific factors. The quantity of soil to be treated affects the size of the soil washing unit and the time on-site. Generally, larger soil volumes reduce the per-ton-treated cost of equipment. An EPA study performed a cost analysis based a pilot study and reported the cost to range between $30 and $110/m3 (USEPA 1997). Cost factors considered included equipment rental, startup, labour, consumables/supplies, health and safety equipment, contingencies, maintenance, and utilities (USEPA 1997). The estimate was based upon the washing of 250,000 tons of soil with an actual processing rate of 18 tons per hour for 300 days per year (USEPA 1997). This cost excluded excavation and mobilization cost, as well as water treatment costs.

By-products
There are four main waste streams generated during soil washing: Contaminated fines and humics from the soil washing unit Wastewater Wastewater treatment sludges and residuals Air emissions. Contaminated clay fines and humics resulting from the process may require further treatment using acceptable remedial technologies in order to permit disposal in an environmentally safe manner. sludge. 96 Most fines remain suspended in the wash-water supernatant after treatment and ultimately settle out to form the wastewater treatment

Discharge water may need treatment to meet appropriate discharge standards prior to release to a local, publicly owned wastewater treatment facility or receiving stream. However this water should be recovered and reused in the washing process. disposal. Any air emissions from the waste preparation area or the washing unit should be collected and treated to meet applicable regulatory standards. The wastewater treatment process residual solids must be appropriately treated before

Performance
Bench, Lab and Pilot Scale Studies Lake Huron (USEPA 1997; USACE 2003) Sediments from lake Huron were contaminated with 1.35 mg/kg PCBs. Sediments were separated in to fines, humics and washed coarse fractions. The residence time of the washing liquid was not specified. Overall removal efficiency was at 86%.

Thunder Bay, ON (USEPA 1993) This was a bench scale study using steam. Sediments were contaminated with PCBs, but concentrations were not specified. Sediments were medium silt or finer particles (<0.038 mm). Soil was washed. The study showed 90% reduction of total organic compounds in the sediments.

Superfund Site, Jackson, TN (USEPA 1993) This was a pilot scale study on two washing agents: de-ionized water and water with 5% surfactant. The soil was collected from a former wood preserving site. The soil was contaminated with PAHs, PCP, PCDD/PCDFs.

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The soil was black silty or clayey sand with 4-10% gravel and 15-18% silt or clay. 38% of the soil particles were smaller than 0.3 mm. Concentrations of PCDF and PCDD were 480 mg/kg in total. Removal efficiencies with de-ionized water and surfactant mixture were 33% and 77%, respectively.

Field Studies No actual field studies on POPs, including PCBs, PCDD/PCDF have been found, during the literature search.

Advantages and Limitations

Advantages of soil washing include: Ability to treat both organics and inorganics in the same treatment system. If no solvent nor volatile organic substance is used in the washwater, there are unlikely to be any significant air or wastewater discharges from the system, making the permitting processes easier than for many treatment systems. This attribute should also make the technology more attractive to local community stakeholders. Most soil washing technologies can treat a broad range of influent contaminant concentrations. Depending upon soil matrix characteristics, soil washing can allow for the return of clean coarse fractions of soils to the site at low cost. Limitations: After treatment, there is a relatively small volume of contaminated solid media and wash-water that must be further treated or disposed. Soil washing is unlikely to be cost-effective for soils with silt/clay content in excess of 30 to 50%. High humic content in the soil, complex mixtures of contaminants, and highly variable influent contaminant concentrations can complicate the treatment process.

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As for any ex-situ technology, there are space requirements for the treatment system.

Applicability to Developing Countries

Wash-water can be recycled. As a result, extra treatment processes are needed for separation and disposal/destruction of the contaminant. This requires safe disposal methods. The system is characterized by high capital costs, which can be unaffordable for developing countries, especially if this method is only used for one specific site. Space requirements can be a limitation, and can increase the cost, if there is a space limitation or high population density in the country of interest. The method has the ability to extract heavy metals, depending on the chelating or surfactant agent being used. Therefore the presence of heavy metals must be considered, and proper disposal methods should be provided (USEPA 1997; Deshpande et al., 1999; Ehsan et al., 2006; Ehsan et al., 2007). The use of chelating agents or surfactants requires purchase from special suppliers, increasing the cost of the technology. If the developing country does not acquire the required equipment to recycle the wash water, this will be very expensive. Since soil washing requires high volumes of water, developing countries with limited available water will not benefit from this technology.

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A-13 Chemical Dehalogenation

Overview
This technology involves direct chemical stripping of halogen atoms from organics in soils, sediments, and sludges. It includes processes in which (1) a chemical reagent is applied directly to the contaminated matrix (soil sediment or sludge), and (2) the reagent reacts with the contaminant to cause the removal of one or more halogen atoms from a molecule of the contaminant. The reaction between the reagent and the contaminant may be a substitution reaction (in which the halogen atoms are replaced by other atoms or chemical groups) or an elimination reaction in which the halogen atoms and other atoms (e.g., hydrogen) are simultaneously removed from an aliphatic compound leaving a double or triple bond behind in the remaining organic molecule (USEPA 1992b). Examples of direct chemical dehalogenation include the alkaline polyethylene glycolate (APEG) processes and base-catalyzed decomposition (BCD) processes; they do not include desorption or extraction processes followed by chemical treatment of the condensate or extraction medium (Taniguchi et al., 1997). Chemical dehalogenation technologies that use an alkaline glycolate or basecatalyzed reagent are applicable to halogenated aromatic compounds, including PCBs, PCDDs, PCDFs, chlorobenzenes, chlorinated phenols, organochlorine pesticides, halogenated herbicides, and certain halogenated aliphatics (e.g., ethylene dibromide, carbon tetrachloride, chloroform, and dichloromethane). If other volatile organic, semivolatile organic, or metal contaminants are present, chemical dehalogenation can be used in conjunction with other technologies, such as low-temperature thermal desorption, solvent extraction, or biodegradation, as part of a treatment train (USEPA 1997). Chemical dehalogenation technologies are applicable to soils, sludges, and sediments. Treatment effectiveness depends on thorough mixing of the contaminants and treatment reagents. This almost always requires that the waste matrix be excavated since in situ 100

applications of the technology are not likely to be effective. Treated soils and residuals from chemical dehalogenation treatment may require post-treatment (e.g., neutralization) prior to their final disposal. Chemical dehalogenation treatment technologies include a number of patented, proprietary processes. However, no published commercial treatment case studies could be found.

Treatment Process
The BCD process was developed by RREL in Cincinnati, Ohio. BCD is an efficient, relatively inexpensive treatment process for PCBs. The process can be employed using either sodium hydroxide, sodium bicarbonate, or aliphatic hydrocarbons as hydrogen donors. The contaminated soil is first screened, processed with a crusher and pug mill, and stockpiled. Soils and other materials are sieved to remove oversize bricks and stones and metals. The oversize material is then crushed and then added to the bulk solids. A maximum particle size of 50 mm is specified. In practice materials are crushed to 35 mm or less to speed up the desorption process. The process can tolerate other inorganic or organic debris providing that this material is smaller than 50 mm or can be shredded down to this size. This stockpile is mixed with sodium bicarbonate (NaHCO3) in the amount of 10 percent of the weight of the stockpile, and is then heated for about 1 hour at 340oC in a rotary reactor (USEPA 1992b). PCBs are completely dechlorinated and partially volatilized in this step. The PCBs in the vapour condensate, residual dust, spent carbon, and filter cake are dechlorinated after about 2 hours at 340oC in a stirred-tank slurry (i.e., liquid/solid) reactor (STR) utilizing a high boiling point hydrocarbon oil, a catalyst, and sodium hydroxide (NaOH) (USEPA 1992b). The APEG chemical dehalogenation system can be applied to aromatic halogenated compounds, including PCBs. APEG partially dehalogenates the pollutant to 101

form a glycol ether or a hydroxylated compound and an alkali metal salt, which are water-soluble by-products. The disadvantages of the APEG process are that it often takes numerous cycles to achieve the desired results, the process is only able to achieve partial dehalogenation, and dioxins and furans often form when the process is implemented (Chen et al., 1997a; Taniguchi et al., 1997).

Site Requirements
A BCD unit with the capacity to treat 1 ton per hour of soil or sediment requires 3000-4000 m2 of space when fully assembled. Diesel fuel or natural gas must be available to heat the primary reactor. Electrical power is required for downstream processing and for operation of the secondary reactor. Water must be accessible for cooling and washing, and provisions for onsite or offsite wastewater disposal must be established. Special handling measures should be provided to hold any process residual streams until they have been tested to determine their acceptability for disposal or release.

Cost
According to one reference (USEPA 1997), chemical dehalogenation using APEG is expected to cost $200 to $500/m3 of waste.

By-products
APEG processes produce partially dechlorinated compounds containing chlorine and hydroxyl groups (making them water soluble and slightly toxic). The BCD process produces only biphenyl and low-boiling olefinics (which are not water-soluble and much less toxic) as well as sodium chloride.

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The treated water and condensate from the treatment process can generally be discharged to a wastewater treatment plant after being pumped through activated carbon.

The treated soil may be suitable for replacement onsite.

Performance
Several laboratories, bench, pilot and field scale studies have been undertaken, with reported removal efficiencies of almost 99.999% (Chen et al., 1997a; USEPA 1997; Rahuman et al., 2000; USEPA 2004b). Rahuman et al. (2002) also reported treatment projects at different sites, which also achieved 99.999% destruction of PCBs, PCDD/PCDFs, and pesticides.

Advantages and Limitations

The primary benefit of the technology is its ability to achieve high removal efficiencies for most POPS. When BCD is applied directly to soil, limitations can be: Removal of residual reagent and treatment by-products from the treated soil before final disposal. pH of the soil may be raised during treatment and may need to be lowered prior to final disposal. During treatment of oily wastes, precautions may need to be taken to avoid releasing contaminants volatilized due to the elevated temperatures. A cooling facility is needed to reduce fire hazards, as demonstrated by a fire which occurred in Australia (McDowall et al., 2004).

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Applicability in Developing Countries

The condensate and water from the process need to be treated by a wastewater treatment plant. Some developing countries do not have primary treatment systems with the ability to treat a wide variety of chemicals, such as that produced by this process. If the treatment facility is not within an urbanized areas, special arrangements are needed to safely transport the water effluents from the site. A reliable electrical power supply is needed to operate this technology. Hence developing countries may need to provide a reliable auxiliary power generation unit, or have a well-maintained infrastructure to provide uninterrupted electrical power. Safety risks, such as those which resulted in a fire in Melbourne in 1995 have now been rectified by adding cooling facilities, leading to extra cost and required space. Modern catalysts for the process are of moderate cost, but consumption is extremely low. However, sodium hydroxide consumption is a major cost item.

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A-14 Phytoremediation

Overview
Phytoremediation uses vegetation, enzymes derived from the vegetation, and other complex processes, to isolate, destroy, transport, and remove organic pollutants from contaminated soils. Phytoremediation has been applied at several sites on the National Priorities List, as well as other hazardous waste sites, to help meet regulatory requirements. The diversity of pollutants to which it can be applied-crude oil, metals, explosives, pesticides, chlorinated solvents and numerous other contaminants - is the prime reason the technology has developed rapidly (Russel 2005). Phytoremediation has become not only a subject of interest to universities and major research centres, but it has also created a new business for contractors and consulting firms. Phytoremediation consultants are able to advise stakeholders on whether phytoremediation would be a suitable cleanup method for their sites, and contractors are able to install the selected remediation system. The U.S. market for phytoremediation was estimated at between $30 and $49 million in 1999 and has since grown (Russel 2005). Phytoremediation is studied heavily in Canada and the United States and draws serious interest abroad. Phytoremediation projects are underway in Ukraine, Sweden, Switzerland, Czech Republic, China, and Poland, to name a few (Russel 2005).

Treatment Process
Semi-volatile organic compounds (SVOCs) such as PCBs, Dioxins and Furans can enter a growing plant through a number of pathways. These include direct uptake from the atmosphere, volatilization from the soil, and root uptake and translocation to the shoots (Hulster et al., 1994; Oconnor 1996; Smith and Jones 2000). The shoots can also become contaminated through direct contact with the soil. Contamination of plant shoots is typically attributed to volatilization from the soil and/or atmospheric deposition.

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However, the processes are not fully understood and difficult to accurately quantify. Due to the hydrophobicity of compounds such as PCBs, root uptake and translocation is often ignored as a possible uptake pathway, and the roots are generally not analyzed during studies (Zeeb et al., 2006). This has resulted in a lack of information on root uptake and translocation as a pathway for plant contamination. The extraction of contaminants from the soil into the roots and translocation within the plant (from roots to shoots) is referred to as phytoextraction. The contaminant must be in contact with the roots of the plant. This limits the remediation of the soil to the depth of the roots.

Performance
Phytoremediation technology is under development and still at the testing phase. Most reported results are based on lab scale experiments. Scientists found that certain cell suspension cultures of Petroselinium hortense and Glycine max were able to degrade 14C DDT (Suresh et al., 2005). Cultures of aquatic plants were shown to degrade DDT to its metabolites, and information on the use of non-target plants and plant tolerance and sensitivity has been provided (Karthikeyan et al., 2004). Studies continue to examine and present possible solutions for phytoremediation of DDT and other POPs. Lunney et al. (2004) reported up to 4.3 g/g DDT in the shoots of C. pepo var. Howden and 2.9 g/g in the shoots of C. pepo var. Goldrush. This study also controlled volatilization of DDT by sealing and covering all contaminated soils. A number of early studies indicated that phytoextraction of PCBs from soil was possible by plant uptake. Zeeb et al. (2006) reported the uptake and translocation of PCBs in soybeans (Glycine max); in carrots (Daucus carota); in beets (Beta vulgaris), turnips (Barssica rapa L.), and beans (Phaseolus vulgaris). In each case, the lower chlorinated congeners were found more abundantly in the shoots than the roots of the various plant species.

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Other studies produced indicated that PCBs were not being taken up or translocated to shoots. A variety of plants were grown in soil contaminated with Fenclor 64 (similar to Aroclor 1260). It was concluded that the primary source of PCB accumulation in plant shoots resulted from PCB volatilization from the soil, rather than translocation from root to shoot (Bacci and Gaggi 1985). Other studies were concerned with the practice of applying PCB-contaminated sewage-sludge to agricultural crops. Fries and Marrow (1981) reported no uptake of PCBs by G. max, contradicting the results of previous studies. Again, the authors concluded that any contamination of the aboveground shoots was due to volatilization from the soil and uptake by the shoots. O'Connor (1996) also reported no uptake of PCBs in F. arundinacea, D. carota, and Cichorium endivia. In both of these reports, the roots were not analyzed and the concentrations of PCBs in soil were low (<1 mg/kg). In a study in which Hordeum vulgare (barley) and Lycopersicon esculentum (tomato) were injected with specific radio-labelled PCB mixtures into the lower stem area once plants were established, the highest PCB concentrations were found in plant leaves. However, there was translocation overall. Epuri et al. (1997) concluded that plants take up PCBs from their environment to a very limited extent and do not modify the extractable congeners appreciably. More recently, the plant uptake of persistent and hydrophobic compounds similar to PCBs has been demonstrated. For example, this was the case for weathered DDE, another contaminant with a long half-life in the environment and the potential to bioaccumulate in the food chain (White, 2002 ). White (2002) reported up to 2.6 mg/kg DDE in the shoots of Curcubita pepo var. Howden. Hulster et al. (1994) provided strong evidence of root uptake and translocation of PCDDs/PCDFs in C. pepo plants. The above studies provide evidence that the uptake of compounds similar to PCBs is possible and that C. pepo is a promising species for phytoremediating persistent organic pollutants.

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Site Requirements
Requirements for site conditions have not been reported. However, the size of a site is a function of the amount of contaminated soil, and the depth accessible to the plant roots.

Cost
Key Cost Drivers (Zeeb et al., 2006) include: Area of contamination. Degree of effort to be devoted to the clean-up. Density of sampling.

The cost of this technology ranges between $150 and $630/m3 (2004 U.S. dollar value) (USEPA, 2005).

By-products
The treatment results in terminated plants, as well as cell mass.

Advantages and Limitations

Phytoremediation has numerous advantages that are fostering acceptance on a broad scale. Primary advantages are: As a solar-driven system, phytoremediation takes advantage of natural plant processes, and thus lowers labour, equipment requirements, and operating costs. Planted sites generally are more aesthetically attractive than for other choices. Lower air and water emissions and secondary waste production makes phytoremediation a safe treatment. Phytoremediation controls runoff and soil erosion.

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Phytoremediation can be used in conjunction with other remediation methods and, therefore, may be more beneficial than a stand-alone technology. Energy costs are almost non-existent. As researchers continue to expand and improve the applications of

phytoremediation some limitations remain. Primary limitations are: Root growth remediation is primarily based on contaminant contact with plant roots, and cleanup is only as deep as the roots reach. A long time is required for the remediation due to time needed for plant growth. This therefore slows the process down. Phytotoxicity Plants need to be tolerant to the contaminants. Some plants are likely to perish. The technique is subject to local climate conditions, planting space, seasonal nature of plants, and possible transmittance of contaminants due to surrounding creatures, thus entering the food chain and causing more contamination problems with in the ecological cycle. All advantages and limitations may not be applicable to each mechanism of phytoremediation. Although phytoremediation has proven to be an effective and efficient method, it is a site- specific technology. Deeper root growth and higher contaminant tolerance may be possible through the development of specially engineered plants.

Applicability to Developing Countries

This method is considered as sustainable, where native plants present in the country of treatment can be used. However, if the site being treated lacks the ability to sustain vegetation, several requirements have to be considered: Accessibility to water resources for irrigating the site. Climate conditions must also be considered. Ideal conditions include moderate annual precipitation, and the contaminated site must not be a flood hazard site.

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If the site is not appropriate for vegetation, soil moving to another land mass is an option. This is unlikely to be favourable if the country is heavily populated and land is very expensive.

Site accessibility must be closed to free-roaming grazing animals, which in turn will enter the food cycle upon which humans rely.

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Appendix B Soil Effect on Cost of Technology

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SOIL EFFECT ON COST OF TECHNOLOGY

Physical and chemical characteristics of the POP-contaminated soil or sediment also determine the types of remedial technologies potentially suitable for the site. The minimum set of soil and sediment measurements desirable for technology prescreening is presented in Table B1. In addition to the physical characteristics of the POPcontaminated media, the presence of other contaminants can have an impact on the effectiveness of a remedial technology and PCB analyses. The values are described as "higher" or "lower" in defining the tendency of these parameters to enhance or inhibit prescreening of a particular treatment process. For example, larger quantities of oil and grease would improve the performance of chemical dehalogenation (i.e., base-catalyzed decomposition). On the other hand, increased oil and grease content would decrease the performance of solidification/stabilization. Inclusion of a rating within the technology group, however, does not ensure that the rating will be applicable to each individual compound or component within a technology group. Table B2 presents critical factors affecting the cost. Several factors, such as site preparation and treatment capacity, are critical to all of the technologies listed. Others, including water usage and long-term monitoring, are critical in some cases. After treatment of the POP-contaminated soil or sediment is completed, residual (lower) concentrations of POPs may remain in the treated medium. If the chosen technology treated the soil or sediment in situ, or if the treated media is to be reused onsite, long-term controls may be required to continue to manage the site. Table B3 summarizes the cost of each technology. This includes a brief description of what the cost covers, as well as adjusting the cost to the 2007 dollar value. The adjustment factors were calculated by multiplying the reported cost by the ratio of the construction cost index factor of 2007 to the construction cost index factor for the given year of reporting. The construction index over time is presented in Table B4.

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Table B1: Soil Characteristics Affecting Cost of Remedial Technology ((USEPA 1989; Evans 1990; USEPA 1991a; USEPA 1992b; USEPA 1994b; USEPA 1995b; USEPA 1997; USEPA 2004a; USEPA 2005)
Gas Phase Chemical Reduction Thermal Desorption

Characteristic Particle size Bulk density Permeability

Moisture content pH and Eh Humic content Total organic content (TOC) Biochemical oxygen demand (BOD) Chemical oxygen demand (COD) Oil and grease content Volatile metals Nonvolatile metals

= Higher values support preselection of technology group. = Lower values support preselection of technology group. = Effect is variable among systems within a technology group. When no symbol is shown, the effect of that characteristic considered to be inconsequential. Alkali Metal Reduction is not included because it is used to treat contaminated oils. Ball Mill is not included because of the limited information available on this technology.

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Phytoremediation

Chemical Dehalogenation

Bioremediation

Solidification/ Stabilization

Soil Washing

Supercritical Extraction

Vitrification

Incineration

Solvent Extraction

Pyrolysis

Table B2: Critical Characteristics Affecting Cost Ranges for Technology Alternatives for Remediating POP- Contaminated Soil and Sediment (Dvila et al., 1993).
Gas Phase Chemical Reduction Thermal Desorption Solvent Extraction Phytoremediation * * * * * * * * * * * * * * * * * * * * * * * * * * * * * *

Characteristic Particle size heterogeneity High moisture content POP concentration Regulatory compliance Residuals/offgases requiring treatment Excavation Site preparation Undersized treatment unit capacity Long term monitoring High clay content Required chemicals Water usage Fuel/electricity usage

* * * * * * * * * * * * *

* * * * * * * * * * * * * *

* * *

* * * * * * *

* * * * * * * *

* * *

* *

* * * *

* * * *

* * * *

* * * * * * *

* * *

Note: Technologies for which a cost factor is identified by "*" generally incur increased cost due to this characteristic. Where a factor increases cost only for the ex situ subgroup of a technology, an "" is shown. Ball Mill technology is not included due to limited available information.

114

Chemical Dehalogenation * * * * * * *

Bioremediation

Solidification/ Stabilization

Alakali Metal Reduction

Soil Washing

Supercritical Extraction

Vitrification

Incineration

Pyrolysis

Table B3:

Cost Summary of Each Technology and the Estimated Cost in 2007 U.S. Dollars using Construction Cost Index
Cost U.S. $/m3 Dollar Year Cost U.S.$/m3 in 2007 Dollars 328-843 Categories included in cost plus treatment Site preparation, permitting, mobilization, demobilization, operation and maintenance, labour, utilities and fuel. Equipment, operation/maintenance (O/M), permitting, mobilization, demobilization, labour and utilities. Plant startup equipment, site preparation, mobilization, demobilization, labour, supplies and consumables. Mobilization, demobilzation, site preparation, O/M and disposal. Equipment, O/M, permitting, mobilization, demobilization, labour, excavation and utilities. Site preparation, capital equipment, mobilization, demobilization, labour, supplies, utilities and O/M. Undisclosed.

Technology

Source USEPA 1997

Incineration

140-360

1989

USEPA 2005

Bioremediation

55-360

2005

63-412

USEPA 1995b

Solvent Extraction

125-400 5008000 50-250 16702000

1995

213-680

Vitrification Solidification/ Stabilization Gas Phase Chemical Reduction

2004

626-10015

AEW 1997; McDowall et al., 2004 USEPA 2000 USEPA 1994a

1992

99-493

1994

2977-3565

Pyrolysis

375-500 Ex-situ: 350-450; In-situ: 350-700 122-154

1997

586-781 Ex-situ: 624-802; In-situ: 438-876 198-250

AEW 1997; Deuren et al., 2002

Thermal Desorption Supercritical Extraction Soil Washing Base-Chemical Dehalogenation Phytoremediation

1994

Capital, labour, O/M, fuel, treatment and disposal of residual waste. Soil handling, excavation, labour and raw material. Equipment rental, startup, labour, consumables, supplies, health and safety equipment, o/m and utilities. Undisclosed. Undisclosed.

USEPA 1991b; Depercin 1995 Montero et al., 1996 USEPA 1997

1996

30-110 200-500 150-360

1997 1990 2004

47-172 441-1102 155-651

USEPA 1997 USEPA, 2005

Ball Mill technology is not included due to limited information. The corresponding construction index is provided in Table B4

115

Table B4: Annual Construction Cost Index

Average Index 1996 505 1997 525 1998 549 1999 570 2000 595 2001 613 2002 619 2003 621 2004 655 2005 717 2006 793 Source:Turner Construction (http://www.turnerconstruction.com/corporate/content.asp?d=20) Year

116

Appendix C Treatment Technology Combinations

117

TREATMENT TECHNOLOGY COMBINATIONS

Two or more of different technologies can be used together for more effective treatment. They can either be integrated processes or a series of treatments combined in sequence to provide the necessary overall degree of treatment. In many cases treatment combinations are used to render a medium more easily treated by one of the technologies, to reduce the amount of waste requiring treatment by a more expensive technology, to prevent the emissions of volatile contaminants and/or to minimize the overall cost of treatment. Figure C1 presents common combinations of treatment technologies used in remedial actions.

Bioremediation

and

Soil vapour extraction

or

Solidification/ Stabilization

Chemical treatment Soil washing Solvent Extraction Thermal Desorption

and

Solidification/ Stabilization Bioremediation

or

Thermal desoprtion Thermal desorption or Vitrification

and

or

and

Solidification/ Stabilization Chemical treatment

or

Incineration

and

Figure C1. Common combinations of treatment technologies applied in remedial actions (USEPA 2004b).

118

Appendix D Chemical abbreviations, synonyms and trade names of 12 POPs identified by UNIDO in the Stockholm Convection

119

Chemical abbreviations, synonyms and trade names of 12 POPs identified by UNIDO in the Stockholm Convection.
POPs Aldrin CAS chemical name 1,2,3,4,10,10-Hexachloro1,4,4a,5,8,8a-hexahydro1,4:5,8dimethanonaphthalene 1,2,4,5,6,7,8,8-octachloro2,3,3a,4,7,7a-hexahydro-4,7methano-1H-indene 1,1'-(2,2,2Trichloroethylidene)bis(4chlorobenzene) Synonyms and Trade Names Aldrec, Aldrex, Aldrex 30, Aldrite, Aldrosol, Altox, Compound 118, Drinox, Octalene, Seedrin. Aspon, Belt, Chloriandin, Chlorkil, Chlordane, Corodan, Cortilan-neu, Dowchlor, HCS 3260, Kypchlor, M140, Niran, Octachlor, Octaterr, Ortho-Klor, Synklor, Tat chlor 4, Topichlor, Toxichlor, Veliscol-1068. Agritan, Anofex, Arkotine, Azotox, Bosan Supra, Bovidermol, Chlorophenothan, Chloropenothane, Clorophenotoxum, Citox, Clofenotane, Dedelo, Deoval, Detox, Detoxan, Dibovan, Dicophane, Didigam, Didimac, Dodat, Dykol, Estonate, Genitox, Gesafid, Gesapon, Gesarex, Gesarol, Guesapon, Gyron, Havero-extra, Ivotan, Ixodex, Kopsol, Mutoxin, Neocid, Parachlorocidum, Pentachlorin, Pentech, PPzeidan, Rudseam, Santobane, Zeidane, Zerdane. lvit, Dieldrite, Dieldrix, Illoxol, Panoram D31, Quintox.

Chlordane

DDT

Dieldrin

Endrin

Hexachlorobenzene Heptachlor

3,4,5,6,9,9-Hexachloro1a,2,2a,3,6,6a,7,7aoctahydro-2,7:3,6dimetanonapth[2,3b]oxirene. 3,4,5,6,9,9,-Hexachloro1a,2,2a,3,6,6a,7,7aoctahydro-2,7:3,6dimethanonaphth[2,3b]oxirene. Hexachlorobenzene 1,4,5,6,7,8,8-Heptachloro3a,4,7,7a-tetrahydro-4,7methanol-1H-indene. 1,1a,2,2,3,3a,4,5,5a,5b,6dodecachloroacta-hydro1,3,4-metheno-1Hcyclobuta[cd]pentalene Toxaphene

Compound 269, Endrex, Hexadrin, Isodrin Epoxide, Mendrin, Nendrin.

Mirex

Amaticin, Anticarie, Bunt-cure, Bunt-nomore, Co-op hexa, Granox, No bunt, Sanocide, Smut-go, Sniecotox. Aahepta, Agroceres, Baskalor, Drinox, Drinox H-34, Heptachlorane, Heptagran, Heptagranox, Heptamak, Heptamul, Heptasol, Heptox, Soleptax, Rhodiachlor, Veliscol 104, Veliscol heptachlor. Dechlorane, Ferriamicide, GC 1283

Toxaphene

Alltex, Alltox, Attac 4-2, Attac 4-4, Attac 6, Attac 6-3, Attac 8, Camphechlor, Camphochlor, Camphoclor, Chemphene

120

POPs

CAS chemical name

Synonyms and Trade Names M5055, chlorinated camphene, Chlorocamphene, Clor chem T-590, Compound 3956, Huilex, Kamfochlor, Melipax, Motox, Octachlorocamphene, Penphene, Phenacide, Phenatox, Phenphane, Polychlorocamphene, Strobane-T, Strobane T-90, Texadust, Toxakil, Toxon 63, Toxyphen, Vertac 90%.

Dioxins Furans PCBs

Polychlorinated dibenzopara-dioxins Polychlorinated dibenzofurans Polychlorinated biphenyls

Aroclor, Pyranol, Pyroclor, Phenochlor, Pyralene, Clophen, Elaol, Kanechlor, Santotherm, Fenchlor, Apirolio, Sovol.

121

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