Environmental Chemistry

Unit 4
Site Remediation

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 Topics
• Site Remediation
• Ex-situ Remediation of Excavated Materials
• Ex-situ Remediation of Groundwater
• In-situ Remediation of Soil
• In-situ Remediation of Groundwater
• In-situ Containment
• Off-gas Treatment
• Overview of Ontario’s Brownfield Legislation

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 Overview
• Site remediation/cleanup and the development of a
site cleanup plan generally involves three basic
steps:
• identification and assessment of cleanup options;
• detailed design and implementation of the chosen cleanup option;
and
• confirmatory sampling and verification of the completed cleanup.

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 Remediation of Simcoe Street Property

April 2011 October 2012

June 2013 4
 Remediation of a former Gas Station at
Pickering Town Centre (2012-2013)

Groundwater Monitoring Well Soil excavation and restoration

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 Site Remediation Prior to Construction of
the Oshawa Courthouse

Looking Northeast at the site of the Excavation removes contaminated soil.

Durham Consolidated Courthouse in
Oshawa (130 Bond Street). (Ex-situ Remediation of Excavated Materials)
Source: Infrastructure Ontario
Contaminated groundwater is pumped
into these steel tanks, treated and
discharged into the municipal sewer
system.
(Ex-situ Remediation of Groundwater)
Potassium permanganate (an oxidant)
is used to treat the soil in-place.
(In-situ Remediation of Soil)

Source: Infrastructure Ontario

A trench is dug for the installation of an
environmental barrier wall.
(In-situ Containment)

Source: Infrastructure Ontario

 Remediation Strategies
• Ex-situ Remediation of Excavated Materials
• Ex-situ Remediation of Groundwater
• In-situ Remediation of Soil
• In-situ Remediation of Groundwater
• In-situ Containment
• Off-gas Treatment

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 Ex-situ Remediation of
Excavated Materials
• "ex-situ" means that the contaminated material is
excavated or removed from its location on the site
either permanently or temporarily while it is treated.
• ex-situ treatment provides an immediate solution
when the excavated material is taken to an
appropriate landfill

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Conventional Excavated Material
Treatment Options
• The four most common treatment options for
excavated materials (e.g., contaminated soils and
rock) are:
• excavation and disposal “(dig and dump)”
• incineration
• solidification/stabilization
• landfarming

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 Conventional Excavated Material
Treatment Options
• Excavation and Disposal “(dig and dump)”
• the most common remediation "technology" used for soils
• contaminated material is excavated and transported to a
licensed waste disposal facility or landfill
• a rapid method of dealing with contaminated
material
• overall costs can be high due to transportation
costs and landfill tipping fees
• does not actually treat the contamination,
merely relocates it

Source: http://eco-web.ca 12
Conventional Excavated Material
Treatment Options
• Incineration
• waste materials are heated to above 1000°C to volatilize and
combust organic contaminants in the presence of oxygen
• can be done on-site (e.g., Smithville) or off-site (e.g., Clean
Harbors, Lambton – South Western Ontario)
• suitable for treating organic contaminates (fuels, PCBs,
pesticides, etc.)
• overall costs can be high due to transportation costs and
Source: http://www.cleanharbors.com/
incinerator tipping fees or incinerator construction costs locations/lambton/incineration_system.html

• public acceptance is generally low

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Conventional Excavated Material
Treatment Options
• Solidification/Stabilization
• contaminants are physically or chemically bound to the medium
(e.g., cement) to produce an inert material that will not leach out the
contaminants
• can be used in-situ or ex-situ
• most applicable to inorganic compounds (i.e., metals)
• time to complete cleanup is relatively short
• Example: Sydney Tar Ponds (Discovery Channel)
• http://www.youtube.com/watch?v=lg2iVw6KWLk&list=PLeDJtpJsNoztsY
bIOuq4R32seE0T1hFm7
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Conventional Excavated Material
Treatment Options
• Landfarming
• excavated soil is spread out to a shallow
depth
• the soil is tilled to enhance aerobic
biodegradation of the contaminants
• applicable to non-halogenated volatiles and
semi-volatiles, fuel hydrocarbons
• not-applicable to heavily contaminated soils
or to contaminants where there are issues
with toxicity (e.g., pesticides)
• simple technology to implement, low capital
costs
• requires a large amount of space
• remediation may take several months or Source: Wardrop

more 15
 Other Excavated Material
Treatment Options (Cont.)
• Chemical Reduction/Oxidation
• Reduction/oxidation chemically converts hazardous contaminants to
non-hazardous or less toxic compounds that are more stable, less
mobile, and/or inert. The oxidizing agents most commonly used are
ozone, hydrogen peroxide, potassium permanganate, hypochlorite,
chlorine, and chlorine dioxide.

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 Other Excavated Material
Treatment Options
• Less conventional or less used technologies include:
• Soil Washing
• Contaminants sorbed onto fine soil particles are separated from bulk soil
in an aqueous-based system on the basis of particle size. The wash water
may be augmented with a basic leaching agent, surfactant, pH
adjustment, or chelating agent to help remove organics and heavy metals.
• Dehalogenation
• Reagents are added to soils contaminated with halogenated organics.
The dehalogenation process is achieved by either the replacement of the
halogen molecules or the decomposition and partial volatilization of the
contaminants.
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 Other Excavated Material
Treatment Options (Cont.)
• Less conventional or less used technologies include:
• Chemical Extraction
• Waste contaminated soil and extractant (e.g., acid) are mixed in an
extractor, thereby dissolving the contaminants. The extracted solution is
then placed in a separator, where the contaminants and extractant are
separated for treatment and further use.

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 Other Excavated Material
Treatment Options (Continued)
• Less conventional or less used technologies include:
• Low/High Temperature Desorption:
• Wastes are heated to volatilize water and organic contaminants. A carrier
gas or vacuum system transports volatilized water and organics to the gas
treatment system.

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 Ex-Situ Remediation of
Excavation Materials
• Implementation at the Oshawa Courthouse

• site was contaminated with

trichloroethylene (TCE)
• soils were excavated, allowed to
drain and segregated
• impacted soil was removed off-site to
a licensed landfill
• soils found to satisfy the applicable
criteria were stockpiled off-site and
later returned to the site

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 Ex-Situ Remediation of
Groundwater (Pump and Treat)
• ex situ treatment of groundwater by "pump and treat"
consists of
• extracting (pumping out) the contaminated groundwater,
• treating the extracted water, and
• discharging or re-injecting treated water

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 Ex-Situ Remediation of
Groundwater (Pump and Treat)
• pumping groundwater to the surface is a strategy which is intended to
contain contamination in the subsurface by hydraulically preventing
groundwater from flowing out of the contaminated zone
• although pumping and treating groundwater may result in partial
remediation of soil and groundwater in the saturated zone, this
approach should not be seen as a way to completely remove
contamination from the saturated zone
• in some cases the pump and treat option is the only one available or
is less expensive than other options even if groundwater has to be
pumped for many years (5+)

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 Ex-Situ Remediation of
Groundwater (Pump and Treat)
• constituents commonly removed from extracted
groundwater are:
• nuisance inorganics (e.g., iron and manganese)
• suspended solids
• free product (e.g. gasoline)
• dissolved organic contaminants (volatile and semi-volatile)
• dissolved inorganic contaminants

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 Ex-Situ Remediation of
Groundwater (Pump and Treat)
• Implementation at the Oshawa Courthouse site:
• groundwater was pumped from extraction wells and/or sumps
located in the base of the remedial excavation
• the groundwater was treated using chemical reduction/oxidation
(potassium permanganate) in an on-site treatment system
• the treated water was discharged to the Region of Durham's
sanitary sewer system under permit

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Reduction/Oxidation of Trichloroethylene
with Potassium Permanganate
• C2HCl3 + 2KMnO4  2CO2 + 2MnO2 + 2K+ + 3Cl- + H+

• The other major decomposition products of

trichlorothylene (dichloroethylene (C2H2Cl2), chloroethane
(C2H5Cl3), and vinyl chloride (C2H3Cl)) are similarly
oxidized/reduced

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 In-situ Remediation of Soil
• “in-situ" means that the contaminated material is
treated in place

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 In-situ Remediation of Soil
• advantages
• may be more cost-effective
• can be used at a site with little disruption to ongoing operations
• minimizes exposing humans and the environment to contaminants

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 In-situ Remediation of Soil
• disadvantages
• generally require longer treatment times than ex-situ treatment
technologies
• less effective for sites with low soil permeability, subsurface
heterogeneities, contaminant distribution, obstructions to treatment
zones
• more difficult to control in-situ treatment processes and the
contaminated material may not be cleaned up uniformly

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 In-situ Remediation of Soil
• Conventional Treatment Methods
• soil vapor extraction (SVE)
• chemical oxidation/reduction
• bioremediation

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 In-situ Remediation of Soil
• Soil Vapour Extraction (SVE)
• vacuum is applied through extraction wells to create a
pressure/concentration gradient that induces gas-phase volatiles to
be removed from soil through extraction wells
• only applicable to volatile compounds with a vapour pressure
greater than 0.5 mm Hg
• can be used for volatile organic compounds and some fuels
• will not remove heavy oils, metals, PCBs, or dioxins
• other factors, such as the moisture content, organic content, and air
permeability of the soil, will also affect in-situ SVE's effectiveness

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Soil Vapour Extraction

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Soil Vapour Extraction Example
• Del Amo Superfund Site, Los Angeles, California
• From 1943 until 1972, the Del Amo Facility site was a center of large-
scale industrial activities. Originally built to produce synthetic rubber
during World War II.
• Groundwater and soils were contaminated with VOCs, PAHs, and
minor amounts of pesticides, PCBs, and heavy metals.
• The significant chemicals found in the soil were benzene,
tetrachloroethene, isopropyltoluene, trichloroethene, benzo(a)pyrene,
endeno(1,2,3-cd)pyrene, benzo(b)fluoranthene, 4,4-DDT, n-
nitrosodiphenylamine, arsenic and copper.
• (3.25 minutes)
• Source : http://www.youtube.com/watch?v=ZqsMkf_IY2U 34
 In-situ Remediation of Soil
• Chemical Oxidation
• oxidation chemically converts hazardous contaminants to non-hazardous
or less toxic compounds that are more stable, less mobile, and/or inert.
• chemical oxidants most commonly used for soil include peroxide, ozone,
and permanganate.
• in general, the oxidants have been capable of achieving high treatment
efficiencies (e.g., > 90 percent) for unsaturated aliphatic (e.g.,
trichloroethylene [TCE]) and aromatic compounds (e.g., benzene), with
very fast reaction rates (90 percent destruction in minutes).
• matching the oxidant and in-situ delivery system to the contaminants of
concern (COCs) and the site conditions is key

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In-situ Remediation of Soil
Chemical Oxidation
 In-situ Remediation of Soil

In-situ chemical oxidation was

completed using five injection
trenches and approximately 153
injection wells.

Potassium permanganate (an oxidant)

is used to treat the soil in-place at the
Oshawa Courthouse.
Source: Infrastructure Ontario
 In-situ Remediation of Soil
• Bioremediation
• The activity of naturally occurring microbes is stimulated by
circulating water-based solutions through contaminated soils to
enhance biological degradation of organic contaminants
• Nutrients, oxygen, or other amendments may be used to enhance
bioremediation and contaminant desorption from subsurface
materials.

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 In-situ Remediation of Soil
• Other Treatment Methods
• Phytoremediation
• plants are used to bioaccumulate
contaminants from soil and then are
harvested (thus removing the pollutants from
the site)
• limited to the surface area and depth
occupied by the roots.
• requires a long-term commitment
• contaminants may continue to leach into the
groundwater while the clean-up continues
• steps must be taken to prevent the
contaminates from entering the food chain
(i.e., requires the safe disposal of the
affected plant material 39
 Phytoremediation
• Crozet, Virginia
• treatment of arsenic contamination
• (10 minutes)
• Source : http://www.youtube.com/watch?v=IabslL-SgqY

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In-situ Remediation of Groundwater
• advantages
• may be more cost-effective
• can be used at a site with little disruption to ongoing operations
• minimizes exposing humans and the environment to contaminants

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In-situ Remediation of Groundwater
• disadvantages
• generally require longer treatment times than ex-situ treatment
technologies
• less effective for sites with low soil permeability, subsurface
heterogeneities, contaminant distribution, obstructions to treatment
zones

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In-situ Remediation of Groundwater
• Conventional Treatment Methods
• free product recovery
• passive/reactive treatment walls

• Note: in most applications, Ex-situ Remediation of

Groundwater is used, with the effluent undergoing further
treatment in a municipal sewage treatment plant.

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In-situ Remediation of Groundwater
• Passive/Reactive Treatment Walls
• A permeable reaction wall is installed across the flow path of a
contaminant plume, allowing the water portion of the plume to
passively move through the wall.
• These barriers allow the passage of water but prevent the
movement of contaminants by employing such agents as zero-
valent metals, chelators, sorbents, microbes, and others.

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In-situ Remediation of Groundwater
• Other Treatment Technologies
• In-well Air Striping – similar to vapour extraction, but the
groundwater is treated without bringing it to the surface
• Thermal Treatment - Steam is forced into an aquifer through
injection wells to vaporize volatile and semivolatile contaminants.
Vaporized components rise to the unsaturated zone where they are
removed by vacuum extraction and then treated.

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 In-situ Containment
• Hydraulic Containment Techniques
• contain contamination by causing or allowing (directing)
groundwater to flow
• Physical Containment Techniques
• attempt to prevent groundwater from flowing out of the site

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 In-situ Containment
• Physical Containment Techniques
• Slurry Walls
• vertically excavated trench that is filled with a slurry (typically soil, bentonite
and water).
• Grout Curtains
• special fluids are injected under pressure into a rock or soil body to seal it
• once in place, these fluids set or gel into the rock or soil voids, greatly
reducing the permeability
• Sheet Pile Walls
• sheet piles made of wood, precast concrete, or steel can be used to form a
continuous containment wall or barrier
• Surface Caps
• A cap provides a physical separation between the contaminants and
humans, animals, and plant roots.
• A cap’s impermeable layer (usually clay or a synthetic liner) must be covered
by an adequately thick layer of soil to avoid damage from freeze/thaw action.
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A trench is dug for the installation of an
environmental barrier wall.
(In-situ Containment)

Source: Infrastructure Ontario

Slurry Wall and Surface Cap

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Slurry Wall and Groundwater
Extraction Well

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Case Study – In-situ Containment
• Sydney Tar Ponds Clean-up
• solidification and stabilization was used to remediate the former Sydney
Tar Ponds in Cape Breton, Nova Scotia
• the contaminated sediment was mixed with cement to bind any hazardous
material in place and to prevent it from escaping into the environment
• in total, 871,650 tonnes of contaminated material was contained - the equivalent
of stacking up 112 football fields, each one a metre deep.
• http://www.youtube.com/watch?v=lg2iVw6KWLk&list=PLeDJtpJsNoztsYbIOuq4R32
seE0T1hFm7 (Discovery Channel)
• http://www.youtube.com/watch?v=883hQKY1YPs (Rick Mercer)
• http://www.youtube.com/watch?v=4QVqF4pFrqk (Today in America)
• http://www.youtube.com/watch?v=ruCfgLnlTWw (Award)

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 Off Gas Treatment
• off-gases may need to be treated to remove or
destroy the contaminants in them
• off-gases come from groundwater and soil treatment
technologies, gases directly from the surface of soil
or groundwater, gases produced from in-situ venting
technologies

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 Off Gas Treatment
• Examples of Off-Gas Treatment included:
• Air Stripping
• Carbon Adsorption (Vapour Phase)
• Biofiltration

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 Air Stripping
• Air stripping involves the extraction of groundwater
and the trickling of the water through a device that
volatilizes contaminants.
• packed towers, diffused aeration, tray aeration, and spray aeration
• only works for volatile contaminants

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Air Stripping

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 Air Stripping
• Advantages:
• treats high concentrations
• can be a permanent solution
• low capital costs
• Disadvantages:
• off-gases and residual liquids may require treatment
• inorganics can clog the stripping column packing material which
then requires washing or replacement
• may require further treatment to meet sanitary water standards

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 Vapour Phase Carbon Adsorption
• off-gases are pumped through a series of canisters or
columns containing activated carbon to which
organic contaminants adsorb.
• periodic replacement or regeneration of saturated
carbon is required

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Vapour Phase Carbon Adsorption
 Biofiltration
• Biofiltration is a low-cost and highly effective air
pollution control (APC) technology in which vapor-
phase organic contaminants are passed through a
bed of porous media and sorb to the media surface
where they are degraded by microorganisms in the
media
• specific strains of bacteria may be introduced into the filter and
optimal conditions provided to preferentially degrade specific
compounds

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 Biofiltration
• The biofilter provides several advantages over
conventional activated carbon adsorbers.
• the maximum adsorption capacity available constantly
• the filter does not require regeneration
• the contaminants are destroyed not just separated

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Biofiltration

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 Off-Gas Treatment
• Basket Creek, Georgia
• treatment of soil contaminated by illegal dumping of industrial
solvents, paint removers, and other toxic wastes
• (6 minutes)
• Source : http://www.clu-in.org/studio/video/

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 Shell Facility - Toronto
• TEDCO Brownfields Redevelopment - Part One and
Part Two
• Clean-up of the former Shell facility on Commissioner Street in
Toronto (1995-1997)
• http://www.youtube.com/watch?v=-TOY0b6MK8I (6.42 minutes)
• http://www.youtube.com/watch?v=eoukcHFTurM&feature=related (7.11
minutes)
• Note: clean-up completed before new Brownfield Legislation

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 Brownfield Legislation
• Purpose:
• to encourage the cleanup and redevelopment of brownfield sites
while ensuring the environment is protected
• to establish clear rules for site assessment and clean-up
• to ensure only qualified people undertake this work
• to provide for a filing of a record of site condition in a public registry
• to reduce liability for property owners, municipalities and others

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 Brownfield Legislation
• two new parts added to the Ontario Environmental
Protection Act
• Part XV.1 sets out the requirements for the assessment and
cleanup of a property and the filing of a “record of site condition” in
the Environmental Site Registry
• Part XV.2 contains provisions reducing the potential liability for
municipalities and secured creditors

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 Part XV.1 of the EPA
• Under Part XV.1 of the EPA, a property owner may file a
record of site condition on the Environmental Site
Registry if the applicable standards are met for soil,
ground water and sediment
• For some types of proposed changes of property use,
such as from industrial to residential, the filing of a record
of site condition is mandatory

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 Part XV.1 of the EPA
• An initial assessment (referred to as a “phase one
environmental site assessment”) is required to determine
the likelihood that contaminants have affected the
property.
• A more detailed assessment (referred to as a “phase two
environmental assessment”) may be required to
determine the concentration of contaminants on the
property.

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 Environmental Site Assessment
• Phase I ESA
• to determine the likelihood that one or more contaminants have
affected all or part of the property
• Under O.Reg 153/04 requires:
• records review, site visit, interviews, evaluation of information, and
preparation of a written report
• No sampling of the soil, groundwater or sediment

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 Environmental Site Assessment
• Phase II ESA
• to determine the location and concentration of one or more
contaminants in the natural environment
• Required:
• if a qualified person deems it necessary following a Phase I ESA
• For some types of change of property use (e.g., industrial to residential)

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 Environmental Site Assessment
• Phase II ESA
• Under O.Reg 153/04 requires:
• planning and conducting a site investigation
• sampling of the soil (mandatory)
• sampling of groundwater and sediment if a “qualified person” deems it
necessary

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 Analytic Protocols and Lab
Accreditation
• Under O.Reg 153/04 requires:
• use of a lab accredited for the analysis of soil, ground water and
sediment
• Adherence to the MOE document:
• “Protocol for Analytical Methods Used in the Assessment of Properties
under Part XV.1 of the EPA”
• Specifies sampling containers, minimum sampling volumes, analytical method,
maximum sample storage times and other QA/QC items

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 Site Condition Standards
• Two options:
• Remediate the site to standards in the document:
• Soil, Ground Water Sediment Standards for Use Under Part XV.1 of the
EPA (Tables 2-5)
• Preparation of a Risk Assessment

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 Risk Assessment
• in some cases it may be difficult to remediate a
property to the standards set out in Tables 1-5
• Requires a site specific risk assessment
• assess potential risks; set a site specific, risk-based condition
standards; and identify any risk management measures that may
be required
• MOE conducts a detailed review of the submission by the Qualified
Professional (16-22 weeks allowed as per regulation) and makes a
final decision whether to accept/reject the Risk Assessment

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 Risk Assessment
• A Certificate of Property Use (CPU) can be issued by
the MOE when it approves a risk assessment
• Sets out specific requirements and actions that must be taken
• monitoring, reporting, limits on use of property
• registration on property title may be required

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 Site Remediation
• Assessment of Options
• Design and Implementation
• Regulatory approvals (waste, air, surface water) may be required
• Confirmatory Sampling

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Record of Site Condition (RSC)
• Summarizes the environmental condition of a
property as determined by a qualified person
• Phase I ESA
• Phase II ESA
• Confirmatory Sampling

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Record of Site Condition (RSC)
• Filed Publically on the Environmental Site Registry
• Example – Oshawa Courthouse
• http://www.environet.ene.gov.on.ca/besr-
public/rscView.do?formatId=html&searchId=gen&rscId=11117

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 References
• Remediation Technologies Screening Matrix and
Reference Guide, 4th Edition, U.S. Army
Environmental Center, January 2002
• http://www.frtr.gov/matrix2/section1/toc.html
• Contaminated Sites Program - Federal Sites,
Technical Assistance Bulletins (TABs)
• http://www.on.ec.gc.ca/pollution/ecnpd/tabs/tab24-e.html

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