REMEDIATION

TECHNOLOGIES
 LECTURE TOPICS
Description of remediation technologies:
• PHYSICAL
• CHEMICAL
• BIOLOGICAL
• NATURAL ATTENUATION
• INTEGRATED (TREATMENT TRAIN)
 PHYSICAL
Physical methods are usually used
in the beginning of a remediation
project (start of cleanup), when
concentration of pollutants are high.
 PHYSICAL
• Pump&treat • Electrokinetic methods
• Venting • Resistance heating
• Soil vapor extraction • Vitrification
• Slurping
• Air sparging
• Air stripping
• Excavation
 CHEMICAL
• Chemical oxidation
• Surfactant flushing
• Precipitation
• Immobilization and solidification
• Chemical stabilization
 BIOLOGICAL
INORGANIC POLLUTANTS ORGANIC POLLUTANTS
• Sulfate reduction • Bioventing
• Biosparging
• Phytoremediation
• Bioslurping
• Constructed wetlands
• Bioaugmentation
• Biosorption • Phytoremediation
• Bioimmobilization • Bioimmobilization
• Biostabilization • Biosorption
• Biological reduction and oxidation • Composting
of metals • Aerobic degradation of pollutants in
• Natural attenuation soil
• Biofiltration • Landfarming
• Denitrification • Co-metabolic degradation
• Biofiltration
• Natural attenuation
 PHYSICAL - PUMPING
WELLS
- Extraction wells
- Injection wells
- Monitoring wells
 EXTRACTION WELL
Borehole = Ø 150 mm to 300 mm
Well casing = Ø 100 mm to 200 mm
PVC or stainless steel
Well screen = slotted PVC or
stainless steel
Filter pack = coarse to medium sand
or fine gravel
Seal: bentonite
Pump: submersible: 100 mm ~ 4.4
L.s-1; 150 mm 7.6 L.s-1
head to pump to surface
Pneumatic: up to 10 0.6 L.s-1 less
fouling problems
PUMP & TREAT - DEFINITION
Pump-and-treat
This involves removing contaminated groundwater from
strategically placed wells, treating the extracted water after it is
on the surface to remove the contaminates using mechanical,
chemical, or biological methods, and discharging the treated
water to the subsurface, surface, or municipal sewer system.
PHYSICAL - PUMP&TREAT
GOALS OF PUMP & TREAT
Restore contaminated water bearing zones by decreasing dissolved
contaminant concentraions to an acceptable level by extraction of
contaminated groundwater with dissolved pollutant.
1. Prevent or contain contaminant migration to protect down-gradient
locations
2. Recover LNAPL by drawing free product into recovery wells
3. Use with other technologies:
- Dewater (lower water table) & SVE
- Use with re-injection for in-situ bioremediation
4. Formation of the cone of depression and lowering of water table
(drawdown)
CONE OF DEPRESSION
 PUMP&TREAT - DESIGN
The well design, pumping system, and treatment
are dependent on the site characteristics and
pollutant type. It is not uncommon to find many
wells extracting groundwater at the same time.
These wells may be screened at different depths to
maximize effectiveness. A major component of any
groundwater extraction system is a ground water
monitoring program to verify its effectiveness.
Monitoring the cleanup allows the operator to make
adjustments to the system in response to changes
in subsurface conditions.
PHYSICAL - PUMP&TREAT
Characterization of the contaminated site before
implementation of pump & treat:
1. Aquifer characterization:
Hydraulic conductivity (K), permeability, aquifer thickness, groundwater
flow direction and gradient, water table fluctuations
2. Geologic characterization
Grain size distribution, porosity, organic content
3. Contamination extent
Horizontal and vertical (plan & profile)
NAPL product (is free phase product present?)
4. Groundwater analysis
Inorganics (hardness, ions), pH, bacteria, pollutant concentration
PUMP & TREAT - LIMITATIONS
• Not efficient when low permeability of the
aquifer (kf < n*10-5 to n*10-6)
• Not applicable whem thickness of an aquifer is
<1m
• Pump & treat systems often take a very long time (e.g., 50 -100
years) to meet cleanup goals, and in many cases they are never
expected to ever achieve those goals.
• Risk of rebounding (see the next page)
• Absolute elimination of pollutants is not possible
 REBOUNDING
Pumping depresses the groundwater level,
leaving residuals sorbed to the soil. After the
groundwater level returns to its normal level,
contaminants sorbed onto soil become
dissolved. This phenomenon is called
„rebound“ Rebound tests should be
performed frequently in the first few years
after a system is turned off, and after major
rain or flooding events.
 WHAT „TREAT“ MEANS?
• Air stripping or steam stripping (organics)
• Carbon adsorption (organics)
• Ion exchange (metals, inorganics)
• Chemical oxidation (organics)
• Biological treatment
• Membrane filtration (reverse osmosis)
• Fluids separation
– Oil:water separation for NAPLs (gravity
separation)
– Liquid/Liquid extraction
PHYSICAL – SOIL VAPOR EXTRACTION
(SVE) (VENTING) - DEFINITION
Venting is an in situ remedial technology that reduces
concentrations of volatile constituents in petroleum products
adsorbed to soils in the unsaturated (vadose) zone. In this
technology, a vacuum is applied through wells near the source of
contamination in the soil. Volatile constituents of the contaminant
mass "evaporate" and the vapors are drawn toward the extraction
wells. Extracted vapor is then treated as necessary (commonly with
carbon adsorption) before being released to the atmosphere. The
increased air flow through the subsurface can also stimulate
biodegradation of some of the contaminants, especially those that
are less volatile. Wells may be either vertical or horizontal. In areas
of high groundwater levels, water table depression pumps may be
required to offset the effect of upwelling induced by the vacuum.
 SVE APPLICATION
This technology has been proven effective in reducing
concentrations of volatile organic compounds (VOCs) and certain
semi-volatile organic compounds (SVOCs) found in petroleum
products at UST sites. SVE is generally more successful when
applied to the lighter (more volatile) petroleum products such as
gasoline. Diesel fuel, heating oils, and kerosene, which are less
volatile than gasoline, are not readily removed by SVE, nor are
lubricating oils, which are non-volatile. Because almost all
petroleum products are biodegradable to a certain degree, these
heavier petroleum products may be suitable for removal by
bioventing. Injection of heated air also can be used to enhance the
volatility of these heavier petroleum products because vapor
pressure generally increases with temperature. However, energy
requirements for volatility enhancement may be so large as to be
economically prohibitive.
SVE - DESIGN
SVE - DESIGN
SVE – SITE CHARACTERIZATION
Some of the factors that determine the effectiveness of SVE
are:
- permeability of the soil,
- soil structure and stratification,
- soil moisture content, and
- depth to groundwater.
The permeability of the soil affects the rate of air and vapor movement through the
soil;
Soil structure and stratification are important to SVE effectiveness
High moisture content in soils can reduce soil permeability
SVE is generally not effective in treating soils below the top of the capillary fringe
 SVE - LIMITATIONS
SVE is generally not appropriate for sites with a
groundwater table located less than 3 feet
below the land surface. Special considerations
must be taken for sites with a groundwater table
located less than 10 feet below the land surface
because groundwater upwelling can occur
within SVE wells under vacuum pressures,
potentially occluding well screens and reducing
or eliminating vacuum-induced soil vapor flow.
 PHYSICAL – AIR STRIPPING
Air stripping is the process of transfering a contaminant from the liquid
phase to the gas phase. In the air stripping process, air and water are
contacted in a packed column designed to maximize the contact
surface area between the water and air. Air stripping performance
depends on factors such as:
- Characteristics of the volatile material (partial pressure, Henry’s
constant, gas-transfer resistance, etc.)
- Water and ambient air temperature
- Turbulence in gaseous and liquid phases
- Area-to-volume ratio
- Exposure time
- Use of a bioreactor on the air waste stream (biofiltration)
AIR STRIPPING - DESIGN
AIR STRIPPING - POLLUTANTS
Air stripping is applicable for the following pollutants:
some organic chemicals (VOCs) including benzene, toluene,
xylene, tri/tetrachloroethylene, trihalomethanes, vinyl
chloride and many others.
Henry’s Constant of the target contaminant should be > 0.1
kPa.m3.mol-1 (0.01 atm. m3.mol-1 or 100 atm)
Fouling can occur when calcium exceeds 40 mg/L, iron
exceeds 0.3 mg/L, magnesium exceeds 10 mg/L,
manganese exceeds 0.05 mg/L. Biological fouling may also
occur depending on the feed water quality.
AIR STRIPPING - THEORY
Theory. Air stripping is the mass transfer of VOCs that are
dissolved in water from the water phase to the air phase.
The equilibrium relationship is linear and is defined by
Henry’s Law (Kavanaugh and Trussell, 1980; Shulka and
Hicks, l984). For low concentrations of volatile
compound a:
pa = Ha xa
At equilibrium, the partial pressure of a gas, pa, above a
liquid is directly proportional to the mole fraction of the
gas, xa, dissolved in the liquid. The proportionality
constant, Ha, is known as the Henry’s constant. The
value of the constant generally increases or decreases
with the liquid temperature (Plambeck, 1995).
AIR STRIPPING - THEORY
As a consequence, the solubility of gases generally
decreases with increasing temperature (Plambeck,
1995). EPA (1998) has published a comprehensive
document, Henry's Law Constants, Fm Values, Fr
Values and Fe Values for Organic Compounds, at
http://www.epa.gov/ttn/oarpg/tl/fr_notices/appj.pdf.
Practical application of the technology for
contaminant removal is generally limited to
compounds with Henry’s constant values greater
than 100 atmospheres. The theory is developed in
textbooks such as McCabe et al. (1993) and Treybal
(1980).
AIR STRIPPING - POLLUTANTS
Henry’s Gas Law: pg = kH.caq

Henry’s Constant: kH = pg /caq (Pa.m3.mol-1)

The amount of a given gas that dissolves in a given type and volume of
liquid is directly proportional to the partial pressure of that gas in
equilibrium with that liquid (at given constant temperature).

Henry’s law constant can be expressed also as the dimensionless ratio

between the aqueous concentration of substance caq and its gas phase
concentration cg:

kH = caq / cg
PHYSICAL – AIR SPARGING
DEFINITION:
Air sparging is a remediation technique used by injecting air
into contaminated ground water. The main purpose of the
air sparging system is to provide biodegradation of volatile
organic compounds (VOCs) in the groundwater passing
through the treatment zone. The addition of oxygen to the
soil and groundwater encourages biodegradation of
contaminants in and above the water table, this act as a
nutrient for bacteria. The VOCs in petroleum are drastically
reduced by the process. The compounds are turned into a
gaseous state, then air is vented through the unsaturated
zone. Air Sparging is mostly used with Soil Vapor
Extraction, which is the most effective. Together they are
called an AS/SVE.
 AIR SPARGING - APPLICATION
The target contaminant groups for air sparging are VOCs and
fuels in groundwater. Air sparging is generally more
applicable to the lighter gasoline constituents such as
benzene, ethylbenzene, toluene, and xylene, chlorinated
solvents. It is less applicable to heavier constituents such as
diesel fuel and kerosene.
 AIR SPARGING - APPLICATION
Important – Injection pressure has to be lower than
fracturing pressure

Pfracture [ psig ] = 0,73 x Dsoil [ ft ]

based on bulk density 1.68 g.cm.cm-3 [105

lb.ft-3]
This pressure is related to the owerburden of weight of the soil
matrix above the injection point.
Field K., Gibbs J., Condit W., Leeson A., Wickramanayake G. (2002): Air Sparging: a project manager´s guide, Beattelle
Press, Columbus, Ohio: pp 45
AIR SPARGING - DESIGN
 AIR SPARGING – RADIUS OF
INFLUENCE
The air sparging system should be designed according to
results of a pilot test. The radius of influence of air sparging
wells should be determined to learn what distance among
wells should be kept.
 AIR SPARGING - LIMITATIONS
Factors that may limit the applicability and effectiveness of the
process include:
- Air flow through the saturated zone may not be
uniform, which implies that there can be
uncontrolled movement of potentially dangerous vapors.
- Depth of contaminants and specific site geology
must be considered.
- Air injection wells must be designed for site-specific
conditions.
- Soil heterogeneity may cause some zones to be
relatively unaffected.
PHYSICAL – RESISTANCE HEATING (ERH)
DEFINITION: ERH is the process of passing
alternating current electricity through the soil
between electrodes installed in the ground, and
heating the soil by Joule heating.
Two primary types of ERH, three-phase and six-
phase soil heating were developed and later
demonstrated in the field. When the temperature
achieves the boiling point of water, steam is
generated in-situ, and extracted via recovery wells.
RESISTANCE HEATING -DESIGN

Six phase heating

RESISTANCE HEATING -
APPLICATION

Electrical resistance heating enhances the recovery of

soils contaminated with volatile and semi-volatile organic
compounds. Electrical resistance heating assists soil
vapor extraction by heating the contaminants in the soil. It
raises the vapor pressure of VOCs and SVOCs,
increasing volatilization and removal. As electrical
resistance heating dries the soil, it also creates a source
of steam that strips contaminants from soils.
PHYSICAL - STEAM INJECTION
• Steam is the best applied for heating the more permeable
subsurface zones, and has seen extensive use in
enhanced oil recovery. Steam is generated aboveground,
and injected via wells screened across the zones of
interest.
APPLICATION:
Volatile organic compounds, semi-volatile organic
compounds like BTEX, chlorinated solvents
STEAM INJECTION - DESIGN
STEAM INJECTION - LIMITATION
Stem injection will not remediate inorganic contaminants (with
the probable exception of volatile metals such as mercury).
Steam injection may not be appropriate for remediation of
very low volatility organics, such as pesticides, some PAHs,
dioxins, and PCBs. Site conditions that may not be
conducive to steam injection include high groundwater
fluxes, buried ordnance or explosive containers, or
presence of critical subsurface facilities or utilities. Where
the size of the treatment volume is large, the cost of steam
injection may also be considered a "limitation," depending
on financial resources.
 PHYSICAL - VITRIFICATION
DEFINITION:
In situ vitrification (ISV) is a process which uses an electric
current to melt soil or other earthen materials at extremely high
temperatures (1,150 to 2,000 °C) and thereby immobilize most
inorganics and destroy organic pollutants by pyrolysis. Inorganic
pollutants are incorporated within the vitrified glass and
crystalline mass. Water vapor and organic pyrolysis combustion
products are captured in a hood, which draws the contaminants
into an off-gas treatment system that removes particulates and
other pollutants from the gas. The vitrification product is a
chemically stable, leach-resistant, glass and crystalline material
similar to obsidian or basalt rock. The process destroys and/or
removes organic materials. Radionuclides and heavy metals are
retained within the molten soil.
VITRIFICATION - PRINCIPLE
VITRIFICATION - APPLICATION
• The target contaminant group for in situ vitrifcation is
generally inorganics (including radionuclides). The
vitrification process can destroy or remove organics and
immobilize most inorganics in contaminated soils, sludge,
or other earthen materials. The process has been tested
on a broad range of VOCs and SVOCs, other organics
including dioxins and PCBs, and on most priority pollutant
metals and radionuclides.
VITRIFICATION - LIMITATIONS
Factors that may limit the applicability and effectiveness of the
in situ vitrification include:
• Depth of contaminants may limit some types of application
processes.
• Like all in situ treatments, confirmatory sampling can be
more difficult than for ex situ treatments.
• The solidified material may hinder future site use.
OUTPUT
• A single melt can treat up to 1000 tons of contaminated soil
to depths of 20 feet, at a typical treatment rate of 3 to 6 tons
per hour.
PHYSICAL – SOIL WASHING
Ex-situ soil separation process
(physical, or phycical/chemical treatment)
Water-based process for scrubbing soils ex-situ to
remove contaminants in one of the following two
ways:
- By dissolving or suspending them in the wash solution
(which can be sustained by chemical manipulation of
pH, surfactant)

- By concentrating them into a smaller volume of soil

through particle size separation, gravity separation,
and attrition scrubbing (similar to those techniques
used in sand and gravel operations).
PHYSICAL – SOIL WASHING

US EPA (1996): available on http://www.clu-in.org/products/costperf/SOILWASH/Kop.htm

 SOIL WASHING

www.decnc.com
CHEMICAL REMEDIATION
TECHNOLOGIES
CHEMICAL – OXIDATION IN SITU
Oxidants:
Potassium permanganate
Hydrogen peroxide
Calcium peroxide
Fenton´s reagent (common catalyst or modified
catalyst)
Activated sodium persulfate
Ozone
 OZONE
Molecular Weight - 48g Equiv. Weight - 24g Solubility - 600
mg/L
Availability – On site generation
3-5% Air
8-12% O2
Reactions Oxidation
O3 + 2H+ + 2e- O2 + H2O Eo = 2.07 V
2OH• + 2H+ + 2e- 2H2O Eo = 2.76v
Hydroxyl Radical Formation
O3 + H2O O2 + 2OH• (Slow)
2O3 + 3H2O2 4O2 + 2OH• + 2H2O (Fast)
Decomposition
2O3 3O2 4HO• 2H2O + O2
HYDROGEN PEROXIDE
Molecular Weight- 34g Equiv. Weight - 17g, 34g (OH•) Solubility
- Miscible Availability - 30%, 50% Solutions Reactions
Oxidation
2OH• + 2H+ + 2e- 2H2O Eo = 2.76v
H2O2 + 2H+ + 2e- 2H2O Eo = 1.77v
HO2 + H2O + 2e- 3OH- Eo = 0.88v
Hydroxyl Radical Formation
H2O2 + Fe2+ Fe3+ + OH• + OH-
2O3 + 3H2O2 4O2 + 2OH• + H2O2
Decomposition
2H2O2 2H2O + O2 + Δ(Above 11% steam is formed)
4HO• 2H2O + O2
CALCIUM PEROXIDE
Molecular Weight- 72g Equiv. Weight - 36g
Solubility – Slightly Soluble Availability – Powder 75%
Purity Reactions
Oxidation
CaO2 + 2H2O + 2e- Ca(OH)2 + 2OH- Eo = 0.9v
HO2- + H2O + 2e- 3OH- Eo = 0.88v
Reduction:
HO2- + OH- O2 + H2O + 2e
Hydrolysis
CaO2 + H2O + OH- Ca(OH)2 + HO2-
Decomposition
2CaO2 + 2H2O 2Ca(OH)2 + O2 + Δ
SODIUM PERSULFATE
Molecular Weight- 238.05g Equiv. Weight - 119.02g Solubility -
56 g/100 mL Availability – Crystalline Solid Reactions
Oxidation
S2O82- + 2e- 2SO42- Eo 2.01v
HSO5 + 2H+ + 2e- HSO4 + H2O Eo 1.8vEST
Sulfate Radical Formation
SO4-• + e- SO4 E = 2.5vEST
S2O8 2SO4
Decomposition
2Na2S2O8 + 2H2O O2 + 2H2SO4 + 2Na2SO4
Hydrolysis
Na2S2O8 + H2O NaHSO4 + NaHSO5
SODIUM PERSULFATE
SODIUM PERSULFATE

MFR = Modified Fenton´s Reagent

SODIUM PERSULFATE
PERMANGANATE (Na/K)
Molecular Weight- 158.04g K; 141.9 Na
Equivalent Weight - 52.6g K; 47.3 Na Solubility -K 64g/l @
20oC; Na >400 g/L @ 20oC
Availability K Purple Crystalline Solid;
Na – 40% Solution
Reactions Oxidation
MnO4 + 4H+ + 3e- MnO2 + 2H2O Eo = 1.695v
Decomposition
4KMnO4 + 4H+ 3O2 +2H2O + 4MnO2 + 4K+
APPLICATION METHODS
Circulation Emplacement
 CIRCULATION METHODS
Injection Only Injection & Recovery
Galleries Galleries & Wells
Wells Trenches
- Vertical Conventional Wells
- Horizontal - Vertical
Trenches - Horizontal
Direct injection Recirculation Wells
REACTIVITY OF OXIDANTS
 REACTIVITY OF OXIDANTS

Heated Persulfate is the most

reactive oxidant
APPLICABILITY OF CHEMOX
 CHEMICAL OXIDATION
The concentrations of oxidant more typically decrease by
dilution through mixing with subsurface pore water and
through consumption via chemical reactions that are not
related to the degradation of the target constituents of
concern. The loss of oxidant due to subsurface reactions
unrelated to contamination oxidation, often referred to as
the natural oxidant demand (NOD), is a significant
consideration in determining the economic viability of
chemical oxidation and in engineering the appropriate
oxidation application dose and approach.
 CHEMICAL OXIDATION
NOD stems from reaction with organic and inorganic chemical
species naturally present in the subsurface. Oxidants that
react with the natural organic material (NOM) are lost and
are, therefore, subsequently unable to react with the target
contaminants. In certain soil types (e.g., peat), the NOM
and therefore the NOD can be extremely high. Inorganic
oxidant demand may exist if naturally occurring reduced
mineral species (e.g., ferrous iron) are present in the
groundwater or saturated soils. These reduced compounds
can also react with the oxidants to remove oxygen available
for reaction with the target contaminants.
Next slide presents a sample of some common inorganic
processes that consume oxygen and oxidants in
groundwater.
 CHEMICAL OXIDATION
Chemical oxidation is not a specific reaction. Part of
the oxidant is consumed for oxidation of another
compounds than a target pollutant.
Natural oxidant demand is very serious issue.
 CHEMICAL OXIDATION
NOD almost always exceeds contaminant oxidant
demand. If insufficient doses of oxidants are
provided to satisfy both demands, the target
contaminants may not be degraded to the desired
level. Bench testing should be used to determine
the NOD for the saturated zone.
NATURAL OXIDANT DEMAND
DECOMPOSITION RATE
OVERVIEW OF COMPOUNDS THAT
CAN BE OXIDIZED:
 MTBE, TBA
 Chlorinated solvents (PCE, TCE, DCA)
 Polychlorinated Biphenols (PCBs)
 Pentachlorophenol (PCPs)
 Solvent stabilizers
 Free product or hot spots
 Fuel hydrocarbons and BTEX
 Pesticides (DDT, DDE, etc.)
FULL-SCALE CHEMICAL OXIDATION
CHEMICAL – SURFACTANT FLUSHING
SEAR stands for
Surfactant Enhanced Aquifer Remediation
• SEAR involves the injection of surfactants to
recover contaminants by either enhanced
solubilization or mobilization due to interfacial
tension reduction and desorption of sorbed
pollutant molecules to solid particles of aquifer
SURFACTANT IONIC TYPE
CLASSIFICATION
 CRITICAL MICELLIAR
CONCENTRATION
Critical micelliar concentration (CMC) – concentration of
surfactant when micelles start to form. When actual
concentration is < than CMC, surfactant is monomeric.
 SURFACTANT FLUSHING
How surfactant works:
• Surfactants can enhance contaminant
solubilization
• Surfactants reduce interfacial tensions thereby
allowing non-ionic pollutant to be recovered by
mobilization
• Surfactants reduce sorption forces between
pollutant molecule and aquifer solid particles
thereby allowing desorption of pollutants
SEAR HOW DOES IT WORK?
SEAR HOW DOES IT WORK?

SURFACTANT WASHING
INTEGRATION WITH OTHER
TECHNOLOGIES
• Pump & treat
• Air sparging
• Bioremediation
• Biosparging
• Bioventing
• Soil washing
SOLIDIFICATION/STABILIZATION

DEFINITION:
STABILIZATION
• Reduces hazard potential of the hazardous waste by
converting contaminants into their least soluble forms.

SOLIDIFICATION
• Converts liquids, sludges and other physically non-stable
hazardous wastes into stable solids.
 SOLIDIFICATION/STABILIZATION
Solidification/stabilization (S/S) reduces the mobility of
hazardous substances and contaminants in the environment
through both physical and chemical means. Unlike other
remedial technologies, S/S seeks to trap or immobilize
contaminants within their "host" medium (i.e., the soil, sand,
and/or building materials that contain them) instead of
removing them through chemical or physical treatment.
Leachability testing is typically performed to measure the
immobilization of contaminants. S/S techniques can be used
alone or combined with other treatment and disposal
methods to yield a product or material suitable for land
disposal or, in other cases, that can be applied to beneficial
use.
 SOLIDIFICATION/STABILIZATION
• Involves mixing portland cement
into contaminated media such
as soil, sediment, sludge or
industrial waste.
• S/S treatment protects human
health and the environment by
immobilizing hazardous
constituents within treated
material.
• Established treatment
technology.
• Selected by USEPA for 24% of
Source Control Remedies in the
Superfund Program.
• Proven technology that treats a
wide variety of hazardous
constituents.
• Remediation of Brownfield Sites
enabling them to be
redeveloped.
• Cost effective –treated material
can often be used at the site.
ALTERNATIVE BINDERS TO CEMENT
SOLIDIFICATION/STABILIZATION IN-
SITU
SOLIDIFICATION/STABILIZATION
IN-SITU
SOLIDIFICATION/STABILIZATION -
LIMITATION
• Depth of contaminants may limit some types of application processes.
• Future usage of the site may "weather" the materials and affect ability
to maintain immobilization of contaminants.
• Some processes result in a significant increase in volume (up to double
the original volume).
• Certain wastes are incompatible with variations of this process.
Treatability studies are generally required.
• Reagent delivery and effective mixing are more difficult than for ex situ
applications.
• Like all in situ treatments, confirmatory sampling can be more difficult
than for ex situ treatments.
• The solidified material may hinder future site use.
• Processing of contamination below the water table may require
dewatering.
BIOLOGICAL REMEDITION
TECHNOLOGIES
INORGANIC POLLUTANTS ORGANIC POLLUTANTS
• Sulfate reduction • Bioventing
• Phytoremediation • Biosparging
• Constructed wetlands • Bioslurping
• Biosorption • Bioaugmentation
• Bioimmobilization • Phytoremediation
• Biostabilization • Bioimmobilization
• Biological reduction and oxidation • Biosorption
of metals • Composting
• Natural attenuation • Aerobic degradation of pollutants in soil
• Biofiltration • Landfarming
• Denitrification • Co-metabolic degradation
• Biofiltration
• Natural attenuation
BIOLOGICAL REMEDITION
TECHNOLOGIES

WHAT IS BIOREMEDIATION? The use of biological

organisms such as plants or microbes to aid in
removing hazardous substances from an area.
APPLICATION:
In-situ as well as ex-situ.
Ex-situ - on site
- off site
BIOLOGICAL REMEDITION
TECHNOLOGIES
• THE AIM OF BIOREMEDIATION:
Transformation of pollutants to less harmful compounds,
which do not pose risk to humans, animals and the
environment.
GENERAL SCHEME OF
BIOREMEDIATION IN-SITU
OPTIMUM CONDITIOND FOR
BIOREMEDIATION
 BIOVENTING
• PRINCIPLE OF BIOVENTING:
The main aim is to supply oxygen to a
vadose zone for biological degradation of
pollutants. The air supply is substantially
lower in comparison with venting (soil vapor
extraction).
• COST:
Cost per 1 kg removed pollutant is
substantially lower in comparison with soil
vapor extraction
BIOVENTING
• The air is mostly extracted, not injected
• The air supply is very low, mostly performed
intermittently, the rate of supply is controlled
according to oxygen consumption by bacteria
BIOVENTING – PILOT TEST
1. Pilot test is performed for determination of:
- respiration rate
- diametr of influence of a well
- air permeability
2. Determination of well number and placement
3. Determination of air flow rate
4. Monitoring
5. Determination of oxygen
consumption rate (up to
10 mg.kg-1.d-1)
 BIOVENTING
• EFFICIENCY OF BIOVENTING DEPENDS ON:
1. Availability and type of final electron acceptor
2. Moisture content in soil
3. pH of soil
4. Temperature of soil
5. Concentration of nutrient (nitrogen, phosphorus)
6. Bioavailability of pollutants
7. Biodegradability of pollutants
8. Permeability of soil
 BIOVENTING – RESPIRATION TEST
• The well must be placed in the source of pollution
• The concentration of oxygen in the soil air should
be 20 %V/V at least
• Aeration at least 24 hours before start of test,
aeration rate 5 m3.h-1 to 10 m3.h-1
• Measurement of 02 and CO2 concentration in soil air
in a short periods (1 to 5 hours)
• Measurement in a reference well
• Concentration of pollutants in soil air and in soil
• Moisture content, pH, temperature
• Concentration of nutrients (nitrogen, phosphorus)
BIOVENTING – RESPIRATION TEST -
Results
BIOVENTING – RESPIRATION TEST -
Results
• Consumption rate of oxygen
• Placement of venting wells
• Air flow rate
• Moisture amendment
• Permeability of soil
EFFECT OF SOIL PERMEABILITY
EFFECT OF THE POLLUTANT
TYPE
BIOVENTING – FULL SCALE
APPLICATION
 BIOSPARGING
Biosparging is an in-situ remediation technology that
uses indigenous microorganisms to biodegrade
organic constituents in the saturated zone. In
biosparging, air (or oxygen) and nutrients (if
needed) are injected into the saturated zone to
increase the biological activity of the indigenous
microorganisms. Biosparging can be used to
reduce concentrations of petroleum constituents
that are dissolved in groundwater, adsorbed to soil
below the water table, and within the capillary
fringe.
 BIOSPARGING
Pollutants – petroleum hydrocarbons
- chlorinated solvents
- various organic compounds
Integration with: - pump and treat
- soil vapor extraction
- enhanced bioremediation
Aims of biosparging – ensure oxygen for biological
degradation of pollutants
- stripping of pollutants to a
vadose zone
- stimulate biodegradation of
pollutants
BIOSPARGING
 BIOSPARGING – PILOT TEST
• Determination of: - diameter of influence of an air
sparging well
- oxygen consumption rate in
groundwater (biodegradation
rate)
- air flow rate
- Monitoring
 BIOSPARGING - EFFICIENCY
• EFFICIENCY OF BIOSPARGING DEPENDS ON:
1. Availability and type of final electron acceptor
2. pH of groundwater
3. Temperature of soil
4. Concentration of nutrient (nitrogen, phosphorus)
5. Bioavailability of pollutants
6. Biodegradability of pollutants
7. Redox potential of groundwater
BIOSPARGING - EFFECT OF SOIL
PERMEABILITY
BIOSPARGING – FULL SCALE
 EX SITU BIOREMEDIATION OF SOIL

SEPARATION+APPLICATION
EXCAVATION TRANSPORTATION
(SHREDDING – if necessary)

MIXING

+ =
DECONTAMINATION SAMPLING
PLATEAU

Process control + moisture amendment, nutrients,

= inoculation if needed, pollutants concentration
EX SITU BIOREMEDIATION OF SOIL
EX SITU BIOREMEDIATION OF SOIL –
DECONTAMINATION PLATEAU
EX SITU BIOREMEDIATION OF SOIL –
SLURRY PHASE

SLURRY
PHASE
SLURRY PHASE

Soil is treated in suspension with water Soil forms approx

25 %w/w in suspension.Desorption could be enhanced
by surfactant addition.
Treatment proceed in slurry bioreactor with mechanical or
hydraulical mixing (air lift). Conditions of bioremediation
could be controlled in the bioreactor – increase of
efficiency.

VERY HIGH ENERGY

CONSUMPTION FOR MIXING
SLURRY PHASE
SLURRY PHASE
 LANDFARMING
DEFINITION:
Landfarming is a bioremediation technique that is
performed in the upper soil zone or in excavated
stockpiled cells. Contaminated soils, sediments and
sludges can be spread on the ground and periodically
tilled to aerate and encourage bacterial growth.
Nutrients, minerals, and/or moisture may be added to
speed degradation. Sometimes bacteria which have
been selected for their success in breaking down
hydrocarbons are added. Contaminants are degraded,
transformed, and immobilized by microbiological
processes and by oxidation. Contaminated material is
usually treated in lifts that are up to 50 cm thick.
 LANDFARMING
Very simple remediation method. It is performed on
common land without any protection of environment.

It is used in the U.S., Australia, Brazil mostly to

treat oil sludges from raw oil pumping.
LANDFARMING
LANDFARMING
BIOIMMOBILIZATION,
BIOSTABILIZATION
BIOIMMOBILIZATION:
• 1st. stage – biotransformation of pollutant
molecules (PAH, chlorinated pesticides,
explosives). The basic aim of biotransformation is
change of polarity of molecules from non-polar to
polar (e.g. Reductive dehalogenation and
hydfroxyl groups addition to a molecule structure)
• Polarity of added groups enables very strong
bonding to a humic substances and formation of
complex molecules which are not harmfull to the
environment. The bonds are irreversible.
BIOIMMOBILIZATION
BIOTRANSFORMATION
followed

by sorption to humic
substances
 BIOSTABILIZATION
BIOSTABILIZATION: Precipitation of haevy metals or
radionuclides by biological reduction (oxidation)
 BIOSTABILIZATION OF METALS
1. Precipitation and stabilization (precipitation
with sulfides)
2. Reduction of metal to non-soluble form
3. Sorption to microbial biomas and to
biopolymeres
4. Bonding to natural organic matter (like humic
substances) and reduction of toxicity
REDUCTION AND PRECIPITATION OF
METALS
REDUCTION OF SULFATE TO SULFIDE
2CH2O + SO42- + H+ ⇒ 2CO2 + 2H2O+HS-

PRECIPITATION OF METAL SULFIDES

Me2+ + HS− ⇔ MeS(solid ) + H+
REDUCTION
 REDUCTION
• Shewanella
oneidensis -
reduction UO2,
• Other metals Mn, Fe,
• The organic
substances are
reduced in the same
time
REDUCTION
PRECIPITATION OF METALS
AROUND THE BACTERIAL CELL
OF SHEWANELLA sp.
 BIOIMMOBILIZATION,
BIOSTABILIZATION

BIOSTABILIZATION
UNDER SULFATE-
REDUVCING
CONDITIONS
 PHYTOREMEDIATION
DEFINITION:
Phytoremediation is the direct use of green plants and
their associated microorganisms to stabilize or reduce
contamination in soils, sludges, sediments, surface
water, or ground water ... Sites with low concentrations
of contaminants over large cleanup areas and at
shallow depths present especially favorable conditions
for phytoremediation." - U.S. Environmental Protection
Agency, 2011
 PHYTOREMEDIATION
PRINCIPLES OF
PHYTOREMEDIATION
 PHYTOREMEDIATION
ADVANTAGES:
• Phytoremediation is less expensive than the old "pump
and treat" method for the treatment of contaminated
water.
• Phytoremediation is also much less expensive than
digging out the contaminated site.
• Up to 95% of TCE present in water could be removed by
simply planting trees and letting them grow. (Gordon,
1996 )
• Phytoremediation takes no maintenance once instituted.
• Since phytoremediation uses plants, it is aesthetically
pleasing.
• After plants are introduced, wildlife is able to flourish at
the once uninhabitable site.
• Solar energy is used to drive the cleansing activity.
PHYTOREMEDIATION
DISADVANTAGES
• Phytoremediation is limited to sites with lower
contaminant concentrations. (USEPA, 1996)
• Phytoremediation is restricted to sites with
contamination as deep as the roots of the plants being
used.
• The food chain could be adversely affected by the
degradation of chemicals.
• The air could be contaminated by the burning of
leaves or limbs of plants containing dangerous
chemicals.
PHYTOREMEDIATION –
CONSTRUCTED WETLANDS
DEFINITION:
A constructed wetland is an artifical swamp, wetland, or
swamp. They use aquatic plants to treat problems like
wastewater or runoff. They behave as biofilters; they
remove sediments and pollutants such as heavy
metals from the water. They consist of a shallow 18
feet deep pit lined with 30 mil plastic, filled with gravel
planted with evenly spaced wetland plants. The
wetland is surrounded a border which holds the liner in
place and keeps surface water from infiltrating the
wetland. They also have subsurface absorption fields
that treat the wastewater.
PHYTOREMEDIATION –
CONSTRUCTED WETLANDS
PHYTOREMEDIATION –
CONSTRUCTED WETLANDS
Constructed wetlands are mostly used for wastewater
treatment.
- from agrictulture,
- from family houses and cottages
- from industry containing haevy metals
- storm water
- landfill leachate
- food industry (dairy)
- steel company
PHYTOREMEDIATION –
CONSTRUCTED WETLANDS
ADVANTAGES:
• Constructed wetlands are typically inexpensive to
build and maintain.
• They require little or no energy to operate.
• They can provide effective tertiary treatment.
• They can provide additional wildlife habitat.
• They can be aesthetically pleasing additions to
homes and neighborhoods.
• They are viewed as an environmentally friendly
technology and are generally well received by the
public.
PHYTOREMEDIATION –
CONSTRUCTED WETLANDS
DISADVANTAGES:
• Constructed wetlands require more land area than
many other treatment options.
• Surface flow wetlands can attract mosquitoes and
other pests.
• Wetlands are not appropriate for treating some
wastewater with high concentrations of certain
pollutants.
• The performance of wetlands may vary based on
usage and climatic conditions.
• There may be a prolonged initial start-up period before
vegetation is adequately established.
BIOFILTRATION OF CONTAMINATED AIR
When applied to air filtration and purification, biofilters use
microorganisms to remove air pollution. The air flows through a
packed bed and the pollutant transfers into a thin biofilm on the
surface of the packing material. Microorganisms, including
bacteria and fungi are immobilized in the biofilm and degrade the
pollutant. Trickling filters and bioscrubbers rely on a biofilm and
the bacterial action in their recirculating waters.
BIOFILTRATION OF WASTE AIR
DEFINITION:
Biofiltration is an air pollution control technology which utilizes
microorganisms to biologically degrade odors and other
volatile air pollutants contained in waste air streams. The
microorganisms exist on the surface, and in a thin water
biofilm surrounding the surface, of the biofilter material.
During the biofiltration process, the contaminated air is
slowly pumped through the biofilter material. The pollutants
are adsorbed onto the filter material´s surface, and absorbed
into the water film. Simultaneously, the microorganisms
biologically consume i.e. metabolize the pollutants,
producing energy, biomass, and metabolic end products,
mainly CO2 and H2O, biomas and energy (heat). The
biofiltration process results in a complete decomposition of
the pollutants, creating no hazardous byproducts.
BIOFILM
BIOFILTRATION OF CONTAMINATED AIR

PACKED
P BED BIOFILTER
A
C
K
E
D

PACKED BED BIOFILTR

BIOTRICKLING
BIOFILM FORMATION
APPLICABILITY OF BIOFILTRATION
Three advantages of biological treatment
over physical-chemical treatment are:

1) Complete mineralization vs. physical-chemical

treatment
2) Capability for in-situ treatment without having to
excavate contaminated soil
3) Generally lower costs for similar wastes
Three disadvantages of biological treatment over
physical-chemical treatment are:

1) More difficult to control as bacterial growth is

influenced by a great number of factors
2) Requires more time, and some particularly toxic
compounds may degrade so slowly as to be
considered persistent if not recalcitrant
3) Requires extensive testing before treatment and
monitoring throughout treatment
ANY
QUESTIONS?
THANK YOU
FOR YOUR
ATTENTION !