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Remediation of Contaminated Soil

• Environmental remediation deals with the removal of pollution or


contaminants from environmental media such as soil, groundwater, sediment,
or surface water for the general protection of human health and the
environment.

•Remediation work is usually describes as:


- ‘On-site’ activities describes work being carried out within the
confines of a remediation project.
- ‘Off-site’ activities are those that are carried out away from the site
such as disposal of material to a landfill site or treatment centre.

•Remediation treatment is usually describes as:


- In-situ remediation techniques involved leaving the soil in its original and
bringing the treatment processes to the soil.
- Ex-situ remediation techniques involved removing the soil from the
subsurface and treat it ‘on-site’ or ‘off-site’.

•In-situ remediation methods cause fever disturbances to the site, less


contaminant exposure to public and less expensive than ex-situ methods.
Excavation
•Excavation of contaminated soil followed by transportation and disposal in landfills is
the most common practice of remediating these soils.

•The soil may require pretreatment to reduce concentration below the land disposal
restrictions by the regulation.

• Excavation is relatively simple, fast and cost-effective for small volumes under any
soil and contaminant conditions.
Vadose Zone (Unsaturated Zone)
•A subsurface zone of soil or rock containing fluid under pressure that is less
than that of the atmosphere. Pore spaces in the vadose zone are partly filled
with water and partly filled with air. The vadose zone is limited by the land
surface above and by the water table below.

Vadose zone divided into:


i) Soil water or root zone
ii) Intermediate vadose
iii) Capillary zone
What does a typical soil remediation system look like?
Remediation techniques for contaminated soil:
i) Physical
ii) Chemical treatment
iii) Biological treatment

Physical and chemical treatment:


i) Soil vacuum extraction/soil vapor extraction (SVE)
ii) Soil washing
iii) Soil flushing
iv) Neutralization
v) Oxidation
vi) Precipitation
vii) Reduction
viii) Carbon adsorption
ix) Ion exchange Biological treatment:
i) Aerobic bioremediation
ii) Anaerobic bioremediation
iii) Biological seeding
iv) Composting
Bioremediation
• Bioremediation refers to the use of
microorganisms to remove undesirable compounds
from soil, sludge, groundwater or surface water so
that these sources will be returned to their "clean &
natural" state.
• It can be applied as in-situ treatment by using
indigenous microorganisms to treat contaminated
soil and ground water in place without moving the
soil or ground water.
• Bioremediation technology : natural attenuation,
biostimulation, and bioaugmentation.
• Bioremediation which occurs without human
intervention other than monitoring is often called
natural attenuation. This natural attenuation
relies on natural conditions and behavior of soil
microorganisms that are indigenous to soil.
• Biostimulation also utilizes indigenous
microbial populations to remediate contaminated
soils. Biostimulation consists of adding
nutrients and other substances to soil to catalyze
natural attenuation processes.
• Bioaugmentation involves introduction of
exogenic microorganisms (sourced from outside
the soil environment) capable of detoxifying a
particular contaminant, sometimes employing
genetically altered microorganisms
• Bioremediation can be implemented in a number of treatment
modes:
- aerobic
- anoxic
- anaerobic
- co-metabolic
• Three primary ingredients for bioremediation are:
- presence of a contaminant,
- an electron acceptor,
- presence of microorganisms that are capable of
degrading the specific contaminant.

Microbes + Electron Donor (Energy & Carbon Source) + Nutrients +


Electron Acceptor → More microbes + Oxidized End Products
Electron donor : waste contaminants as energy source
Electron acceptor: O2, NO3, SO4, CO2, organic carbon
Aerobic and anaerobic bacteria can be identified by growing them in liquid
culture:
1: Obligate aerobic (oxygen-needing) bacteria gather at the top of the test tube in
order to absorb maximal amount of oxygen.
2: Obligate anaerobic bacteria gather at the bottom to avoid oxygen.
3: Facultative bacteria gather mostly at the top, since aerobic respiration is the most
beneficial one; but as lack of oxygen does not hurt them, they can be found all along
the test tube.
4: Microaerophiles gather at the upper part of the test tube but not at the top. They
require oxygen but at a low concentration.
5: Aerotolerant bacteria are not affected at all by oxygen, and they are evenly spread
along the test tube.
• In situ bioremediation causes minimal disturbance
to the environment at the contamination site. In
addition, it incurs less cost than conventional soil
remediation or removal and replacement
treatments because there is no transport of
contaminated materials for off-site treatment.
• in situ bioremediation has some limitations:
• 1) it is not suitable for all soils,
• 2) complete degradation is difficult to achieve, and
3) natural conditions (i.e. temperature) are hard to
control for optimal biodegradation. Ex situ
bioremediation, in which contaminated soil is
excavated and treated elsewhere, is an alternative.
• Ex situ bioremediation approaches include use of
bioreactors, landfarming, and biopiles. In the use of a
bioreactor, contaminated soil is mixed with water and
nutrients and the mixture is agitated by a mechanical
bioreactor to stimulate action of microorganisms. This
method is better-suited to clay soils than other methods
and is generally a quick process

• Microorganisms have limits of tolerance for particular


environmental conditions, as well as optimal conditions for
optimum performance. Factors that affect success and
rate of microbial biodegradation are nutrient availability (N,
P, trace metal), moisture content, pH, oxygen level and
temperature of the soil matrix. Inorganic nutrients
including, but not limited to, nitrogen, and phosphorus are
necessary for microbial activity and cell growth
Environmental factor affecting bioremediation
• Microbial population
- An acclimated indigenous population of microbes capable of
degrading the compounds of interest must exist at the site. If
these microbes does not exist, inhibitory or toxic compounds at
the site should be suspected and alternatives remediation
techniques should be considered.
• Oxygen
- O2 is the preferred electron acceptor because it yield
maximum energy to the microorganism, thus higher cell
production and organism growth per unit electron donor utilized.
- It need for aerobic biodegradation process: > 1 mg/l in aq
phase; > 2% vol. in gas phase for vapor systems to ensure that
O2 is not limiting factor.
- Clay content of soil may affect oxygen content in soil. Higher
moisture content in clay restrict O2 diffusion.
- Loss of O2 due to aerobic biodegradation induces a change in
the activity of microbial population. Obligate anaerobic and
facultative anaerobic microorganisms become the dominant
population.
Comparison of Free Energy Values for Metabolism of Glucose in
the Presence of Various Electron Acceptors

Equation kcal/electron equivalent


• Soil moisture
- is an important factor affecting the effectiveness of using
bioremediation for contaminated soil because microbes rely on
soil moisture for their growth and survival.
- Soil water provide as media for transfer of contaminants from
solid phase to microorganisms.
- Soil water content ranges 25 – 85 % of field capacity (water
content of soil after freely drains by gravity) is needed to
sustain microbial activity.
Example:
Bioremediation of PAH at different soil moisture content

PAH Moisture content Half life


Antracene 60-80 % 37 d
Antracene 20-40 % 43 d
Fluoranthene 60-80 % 231d
Fluoranthene 20-40 % 559d
• pH
- pH 7 is the optimal condition for biological treatment
performance. Because of pH in soil is difficult to modify, it
can be used as indicator in assessment for using
bioremediation technique.

• Temperature
- Biological system can be operated in a wide range of
temperature 5 – 60 deg C
- 3 temperature ranges were identified based on the growth
of microbes:
Psychrophilic (< 15 deg C),
Mesophilic (15 – 45 deg C),
Thermophilic (>45 deg C)
• Nutrients
- Major nutrient: N, P
- Minor nutrient: Na, K, Ca, Mg, Fe, Cl, S
- Trace nutrient: Mn, Co, Ni, Va,Cu, Zn
- Ratio of nutrient require is C:N:P = 100:10:1 (the ratio in cell ~
50:10:1) with assumption that half of C is used for cell
production and half for energy production by the cells.

• Toxicants in waste
- Any material can disrupt the biochemical process in
microorganisms employed in the treatment system, will cause
failure of the system.
- The microorganisms presence within the treatment system
can acclimate to some of the pollutants or by design like
blending the contaminated soil with uncontaminated soil to
reduce the toxicity level (in a soil pile or land farm system).
• Bioventing – in situ aeration of soil
• Composting – addition of moisture and
nutrients, regular mixing for aeration
• Biopiles – ex situ aeration of soil
• Land farming/treatment – application of
organic materials to natural soil followed
by irrigation and tilling
Bioventing
• Bioventing is an in-situ remediation technology
that uses indigenous microorganisms to
biodegrade organic constituents adsorbed to
soils in the unsaturated zone.
• In bioventing, the activity of the indigenous
bacteria is enhanced by inducing air (or oxygen)
flow into the unsaturated zone (using extraction
or injection wells) and, if necessary, by adding
nutrients.
• Air delivery from atmosphere to the soil above water
table through injecting well. Air blower may be used
to push air into the soil through injection wells.
• Air flow through the soil, and the oxygen present in
the air is used by microorganism.
• When extraction wells are used for bioventing, the
process is similar to soil vapor extraction (SVE).
However, while SVE removes constituents primarily
through volatilization, bioventing systems promote
biodegradation of constituents and minimize
volatilization (generally by using lower air flow rates
than for SVE).
• In practice, some degree of volatilization and
biodegradation occurs when either SVE or
bioventing is used.
• Applicable for BTEX, PAH, some chlorinated aliphatic
compounds (TCE)
• High molecular weight and less volatile hydrocarbons like
diesel, kerosene are better treatment by bioventing than
SVE
An initial screening of bioventing effectiveness, which will allow
you to quickly gauge whether bioventing is likely to be effective,
moderately effective, or ineffective.

These factors are:


(a) The permeability of the petroleum contaminated soils. This
will determine the rate at which oxygen can be supplied to the
hydrocarbon-degrading microorganisms found in the
subsurface.
(b) The biodegradability of the petroleum constituents. This will
determine both the rate at which and the degree to which the
constituents will be metabolized by microorganisms.
A screening tool that may use as an initial assessment of the potential effectiveness of
bioventing.
Soil Texture
 How to use the diagram?
 Example: A soil containing 35 % clay, 30 % silt and 35 %
sand – clay loam
Detailed Evaluation Of Bioventing Effectiveness
Site Characteristics
Intrinsic Permeability
• Intrinsic permeability is a measure of the ability of soils
to transmit air and is the single most important factor
in determining the effectiveness of bioventing because
it determines how much oxygen can be delivered (via
extraction or injection) to the subsurface bacteria.
• To degrade large amounts of petroleum
hydrocarbons, a substantial bacterial population is
required which, in turn, requires oxygen for both the
metabolic process and the growth of the bacterial
mass itself. Approximately 3 to 3½ pounds of oxygen
are needed to degrade one pound of petroleum
product.
• Coarse-grained soils (e.g., sands) have higher
intrinsic permeability than fine-grained soils (e.g.,
clays, silts). The ability of a soil to transmit air, which
is of prime importance to bioventing, is reduced by
the presence of soil water, which can block the soil
pore and reduce air flow.
Soil Structure And Stratification
• Soil structure and stratification are important to
bioventing because they affect how and where soil
vapors will flow within the soil matrix when
extracted or injected.
• Structural characteristics such as microfracturing can
result in higher permeabilities than expected for
certain soils (e.g., clays). Increased flow will occur
in the fractured but not in the unfractured media.
• Stratification of soils with different permeabilities can
dramatically increase the lateral flow of soil vapors in
more permeable strata while reducing the soil vapor
flow through less permeable strata. This preferential
flow behavior can lead to ineffective or extended
remedial times for less-permeable strata or to the
possible spreading of contamination if injection
wells are used.
Microbial Presence
• Soil normally contains large numbers of diverse
microorganisms including bacteria, algae, fungi and
protozoa. In well aerated soils, which are most
appropriate for bioventing, these organisms are
generally aerobic.
• Bacteria require a carbon source for cell growth and
an energy source to sustain metabolic functions
required for growth.
• Microbes are classified by the carbon and TEA
sources they use to carry out metabolic processes.
Bacteria that use organic compounds (such as
petroleum constituents and other naturally occurring
organics) as their source of carbon are called
heterotrophic; those that use inorganic carbon
compounds such as carbon dioxide are called
autotrophic.
• For bioventing applications directed at petroleum
products, bacteria that are both aerobic (or
facultative) and heterotrophic are most important in
the degradation process.
Soil pH
• The optimum pH for bacterial growth is
approximately 7; the acceptable range for soil pH
in bioventing is between 6 and 8. Soils with pH
values outside this range prior to bioventing will
require pH adjustments during bioventing
operations.
Moisture Content
• Bacteria require moist soil conditions for proper growth.
Excessive soil moisture, however, reduces the
availability of oxygen, which is also necessary for
bacterial metabolic processes, by restricting the flow of
air through soil pores.
• The ideal range for soil moisture is between 40 and 85
percent of the water-holding capacity of the soil.
• The capillary fringe usually extends from one to several
feet above the elevation of the groundwater table.
Moisture content of soils within the capillary fringe may
be too high for effective bioventing.
• Depression of the water table by groundwater pumping
may be necessary to biovent soils within the capillary
fringe.
Soil Temperature
• Bacterial growth rate is a function of
temperature. Soil microbial activity has been
shown to decrease significantly at temperatures
below 10 C and essentially to cease at 5 C.
• Microbial activity of most bacteria important to
petroleum hydrocarbon biodegradation also
diminishes at temperatures greater than 45 C.
Nutrient Concentrations
• Bacteria require inorganic nutrients such as
ammonium and phosphate to support cell
growth and sustain biodegradation processes.
Nutrients may be available in sufficient quantities
in the site soils but, more frequently, nutrients
need to be added to soils to maintain bacterial
populations.
Depth To Groundwater
• Bioventing is not appropriate for sites with groundwater
tables 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
bioventing wells under vacuum pressures, potentially reducing
or eliminating vacuum-induced soil vapor flow.
• This potential problem is not encountered if injection wells
are used instead of extraction wells to induce air flow.
Constituent Characteristics
Chemical Structure
• The chemical structures of the constituents present in
the soils proposed for treatment by bioventing are
important for determining the rate at which
biodegradation will occur.
• Although nearly all constituents in petroleum products
typically found at UST sites are biodegradable, the
more complex the molecular structure of the
constituent, the more difficult and less rapid is
biological treatment.
• Most low-molecular weight (nine carbon atoms or
less) aliphatic and mono aromatic constituents are
more easily biodegraded than higher-molecular-
weight aliphatic or polyaromatic organic constituents.
• Evaluation of the chemical structure of the constituents
proposed for reduction by bioventing at the site will allow
you to determine which constituents will be the most
difficult to degrade.
Vapor Pressure
• Vapor pressure is important in evaluating the extent to which
constituents will be volatilized rather than biodegraded.
• Constituents with vapor pressures higher than 0.5 mm Hg
will likely be volatilized by the induced air stream before they
biodegrade.
• Constituents with vapor pressures lower than 0.5 mm Hg will
not volatilize to a significant degree and can instead undergo
in situ biodegradation by bacteria.
Product Composition And Boiling Point
• Boiling point is another measure of constituent volatility.
• Nearly all petroleum-derived organic compounds are capable
of biological degradation, although constituents of higher
molecular weights and higher boiling points require longer
periods of time to be degraded.
• Products with boiling points of less than about 250 C to 300
C will volatilize to some extent and can be removed by a
combination of volatilization and biodegradation in a
bioventing system.
Henry*s Law Constant
• Another method of measuring the volatility of a constituent
is by noting its Henry*s law constant.
• Henry*s law constants for several common constituents
found in petroleum products are shown in table.
Constituents with Henry*s law constants of greater
than100 atmospheres are generally considered volatile
and are more likely to be volatilized rather than
biodegraded.
Components Of A Bioventing System
1) Extraction Wells
i) Well Orientation
• A bioventing system can use either vertical or horizontal
extraction wells. Orientation of the wells should be based on
site-specific needs and conditions.
ii) Well Placement and Number of Wells

• The number and location of extraction wells can be


determined by using several methods.
a) In the first method, divide the area of the site requiring
treatment by the area corresponding to the design ROI of
a single well to obtain the total number of wells needed.
Then space the wells evenly within the treatment area to
provide areal coverage so that the areas of influence cover
the entire area of contamination.

Area of influence for single extraction well = Π (ROI)2

Treatment area (m2)


Number of wells needed =
Area of influence for single extraction well
(m2/well)
ROI of Bioventing system

•The ROI is the radial distance from an extraction well that


has adequate air flow for effective removal of contaminants
when a vacuum is applied to the extraction well.
b) In the second method, determine the total extraction
flow rate needed to exchange the soil pore volume within
the treatment area in a reasonable amount of time (3 to 7
days). Determine the number of wells required by dividing
the total extraction flow rate needed by the flow rate
achievable with a single well.
Number of well needed = (µV/t)/q

µ = soil porosity (m3 vapor/m3 soil)


V = volume of soil in treatment area (m3 soil)
q = vapor extraction rate from single extraction well
t = time for exchange pore volume (hr)
In the example below, an 7 d exchange time is used,
m3 vapor m3 soil
m3 soil 168 h
Number of well needed =
m3 vapor
h
• Consider the following additional factor in determining well
spacing:
- use closer spacing in areas of high contaminant
concentration to increase oxygen flow and accelerate
biodegradation rate

- at sites with stratified soils, wells that are screened in


strata with low intrinsic permeabiliies should be spaced
more closely than wells that screened in strata with higher
intrinsic permeabilities

- if surface seal exists or is planned for the design, space


the well slightly farther apart. A surface seal increase the
ROI by forcing air to be drawn from a greater distance by
preventing short-circuiting from land surface. However,
passive vent wells or injecting wells may be required to
supplement flow of air in the subsurface
iii) Well construction
• a) Vertical extraction wells are usually constructed of
PVC casing and screening. Extraction well diameters
typically range from 2 to 12 in
• Vertical extraction wells are constructed by placing
the casing and screen in the center of borehole.
Filter pack material is placed in the annular space
between casing/screen and the walls of the
borehole.

• The filter pack material extends 1 to 2 ft above the


top of the well screen and is followed by a 1 to 2 ft
bentonite seal. Cement-bentonite grout seals the
remaining space up to the surface.

• Filter pack material and screen slot size must be


consistent with the grain size of the surrounding
soils.
• The location and length of the well screen in vertical extraction
or injection wells can vary and should be based on the depth to
groundwater, the stratification of the soil, and the location of
contaminants.

• The ROI is affected by the intrinsic permeability of the soils in


the screened interval (lower intrinsic permeability will result in a
smaller ROI, other parameters being equal), the placement of
the screen can affect the ROI.

• At a site with homogeneous soil conditions, ensure that the well


is screened throughout the contaminated zone. The well screen
may be placed as deep as the seasonal low water table. A
deep well helps to ensure remediation of the greatest amount of
soil during seasonal low groundwater conditions.

• At a site with stratified soils, the screened interval can be


placed at a depth corresponding to a zone of lower
permeability. This placement will help ensure that air passes
through this zone rather than merely flow through adjacent
zones of higher permeability.
b) Horizontal extraction well systems are generally used
in shallow groundwater conditions.
• Horizontal extraction wells are constructed by placing
slotted PVC piping near the bottom of an excavated
trench. Gravel bedding surrounds the piping. A bentonite
seal or impermeable liner is added to prevents air
leakage from the surface.
• When horizontal wells are used, the screen must be high
enough above the groundwater table so that normal
groundwater table fluctuations do not submerge the
screen.

• Additionally, if vacuum extraction is used, pressures


should be monitored to ensure that induced groundwater
upwelling does not closed up/occlude the screen(s).
2) Air Injection Wells
• Air injection wells are similar in construction to extraction
wells. Horizontal wells are also applicable for air injection.
• Active injection wells force compressed air into soils.
Passive injection wells, or inlets, simply provide a
pathway that helps extraction wells draw air from the
atmosphere into the subsurface.
• Air injection wells can be used alone or, more commonly,
in conjunction with extraction wells. The injection
well/extraction well combination is often used at sites.
• Air injection wells are seldom used by themselves
primarily because the contaminated offgas can not be
collected. Without the ability to collect the offgas,
contaminated vapor may spread to previously
uncontaminated areas.
3) Vapor Pretreatment
• Extracted vapor can contain particulates that can
damage blower parts and inhibit the effectiveness of
downstream treatment systems.

• In order to minimize the potential for damage, vapors


are usually passed through a moisture separator and a
particulate filter prior to entering the blower.

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