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Environmental Remediation

• 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.

• Bioremediation is an engineered technology that


modifies environmental conditions (physical, chemical,
biochemical, or microbiological) to encourage
microorganisms to destroy or detoxify organic and
inorganic contaminants in the environment.

• The process can be applied above ground in land farms,


tanks, biopiles, or other treatment systems or below
ground in the soil or groundwater such as soil flushing,
bioventing, biosparging etc.
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 and ground water:
i) Physical
ii) Chemical treatment
iii) Biological treatment
Physical and chemical treatment: Soil Groundwater
i) Soil vacuum extraction/soil vapor extraction (SVE) i) Air sparging
ii) Soil washing ii) Pump and treat
iii) Soil flushing iii) Insitu flushing
Neutralization
Oxidation
Precipitation
Reduction
Carbon adsorption
Ion exchange

Biological treatment: Soil Groundwater


i) Bioventing i) Biosparging
ii) Phytoremediation ii) Phytoremediation
iii) Biopile
iv) Composting
v) Land farming
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.
• Bioremediation is a grouping of technologies that
use microbiota (typically, heterotrophic bacteria and
fungi) to degrade or transform hazardous
contaminants to materials such as carbon dioxide,
water, inorganic salts, microbial biomass, and other
byproducts that may be less hazardous than the
parent materials.
• Numerous applications of bioremediation are now
widely accepted as a remedial alternative and are
in wide use at sites contaminated with petroleum
products and/or hazardous wastes.
• Some bioremediation technologies, such as
cometabolic bioventing, are still in development and
should be considered innovative.
• Other bioremediation technologies, such as anaerobic
bioventing, are current topics of research.
• The following contaminants have been bioremediated
successfully at many sites:
● Halogenated and non-halogenated volatile organic
compounds (VOCs) (High vapor pressure and low
boiling points, <250 degree C)
● Halogenated and non-halogenated semi-volatile
organic compounds (SVOCs) (boiling points 250-400
degree C)

• Contaminants with a more limited bioremediation


performance include:
● Polycyclic aromatic hydrocarbons (PAHs)
● Organic pesticides and herbicides
● Polychlorinated biphenyls (PCBs)
In-situ and Ex-situ bioremediation
• Bioremediation technologies may be applied to in situ or ex
situ media. In situ processes treat soils and ground water in
place, without removal.
• 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 processes may be limited by the ability to control or
manipulate the physical and chemical environment in place.
• 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.
• An example of an in situ bioremediation
technology is aerobic bioventing, which has
been used at many sites to treat subsurface
soils contaminated by fuels.
• In aerobic bioventing, air is typically injected
into the subsurface to facilitate aerobic
metabolism of hydrocarbons.
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 processes involve the removal of the contaminated media to a treatment
area.
• Examples of ex situ processes include land treatment bioreactor, biopile and
composting.
• In these processes, soils are excavated, mixed with amendments, and operated
in a manner that facilitates degradation of the contaminants of concern.
• 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
Intrinsic bioremediation and enhanced
bioremediation
•There are two major types of in situ bioremediation:
intrinsic and enhanced. Both rely on natural processes to
degrade contaminants with (enhanced) or without
(intrinsic) amendments.
•Intrinsic bioremediation depends on indigenous
microflora to degrade contaminants without any
amendments. This approach is used in situ and takes
advantage of pre-existing processes to degrade
hazardous wastes.
•Intrinsic bioremediation requires careful site assessment
and monitoring to make sure that the ongoing processes
are protective of environmental receptors.
• Intrinsic bioremediation may play a role in monitored natural
attenuation (MNA) sites.
• Natural attenuation (NA) relies on natural physical,
chemical, and biological processes to reduce or attenuate
contaminant concentrations.
• Natural processes involved in NA include dilution,
sorption, volatilization, chemical reactions such as oxidation and
reduction, biological reactions, and stabilization.
• While MNA is somewhat passive in that nothing is
being added to the contamination zone, MNA requires
active monitoring, which should be included as part of
the design plan for a site.
• In some cases, such long-term monitoring may be more expensive
than active remediation.
• Enhanced bioremediation facilitates biodegradation
by manipulating the microbial environment, typically by
supplying chemical amendments such as air, organic
substrates or electron donors, nutrients, and other
compounds that affect metabolic reactions
• Enhanced bioremediation can be applied to ground
water, vadose zone soils, or, more rarely, aquatic
sediments.
• Enhanced bioremediation may also be called
biostimulation when only chemical amendments
are added. Examples of biostimulation include
bioventing, land farming or land treatment, biopiles,
composting, and sometimes anaerobic reductive
dechlorination.
• In some cases, bioaugmentation, which involves the
addition of microbial cultures, is used to enhance
biotreatment. Bioaugmentation may be needed for
specific contaminants that are not degraded
by the indigenous organisms.
• Bioaugmentation is almost always performed in
conjunction with biostimulation.
• For example, bioaugmentation has been used at some
chlorinated solvent sites as a modification of anaerobic
reductive dechlorination when indigenous microbes
were unable to completely dechlorinate the
contaminants of concern.
• 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.
Aerobic Respiration
• Aerobic bacteria use oxygen to oxidize organic
molecules by removing electrons and converting the
organic molecules to carbon dioxide and water.

• Aerobic bioremediation most commonly takes place in


the presence of oxygen and relies on the direct
microbial metabolic oxidation of a contaminant. The
primary concern when an aerobic bioremediation
system designed is delivery of oxygen, which is the
electron acceptor.
• Aerobic bioremediation is most effective in treating non-
halogenated organic compounds. Many reduced contaminants
can be aerobically degraded by aerobic bacteria already present
in the subsurface environment.
• Oxygen can be added directly to the subsurface, or chemical
oxidants can be applied, which release oxygen as they dissolve
or decompose.
• Above ground, aerobic environments are found everywhere
because they are in contact with the atmosphere, but oxygen
below ground surface can quickly be depleted by any aerobic
microbial activity in groundwater.
Anaerobic Respiration
• When oxygen is not present, bacteria commonly use
nitrate, iron (III), manganese (IV), sulfate, carbonate, or
other available electron acceptors to oxidize organic
matter, producing carbon dioxide and other byproducts.
• Anaerobic metabolism involves microbial reactions
occurring in the absence of oxygen and involves many
processes including fermentation, methanogenesis,
reductive dechlorination, sulfate-reducing activities, and
denitrification.
• For example, in anaerobic reductive dechlorination,
chlorinated solvents may serve as the electron acceptor.
• This approach is often applied at petroleum-contaminated
sites where oxygen has already been depleted.
• Nitrate is the first choice for electron acceptor after
oxygen is depleted, and many aerobic bacteria possess
the enzymes to use nitrate to oxidize contaminants.

• Reduction of nitrate generates a sequence of byproducts
consisting of nitrite ions and the gases nitric oxide, nitrous
oxide, and finally nitrogen.
• Use of nitrate as electron acceptor is termed “denitrification”
because it consumes nitrate.
• Manganese and iron are often available for microbial use in the
soil or groundwater. Iron-reducing bacteria use iron (III) as an
electron acceptor, reducing it to iron (II), or they can use
manganese (IV), reducing it to manganese (II).
• Once iron and manganese have been reduced, sulfate serves
as an electron acceptor and is converted by sulfur-reducing
bacteria to sulfide, sulfite, or elemental sulfur.
• When all external terminal electron acceptors have been
exhausted, bacteria can use organic molecules
as both electron acceptors and donors in a metabolic pathway
called fermentation.
• Anaerobic conditions may be used to degrade highly
chlorinated contaminants, such as tetrachloroethene and
trichloroethene to ethene, 1,1,1- trichloroethane (1,1,1-
TCA) to ethane, carbon tetrachloride (CT) to methane, or
perchlorate to chloride and oxygen.
Direct Metabolism
• Most bioremediation systems use a direct metabolic
pathway, in which the contaminant of concern is
either an electron donor or acceptor, and the remedial
system provides the presence of a complementary oxidant or
reductant and the right bacteria to take advantage of them.
• The growth rate of bacteria depends on the concentration of
substrate, which is the contaminant. As contaminants are
treated by a remedial system, contaminant concentrations
may approach the minimum required for
bacterial growth, and cause treatment to slow or stop.
Cometabolism
• Cometabolism occurs when microorganisms using one
compound as an energy source and produce an enzyme that
chemically transforms another compound. Organisms thus
can degrade a
contaminant without gaining any energy from the reaction.
• Technologies based on cometabolism are more difficult to use
since the microbes do not benefit from the desired reactions.
• Cometabolism is defined as the simultaneous degradationof
two compounds, in which the degradation of the second
compound (the secondary substrate) depends on the
presence of the first compound (the primary substrate).
• Cometabolic bioventing is an example of cometabolism. In this
technology, microbes may be fed propane, and they degrade
trichloroethylene (TCE) or less chlorinated ethenes as well.
• Cometabolic degradation is a process that
often happens concurrently in bioremediation systems designed for
direct metabolism of contaminants;
however, some systems have been designed to specifically take
advantage of cometabolic processes.
• Some of the molecules that are cometabolically degraded by bacteria
persistent compounds, such as PCE (tetrachloroethene), TCE, and
PCB, that have harmful effects on several types of environments. Co-
metabolism is thus used as an approach to biologically degrade
hazardous solvents
Environmental factor affecting
bioremediation
• Removal rates and extent vary based on the contaminant of
concern and site-specific characteristic.
• Removal rates also are affected by variables such as
contaminant distribution and concentration; indigenous
microbial populations and reaction kinetics; and parameters
such as pH, moisture content, nutrient supply, and temperature.
• 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.
• 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 /(100:5:1) (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).

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