Lecture 4

Biological Treatment of
Hazardous Waste

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 Biological Methods
• By the 1950s, the expansion of the synthetic
chemicals industry had sparked the widespread
use of biological treatment of industrial process
waters.
• Use of synthetic chemicals resulted in
contamination of groundwater and soil with
xenobiotic (synthetic or unnatural) compounds.
• A number of these xenobiotics are classified as
hazardous waste.
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Biological Methods

• A vast majority of organic hazardous wastes can be

treated biologically because virtually all organic
chemicals can be degraded if the proper microbial
communities are established, maintained and
controlled.
• Successful biological treatment projects require a
basic understanding of the microbiology involved as
well as the engineering factors required for design,
implementation and operation.
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 Basics of Microbial Metabolism
• Biological treatment systems rely on the
interactions of different types of living organisms
including bacteria, fungi, algae and protozoa.
• All living organisms require organic carbon for use
as building blocks of cellular components, as well as
a source of energy to power the biochemical
reactions taking place within cells.
• Of the many different organisms involved in
biological treatment of HWs, the most commonly
relied on are authotrophic & heterotrophic
bacteria
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 Types of microorganisms
Classifications of MO Energy source Carbon source

1. Autotrophic

A. Photoautotroph Light Carbon dioxide

B. Chemoautotroph Oxidation reduction
reactions of inorganic Carbon dioxide
organics

2. Heterotrophic

A. Photoheterotroph Light Organic carbon

B. Chemoheterotroph Oxidation reduction
reactions of inorganic Organic carbon
organics
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Types of microorganisms

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 Cellular metabolism
• Microbial behaviour has two principle goals: to
maintain the living state, and to grow/reproduce
• Complex substrates are enzymatically degraded
into simpler molecules, providing the cell with
organic carbon and energy in the form of ATP in a
process known as catabolism.
• At the same time, the cell is synthesizing complex
molecules and polymers needed for life from these
simpler molecules using energy provided by ATP in
a process known as anabolism.

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 Cellular metabolism
• The anabolic (cell building) processes produce
protoplasm as an end product which is composed of
proteins, carbohydrates, DNA and other components.
• Bacterial protoplasm is 75-80% water. The solids are
90% organic and 10% inorganic.
• An empirical formula for the organic portion is simply
C5H7O2N.
• The inorganic material consists of: phosphorus,
sodium, sulfur, potassium, calcium, magnesium, iron
and trace metals.

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 Cellular metabolism

• The sum total of all biochemical reactions taking place within

a cell is collectively known as cellular metabolism.
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 Cellular metabolism

• Degradation alters the molecular structure of organic

compounds.
• The degree of alteration determines whether
biotransformation or mineralization has occurred.
• Biotransformation refers to the simplification of an
organic compound to a daughter compound. (Partial
degradation)
• Mineralization is the complete breakdown of organic
molecules into cellular mass, carbon dioxide, water
and inert inorganic residuals (Complete degradation)
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Oxygen relationships of microorganisms

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 Cometabolism
• İs Special forms of metabolism allows xenobiotics
(Trichloroethylene, cyclohexane, alkylbenzene
sulfonate, etc) to be biologically treated.

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 Enzymatic processes
• Enzymes are large protein molecules
composed primarily of amino acid twisted into
complex shapes by peptide links and hydrogen
bonding.
• Their role in metabolism is to lower the energy
required to activate a reaction & thereby
speed up biological activity.

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 Enzymatic processes
• Two types of enzymes
1. Extracellular Enzymes
• The enzymatic reaction takesplace out of the cell.
2. Intracellular Enzymes
• The enzymatic reaction takesplace within the cell.

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 Enzaymatic processes
• Upon contact of the bacteria with substrate,
enzymes produced by the bacteria will form
complexes with substrate molecules.
• These complexes allow the substrate to pass
through the cell walls.
• Some chemicals are too large and liquefaction
takes place on the surface of the bacteria cell.
• Lastly, some organic chemicals can pass into
bacterial cell walls directly.

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Enzymatic processes

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 Enzyme inhibition
• 1. Competiive inhibitor : Interferes with active site of
the enzyme so that the substrate can’t bind.
• 2. Non-competitive inhibitor : changes the shape of
the enzyme so that the substrate can’t bind .

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 Biodegradation of Xenobiotics

• Most synthetic organics are biodegradable but those that

resist degrading are termed recalcitrant/ refractory.
• If the degradation occurs too slowly to be efficient they
are known as persistent compounds. (eg. dioxin and PCBs)
• Conditions, either individually or in combination are
associated with persistance /recalcitrance;
 Halogenation
 Large numbers of halogens
 Highly branched
 Low solubility in water

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Some general conclusions regarding the ability of microorganisms to degrade specific organic chemicals:

• Straight-chain aliphatics are easily aerobically degraded.

• Simple aromatics are usually degradable by several
mechanisms of ring cleavage.
• Even highly chlorinated aromatic compounds like PCBs
can be degraded, but slowly.
• Biodegradation of nitorgen-and sulfur-containing
compounds is linked to their utilization as nutrient
sources.
• Polymeric materials (e.g. Polystyrene) are among the
most resistant to microbial attack.

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 The successful biodegradationof a xenobiotic requires;

• The existence of microbial enzymes able to

effect a change in the molecule,
• The availability of organisms possessing such
enzymes,
• The presence of environmental conditions
favorable for microbial growth.

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Factors affecting biological treatment
 A number of factors influence the effectiveness of
biological treatment, including;

• The type and concentration of carbon sources

• Electron acceptors
• Temperature
• pH
• Inorganic nutrients
• Presence of toxic or inhibitory substances
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 Bacterial growth
• Bacterial growth has five phases. These are:
1. Lag phase: The cells require a period to adapt
to the new environment before beginning their
growth (this is a period of enzyme synthesis);
2. Exponential growth phase: The biomass grows
exponentially as cells divide as a constant rate
that exceeds the rate at which the cells are dying.
3. Stationary phase: On approaching exhaustion
of the substrate or limiting nutrient, the number
of dying cells equals the number of new cells.
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 Bacterial growth
4. Death phase: Without the addition of substrate,
dying cells exceeds new cells.
5. Endogenous phase: In some cases, the rate of
population decline slows as the number of dead cells
becomes adequate to supply the nutrients needed for
new cells.

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 Treatment of toxic or inhibitory
compounds
• Many HWs can inhibit their own degradation
at increased concentrations.

İnhibition Substrate withtoxic inhibition

İnhibition Substrate
with toxic inhibition

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 Biological treatment

Some of the most important uses of microorganisms to

treat metals and inorganics include:
• Changing the valence state of metals, reducing their
toxicity and/or solubility
• Removing heavy metals and radionuclides from water by
adsorption
• Detoxifying the comppounds
• Removing excess nitrogen compounds (ammonia and
nitrate) from soils/groundwater through nitrification
• Changing the structure and properties of certain metals
through methylation.
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 Lecture 5

• Stabilization and Solidification of

Hazardous Wastes

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 Introduction
• Stabilization is a process where additives
(reagents) are mixed with waste to minimize
the rate of contaminant migration from waste
and reduce the toxicity of waste.
• Solidification is a process employing additives
by which the physical nature of the waste
(strength, permeability) is altered during the
process.

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 Definitions

• Fixation: is often used synonymously with stabilization.

 Stabilization is accomplished through the addition of
reagents that:
• Improve the handling and physical characteristics of
waste.
• Decrease the surface area across which transfer of
contaminants can occur.
• Limit the solubility of any pollutants contained in waste.
• Reduce the toxicity of the contaminants.

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 Definitions
Leaching : is the process by which contaminants are
transferred from a stabilized matrix to a liquid medium
such as water.
• Stabilization must be considered as a waste treatment
process that reduces the pollutants to an acceptable
value or movement of contaminants into environment.
• Zn3(PO4)2 ores provide the source of Zn for metallurgical
processes, and a stabilization technique that precipitates
Zn as Zn3(PO4)2 is likely to be the optimum technique in
terms of environmental effectiveness

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 Applications

 The three major areas of application for

stabilization technologies are:
 Land disposal – the stabilization of waste prior
to secure landfill disposal.
• Site remediation – the remediation ( cleaning)
of contaminated sites.
• Solidification of industrial wastes – the
solidification of nonhazardous, unstable
wastes, such as sludges.

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 Applications
Land disposal

• Land disposal of liquid waste increases the likelihood of

contaminant migration. Liquid waste (wet sludges) must be
stabilized prior to landfilling.
• To effectively stabilize liquids, the stabilization agents
cannot be absorbents .
• Liquids absorbed by agents could be easily desorbed in
landfill when compressed under additional loads.
• Liquids must be chemically/physically bounded by reagents
so that they are not expelled by consolidation stresses or
leached out by downward percolation of precipitation.

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Site remediation

 Remediation of contaminated sites having organic

wastes, inorganic wastes, and/or contaminated soils
may be accomplished by employing stabilization
technology.
 For site remediation, stabilization is used to;
• improve the handling and physical characteristics of
wastes
• decrease the rate of contaminant migration by
decreasing the surface area across which the transfer
of pollutants can occur and by limiting the solubility
of pollutants
• reduce the toxicity of certain contaminants 32
 Solidification of industrial waste

• Many of the nonhazardous industrial waste may

not affect the public health or the environment.
• However, these wastes are frequently structurally
unstable, aesthetically unsuitable, and their
condition precludes other uses of the site area.
• Primary goal is to improve the structural integrity
of waste
• Effectiveness of the process can often be
evaluated by measuring of material’s strength.
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 2. Mechanisms

• Successful stabilization employs one or more of

the following mechanisms:
• Macro-encapsulation
• micro-encapsulation
• absorption
• adsorption
• precipitation
• detoxification

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 Macro-encapsulation

• The mechanism by which HW constituents are

physically entrapped in a larger structural
matrix; that is, the HW constituents are held in
discontinuous pores within the stabilizing
materials.

Fig. Cross-section of macroencapsulated

heterogeneous debris in phosphate ceramics
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 Micro-encapsulation

• HW constituents are entrapped within the

crystalline structure of the solidified matrix at
a microscopic level.
• As with macro-encapsulation, because the
waste is not chemically altered or bounded,
the release of contaminant from the matrix is
a possibility with lesser risk.

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 Absorption

• It is the process by which contaminants are

taken into the sorbent in the same way that a
sponge takes in water.
• Primarily used to remove free liquid to improve
waste-handling characteristics, that is, to solidify
the waste.
• Liquids are free to squeeze out of the material if
the mass is subjected to consolidating stresses.
• Use of absorption is considered a temporary
measure.
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Adsorption
• İs Phenomenon by which contaminants are electro-
chemically bonded to stabilizing agents within the matrix.
• These are typically considered surface phenomena and
the nature of bonding may be through van der Waal's or
hydrogen bonding.
• Unlike macro- and microencapsulation, additional
physicochemical stress is necessary to desorb the
material from their adsorbing surfaces.
• As a result, adsorption is considered more permenant.

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 Organic waste molecules are adsorbed to
clay.

Fig. Organic waste adsorped to an organophilic

clay
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 Precipitation

• Certain processes precipitate contaminants from

waste, resulting in a more stable form of the waste
constituents.
• Precipitates such as sulfides, silicates, carbonates
and phosphates are then contained within the
stabilized mass
• This phenomenon is applicable to the stabilization of
inorganic wastes such as metal hydroxide sludges.
• Metal carbonates are less soluble than metal
hydroxides.
• Me(OH)2 + H2CO3 MeCO3(s) + 2H2O
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Detoxification

• Detoxification is any mechanism that changes a

chemical constituent that is either less toxic or
nontoxic.
• As example is the reduction of Cr(VI) to Cr(III)
during stabilization with cement-based materials.
• Cr(III) has a lower solubility and toxicity than Cr(VI).
• Leaching of the reduced Cr(III) poses a lesser threat
to the environment than the leaching of the
original Cr(VI).

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 Cement

• Used as principal reagent in the stabilization of HWs.

• suited for inorganic wastes containing heavy metals.
• As a result of high pH, metals are retained in the form of
OH- or CO3-2 salts within the hardened structure.
• Pb, Cu, Zn, Sn and Cd are bound in the matrix by
chemical fixation, forming insoluble compounds
• Hg is predominantly held by physical
microencapsulation.
• Other additives (modified or natural clays) may be added
to avoid the interference and enhance stabilization.
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 Advantages of cement
• Well known, including handling, mixing, setting &
hardening
• Widely employed in construction field, thus material
costs are relatively low, equipment & personnel readily
available.
• The alkalinity of cement can neutralize the acidic
wastes.
Disadvantages of cement
• Sensitivity of cement to certain contaminants that could
retard or prohibit proper hydration & hardening of
material.
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 Lime

• Stabilization of sludges is frequently

accomplished through the addition of Ca(OH)2
(=hydrated Iime).
• Lime may also be added to raise the pH of acidic
sludges with fly ash that provide the main
stabilization reactions.
• Lime-based stabilization is best suited for
inorganic contaminants & has been widely used
for metal sludges.
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 Vitrification

• Vitrification is A stabilization technique without

addition of reagents.
• vitrification involves melting of materials at
temperatures above 1600°C followed by rapid
cooling .
• Considered as a S/S process, because it renders the
waste more structurally stable with a reduced
potential for contaminant migration into the
environment.
• Applied both in situ and in-plant.
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 In situ vitrification
• High temperatures needed to melt the soil into
a molten mass are achieved by applying electric
current.
• As temperature increases, organic materials first
vaporize and then pyrolyze into elemental
components.
In-plant vitrification
• Has potential to treat HW (contaminated soil) &
produce a product that may be usable (e.g., as a
road aggregate).
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 Testing
Extraction and leaching tests
• Reduction in the rate at which contaminants can
migrate into the environment is the first and
foremost reason for selecting S/S as a HW
management technique.
• Extraction and leaching are used interchangeably
and are the process by which contaminants are
transferred from a solid or stabilized matrix to the
leachate.
• Finally, the overall ability of a stabilized material to
leach contaminants is termed leachability.
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