Aspects of transformations in atmosphere (microbial

degradation of organics-environmental degradation of

polymers, atmospheric lifetime, toxicity). Green
Chemistry and Industrial Ecology.

➢ Chemistry of the Environment, Second Edition by R. A. Bailey, H. M. Clark, J. P. Ferris, S. Krause, R.

L. Strong

➢ Principles of Environmental Chemistry By James E. Girard

 Microbial degradation of organics
Environmental degradation of polymers
Biodegradation :

1. Breakdown of organic matter by living microorganism like bacteria, fungi and other biological means.

2. It can be degraded by aerobically (in presence of oxygen) or anaerobically (in absence of oxygen).

3. Biodegradable materials provides nutrition to the microorganism.

Biotransformation:

Part of organic matter is degraded. Remaining part is converted to smaller organic molecules.

Example: Fermentation of sugar into ethanol.

Bioremediation : Use of either naturally occurring or deliberately introduced microorganisms to consume and
break down environmental pollutants.
 Organic Pollutants
Soil Humus: The soil organic matter consists of a whole series of products

that ranges from undecomposed plant and animal tissue to fairly Amorphous

Brown to black material bearing no trace of the anatomical structure of the

material.

Advantages:

1. It protects soil from erosion and helps in forming good soil structure.

2. It provides good aeration and better water movement by loosening the

soil.
3. For achieving maximum benefit organic matter must be decomposed and
replenished with fresh organic materials.
 Xenobiotics

➢ Xenobiotic chemicals are biologically active molecules that are foreign to an organism.

➢ Xenobiotic chemicals include herbicides, growth regulators, fungicides, and insecticides.

Drugs Plastic Food Additives

Originated from the greek word (Antibiotics) (Polyvinyl (Sodium nitrites))
chloride)
Xenos: Foreigner or stranger
Bios: life Pesticides Heavy Metals
Tics: suffix Cosmetics
(DDT) (As)
(Moisturizer)

Industrial
chemical
(Formalin)
 Man-made Xenobiotics

H2O

PET
Polyethylene terephthalate
 Natural product can also be a Xenobiotic like phytotoxins.

Abrin is an extremely toxic plant protein found in the seeds of

the rosary pea (or jequirity pea).

 Detoxification of Xenobiotics by Liver
Hepatic
enzymes Expose Conjugate
Xenobiotics polar with Excrete in
in Liver groups of sulphate, bile or in
Oxidation, these acetate or urine
reduction, chemicals glutathione
hydrolysis

Example: Benzene Phenol Phenyl sulfate

Complete removal is not possible.

Bioremediation
The breakup of the spill is slowed if it is washed up on the
shore.
• Dispersal and degradation will continue if there is a
strong wind and surf,
• but oil spills in quiet bays or lagoons may take 5-10 years
to disperse in the absence
of wave and wind action.
• The toxic effects on marine life likewise persist for 5-10
years in these environments

Difficulty of achieving sufficient oil removal by

physical washing and collection, especially for oil
that had moved into the subsurface,
bioremediation became a prime candidate for
continuing treatment of the shoreline.
1. If an oil spill reaches the shore, it takes longer to break up.
2. When there's a strong wind and waves in the area, the spilled oil can spread and break down.
3. However, in calm and quiet places like bays or lagoons, it can take 5-10 years for the oil to naturally disperse if there's no wind or wave
action.
4. The harmful effects of the oil on marine life also last for 5-10 years in such calm areas.
5. It's challenging to physically clean up the oil, especially if it has gone below the surface. So, using bioremediation (natural processes to
break down the oil) is a good option for ongoing cleanup on the shoreline.
Petroleum hydrocarbons occur naturally in all marine environments, there has been time for numerous diverse
microorganisms to evolve the capability of utilizing hydrocarbons as sources of carbon and energy for growth.
Oil-degrading microorganisms are ubiquitous
 Decomposition of various organic compounds

➢ Different organic residues contain different groups of organic compounds, so their decomposition procedure and rate
differ.

➢ Very slowly decomposed compounds are lignin, fat, wax, cellulose, and hemicellulose.

➢ Rapidly decomposed compounds are proteins, sugar, and starch.

Enzyme

Biodegradation is defined as the biologically catalyzed reduction in complexity of chemical compounds.

The enzyme is a substance, composed of proteins capable of lowering the activation energy of the reaction.
ases
The most representative enzymes involved in bioremediation include cytochrome P450s, laccases, hydrolases,
dehalogenases, dehydrogenases, proteases, and lipases, which have shown promising potential in degradation of
polymers, aromatic hydrocarbons, halogenated compounds, dyes, detergents, agrochemical compounds, etc
Enzyme activity
 Mechanism of degradation by microorganism
The microbial organisms transform the substance through
metabolic or enzymatic processes. It is based on two processes:
growth and cometabolism.

1. In growth, an organic pollutant is used as sole source of

carbon and energy. This process results in a complete
degradation (mineralization) of organic pollutants.

2. Cometabolism is defined as the metabolism of an organic

compound in the presence of a growth substrate that is used
as the primary carbon and energy source.

3. Several microorganisms, including fungi, bacteria involved in

the biodegradation process.
Cometabolism
The cometabolic degradation phenomenon was first reported in 1958
observing that the methane-utilizing bacterium Pseudomonas
methanica could oxidize ethane and propane, but was unable to use
these compounds as a carbon and energy source.

Methane is a growth substrate for the methane-oxidizing bacterium,

while ethane and propane are co-metabolic substrates. Subsequent
studies have found that methanotrophs can cometabolically
transform polycyclic aromatic hydrocarbons (PAHs), dioxane,
polychlorinated biphenyls (PCBs), pesticides, and methyl tertiary-butyl
ether (MTBE).

NADPH: Nicotinamide adenine dinucleotide phosphate

➢ Numerous oxygenase enzymes, including methane-, ammonia-, propane-, butane-, alkane-, and toluene-oxygenases, are
known for their ability to degrade xenobiotic compounds cometabolically.

➢ Among oxygenases reported, methane monooxygenase (MMO) expressed by methane-oxidizing bacteria (i.e.,
methanotrophs) is one of the well-studied oxygenases. Methanotrophs can express two types of MMOs, particulate
(pMMO) and soluble (sMMO). Compared to pMMO, sMMO has a broader substrate range and is known for its ability to
degrade various environmental contaminants with some of the most persistent organics like pesticides, and halogenated
aliphatic and aromatic compounds.

➢ During cometabolic degradation of trichloroethylene (TCE; a chlorinated solvent), methanotrophs use MMO to oxidize
both methane (growth substrate) and TCE (co-metabolic substrate) with an expense of reducing energy, reduced
nicotinamide adenine dinucleotide (NADH), and oxygen. During methane oxidation, MMO will first convert methane to
methanol, which is further oxidized to formaldehyde, formate and then carbon dioxide, resulting in a net production of
reducing energy (NADH) and metabolites (formaldehyde and/or CO2) available for microbial cell growth.
There are two forms of MMO: the well-studied soluble form (sMMO) and the particulate form (pMMO). The active
site in sMMO contains a di-iron center bridged by an oxygen atom (Fe-O-Fe), whereas the active site in pMMO
utilizes copper. Structures of both proteins have been determined by X-ray crystallography; however, the location
and mechanism of the active site in pMMO is still poorly understood and is an area of active research.
Proposed catalytic cycle and mechanism sMMO
➢ As MMO is responsible for both methane and TCE oxidation, competitive inhibition of TCE degradation has
resists
been observed in the presence of methane.

➢ Different from methane oxidation, TCE is oxidized to TCE epoxide, which is quickly hydrolyzed to chlorine
and carbon dioxide, resulting a net loss of reducing energy.

➢ Another unfavorable consequence is product toxicity- metabolites like TCE epoxide cause damage to cells
and the degradative enzymes – limiting the amount of TCE can be biotransformed per cell.
 TCE degradation
NADH

PQQ: Pyrroloquinoline
quinone. Peptide
derived redox cofactor

Methane and TCE oxidation pathways in methane-oxidizing bacteria. Enzymes: 1, MMO; 2, methanol dehydrogenase; 3,
formaldehyde dehydrogenase; 4, formate dehydrogenase.
Aerobic and Anaerobic
In situ Bioremediation
 Pollutants
Most organic and inorganic chemicals are subject
to enzymatic attack through the activities of living
organisms
Type of pollutants
BTEX (Benzene, Toluene, Ethylbenzene, Xylene)
PAH (Polycyclic aromatic hydrocarbon)
Nitroaromatic compounds
PCB (Polychlorinated biphenyls)
Chlorinated aliphatic compounds like, trichloroethylene (TCE), dichloroethylene (DCE), vinyl
chloride (VC)
MTBE: Methyl tert-butyl ether
Agricultural chemical wastes (Triazine, DDT)
 Compounds with differential aerobic vs. anaerobic
degradation potential
Benzene, polynuclear aromatic
hydrocarbons (PAH)

Stable ring structures, aerobes

utilize oxidizing power of
oxygenases to initiate degradation

Anaerobes lack similarly powerful

oxidants
Compounds are readily degraded
aerobically, but persistent in
anaerobic environments
Creosote is derived from the
distillation of tar from wood or coal
and is used as a wood preservative.

Atrazine is a chlorinated triazine

systemic herbicide that is used to
selectively control annual grasses
and broadleaf weeds before they
emerge.
 Question
Q1. Which one of the following is correct?

Methane mono-oxygenase enzyme expressed by methane-oxidizing bacteria helps in the following organic convertion.

1. Methane to formaldehyde
2. Methane to methanol
3. Methane to formic acid
4. Methane to carbon dioxide