Transformation and Degradation of Pollutants

Important Variables for Contaminant Transformations

2. Chemical Structure of the Contaminant
3. Presence of Transforming Species
4. Physical Availability of the contaminant.
5. Dissolved Oxygen
6. pH
7. Temperature
 Abiotic Transformation of Pollutants

1. Nucleophilic Substitution
2. Elimination Reaction
3. Oxidation/Reduction

OH = One of the most important oxidants found in air,

water and biological systems.
Sources of OH Radical:
g. Fenton Reaction
h. Reaction of Ozone wigth NOx
Biodegradation Reactions and Pathways of Hazardous
Contaminants
 Microbial Transformation of Pollutants

Microorganisms involved in Biotransformations

2. Bacteria
3. Fungi
4. Algae
5. Protozoan
 Classification of Bacteria in Microbial Metabolism

1. Based on Energy Sources

b. Chemotrophs
c. Phototrophs
2. Based on Sources of Carbon
e. Autotrophs
f. Heterotrophs
3. Based on Sources of Electrons
h. Organotrophs
i. Lithotrophs
Microbial Population Microbial Growth Pattern

Stationary Phase

Log Phase Death Phase

Lag Phase

Time
 Conceptual Basis for Biodegradation Reaction

Contaminant + Xox Product + Xred

 Redox Couple

Substrate Redox Couple

» Eo’ (V)

• Succinate + CO2 + 2H + 2e a-ketoglu + H2O -0.67

• AcetylcoA + CO2 + 2H + 2e  Pyruvate + COAsH -0.48
• A-ketoglu + CO2 + 2H + 2e isocitrate -0.38
• Acetaldehyde + 2H + 2e  ethanol -0.20
• Pyruvate + 2H + 2e  Lactate -0.19
• Oxaloacetate + 2H + 2e  Malate -0.17
• Fumarate + 2H + 2e  Succinate 0.03
ETS Couple (Aerobic Respiration

2H + 2e - H2 -0.42
Ferridoxin (Fe3+) + 1e  Ferridoxin (Fe2+) -0.42
NAD + H+ + 2e --- NADH -0.32
NADP + H+ + 2e - NADPH -0.32
FAD + 2H + 2e - FADH2 -0.18
ETS Couple (Aerobic Respiration

• 2H + 2e - H2 -0.42
• Ferridoxin (Fe3+) + 1e  Ferridoxin (Fe2+) -0.42
• NAD + H+ + 2e --- NADH -0.32
• NADP + H+ + 2e - NADPH -0.32
• FAD + 2H + 2e - FADH2 -0.18
• Cytb(Fe2+) + 1e  Cytb(Fe2+) 0.10
• Cytc (Fe3+) + 1e  Cytc (Fe2+) 0.25
• Cyta3 (Fe3+) + 1e  Cyta3 (Fe2+) 0.55
• O2 + 4H +4e - 2H2O 0.82
ETS Couple (Anaerobic Respiration

SO42- + 3H + 2e - HSO3- + H2O -0.52

NO3- +2H + 2e  NO2- + H2O +0.42
NO2- + 8H + 6e  NH4+ + 2H2O +0.44
Fe3+ + 1e - Fe2+ +0.77
 Dependence of Bacteria on Electron Acceptor
• Aerobic Reaction- O2 is the e- acceptor
• Anaerobic Process: 3 Pathways
• 1. Anaerobic Respiration
• 2. Fermentation
• 3. Methanogenesis
 Aerobic Metabolism Pathways

• Emden-Meyerhof Pathway
• TCA
• Electron Transport System
• Glucose Metabolism:
• Glucose  Pyruvate 2 ATP and 2 NADH
• 2 Pyruvate  2 AcetyCoA 2 NADH
• 2 AcetylcoA  4 CO2 + 2 H2O 6 NADH, 2 FADH, 2 ATP
• Lactate Fermentation
• Glucose + 2 NAD+ + 2 ADP + 2Pi  2 Pyruvate
+ 2 NADH + 2 H+ + 2 ATP
• 2 NADH + 2 H + 2 Pyruvate  2 Lactate
• Glucose + 2 ADP + 2Pi  2 Lactate + 2 ATP
Ethanol Fermentation

Glucose + 2 NAD+ + 2 ADP + 2Pi  2 Pyruvate + 2 NADH + 2 H + 2 ATP

2 Pyruvate - 2 Acetaldehyde + 2 CO2
2 Acetaldehyde + 2 NADH + 2 H - 2 Ethanol + 2 NAD+
Glucose + 2 ADP + 2 Pi - 2 Ethanol + 2 CO2 + 2 ATP

Methanogenesis:
CH3COOH -- CH4 + CO2
• Important Bacteria in Hazardous Waste Systems:

• White Rot Fungus or Wood Rot Fungus

Examples:
Phanerochaete Chrysosporum
Phanerochaete sordida
-These fungi have been shown to degrade PAH, PCB,
pentachlorophenol, DDT through the activity of extracellulase
peroxidase enzyme
Important Bacteria in Hazardous Waste Systems:
i. Pseudomonas
j. Nocardia
k. Mycobacterium
l. Arthrobacteria
m. Bacillus
 Biodegradation Reactions and Pathways of
Hazardous Contaminants
• 1. Contaminants pass through the cell membrane.
• 2. Compounds too large to pass through the cell
membrane may be partially degradaded by exoenzymes
which are secreted through the cell wall.
• 3.The following reactions will occur in the cytoplasm:
Hydroxylation, Hydrolysis, Dehalogenation, Dealkylation
and Reduction
• 4. Dehydrohalogenation
 Oxidative Processes for which Oxygen is the
Electron Acceptor

• Monooxygenases are characterized by their ability to

introduce one of the atoms of O2 into an organic
substrate, S and the other being incorporated into a
molecule of water.
• S + O2 + AH + H+ -- SO + A + H2O
• Reactions catalyzed by Monooxygenases:
• 1. Hydroxylation at Saturated and Unsaturated Carbon
• 2. Epoxidation of Olefin
• 3. Baeyer-Villiger Oxidation of Ketones
• 4. Oxidation at S and N
• 5. Heteroatom Dealkylation
Protoporphyrin Ring

N
N

Fe2+

N
S(Cys-Protein)
N

CO2-
CO2-
 • Cytochrome P450-
Dependent
S(O) S, 1e monooxygenase delivers
Fe3+ oxygen to the substrate in
the form of a heme-iron
4+
Fe=O
oxo complex
• Responsible for the
S
Fe2+---S majority of biological
H2O hydroxylation,
epoxidation, and
3+
H+ S--- Fe O2, e, H+ heteroatom dealkylation
OOH

H+ Fe3+(OOH)
1e Fe3+(O -) ------->
Fe2+P + O2 -----> Fe3+ (O2-) -----> 2

Homolytic
Bond Cleavage Fe3+(OOH)----> Fe4+(O2-) + HO .

Heterolytic Fe3+(OOH)---->Fe4+P(O2-) + HO-

Bond Cleavage
Hydroxylation of Alkane Hydroxylation of Benzylic Carbon, Amines
Fe3+P(OOH) + CH4  Fe4+P(O2-) and Mercaptans
+ CH3. +H2O -Hydroxylation of the substrate can occur
Fe4+P(O2-) + CH3. ---> Fe3+P-OCH3 following the removal of one electron from
the aromatic ring.
--
[Fe3+P] + HOCH3
HO
R Fe3+P(OOH) R
Epoxidation of Alkene +.
R
.
R

Fe4+P(O-2) + HO.

Fe3+P(OOH) + CH2=CH2 
Fe3+P(OH) + epoxide
Fe4+PO. + CH3NH2 ----> Fe4+PO- + CH3NH2+. ----> CH2=NH2+
O
Fe4+P(O2-)
Enzyme
Recycling
PFe3+ + CH3-N+-O- Fe3+PO-N(CH3)3+

OH O
Fe4+O. + -S- ------> Fe4+-O- + -S+-

Enzyme O
Recycling Fe3+ +
-S-
Initial Degradation of Benzene