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. 2. 3. Nucleophilic Substitution Elimination Reaction 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 Growth Pattern

Microbial Population

Stationary Phase

Log Phase Lag Phase

Death 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 AcetylcoA + CO2 + 2H + 2e  Pyruvate + COAsH A-ketoglu + CO2 + 2H + 2e isocitrate Acetaldehyde + 2H + 2e  ethanol Pyruvate + 2H + 2e  Lactate Oxaloacetate + 2H + 2e  Malate Fumarate + 2H + 2e  Succinate

-0.67 -0.48 -0.38 -0.20 -0.19 -0.17 0.03

ETS Couple (Aerobic Respiration 2H + 2e - H2 -0.42 -0.42

Ferridoxin (Fe3+) + 1e  Ferridoxin (Fe2+) NAD + H+ + 2e --- NADH NADP + H+ + 2e - NADPH FAD + 2H + 2e - FADH2 -0.32 -0.32 -0.18

ETS Couple (Aerobic Respiration

• • • • • • • • •

2H + 2e - H2 Ferridoxin (Fe3+) + 1e  Ferridoxin (Fe2+) NAD + H+ + 2e --- NADH NADP + H+ + 2e - NADPH FAD + 2H + 2e - FADH2 Cytb(Fe2+) + 1e  Cytb(Fe2+) Cytc (Fe3+) + 1e  Cytc (Fe2+) Cyta3 (Fe3+) + 1e  Cyta3 (Fe2+) 0.55 O2 + 4H +4e - 2H2O
SO42- + 3H NO3NO2Fe3+ + 2e - HSO3- + H2O -0.52 +0.42 +0.44 +0.77

-0.42 -0.42 -0.32 -0.32 -0.18 0.10 0.25 0.82

ETS Couple (Anaerobic Respiration

+2H + 2e  NO2- + H2O + 8H + 6e  NH4+ + 2H2O + 1e - Fe2+

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+
S(Cys-Protein)
N

N

CO2-

CO2-

S(O) Fe3+

S, 1e

4+

Fe=O

S

Fe2+---S

H2O

3+ H+ S--- Fe

O2, e, H+
OOH

• Cytochrome P450Dependent monooxygenase delivers oxygen to the substrate in the form of a heme-iron oxo complex • Responsible for the majority of biological hydroxylation, epoxidation, and heteroatom dealkylation

1e H+ Fe2+P + O2 -----> Fe3+ (O2-) -----> Fe3+(O2-) -------> Fe3+(OOH) Homolytic Bond Cleavage Heterolytic Bond Cleavage Fe3+(OOH)----> Fe4+(O2-) + HO . Fe3+(OOH)---->Fe4+P(O2-) + HO-

Hydroxylation of Alkane Fe3+P(OOH) + CH4  Fe4+P(O2-) + CH3. +H2O Fe4+P(O2-) + CH3. ---> Fe3+P-OCH3 -- [Fe3+P] + HOCH3 Epoxidation of Alkene Fe3+P(OOH) + CH2=CH2  Fe3+P(OH) + epoxide
O

Hydroxylation of Benzylic Carbon, Amines and Mercaptans -Hydroxylation of the substrate can occur following the removal of one electron from the aromatic ring.

HO R Fe3+P(OOH) +. R Fe4+P(O-2) + HO. . R R

Fe4+PO. + CH3NH2 ----> Fe4+PO- + CH3NH2+. ----> CH2=NH2+ Enzyme Recycling PFe3+ + CH3-N+-OFe4+P(O2-) Fe3+PO-N(CH3)3+

OH

O

Fe4+O. + -S-

------> Fe4+-O- + -S+-

Enzyme Recycling

Fe3+ +

O -S-

Initial Degradation of Benzene

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