1. CE 510 Hazardous Waste Engineering
Department of Civil Engineering
Southern Illinois University Carbondale
Instructors: Jemil Yesuf
Dr. L.R. Chevalier
Lecture Series 7:
Biotic and Abiotic Transformations

2. Course Goals
Review the history and impact of environmental laws in the United States
Understand the terminology, nomenclature, and significance of properties of hazardous wastes and hazardous materials
Develop strategies to find information of nomenclature, transport and behavior, and toxicity for hazardous compounds
Elucidate procedures for describing, assessing, and sampling hazardous wastes at industrial facilities and contaminated sites
Predict the behavior of hazardous chemicals in surface impoundments, soils, groundwater and treatment systems
Assess the toxicity and risk associated with exposure to hazardous chemicals
Apply scientific principles and process designs of hazardous wastes management, remediation and treatment

3. Abiotic and Biotic Transformations
Chemical and physical transformations
Hydrolysis, Redox reactions, Photolysis,…
Biotic
Transformation of contaminants through biological processes
Results in mineralization of both natural and engineered organic compounds

4. BIOLOGICAL TREATMENT OF HAZARDOUS WASTE
DEGRADATION OF ORGANIC WASTE BY THE ACTION OF MICROORGANISMS
This degradation alters the molecular structure of the organic compound

5. TWO DEGREES OF
DEGRADATION
MINERALIZATION
Complete breakdown of organic compound into cellular mass, carbon dioxide, water and inert inorganic residuals
BIOTRANSFORMATION
Breakdown of organic compound to daughter compound

6. Schematic diagram of biodegradation process
bacterial
cell A A A A A A
An organic reactant A is bound to an extracellular enzyme

7. Schematic diagram of biodegradation process
bacterial
cell A A A A A A
The enzyme transports the organic reactant A into the cell.

8. Schematic diagram of biodegradation process
The organic reactant provides the energy to synthesize new cellular material, repair damage, and transport nutrients across the cell boundary
CO2 A B
H20 C O2

9. Schematic diagram of biodegradation process
Transport of chemicals across the cell boundary
Enzyme bound chemicals A A
bacterial
cell A
bacterial
cell A A A A A A A A A A A
CO2 A B
Breakdown of chemicals
H20 C O2

10. Definitions Microbes need carbon and energy source (electron donors)
Light – phototrophs – carry out photosynthesis
Chemical sources – chemotrophs
Inorganic source – lithotroph
Ammonia, NH3, Ferrous iron, Fe2+, Sulfide, HS-Manganese, Mn2+
NH3 + O2  NO2- + H2O + Energy
Organic source – organotrophs
Examples include the food you eat
C8H O2  8CO2 + 5H2O + Energy
Autotrophs – obtain carbon from carbon dioxide
6CO2 + Energy + 6H2O  C6H12O6 + 6O2
Heterotrophs – obtain carbon from organic matter
C8H O2  8CO2 + 5H2O + Biomass

11. Definitions Microbes also need electron acceptor
Source: Newell et al., 1995
The biochemical energy associated with alternative degradation pathways can be represented by the redox potential of the alternative electron acceptors
The more positive the redox potential, the more energetically favorable is the reaction utilizing that electron acceptor.
See Textbook example 7.7

12. Governing Variables Chemical structure and Oxidation state
Persistent hazardous wastes – some halogenated solvents, pesticides, PCBs  xenobiotics
Branching, hydrophobicity, HC saturation and increased halogenation are reported to decrease rates of biodegradation and reactivity
Oxidation state of a contaminant is an important predictor of abiotic and biotic transformation
This number changes when an oxidant acts on a substrate.
Redox reactions occur when oxidation states of the reactants change

13. Class Example What is the average oxidation state of carbon in Methane
TCA
TCE
PCE

14. Solution
Methane (-IV)
TCA (0)
TCE (I)
PCE (+II)

15. Governing Variables Presence of reactive species Availability
Abiotic and biotic transformations require the presence of
Oxidant
Hydrolyzing agent (nucleophile)
Microorganisms
Appropriate transforming species
Availability
Sorption
NAPLs

16. Other Variables Dissolved oxygen Temperature pH
Aerobic and anerobic biodegradations
Temperature
Two fold increase in reaction rate for each rise of 10ºC
Empirical equation in biological treatment engineering: k2 = k1 Θ(T2-T1) pH
Optimal pH for growth varies

17. Oxidation-Reduction (Redox) Reactions
Living organisms utilize chemical energy through redox reactions
This is a coupled reaction
Transfer of electrons from one molecule to another
Electron acceptor - Oxidizing agents
Electron donor - Reducing agents

18. Redox Reactions e-
The tendency of a substance to donate electrons or accept electrons is expressed as the reduction potential Eo (measured in volts)
Negative Eo – donors
Positive Eo - acceptors e-

19. Redox Reactions e- e- Oxidation
Process in which an atom or molecule loses an electron
Reduction
Process in which an atom or molecule gains an electron e-

20. Redox Reactions e- e- Oxidation
Process in which an atom or molecule loses an electron
Na(s) Na+ + e-
Reduction
Process in which an atom or molecule gains an electron e-
Cl2(g) + 2e-  2Cl-

21. Redox Reactions These “half reactions” occur in pairs.
Together they make a complete reaction.
2Na(s) 2Na+ + 2e-
Cl2(g) + 2e-  2Cl-
Na(s) + Cl 2(g)  Na+ + 2Cl-

22. Tables for Half Reactions
Reduction
Standard
Potential
Half-Reaction
E° (volts)
Li+(aq) + e- -> Li(s)
-3.04
Ca2+(aq) + 2e- -> Ca(s)
-2.76
Na+(aq) + e- -> Na(s)
-2.71
Mg2+(aq) + 2e- -> Mg(s)
-2.38
2H+(aq) + 2e- -> H2(g)
Fe3+(aq) + e- -> Fe2+(aq)
0.77
Ag+(aq) + e- -> Ag(s)
0.8
Hg2+(aq) + 2e- -> Hg(l)
0.85
2Hg2+(aq) + 2e- -> Hg22+(aq)
0.9
NO3-(aq) + 4H+(aq) + 3e- -> NO(g) + 2H2O(l)
0.96
O2(g) + 4H+(aq) + 4e- -> 2H2O(l)
1.23
O3(g) + 2H+(aq) + 2e- -> O2(g) + H2O(l)
2.07
F2(g) + 2e- -> 2F-(aq)
2.87
These equations are written as reductions.
For oxidation, the equation would be in reverse.
Eo would also change signs.

23. Tables for Half Reactions
Reduction
Standard
Potential
Half-Reaction
E° (volts)
Li+(aq) + e- -> Li(s)
-3.04
Ca2+(aq) + 2e- -> Ca(s)
-2.76
Na+(aq) + e- -> Na(s)
-2.71
Mg2+(aq) + 2e- -> Mg(s)
-2.38
2H+(aq) + 2e- -> H2(g)
Fe3+(aq) + e- -> Fe2+(aq)
0.77
Ag+(aq) + e- -> Ag(s)
0.8
Hg2+(aq) + 2e- -> Hg(l)
0.85
2Hg2+(aq) + 2e- -> Hg22+(aq)
0.9
NO3-(aq) + 4H+(aq) + 3e- -> NO(g) + 2H2O(l)
0.96
O2(g) + 4H+(aq) + 4e- -> 2H2O(l)
1.23
O3(g) + 2H+(aq) + 2e- -> O2(g) + H2O(l)
2.07
F2(g) + 2e- -> 2F-(aq)
2.87
A full redox reaction is a combination of a reduction equation and an oxidation equation

24. Redox Equations
Redox pairs (O/R) are expressed such that the oxidizing agent (electron acceptor) is written on the left, while the reducing agent (electron donor) is written on the right.
To pair two reactions as redox, one of the pairs are written as a reduction, the other as oxidation.
CO2/C6H12O6 and O2/H2O

25. Redox Equations
To determine whether a chemical is oxidized or reduced, consider Eo from the standard reduction table. For the pairs below:
CO2/C6H12O6 and O2/H2O
6CO2 + 24H+ +24e- = C6H12O6 Eo = V
O2(g) + 4H+ + 4e- = 2H2O Eo = 0.82 V
The negative E0 value indicates that this reaction should be written in reverse (oxidation)

26. Balancing Redox Equations
Consider the metabolism of glucose by aerobic microorganisms. Write the balanced reaction that combines the redox pairs CO2/C6H12O6 and O2/H2O.
(work as class example)

27. Solution
Glucose is the energy source, and the electron donor. It will be oxidized. Oxygen, on the other hand, is the electron acceptor, it will be reduced.
Write the two half reactions

28. Solution 2. Balance the main elements other than oxygen and hydrogen
3. Balance oxygen by adding H20 and hydrogen by adding H+

29. Solution 4. Balance the charge by adding electrons
5. Multiply each half reaction by the appropriate integer that will result in the same number of electrons in each. Then add the two half reactions to come up with the balanced reaction.

30. Solution

31. Example
Balance the redox reaction of sodium dicromate (Na2Cr2O7) with ethyl alcohol (C2H5OH) if the products of the reaction are Cr+3 and CO2
strategy

32. Strategy Balance the principal atoms Balance the non-essential ions
Balance oxygen with H2O
Balance hydrogen with H+
Balance charges with electrons
Balance the number of electrons in each half reaction and add together
Subtract common items from both sides of the equation.

33. Solution

34. Solution

35. Free Energy of Formation, Gfo
Energy released or energy required to form a molecule from its elements
By convention, Gf0 of the elements (O2, C, N2) in their standard state is zero.
Some representative values Gf0 are given on the next slide

36. Free Energy of Formation, Gfo
Compound
Gfo, kJ/mole
C6H12O6
CO2
-394.4 O2
H20
CH4
-50.75
N20
104.18
Using Gf0 you can calculate whether a reaction will occur. For the reaction
aA + bB  cC + dD
DGo = cGfo(C)+dGfo(D) –
aGf0(A) – bGfo(B)

37. Class Example
One mole of methane (CH4) and two moles of oxgyen are in a closed container. Determine if the reaction below will proceed as written based on DGo.
CH4 + 2O2  CO2 + 2H20

38. Solution DGo = cGfo(C)+dGfo(D) – aGf0(A) – bGfo(B)
Compound
Gfo, kJ/mole
CO2
-394.4 O2
H20
CH4
-50.75
DGo = cGfo(C)+dGfo(D) –
aGf0(A) – bGfo(B)
=(-394.4)+2( )
-(-50.75)-2(0)
= kJ/mole
This is a large negative value, the reaction will proceed as written.
CH4 + 2O2  CO2 + 2H20

39. Relationship between DGo and DEo
The electromotive force, Eo is related to ΔGo
Where
ΔGo = the Gibbs energy of reaction at 1 atm and 25oC
n = number of electrons in the reaction
F = caloric equivalent of the faraday = kcal/volt-mole
Eo is related to the equilibrium constant, K, by:
Where:
R=universal gas constant= kcal/mol-oK
T=temperature(oK)

40. Binary Fission 1 2 4 8 16 32 P = Po(2)n
P = Po(2)n
Po is the initial population at the end of the accelerated growth phase
P is the population after n generations

41. Microbial Growth
Bacterial numbers
(log)
Time

42. Microbial Growth Lag Phase
Bacterial numbers
(log)
Lag
Phase
Adjustment to new environment, unlimited source of nutrient and substrate
Time

43. Microbial Growth Accelerated growth phase
Bacterial numbers
(log)
Lag
Phase
Accelerated growth phase
bacteria begin to divide at various rates
Time

44. Microbial Growth Exponential growth phase
differences in growth rates not as significant because of population increase
Bacterial numbers
(log)
Lag
Phase
Accelerated growth phase
Time

45. Microbial Growth
Stationary phase substrate becomes exhausted or toxic by-products build up resulting in a balance between the death and reproduction rates
Bacterial numbers
(log)
Exponential
growth phase
Lag
Phase
Accelerated growth phase
Time

46. Microbial Growth Stationary phase Death phase Lag Phase Exponential
Bacterial numbers
(log)
Lag
Phase
Exponential
growth phase
Accelerated growth phase
Time

47. Rates of Transformation
Kinetics of transformations are difficult to quantify
Furthermore, soil, groundwater and hazardous waste treatment systems are so complex that the exact transformation pathway cannot be elucidated
However, the prediction of rates is necessary in order to
Perform site characterization
Perform facilities assessment
Design treatment systems

48. Rates of Transformation
Generalized equation
C = Contaminant concentration
k = proportionality constant (units dependent on reaction order)
n = reaction order

49. Zero Order Kinetics

50. First Order Kinetics

51. Second Order Kinetics

52. Text Problem 7.4 Where, k=3X10-15 L/cell-h
The biodegradation rate of benzo[a]pyrene has been described by the expression
During a bioremediation project of a contaminated groundwater, the biomass concentration reached a steady state at 7.1X1011 cell/L during treatment and remained at approximately that concentration through out the project. If Co is 25 ug/L and the hydraulic detention time of the groundwater as it passes through the control volume is 10 days, determine the effluent concentration of benzo[a]pyrene as the water exits the system.
Where, k=3X10-15 L/cell-h
[C] = conc. of benzo[a]pyrene
[X] = biomass conc.

53. Solution
[X] = 7.1X1011 cell/L t = 240 days Co = 25 ug/L k’ = k[X] = (3x10-15 L/cell-hr)(7.1x1011 cell/L) = hr-1 Therefore, C = Coe-k’t = (25 ug/L) e-( hr-1 x 240 hr) = 15 ug/L
…end of solution

54. Michaelis-Menton Kinetics
It is a saturation phenomena described by:
where
V = rate of transformation (mg/Lh)
Vmax = maximum rate of transformation (mg/Lh)
C = contaminant concentration (mg/L)
Km = half-saturation constant (mg/L)

55. Michaelis-Menton Kinetics

56. Class Example
Describe how you would get Km and Vmax from the following data.
Initial Conc. (mg/L)
Initial Rate (mg/(L-min)) 8
1.2 14
1.6 23
2.4 32
2.7 47
2.8 55 65

57. Summary of Important Points and Concepts
Biotransformation refers to the breakdown of a chemical into daughter compounds whereas mineralization is the complete breakdown of a compound
Redox reactions can be used to determine the biological or chemical oxidation/reduction of waste
Estimates of the kinetics of waste reduction are necessary to assess and design treatment of hazardous waste.