1. Chapter 20 – Organic Pollutants
Objectives
Be able to give examples of pollutants that have unique structures and structures similar to naturally-occurring organic compounds
Be able to define carrying capacity
Be able to list the four factors that affect biodegradability of an organic compound in the environment
Be able to list properties of a molecule that can make it difficult to degrade
Be able to define biodegradation terminology including transformation, mineralization, biosynthesis, and cometabolism
Be able to list the various approaches to bioremediation

2. 1. natural vs. anthropogenic
There are many different organic contaminants that are spilled into the environment.
Points of concern:
natural vs anthropogenic Cl OH
O – CH2 - COOH Cl
Natural vs. Anthropogenic
Domestic waste Herbicides/pesticides
Paper Plastics
Acid mine drainage Detergents
Oil Chlorinated solvents
Metals
2. quantity added or spilled
- carrying capacity or self purification

3. Extent of problem
300 million metric tons/yr
> 1,200 Superfund sites
Cleanup costs estimated to exceed 1 trillion $
Metals
Pesticides
Petroleum
Chlorinated solvents
Emerging Contaminants
Radionuclides

4. Factors affecting biodegradability
1. Bioavailability
low water solubility
sorption
In most cases there are two steps required for biodegradation:
1) uptake and transport of the contaminant into the cell and 2) metabolism. Compounds with low solubility and/or high sorption are not in the aqueous solution surrounding the cell and therefore their uptake is limited.
Example:
Compound Solubility (mg/L) Biodegradation in 5 days
C7H complete
C16H ~ 64%
C40H very, very low ~ 5%

5. How do microbes increase bioavailability in the environment?
Scenario –an ocean oil spill
A - Uptake of solubilized hydrocarbon
B – Uptake of hydrocarbon at the oil-water interface
C – Uptake of dispersed droplets of oil
D – Production of biosurfactants to increase the oil-water interfacial area

6. 2. Genetic makeup - lack of appropriate degrading genes
Each step in a biodegradation reaction is catalyzed by an enzyme. If the appropriate enzymes are not present, biodegradation will not occur. Since each enzyme is encoded by a gene, the genetic makeup of the microbial population is a critical factor in determining whether biodegradation will occur.
3. Contaminant structure (steric hindrance or unusual functional groups)
The presence of the following structures generally inhibit biodegradation
unusual atoms (halogens)
R - CH2 - Cl
branching
R - C - CH3
CH3
aromatic ring systems
high molecular weight
-(CH2 – CH2 – CH2 – CH2)n-

7. How different substituents influence biodegradation of phenol

8. Given a pair of structures you should be able to predict which of the pair will degrade more rapidly.
CH3 - C - CH2 - CH2 - C - CH3
CH3
2,2,5,5-tetramethylhexane
vs.
CH3 – CH2 – CH2 – CH2 – CH2 – CH3
hexane

9. Benzene
vs.
Benzo(a)pyrene

10. CH2 - COOH Cl
2, 4- D
vs.
CH2 - COOH Cl
2, 4, 5 - T

11. C = C H Cl
TCE
vs.
CH3 - CH2 - OH
ethanol

12. 4. Environment (biotic and abiotic)
moisture content (too much limits oxygen availability, too little
inhibits microbial activity in general)
oxygen (required for rapid biodegradation processes)
pH (extremes limit microbial activity)
nutrient availability (includes mineral nutrients and organic matter)
competition (are the microbes of interest active, do added microbes
survive?)
All of these need to be with acceptable ranges to allow optimal
biodegradation activity.

13. Biodegradation terminology
Transformation - any single biodegradation step in a pathway is a transformation reaction. A transformation can result in partial or complete detoxification of a contaminant or can create a compound even more toxic than the parent compound.
Mineralization - the parent compound is completely degraded to CO2, new cell mass, and water. This is a highly desirable result for toxic contaminants. Cl N
NH - CH CH 3
- CH 2
- NH
Atrazine
mineralization
CO2 + cell mass + H2O Cl N
NH - CH CH 3 H
- CH 2
NH2 +
transformation
product is not
degraded further

14. Biodegradation terminology (cont.)
Cometabolism - Sometimes an enzyme can act nonspecifically on a substrate leading to a transformation reaction that does not provide energy to the microbe. A good example is oxidation of TCE by methane-utilizing microbes. Cl OH
COOH
lack of enzyme specificity
detoxification

15. Biosynthesis - partial or incomplete degradation can also result in polymerization or synthesis of compounds more complex and stable than the parent compound. Cl NH
– C – CH2 – CH3 = O
Propanil
Abiotic/biotic polymerization
– C – CH2 – CH3 = O HO
CO2 + cell mass + H2O
Mineralization
Binding to humus Cl
NH2 Cl N
= N Cl N
= N H
tetrachloroazobenzene
dichloroanilino - trichloroazobenzene

16. Biodegradation pathways
Most contaminants can be categorized into one of three structure types, all commonly found in petroleum products. Some contaminants contain a combination of these structures.
Aliphatics:
CH3 – (CH2 – CH2 )n – CH3 OH
Alicyclics:
Aromatics:
Note to instructors: No actual pathways are presented in this slide show. You will have to decide what pathways (aerobic and anaerobic) you want to present.

17. Bioremediation
For successful and cost-effective bioremediation, there need to be degrading microbes, adequate bioavailability, and suitable environmental conditions. For petroleum spills, there are normally degrading microbes present so the issues become bioavailability and environmental conditions.
In ocean oil spills, access to the oil is limited to the surface area between the oil-water interface. In general oxygen is not limiting but as shown below, nitrogen and phosphorus are limiting.
From Atlas and Bartha studying degradation constraints in an oil spill:
Treatment in seawater % biodegradation
1. oil alone
2. oil + microorganisms
3. oil + micro. + P
4. oil + micro. + N
5. oil + micro. + N + P

18. In subsurface terrestrial environments, there are many options
In subsurface terrestrial environments, there are many options. These include both in situ and ex situ treatment.
In the subsurface, the most limiting factor is generally oxygen. Therefore, addition of oxygen is one of the most common approaches to cleanup of subsurface contamination.
In addition, nutrients such as N and P may be added.
In some cases, natural activities are fast enough to control the contaminant plume. This is called intrinsic bioremediation or natural attenuation. This approach is desirable because it requires only monitoring of the contaminant plume. Must address the questions:
Is intrinsic activity fast enough?
Will the plume impact human or ecological health?

19. If a more aggressive approach is required, there are several options available:
In situ treatments
Bioventing
Air sparging
Permeable reactive barriers
Ex situ treatments
Biofiltration
Soil vapor extraction and treatment
Groundwater extraction and treatment

20. Example 1
In situ bioremediation in the vadose zone and groundwater. Nutrient and oxygen are being pumped into the contaminated area to promote in situ processes. Water is being pumped to the surface for ex situ treatment in an aboveground bioreactor. Following treatment, an injection well is returning the contaminant-free water to the aquifer.

21. Example 2
Bioventing and biofiltration in the vadose zone. Air is slowly drawn through the contaminated site (bioventing) which stimulates in situ aerobic degradation. Volatile contaminants removed with the air can be treated biologically using a biofilter as shown or by adsorption on activated carbon, or by combustion.

22. Example 3
Bioremediation in groundwater by air sparging. Air is pumped into the contaminated site to stimulate aerobic biodegradation Volatile contaminants brought to the surfaced are treated by biofiltration, activated carbon, or combustion.