Presentation on theme: "Chapter 20 – Organic Pollutants"— Presentation transcript:
1 Chapter 20 – Organic Pollutants ObjectivesBe able to give examples of pollutants that have unique structures and structures similar to naturally-occurring organic compoundsBe able to define carrying capacityBe able to list the four factors that affect biodegradability of an organic compound in the environmentBe able to list properties of a molecule that can make it difficult to degradeBe able to define biodegradation terminology including transformation, mineralization, biosynthesis, and cometabolismBe 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 anthropogenicClOHO – CH2 - COOHClNatural vs. AnthropogenicDomestic waste Herbicides/pesticidesPaper PlasticsAcid mine drainage DetergentsOil Chlorinated solventsMetals2. quantity added or spilled- carrying capacity or self purification
3 Extent of problem300 million metric tons/yr> 1,200 Superfund sitesCleanup costs estimated to exceed 1 trillion $MetalsPesticidesPetroleumChlorinated solventsEmerging ContaminantsRadionuclides
4 Factors affecting biodegradability 1. Bioavailabilitylow water solubilitysorptionIn 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 daysC7H completeC16H ~ 64%C40H very, very low ~ 5%
5 How do microbes increase bioavailability in the environment? Scenario –an ocean oil spillA - Uptake of solubilized hydrocarbonB – Uptake of hydrocarbon at the oil-water interfaceC – Uptake of dispersed droplets of oilD – 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 biodegradationunusual atoms (halogens)R - CH2 - ClbranchingR - C - CH3CH3aromatic ring systemshigh 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 - CH3CH32,2,5,5-tetramethylhexanevs.CH3 – CH2 – CH2 – CH2 – CH2 – CH3hexane
12 4. Environment (biotic and abiotic) moisture content (too much limits oxygen availability, too littleinhibits 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 microbessurvive?)All of these need to be with acceptable ranges to allow optimalbiodegradation 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.ClNNH - CHCH3- CH2- NHAtrazinemineralizationCO2 + cell mass + H2OClNNH - CHCH3H- CH2NH2+transformationproduct is notdegraded 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.ClOHCOOHlack of enzyme specificitydetoxification
15 Biosynthesis - partial or incomplete degradation can also result in polymerization or synthesis of compounds more complex and stable than the parent compound.ClNH– C – CH2 – CH3=OPropanilAbiotic/biotic polymerization– C – CH2 – CH3=OHOCO2 + cell mass + H2OMineralizationBinding to humusClNH2ClN= NClN= NHtetrachloroazobenzenedichloroanilino - 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 – CH3OHAlicyclics: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 BioremediationFor 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 % biodegradation1. oil alone2. oil + microorganisms3. oil + micro. + P4. oil + micro. + N5. 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 treatmentsBioventingAir spargingPermeable reactive barriersEx situ treatmentsBiofiltrationSoil vapor extraction and treatmentGroundwater extraction and treatment
20 Example 1In 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 2Bioventing 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 3Bioremediation 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.