24

REMEDIATION

ENGINEERING

Biochemical transformations of organic compounds are especially important, because

many reactions discussed in previous sections, although thermodynamically feasible, occur
extremely slowly because of kinetic limitations. Microorganisms enable such reactions to
proceed via two important approaches. The first approach involves the use of special proteins,
called enzymes, that serve as catalysts. Enzymes can lower the activation energy of reactions,
thereby speeding the transformations by many orders of magnitude. Second, microorganisms
may invest energy to convert oxidative reagents into more re active species. For example,
molecular oxygen is converted to a more reactive species by a biochemical agent before it
is used to oxidize some compounds
Microbial metabolic reactions can be broadly classified into aerobic, anaerobic, and anoxic
modes. If biodegradation results in the formation of inorganic species (e.g., CO2, H20, and
mineral salts), it is referred to as mineralization. Complete mineralization typically involves
oxidation using oxygen, but can also occur under anaerobic and anoxic conditions. Attention
should also be paid to differentiation between degradation of compounds as a primary substrate
in contrast to cometabolic degradation of certain compounds. Detailed description of these
reactions involving various contaminants is provided in Chapter 5 and Chapter 8.
Microorganisms in the subsurface environment, especially in groundwater, are more
likely to be attached to grains of soil matrix than to be moving with the water. It appears to
be advantageous for microbes in the subsurface environment to remain in one place and
harvest substrate (contaminants) and nutrients that are transported primarily by advection
rather than move with the water and rely solely on dispersion.l? If the metabolism of the
compounds results in substantial energy yield ancl/or cell-building materials, then the microbial population will increase. As populations of attached microorganisms increase, the organisms start to accumulate on top of one another, gradually building up a layer of microbes
with the help of attaching material (polysaccharides). This is referred to as the biofilm and
can be very effective in degrading contaminants by diffusion into the biofilm.

2.7

SUMMARV

Various aspects of contarninant partitioning and the resulting fate and transport were
discussed in previous sections of this chapter. It is important to understand the behavior of
contaminants in the subsurface environment to properly design and successfully implement
a remediation system. Conceptual models of contaminant partitioning in the subsurface are
shown in Figures 2.4 and 2.5.

Remediation of contarninants present in the subsurface environment should be understood

(from a chemistry point of view) as perturbation of partitioning of the contaminants to the
most favorable compartment and/or phase. However, the efforts to perturb the system may
have nonequilibrium limitations.'! Thesenonequilibrium limitations have a significant impact
on the tailing effect of contaminant concentration levels at various remediation sites." This
tailing effect has been observed even at sites where a significant amount of money and time
have been spent implementing the most state-of-the-art remediation technologies.
The reasons for the tailing effect of contarninant concentration levels can be summarized
as below:

nonhomogeneous advective ftow

film limitations
sorption effects
transport effects
intraparticle diffusion
micropore diffusion
macropore diffusion

CONTAMINANT

Figure 2.4

CHARACTERISTICS

Unsaturated

AND PARTITIONING

zone partitioning

25

model.

Figure 2.5

Saturated zone partitioning

model.

REFERENCES
1. Knox, R. c., Sabati ni , D. A., and Canter, L. w., Subsurface Transport and Fate Processes,
Lewis Publishers, Boca Raton, FL, 1993.
2. Wilson, S. B. and Brown, R. A., In Situ Bioreclamation: A Cost Effective Technology to
Remediate Subsurface Organic Contarnination, Ground Water Monitoring Rev., Winter, 1989.
3. Graedel, T. E., ChemicaL Compounds in the Atmosphere, Academic Press, New York, 1978.
4. Pankow, J. F. and Cherry, J. A., Dense Chlorinated SoLvents and other DNAPLs in Groundwater,
Waterloo Press, Portland, OR, 1996.