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McKay, Donald. "Front matter" Multimedia Environmental Models ...

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halogentated hydrocarbons), they experience considerable difficulty, and they may<br />

or may not be able to perform useful chemical conversions. In such cases, if environmental<br />

degradation does take place, it is often the result of abiotic processes such<br />

as photolysis or reaction with free radicals.<br />

Our aim is to be able to define a half-life or rate constant for microbial conversion<br />

of the chemical, usually in water but often also in soil and in sediments. These rate<br />

constants may be measured by introducing the chemical into the medium of interest<br />

and following its decay in concentration. If first-order behavior is observed, a rate<br />

constant and half-life may be established. Care must be taken to ensure that the<br />

decay is truly attributable to biodegradation and not to other processes such as<br />

volatilization.<br />

In many cases, non-first-order behavior occurs. For example, it is suspected that,<br />

in some situations, the concentration of chemical is so low that the enzymes necessary<br />

for conversion do not become adequately activated, and the chemical is essentially<br />

ignored. At high concentrations, the presence of the chemical may result in<br />

toxicity to the microorganisms, and therefore the conversion process ceases. The<br />

number of active enzymatic sites may also be limited, thus the rate of conversion<br />

of the chemical species becomes controlled not by the concentration of the species<br />

but by the number of active sites and the rate at which chemicals can be transferred<br />

into and out of these sites. Under these conditions of saturation, a Michaelis–Menten<br />

type equation can be applied as described earlier.<br />

Much to the chagrin of microbiologists, we will adopt a simple expedient assuming<br />

that a first-order rate constant (or half-life) applies and that the rate constant can<br />

be estimated by experiment or from experience. This is necessarily an approximation<br />

to the truth and often involves merely a judgement that, in a particular type of water<br />

or soil, this compound is subject to biodegradation with a half-life of approximately<br />

x hours. The rate constant is therefore 0.693/x hours. Valiant efforts have been made<br />

to devise experimental protocols in which chemicals are subjected to microbial<br />

degradation conditions in the field or in the laboratory using, for example, innoculated<br />

sewage sludge. Such estimates are of particular importance in the prediction<br />

of chemical fate in sewage treatment plants. Even more valiant attempts are being<br />

made to predict the rate of biodegradation of chemicals purely from a knowledge<br />

of their molecular structure. Others have been content to categorise organic chemicals<br />

into various groups that have similar biodegradation rates or characteristics.<br />

Several standard and near-standard tests exist for determining biodegradation<br />

rates under aerobic and anaerobic conditions in water and in soils. Simplest is the<br />

biochemical oxygen demand (BOD) test as described in various standard methods<br />

compilations by agencies such as ASTM and APHA. More complex systems involve<br />

the use of chemostats and continuous flow systems, which are analogous to benchtop<br />

sewage treatment plants.<br />

An important characterization of biodegradation relates to whether the organism<br />

requires an oxygenated environment to thrive. All organisms require energy, which<br />

is obtained by performing chemical reactions. The most common reaction is oxidation,<br />

which is performed by aerobic organisms when oxygen is present. Oxidation<br />

of ethanol to acetic acid is an example. When oxygen is absent and anaerobic<br />

conditions prevail, the organism can obtain energy by processes such as reducing<br />

©2001 CRC Press LLC

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