Course Code: 410

Chapter 2: Biodegradation of Recalcitrant Waste

Xenobiotic Compounds:

A xenobiotic is a foreign chemical substance found within an organism that is not naturally
produced by or expected to be present within the organism. It can also cover substances that
are present in much higher concentrations than usual. Specifically, drugs such as antibiotics
are: xenobiotics in humans because the human body does not produce them itself, nor are
they part of natural food groups. The term xenobiotic, however, is very often used in the
context of pollutants such as dioxins and polychlorinated biphenyls and their effect on the
natural biota, because xenobiotics are understood as substances foreign to an entire
biological system, i.e. artificial substances, which did not exist in nature before their synthesis
by humans.

The term xenobiotic is derived from the Greek word -xenos - meaning foreigner, stranger and
bios, vios -meaning life, plus the Greek suffix for adjectives - (tic).

Xenobiotics in the Environment:

►Sources include -waste products & toxic materials which are released in the environment.
►Xenobiotics are a threat to the flora and fauna and the ecosystem as well.
►Increasing amounts of fuels, industrial chemicals, fertilizer, pesticides, pharmaceutical
wastes, food wastes etc. are causes of xenobiotic formation.
►Pharmaceutical treatment techniques such as chemical coagulation, filtration, ion
exchange and activated carbon adsorption - though useful in detoxifying and destroying
xenobiotics -but are yet to become commercially attractive.
►In many cases, some chemicals themselves may act as pollutant.
►The unavailability of low cost and effective xenobiotic treatment have favored biological
treatment of industrial waste.
Organic pollutant to harmless/ innocuous end product compatible with the
ecosystem
►Biological treatments have become accepted as effective, cost effective, environmentally
compatible and friendly methods.
What is Biodegradable waste?
Biodegradable waste includes any organic matter in waste which can be broken down into
carbon dioxide, water, methane or simple organic molecules by microorganisms and other
living things using composting, aerobic digestion, anaerobic digestion or similar processes. In
waste management, it also includes some inorganic materials which can be decomposed by
bacteria.
What is Persistent waste?
Persistent organic pollutants/wastes (POPs) are hazardous organic chemical compounds that
are resistant to biodegradation and thus remain in the environment for a long period of time.
They are resistant to environmental degradation through chemical, biological and photolytic
processes. Because of their persistence, POPs bioaccumulate with potential adverse impacts
on human health and the environment.
What is Recalcitrant waste?

New synthetic compounds/wastes that are slowly biodegradable or non-biodegradable are

known as recalcitrant compounds. They range from simple halogenated hydrocarbons to
complex polymers including dyes, pesticides, explosives, heavy metals, polyalcohols, furan
derivatives and phenolic substances. As they remain in the environment, they are capable of
long range transportation, bioaccumulation, in human and animals and biomagnifications in
food chain.

Reasons for being Recalcitrant:

 Chemical structure.

 Inability of microbes to assimilate it.

The Chemical Structure influences the biodegradability of a compound in 2 ways:

i. The molecule may contain groups or substituent which prevents catabolism by
constitutive or inducible enzymes.
ii. Alternatively, the compound may exist in such a physical state (absorbed, gas phase.
insoluble form etc.) where microbial degradation does not occur.
Some examples are given below:
 Non-biodegradability usually occurs with lipophilic compounds such as chlorinated
pesticides, which have very low solubility in water.
 Another good example of structure-recalcitrant is that amorphous cellulose fiber is
much more susceptible than crystalline cellulose fiber. This is possible because closely-
packed nature of crystallized portion of the fiber would reduce the penetration of
enzyme.
 The type, number and position of the substituent are important for simple organic
molecule. These attributes markedly influence susceptibility to biodegradation. For
example: the introduction of -OH, -COOH, -NH2 or -CH3 groups to an aromatic ring
increases biodegradability, whereas the introduction of -F, -CI, -NO 2, -SO2H groups
make the structure more resistant to biodegradation.

Factors affecting microorganisms to degrade Xenobiotics:

The inability of microbes to degrade organic molecules may result from one of the following
factors:
i. The absence of specific enzymes to catalyze the organic compound.
ii. The compound in question do not penetrate into the cell (non-permeability of the
compound).
iii. A required catabolic enzyme may be repressed by another compound.
iv. The environmental condition may not allow for the proliferation of the required
microbes or for the function of the needed enzyme.
 Fig: Ortho, meta and para positions in Benzene(phenol) ring.

Phenol metabolic pathway of C. tropicalis

Many studies have focused on biodegradation of phenol and phenolic compounds with
respect to degradation pathways. The aerobic aromatic catabolic pathway generally consists
of three stages namely the:--
1) conversion of the growth substrate to catechol
2) ring-cleavage
3) metabolism of the ring cleavage product to central metabolites by either the ortho or
meta-pathways.

Description:

The first reaction in phenol degradation is catalyzed by enzyme phenol hydroxylase (PH)
where- one oxygen atom of molecular oxygen is used into the aromatic ring to form catechol
as the central intermediate. This catechol is then converted to cis, cis-muconic acid through
Ortho-cleavage pathway. This pathway is also known as B-ketoadipate pathway which is
catalayzed by catechol 1,2-dioxygenase (C1,2D). Through the Meta-cleavage pathway after
catechol formation, it is converted to 2-hydroxymuconic semialdehyde (2-HMSA) which is
catalyzed by catechol 2,3-dioxygenase (C2,3D). After several subsequent reactions, Ortho
pathway will lead to succinyl-CoA and acetyl-CoA. On the other hand, Meta pathway will lead
to pyruvate and acetyl dehyde. Finally, both pathways will have incorporated into the
tricarboxylic acid cycle (TCA) or Krebs cycle. Therefore, from these phenol metabolic
pathways, cis, cis-muconic acid (MA) is considered the indicator for Ortho-cleavage pathway
and 2-hydroxymuconic semialdehyde (2-HMSA) is the indicator for Meta-cleavage pathway.