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ABIOTIC TRANSFORMATION

• Transformation or degradation: the disappearance of the

parent compound from the environment by a change in its
chemical structure
• If the change by microorganisms  primary biodegradation or
biotransformation
• Transformation can be brought also by abiotic processes:
- hydrolysis
TRANSFORMATION - oxidation
- reduction
- photochemical degradation
• Transformation and mineralization (converting chemicals to
simple molecule and ions: CO2, CH4, H2O, chloride)  alter
the physicochemical and toxicological properties

RATE OF DEGRADATION HYDROLYSIS

• Its availability for reaction
• Its intrinsic reactivity
• The availability of reactant
• The reactivity of reactant
All of these depend on:
pH, temperature, light intensity, and redox condition
• Chemical reaction of organic compounds with water
• Hydroxide replaces another chemical group
• Certain functional group often inert to hydrolysis
(alkanes, alkenes, benzenes, byphenyls, (halogenated)
polycyclic aromatics (e.g. PCBs, PAHs), alcohol, esters,
and ketones)
• Polar products are formed  more water soluble, less
lipophilic
• Commonly catalyzed by hydrogen or hydroxide ions
• The rate depends on pH  pseudo first order kinetics
reaction
ln Ct = ln C0 – kobs . T

Kobs : pseudo-first constant (l/s)

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OXIDATION
• Chemical process in which an electron-deficient particle
(oxidant) accepts electrons from the compound to be oxidised
• Example oxidants that occurs under environmental conditions:
- alkoxy radicasl (RO.)
- Peroxy radicals (RO2.)
- Hydroxy radicals (HO.)
- Singlet oxygen (1O2)
- Ozon (O3)
• Most oxidant direct or indirectly interact with solar radiation
forming an ‘excited state’ of the molecule
• Oxidation in the main transformation for the most organic
compounds in the troposphere and various micropollutants in
surface water
• Common processes are:
- H-atom transfer
- addition to double bonds
- HO addition to aromatics
- RO2 transfer of O atom to nucleophilic species

REDUCTION

• Kinetic rate • Chemical process by which electrons are transferred from an

Rox = Kox. [C].[OX]
• Rox = sum of the rates of reaction of each oxidant
Rox = kRO2.[C].[RO2] + kRO. [C].[RO] + kOH.[c].[OH]
electron donor (reductant) to the compound to be reduced
• Can contribute significantly to the removal of several
micropollutants: nitroaromatic, azo-compounds, halogenated
aliphatic, and aromatic compounds
• Take place in a variety of reducing (non-oxic) systems in
sewage sludge, anaerobic biological systems, saturated soil
system, anoxic sediments, reducing iron porphiryn system, etc.
• Reduction rate depends on redox potential, temperature, pH
and physical and chemical characteristics of the
micropollutant to be reduced
• Products: more polar and susceptible to further chemical
attack and less likely to accumulate

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PHOTOCHEMICAL DEGRADATION

• Require the penetration of radiation (light, including

UV light) in aqueous or atmospheric environments
• Absorption of a photon by a compound  photon
energy needs to be transferred to the reactive site
within the molecules or transferred to another
molecule
• Not every photon induced chemical reaction
• Possible process: include reemission of light through
fluorescence and phosphorescence, an internal
conversion of the photon energy into heat and the
excitation of other molecules

METHOD FOR MEASURING ABIOTIC

DEGRADATION
• Fraction of absorbed photon causes the desired • Standard method only available for hydrolysis as a
reaction : the quantum yield  always less than or equal
to 1 function of pH
• Quantum yield depends on the nature of the molecule • Is determined as a function of time, at specific
which absorb light and the reaction undergo temperature, and a specific pH
• Types:
- direct photoreactions: reacting molecule directly  at least at 3 pHs
absorbs light • Photochemical transformation: amount of light
- indirect or sensitized photolysis light absorbing molecule intensity at a function of wavelength and absorbed
transfers its excess energy to an acceptor molecule
causing the acceptors to react by chemicals
• Direct: proportional to light intensity at a specific
wavelength and quantum yield
-dC/dt = kp.I.C

BIODEGRADATION

• Microbial degradation plays a key role in the removal of • Environmental factors affect population distribution
synthetic chemicals from aquatic and terrestrial environment
and biochemistry of bacteria
• If too slow  bioaccumulate
• Persistence • Sediment and soil are more less aerobic unless the
• Ultimate biodegradation or mineralization oxygen consumption by microorganisms (due to
• The heterothrophic microorganisms is characterised by abundance substrate) is higher than oxygen supply
catabolic versatility
• Cometabolism: biodegradation of synthetic
 adaptation or acclimatization
 mixed microfloras vs monocultures
chemicals does not always result in bacterial
• Enzymatics machinery of microorganisms  involved in growth
metabolic cycles and adaptive or induced enzymes
• This enzymes enable bacteria to utilizes organic compounds
which are not appropriated for immediate use

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AEROBIC DEGRADATION

• Three major oxidative mechanisms

• Environmental condition and chemical structure
may hinder these reactions:
• - ω oxidation: initial attack on aliphatics chain at
the terminal methyl group, oxidized to yield fatty
acid
• - β oxidation: sequential oxidation – two carbon at
a time – fatty acid chain catalyzed by enzymes
• - aromatics oxidation: start with the formation of
catechol from benzene derivatives such as
benzoate, phenol, etc.  enzyme-catalyzed
oxidation with molecular oxygen

ANAEROBIC DEGRADATION

• Important in anoxic sediment, soil, and

groundwater
• Slow compared to aerobic biotic processes
• Biodegradation of anaerobic bacteria are difficult
to conduct

CHEMICAL PERSISTENCY

• Chemical structure
• Environment conditions: temperature (spychrophilic
bacteria, mesophilic bacteria); inorganic nutrient
status, pH
• Bioavailability: if it is trapped, the chemicals cannot
be interracted with microorganisms

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CHEMICAL STRUCTURE `

BIOTRANSFORMATION TYPES OF BIOTRANSFORMATION

• Biotransformation reaction involve enzymes as

biological catalysis
• Influence the toxicity of a compounds
• Transformation to a more toxic is called
bioactivation
• Reduction of toxicity to less harmful transformation is
called detoxification
• Enzymes determine the qualitative and quantitative
aspect of biotransformation

• Phase I
Oxidation, reduction, hydrolysis

• Phase II
to larger polar group  hydrophilic  rapid
excretion

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METHODS FOR MEASURING

BIOTRANSFORMATION
• Enzyme kinetics
• In vitro methods: isolated cells of the organ in which
biotransformation is measured
- quantifying biotransformation products
- quantifying enzyme activity
• in vivo methods: laboratory studies with animals
- quantifying biotransformation products
- enzyme inhibition
- mass balance
- physicochemical properties