R

Pr

op

er

ty

of

IN

Chapter II
Fate of pollutants in the environment

IV. Fate of pollutants

1. The phases of a pollution

Emission phase

op

er

ty

of

IN

The emission is characterized by its location and its intensity, two factors that modulate
the capacity of the ecosystem to recover (high or low intensity, air, water, soil)

Pr

R
A

Pollution are characterized by 3 phases that determine the fate of pollutants: Emission,
dispersion and transformation.

IV. Fate of pollutants

Dispersion phase

op

er

ty

of

IN

R
A

The dispersion of the pollutants corresponds to a movement of the pollutants due

transfer processes (diffusion, wind, water flow, transport).
A rapid dispersion may prevent local accumulation by decreasing the apparent levels of
pollutants in the environment. However, a rapid spreading of the pollution allows the
contamination of other sites.

Pr

1. The phases of a pollution

IV. Fate of pollutants

Transformation phase

op

er

ty

of

IN

R
A

The transformation phase could occur at any step of the pollution. Thus, a substance
emitted at low intensity and rapidly transformed may have a weak impact on the living
organisms. Conversely a pollutant intensively and rapidly emitted, slowly dispersed and
transformed has the potential to have great impacts on living organism

Pr

1. The phases of a pollution

1. The phases of a pollution

R
A

IV. Fate of pollutants

Dispersal of a pollution
Case of slow dispersion
at the emission point.

Delay

- - - - - Analysis of the pollutant concentration

at a point away from the emission point. The

delay in the appearance of the pollutant is
due to the dispersion time. Note that the
concentration is always lower than that of the
origin
because
of
spreading
and
transformation of the pollutant.

of
Time

op

er

ty

50

Pr

[Pollutant]

100

IN

______ Analysis of the pollutant concentration

Case of rapid dispersion

______ Analysis of the pollutant concentration

at the emission point.

- - - - - Analysis of the pollutant at a point
away from the emission point.

IV. Fate of pollutants

1. The phases of a pollution

Distance
Delay
Area
Time
Conc.

R
A

Contamination point
Time to

Distance
Delay
Area
Time
Conc.

Evolution of pollution
Dispersion only due to
diffusion (above), and due
to diffusion and external
factors (wind, air stream,
water flow) (below)

ty

Contaminated area

of

IN

tn

op
tn

Pr

Distance
Delay
Area
Time
Conc.

er

Stream

Contaminated area

Contamination point
Time to

Distance
Delay
Area
Time
Conc.

IV. Fate of pollutants

2. Transfer of pollutants in the environment

Transfer of pollutants emitted in the atmosphere

IN

The pollutants emitted in the atmosphere are gas, vapors, solids matters and sprays.
After emission, pollutants undergo a dispersion in the atmosphere that depend both on
the importance of air streams, the density of the pollutants and their diffusion velocity.

er

ty

of

Gas and Vapors

Gas and vapors of volatile substances (Solvents, metal vapors, solid substances with
high vapor pressure) can diffuse relatively easily, especially in there are lighter than air.
Gas and vapors undergo a rather rapid diffusion in the atmosphere. They can be
dissolved in the water in suspension in air and reach the earth surface in rains.
Examples of gas: Chlorofluorocarbons (CFC, ozone destroyer), CO2 SO2, Nitrogen
oxides (NOx), H2S, HCl, NH3, benzene vapors, Mercury vapors

op

Solid matters and sprays

Light matters such as fumes, dusts (asbestos, coal), nanoparticles or sprays (a spray
is a suspension of small liquid droplets). Dusts and sprays will undergoes a
sedimentation after an eventual dispersion by winds.

Pr

R
A

2. Transfer of pollutants in the environment

IV. Fate of pollutants

2. Transfer of pollutants in the environment

Transfer of pollutants emitted in the atmosphere (ctd)

R
A

The atmospheric pollutants may follow two ways that determine they toxicity:

IN

A penetration in terrestrial and aerial organisms

The penetration can occur through lungs or teguments and skin.

Transfer of pollutants emitted on soils and in water

op

er

Pollutants emitted on soils surface and in water environment are:

Liquids, substances in solutions, solid substances that can dissolve or undergo a
degradation.
The transfer of these pollutant are the same than those having reached the soil surface
or water environment.

Pr

ty

of

They can reach the earth surface

In the aquatic environment, they can penetrate the organism or can be linked to
organic and mineral matter.
In soil, they can deposit on soil surface, or can undergo transfer processes: infiltration,
drainage (free form), lixiviation/leaching (adsorbed form) and exfiltration.

IV. Fate of pollutants

2. Transfer of pollutants in the environment

of

IN

R
A

General scheme of pollutant transfer in the environment

op

Groundwater

Pr

Telluric biomass

Infiltration
Drainage
Lixiviation

Exfiltration

er

ty

Stream

Trophic transfer
Sediments

IV. Fate of pollutants

2. Availability of environmental pollutants

3. Availabilty of environmental pollutants

R
A

In all media, a substance undergoes exchange processes that determine it distribution

in the environment.
A substance may have different states:

ty

of

IN

In air
- Free substance (dusts and particles, gas, vapor, microorganisms and virus)
- Substance adsorbed on particles and dusts
- Substance dissolved in or associated with atmospheric water
(HCl, SO2, microorganisms and virus)

Pr

op

er

In water and soils

- Dissolved substances and water-miscible liquids (water soluble, water mixable )
- Liquid in heterogeneous phase (non water miscible liquids)
- Substances in suspension: particles, colloids (2-200 nm)
- Substances adsorbed on mineral particulate fraction (soil matrix, colloids, sediments)
or organic particulate fraction (organic matter, microorganisms)

IV. Fate of pollutants

3. Availability of environmental pollutants (ctd)

A particulate phase : Adsorbed substance (SA)

: Linked substance (SL)

: Dissolved substance (in water) or free substance (in air) (SF)

IN

A free phase

R
A

Whatever the substance, it is distributed into 2 phases:

SF

Strongly adsorbed

Pr
Linked

ion
De
so
rp
tio
n

So
rp
t

Particles

op

Adsorbed/Sorbed

SL

n
tio
rp
n
So
tio
rp
so
De

er

Free/Dissolved

ty

of

The disposition (or availability) of a substance, corresponds to its state at a given time,
which is in equilibrium between 3 states

SA

IV. Fate of pollutants

3. Availability of environmental pollutants (ctd)

k+1

Free/Dissolved

k- 1

Strongly adsorbed

k+1 Sorption constant (time-1)

k-1 Desorption constant (time-1)

IN

Adsorbed

R
A

A substance bound to a particulate fraction can be released

Weakly adsorbed, easy release

k+1 << k-1

Strongly adsorbed, difficult release

k+1 k-1

Apparent equilibrium, easily displaced

er
op

Linked

ty

of

k+1 >> k-1

Linked

Original substance

Linked

Modified substance

Slow process

Pr

Linked

Note : k are time constants, or velocity constants (time-1)

IV. Fate of pollutants

4. Transformation of pollutants in the environment

R
A

Organic substances

Organic substances include a very large part of pesticides. Organic substances may
undergo two degradation processes:

ty

of

IN

Physico-chemical processes
- Hydrolysis
- Photolysis (solar and cosmic radiations)
- Oxydo-reduction reactions
- Thermolysis (fire, high ambient temperature, volcanic activity)
- Reaction with environmental molecules (including xenobiotics)
Physico-chemical transformation of a substance results in transformations products

op

er

Biological processes
- The biological degradation of pollutants is the biotransformation of the metabolization.
- The environmental degradation involves main microorganisms.
- The biotransformation involves oxidases, reductases, hydrolases and conjugation
enzymes.
The biotransformation products are metabolites.

Pr

IV. Fate of pollutants

4. Transformation of pollutants in the environment

R
A

Transformation of pollutants in the environment

Parent compound

IN

Parent compound

Metabolization

of

PhysicoPhysico-chemical
transformation

Transformation
products

ty

PT2
PT2

PTn

er

PT1
PT1

Secondary
products

PT3

op

PT2

Pr

PT1

Metabolites

M1

M2

M3

Mn

M3
M3

Mn
Mn
Secondary
metabolites

IV. Fate of pollutants

4. Transformation of pollutants in the environment

50

ty

Biological degradation

DT90

op

DT50

er

Global degradation

10
0

Time

Environmental degradation of a pollutant

DT50 and DT90 are the degradation times
50% and 90%, times for which 50% and 90%
of the product are degraded, respectively.
DT50 and DT90 represent indicator of the
degradation velocity.
In term of impacts on the ecosystem, DT90
is preferred to DT50.
DT50 is also called the half-life of the
compound.

of

PhysicoPhysico-chemical degradation

Pr

[Pollutant], (%)

100

IN

R
A

Kinetic of environmental transformation

IV. Fate of pollutants

Radionuclides

IN

R
A

Most of the radionuclides generated by nuclear activity are heavy metals. They present
both chemical and radiological toxicity.
They can ionize matter, especially biological molecules, and induce irreversible
damages to DNA.

of

If N is the number of radionuclides able to disintegrate and No the initial number of

radionuclides able to disintegrate, the law of radioactive disintegration is:
N = No . e-k.t

ty

N = No . e-Ln2.t/T

op

er

Where N is the number of disintegration at the time t

k, the radioactive constant (k = Ln2/T)
T, the period of the radionuclide, time for which half of the radioactivity disintegrates
No, the initial number of disintegration

Pr

4. Transformation of pollutants in the environment

IV. Fate of pollutants

4. Transformation of pollutants in the environment

Disintegration kinetic of radionuclides

IN

R
A

The disintegration curve is asymptotic. For each time equivalent to T, the period or the
half-life of the radionuclide, half of the radionuclides disintegrates.

of

80
60

ty

40

op

er

20

Time (number of T)

Pr

Radioactivity (% Initial RA)

100

T of some radionuclides
60C

cobalt
235U uranium
32P phosphore
125I iodine
3H hydrogen
14C carbon

5.27 years
704 M years
14.2 days
60.1 days
12.3 years
5730 years

IV. Fate of pollutants

Radionuclides (ctd)

R
A

In living organism, radionuclides have a fate that depends on their affinity for biological
tissues.

IN

For example, iodine has an affinity for thyroid, lead and strontium are stored in bones,
cadmium is accumulated in liver and kidney.

of

The toxicity of the radionuclides depends on the quantity of radioactivity, the type and
the energy of radiations emitted and the half-life of the radionuclide in the organism
(effective half-life).

TR . TB
TR + TB

op

TE < TB and TE< TR

er

TE =

ty

The effective half-life (TE) on the radionuclide is a function of the biological half-life (TB)
and the radiological half-life (TR).

Tritium 3H:
TR = 12.3 years TB 10 days TE slightly less than 10 days
90
Strontium Sr: TR = 29 years - TB 50 years TE = 18 years

Pr

4. Transformation of pollutants in the environment

IV. Fate of pollutants

4. Transformation of pollutants in the environment

ty

Radioactivity

20

er

Global elimination

Time

op

TR < TB

100
80

Radioactivity

60

of

Biological elimination

40

R
A

IN

80
60

Radioactivity (% Initial RA)

100

Pr

Radioactivity (% Initial RA)

Elimination of radioactivity in living organisms

40

Biological elimination

20
Global elimination
0

Time

TR > TB

IV. Fate of pollutants

Metal trace elements

R
A

For metal trace elements (MTE) this is no metabolization but a speciation

The speciation corresponds to the distribution of one element into different physicochemical species.

IN

Speciation is a continuous sequence of processes in an environmental continuum.

The speciation has an history.

ty

of

Speciation involves different phenomena

Oxydo-reduction (redox) reactions (electron transfers). They depends on redox

potential of chemical species in presence
Chemical reactions with surrounding molecules

Biological reactions. They lead to a change in the chemical state of the MTE or to
its complexation with other biological molecules.

op

er

The speciation state determines the toxicity MTE for biological organisms

Pr

4. Transformation of pollutants in the environment

IV. Fate of pollutants

4. Transformation of pollutants in the environment

R
A

In aquatic medium, speciation depends on:

Oxygen concentration

MTE in presence

Microorganisms (production of ROS and action of monooxygenases)

Nature of the particulate fraction: sediments, colloids, Organic and mineral

matters

Pr

op

er

ty

of

IN

IV. Fate of pollutants

4. Transformation of pollutants in the environment

In soils, speciation depends on:

Oxygen concentration (changing with the depth)

Nature of the soil matrix

The soil solution

Microorganisms

Organic matter

of

IN

R
A

ty

Soil surface

Aerobic microorganisms

er

Oxic zone [O2] [O2]air

Aero-anaerobic microorganisms

op

Suboxic zone [O2] < [O2]air

Pr

Anoxic zone [O2] << [O2]air

Anaerobic microorganisms

Repartition of oxygen in soils

[O2]
Invertebrates +++
Invertebrates ++
Invertebrates +/0

IV. Fate of pollutants

4. Transformation of pollutants in the environment

R
A

Example of iron (Fe)

Fe(OH)2

Fe(OH)(CH3-COO-)

Ferrous hydroxide

IN

Ferric acetate

Fe2+

Metal iron

ty

Ferrous iron

er

FeO

Pr

op

Ferrous oxide

Fe3+

of

Fe

Ferric iron

Fe2O3

Ferric oxide

Fe3O4

FerrosoFerroso-ferric oxide

Fe(NO3)3
Ferric nitrate

IV. Fate of pollutants

4. Transformation of pollutants in the environment

Example of lead

Pb3+

IN

Pb2+

Pb

R
A

Lead can exist under two oxidized states in equilibrium

Lead can also exist as organic lead as shown in the following examples

of

O
O

Pb

Pb

er

CH3

CH3

O Pb O
Lead acetate

Pr

H3C

O
Lead catechol

op

O
Lead phtalate

ty

H3C

Pb CH3

CH3
Tetramethyl lead

C2H5

C2H5
Pb C2H5
C2H5

Tetraethyl lead

IV. Fate of pollutants

4. Transformation of pollutants in the environment

Hg+

Hg2+

Mercurous salt
Hg I

Mercuric salt
Hg II

IN

Hg

R
A

Example of mercury
Mercury can exist under two oxidized states in equilibrium

op

er

ty

of

Mercury can also exist as organic mercury as shown in the following examples
Methyl mercury
CH3-Hg+
Dimethyl mercury
CH3-Hg-CH3
Ehtyl mercury
C2H5-Hg+
Diethyl mercury
C2H5-Hg-C2H5
Methylmercury is the most toxic derivative and inhibits fetal brain development.
Dimethyl mercury can cross the BBB and is neurotoxic (lack of coordination, sensory
disturbance, change in mental state.
Organic mercury is produced by soil and water microorganisms and can bioaccumulate
in a trophic chain and undergoes a biomagnification.
Microorganisms

Organic Hg

Pr

Inorganic Hg

Phytoplancton

Zooplancton

Fish

Man