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Chapter II
Fate of pollutants in the environment

IV. Fate of pollutants
1. The phases of a pollution

Emission phase

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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…)

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

transport…). Pr ™ 1. water flow. 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.IV. However. a rapid spreading of the pollution allows the contamination of other sites. A rapid dispersion may prevent local accumulation by decreasing the apparent levels of pollutants in the environment. wind. The phases of a pollution .

slowly dispersed and transformed has the potential to have great impacts on living organism Pr ™ 1. Conversely a pollutant intensively and rapidly emitted. The phases of a pollution . Fate of pollutants Transformation phase op er ty of IN R A The transformation phase could occur at any step of the pollution.IV. Thus. a substance emitted at low intensity and rapidly transformed may have a weak impact on the living organisms.

Fate of pollutants Dispersal of a pollution Case of slow dispersion at the emission point.. .. Delay .. Note that the concentration is always lower than that of the origin because of spreading and transformation of the pollutant.Analysis of the pollutant concentration at a point away from the emission point. of Time op 0 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.... . The delay in the appearance of the pollutant is due to the dispersion time.Analysis of the pollutant at a point away from the emission point.1. The phases of a pollution R A IV...

↓ R A Contamination point Time to Distance ↑ Delay ↑ Area ↑ Time ↑ Conc. water flow…) (below) ty Contaminated area of IN tn op tn Pr Distance ↑ Delay ↑ Area ↑ Time ↑ Conc. air stream. and due to diffusion and external factors (wind. Fate of pollutants 1.IV.↓ er Stream Contaminated area Contamination point Time to Distance ↑ Delay ↑ Area ↑ Time ↑ Conc. The phases of a pollution Distance ↑ Delay ↑ Area ↑ Time ↑ Conc.↓ .↓ Evolution of pollution Dispersion only due to diffusion (above).

vapors. Transfer of pollutants in the environment Transfer of pollutants emitted in the atmosphere IN The pollutants emitted in the atmosphere are gas. solid substances with high vapor pressure) can diffuse relatively easily. H2S. especially in there are lighter than air. Pr ™ R A 2. pollutants undergo a dispersion in the atmosphere that depend both on the importance of air streams. Mercury vapors… op Solid matters and sprays Light matters such as fumes.IV. the density of the pollutants and their diffusion velocity. er ty of Gas and Vapors Gas and vapors of volatile substances (Solvents. After emission. They can be dissolved in the water in suspension in air and reach the earth surface in rains. Fate of pollutants 2. dusts (asbestos. nanoparticles or sprays (a spray is a suspension of small liquid droplets). Gas and vapors undergo a rather rapid diffusion in the atmosphere. benzene vapors. ozone destroyer). HCl. coal…). NH3. metal vapors. Transfer of pollutants in the environment . Nitrogen oxides (NOx). Examples of gas: Chlorofluorocarbons (CFC. CO2 SO2. Dusts and sprays will undergoes a sedimentation after an eventual dispersion by winds. solids matters and sprays.

solid substances that can dissolve or undergo a degradation. 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. drainage (free form). Pr ™ ty of They can reach the earth surface In the aquatic environment. lixiviation/leaching (adsorbed form) and exfiltration. they can deposit on soil surface.IV. 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. In soil. they can penetrate the organism or can be linked to organic and mineral matter. . Fate of pollutants ™ 2. The transfer of these pollutant are the same than those having reached the soil surface or water environment. or can undergo transfer processes: infiltration.

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 .

vapor. microorganisms) . Availabilty of environmental pollutants R A In all media. water mixable ) . gas. colloids.Liquid in heterogeneous phase (non water miscible liquids) . colloids (2-200 nm) .Substance adsorbed on particles and dusts .Substances in suspension: particles. A substance may have different states: ty of IN In air . Availability of environmental pollutants 3.Substance dissolved in or associated with atmospheric water (HCl.Substances adsorbed on mineral particulate fraction (soil matrix.Free substance (dusts and particles. Fate of pollutants 2. microorganisms and virus) .IV. a substance undergoes exchange processes that determine it distribution in the environment. microorganisms and virus…) Pr op er In water and soils . sediments) or organic particulate fraction (organic matter.Dissolved substances and water-miscible liquids (water soluble. SO2.

IV. 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. Fate of pollutants 3. 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 .

Availability of environmental pollutants (ctd) k+1 Free/Dissolved k.IV.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. Fate of pollutants 3. 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. easy release k+1 << k-1 Strongly adsorbed. or velocity constants (time-1) . difficult release k+1 ≈ k-1 Apparent equilibrium.

Reaction with environmental molecules (including xenobiotics) Physico-chemical transformation of a substance results in transformations products op er Biological processes .Thermolysis (fire. . volcanic activity) . The biotransformation products are metabolites.The biological degradation of pollutants is the biotransformation of the metabolization.Oxydo-reduction reactions .Photolysis (solar and cosmic radiations) . hydrolases and conjugation enzymes. Fate of pollutants 4.IV. high ambient temperature. .The environmental degradation involves main microorganisms. reductases. Pr ™ .Hydrolysis . Organic substances may undergo two degradation processes: ty of IN Physico-chemical processes . Transformation of pollutants in the environment R A Organic substances Organic substances include a very large part of pesticides.The biotransformation involves oxidases.

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.

times for which 50% and 90% of the product are degraded. 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%. Fate of pollutants 4. DT90 is preferred to DT50. DT50 is also called the half-life of the compound.IV. (%) 100 IN R A Kinetic of environmental transformation . respectively. of PhysicoPhysico-chemical degradation Pr [Pollutant]. DT50 and DT90 represent indicator of the degradation velocity. In term of impacts on the ecosystem.

time for which half of the radioactivity disintegrates No. They present both chemical and radiological toxicity. and induce irreversible damages to DNA.IV. e-Ln2. Transformation of pollutants in the environment . the law of radioactive disintegration is: N = No . of If N is the number of radionuclides able to disintegrate and No the initial number of radionuclides able to disintegrate.t/T op er Where N is the number of disintegration at the time t k. the period of the radionuclide. especially biological molecules. the radioactive constant (k = Ln2/T) T.t ty N = No . They can ionize matter. e-k. Fate of pollutants Radionuclides IN R A Most of the radionuclides generated by nuclear activity are heavy metals. the initial number of disintegration Pr ™ 4.

1 days 12.IV. Transformation of pollutants in the environment Disintegration kinetic of radionuclides IN R A The disintegration curve is asymptotic.27 years 704 M years 14.3 years 5730 years . the period or the half-life of the radionuclide. of 80 60 ty 40 0 1 op 0 er 20 2 3 4 5 Time (number of T) Pr Radioactivity (% Initial RA) 100 6 7 T of some radionuclides 60C cobalt 235U uranium 32P phosphore 125I iodine 3H hydrogen 14C carbon 5.2 days 60. half of the radionuclides disintegrates. Fate of pollutants 4. For each time equivalent to T.

TB ≈ 50 years – TE = 18 years Pr ™ 4. Fate of pollutants Radionuclides (ctd) R A In living organism. the type and the energy of radiations emitted and the half-life of the radionuclide in the organism (effective half-life).IV. Transformation of pollutants in the environment . of The toxicity of the radionuclides depends on the quantity of radioactivity. 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). IN For example. lead and strontium are stored in bones. Tritium 3H: TR = 12. iodine has an affinity for thyroid. radionuclides have a fate that depends on their affinity for biological tissues. TR .3 years – TB ≈ 10 days – TE slightly less than 10 days 90 Strontium Sr: TR = 29 years . cadmium is accumulated in liver and kidney.

Transformation of pollutants in the environment ty Radioactivity 20 er Global elimination Time op 0 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 . Fate of pollutants 4.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.IV. They lead to a change in the chemical state of the MTE or to its complexation with other biological molecules. They depends on redox potential of chemical species in presence Chemical reactions with surrounding molecules ƒ Biological reactions. op er ƒ The speciation state determines the toxicity MTE for biological organisms Pr ™ 4. ty of Speciation involves different phenomena ƒ Oxydo-reduction (redox) reactions (electron transfers). The speciation has an history. IN Speciation is a continuous sequence of processes in an environmental continuum. Transformation of pollutants in the environment .

Fate of pollutants 4.IV. speciation depends on: Oxygen concentration ƒ MTE in presence ƒ Microorganisms (production of ROS and action of monooxygenases) ƒ Nature of the particulate fraction: sediments. colloids. Organic and mineral matters Pr op er ty of IN ƒ . Transformation of pollutants in the environment R A In aquatic medium.

Transformation of pollutants in the environment In soils.IV. speciation depends on: Oxygen concentration (changing with the depth) ƒ Nature of the soil matrix ƒ The soil solution ƒ Microorganisms ƒ Organic matter of IN R A ƒ 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 . Fate of pollutants 4.

Fate of pollutants 4.IV. 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 O Pb Pb O er CH3 O CH3 O Pb O Lead acetate Pr H3C O Lead catechol op O Lead phtalate ty O H3C Pb CH3 CH3 Tetramethyl lead C2H5 C2H5 Pb C2H5 C2H5 Tetraethyl lead .

change in mental state. sensory disturbance.IV. 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. Microorganisms Organic Hg Pr Inorganic Hg Phytoplancton Zooplancton Fish Man . Organic mercury is produced by soil and water microorganisms and can bioaccumulate in a trophic chain and undergoes a biomagnification. Fate of pollutants 4. Dimethyl mercury can cross the BBB and is neurotoxic (lack of coordination.