Chapter 6

Environmental
Organic Chemistry
• Diversity of organic compounds
• The fate of organic contaminants
• Chemical Partitioning
• Chemical transformation and degradation
• Chemical transformation through photochemistry
CO & PO FOR CEV420
 Course Outcome (CO)
 Explain the physical and chemistry of the atmosphere, water and solid earth, as well
as the concepts of environmental organic chemistry and biogeochemical cycling of
chemicals (CI, C2, A1).
 Apply the environmental sciences knowledge to solve the chemical processes
problems (C3, C4, A1).
 Evaluate the environmental sciences approach in solving problems related to
environmental issues (C6, A1).

 Programme Outcome (PO)

 PO1:Ability to apply knowledge of mathematics, science, engineering fundamentals

to solve complex engineering problems in chemical and environmental engineering.
 PO2:Ability to identify, formulate, analyze and solve complex chemical and
environmental engineering problems using the principles of mathematics, applied
science and engineering.
Course Learning Outcomes:
 The student should be able to :
 Identify the diversity of organic compound
associated with environmental aspect and its
characteristics.
 Explain the fate of organic contaminants and its
portioning behavior in the environment
 Analyze the chemical transformation and
degradation naturally and through
photochemistry.
Environmental Organic Chemistry (EOC)
 EOC is an exciting branch of chemistry that has developed
over the last few decades.

 Probably the best known for the study into the fate and
behaviour of antropogenic( man-made pollutant)

 GC-MS and LC-MS analysis:

 -enables analysis of pollutant degradates and metabolites in
aqueous systems and
 -has led to the screening of pharmaceuticals, verterinary
drugs and antibiotics in both surface and ground water.
Diversity of organic compounds……
Organic compounds..
 An organic compound is any member of a large class of gaseous, liquid,
or solid chemical compounds whose molecules contain carbon.
 In chemistry, an open-chain compound (also spelled as open chain
compound) or acyclic compound (Greek prefix "α", without and "κύκλος",
cycle) is a compound with a linear structure, rather than a cyclic one. [
 An alicyclic compound is an organic compound that is both aliphatic and
cyclic. They contain one or more all-carbon rings which may be either
saturated or unsaturated, but do not have aromatic character.[1] Alicyclic
compounds may have one or more aliphatic side chains attached.
 Aliphatic: Relating to organic compounds whose carbon atoms are linked in
open chains, either straight or branched, rather than containing a benzene
ring. Alkanes, alkenes, and alkynes are aliphatic compounds.
 Aromatic compounds, also known as arenes or aromatics, are chemical
compounds that contain conjugated planar ring systems with delocalized pi
electron clouds instead of discrete alternating single and double bonds.
Typical aromatic compounds are benzene and toluene.
 Diversity of organic compounds……
 The wide range of organic compounds subject to research within EOC,
encompass a broad range of physical-chemical properties, but can be
categorised according to either molecular weight, volatility, and/or
reactivity.

 Figure 1 provides examples of a range of molecules that have vapour

pressures spanning orders of magnitude, and are subject to research
because of their interesting chemistry in the atmosphere, aquatics
systems and/or soil and sediments.

 Many of more volatile compounds (C1-C6) emitted into the atmosphere

have an important impact on atmospheric photochemical processes.

 Ex (Chapter 3): Oxidation of CH4 through the reaction with OH radical,

form short-lived peroxy (HO2) and alkoxyradicals (RO2) that are
important for converting NO to NO2 in the polluted atmosphere and
hence allowing the build up of ground-level ozone during warm sunny
weather.
Environmental related Organic Compounds….
 Coal Mining Petroleum Toxic Release
Metal 0.2% Utilities 0.1%
Mining
47.3%
16.2% Inventory (TRI)
Chem
2000 Figures
Distrib
0.0% Total releases of chemicals
regulated according to TRI
Haz Waste 7.1 billion pounds (2000)
4.0%
Mfg
32.2%

Other
Pesticides Dioxins
Mercury Total PBT releases
PCBs
12 million pounds (2000)
Persistent, bioaccumulative, and toxic
substances (PBTs)

PAHs
Source: www.epa.gov/tri 9
Environmental organic
compound
 TRI = toxic release inventory programme
 Persistent, bioaccumulative and toxic (PBTs)
substances are a class of compounds that have high
resistance to degradation from abiotic and biotic factors,
high mobility in the environment and high toxicity.
 Because of these factors PBTs have been observed to
have a high order of bioaccumulation and
biomagnification, very long retention times in various
media, and widespread distribution across the globe.
 Majority of PBTs in the environment are either created
through industry or are unintentional byproducts
Environmental organic
compound
 Polychlorinated biphenyl, PCB (CAS number 1336-36-
3 ) is a synthetic organic chemical compound of chlorine
attached to biphenyl, which is a molecule composed of
two benzene rings.

 Polycyclic aromatic hydrocarbons, PAHs (also known

as polynuclear aromatic hydrocarbons) are composed of
two or more aromatic (benzene) rings which are fused
together when a pair of carbon atoms is shared between
them.
Organic Chemical Fate
Arrows indicate pathways

12
Organic Chemical Fate
 The major loss pathways of pesticides to the environment are
volatilization into the atmosphere and aerial drift, runoff to
surface water bodies in dissolved and particulate forms, and
leaching into groundwater basins.
 The fate and transfer pathways of pesticides applied to
croplands are complex, requiring some knowledge of their
chemical properties, their transformations (breakdown), and
the physical transport process. Transformations and transport
are strongly influenced by site-specific conditions and
management practices.
 Chemical Partitioning
 The transfer of chemicals between two or more environmental
compartments or phases can be described by equilibrium
partitioning – essential for understanding and describing
chemical fate in the environment.

 Chemical partitioning takes place between adjacent phases such

as between:
 a solid and a liquid (dissolution)
 a liquid and a gas (volatilisation)
 a solution and a solid surface (adsorption)
 a solution and an immiscible liquid (solvent partitioning)

 The net transport of an organic compound from one phase to

another (eq. air to water) is limited constraints and can be
quantified according to partitioning constant or coefficient (K).
 Chemical Partitioning
Partitioning is the phenomenon where a
chemical substance distributes itself based on
its ability to dissolve in the media involved.

K12 = C1/C2 = S1/S2

K12 : Chemical Partition Coefficient between media 1 and 2 (unitless)
C1 : Concentration in medium 1 (mol/m3)
C2 : Concentration in medium 2 (mol/m3)
S1 : Solubility of chemical in medium 1 (mol/m3)
S2 : Solubility of chemical in medium 2 (mol/m3)
Chemical partitioning between mediums……
Example:
Partitioning of DDT

Organic Concentration in
phase organic phase:
Co = 10,000 mol/m3

Concentration in
Water water
Cw = 2 mol/m3

Kow = Co/Cw = 5,000

Example:
Partitioning of NaCl

Concentration in
Organic
organic phase:
phase
Co = 0.001 mol/m3

Concentration in
Water water:
Cw = 10,000 mol/m3

Kow = Co/Cw = 0.0000001

 Soil – water partitioning
 Soil-water distribution ratio (Kd)
 Describe partitioning between heterogeneous solid phase
(soil) and soil-water (containing a variety of dissolved solids
and organic material)

• Organic-carbon to water partitioning coefficient (Koc)

 Describes chemical partitioning between the organic-carbon
fraction of a soil or sediment and water and is frequently
used to describe pesticide fate in agricultural soils.
 Air – water partitioning
 Henry’s Law Constant (H)
 Defined as the ratio of the partial pressure (p) of a chemical
in the air to its mole fraction (or molar concentration)
dissolved in water (Cw) at equilibrium.

Unit: Pa m-3 mol-1

• “Dimensionless” Henry’s Law Constant (H’) or Kaw

 By applying ideal gas law:

R : Pa m-3 mol-1 K-1

 Chemical Transformation and degradation
 Chemical degradation may proceed by wide processes and the reactivity of
chemical is governed by its;
-stereochemistry (3-dimensional structure),
-bond strengths and
-the presence of functional group.

 Both abiotic and biotic processes can be broadly grouped under following
reaction; oxidation, reduction, hydrolysis and photolysis.

 These generic reactions are not mutually exclusive, as the generation of

oxidants present in the atmosphere that requires the action of sunlight on
precursors molecules (e.g :the formation of OH radical from ozone-
photolysis).
 Chemical transformation through
photochemistry
 Organic pollutant are susceptible to photochemical transformation and
degradation in both atmosphere and surface waters.
 Photochemical degradation can occur in any environmental medium
that is subject to sunlight and includes surface reactions whereby
chemicals sorbed to environmental surfaces such as plant material,
airborne particles and even snow and ice are affected by sunlight.
 Both direct and indirect photochemistry  lead to the destruction of the
pollutant and /or its phototransformation.
 Some cases lead to more persistent, or toxic, photoproducts such as
the photochemical transformation of chlorobenzenes to poly-chlorinated
biphenyls (PCBs) in ice.
 Therefore, the assessment of photochemistry on the fate of organic
chemicals is a necessary step in risk assessment procedure (ex;
required for pesticide registration)
 US-EPA/ European Chemical Bureau/OECD – provide protocols for
conducting laboratory on photochemical fate studies.