Major classes of contaminants

 No universal classification
 Source (natural, synthetic)
 Target organ (neurotoxin, hepatotoxin, nephrotoxin,
etc.)
 Physiological effects (carcinogen, teratogen,
endocrine disruptor, etc.)
 Chemical nature (organic, inorganic)
 Toxicity (highly toxic, less toxic)
 Persistence in the biosphere (highly persistent,
biodegradable)
EPA classification of pollutants http://
www.epa.gov/ebtpages/pollutants.html

 Agricultural Chemicals
 Air Pollutants (Aerosols, Asbestos, Carbon Monoxide, etc.)
 Biological Contaminants
 Carcinogens
 Chemicals (Benzene, Chlorinated Solvents, Dioxins, Endocrine Disruptors,
Heavy Metals, etc.)
 Extremely Hazardous Substances (EHS)
 Microorganisms
 Coliform, Cryptosporidium, Pfiesteria, Viruses
 Multimedia Pollutants
 Ozone
 Radiation
 Soil Contaminants
 Toxic Substances (Persistent Bioaccumulative Toxic Pollutants (PBTs),
Persistent Organic Pollutants (POPs), Toxicological Profiles )
 Water Pollutants
Organic Pollutants
 Polychlorinated Diphenyls, Dioxins, and
Dibenzofurans
 Polychlorinated Aromatic Hydrocarbons
 Pesticides
Polychlorinated Biphenyls (PCBs) and Dioxins

 PCBs – Arochlor, Chlophen, Kanechlor and Fenchlor

 - produced by chlorination of biphenyl with Fe or FeCl3
 Dioxins or PCDDs (Polychlorinated dibenzo [1,4]dioxins

-produced as unwanted by-products in chemical processes

involving chlorine and combustion processes.
Very Toxic Dioxin – TCDD (2,3,7,8-tetrachlorodibenzo [1,4]dioxin)
Nomenclature of PCBs

 The ring with the smaller number of chlorine is the

one given the prime or dashed number scheme.
 The carbon atoms of each ring are numbered in 3' 2' 2 3
such a way that the chlorine substituents are 4'
1' 1
4
attached to carbon atoms with the lowest possible 5
5' 6' 6
number
 Arochlor from Monsanto Corp. has four digit code; ClCl
the first 2 digits indicate the number of carbon Cl
atoms; the last 2 digits indicate the percentage of
chlorine in the structure of the biphenyl. Cl Cl

2,2’,4,5,5’-pentachlorobiph
enyl
Nomenclature of Dioxins
1
f Oa
-The [1,4] dioxin portion of the name
e b
refers to the middle ring of the
tricyclic structure. O c
d
4
-The [b,e] denotes the sides of the [1,4]
dioxin ring to which the phenyl rings
are fused.
9
9a O 10a
8 2
3
7 O
6 5a 5 4a 4
dibenzo [b,e][1,4]dioxin
Sources of Environmental Contamination of PCBs

1.Open burning or incomplete combustion of PCB-containing solid waste.

2. Vaporization of PCBs in open applications.
3. Accidental spills or leakages of PCBs in closed system applications.
4. Disposal into sewarage systems and subsequent dispersal of sewage
sludge.
Usage Categories of PCBs
Controllable Noncontrollable
Open System Closed System Open uses
Large capacitors small capacitors plasticizer and/or
Large transformers Hydraulic fluids, fireproofing agent
Lubricating fluids in paints, plastics,
adhesives, inks and
copying paper
Sources of Contamination of Dioxins

1.Chemical processes involving chlorine

-manufacture of organochlorine, bleaching of pulp and paper mills
2. Combustion processes
- Presence in the combusted material
- Formed from organochlorine precursors (e.g., chlorophenols, PCBs)
presence in the combusted material during the combustion process.
- Formed from high-temperature reactions between nonchlorinated organic
molecules and chloride ions.
* Reactions which utilize ortho-halogenated phenols in the preparation are
highly likely to be associated with the presence of dioxins. This is
particularly true when reaction conditions such as high temperature,
alkalinity or the presence of free halogens are involved.
 Synthesis of 2,4,5-T

Cl Cl Cl OH
NaOH NaOH Cl O-
ethylene ethylene
Cl Cl glycol Cl Cl glycol Cl Cl

Cl OCH2CO2H
ClCH2CO2H

Cl Cl
2,4,5- T (2,4,5-trichlorophenoxyacetic acid
Side-Product

Cl O- Cl Cl Cl O Cl
+
- Cl O Cl
Cl Cl O Cl
Physical Chemical Properties of PCBs and Dioxins

1. Low aqueous solubility

2. Nonflammability
3. Resistance to Oxidation
4. Resistance to Hydrolysis
5. Low Electrical Conductivity

PCBs need to be mixed with a large excess of combustible material in order to generate
the high T for decomposition
Combustion of PCB mixture at low T (<700 oC) in the presence of O2 leads to the
formation of PCDF’s
Kow’s of PCBs increase with increase in chlorine substituents
Log Kow: biphenyl= 3.76
Log Kow: 2,2’,4,5,5-pentachlorobiphenyl- 6.38
Among PCBs with equal numbers of chlorine, those with substituents in one or more of
the 2,2’,6,6’ positions possess relatively low Kow values and high aqueous
solubility.
Physical Chemical Properties of Biphenyl,
2,2’4,5,5’-Pentachlorobiphenyl and Decachlorobiphenyl

Biphenyl 2,2’,4,5,5’-PCB Decachloro-BP

Log Kow 3.76 6.38 8.20

Aq.Solubility 4.4 x 10-2 4.7x10-5 1.3x10-9
(mol m-1)
Vapor pressure 9.4x10-1 1.1x10-3 6.9x10-9
(Pa, 25 oC)
Melting Pt (K) 344 349.5 578.5
Physical Chemical Properties of 2,3,7,8-TCDD (most toxic)

Molecular wt – 322
logKow – 6.80
Aq. Solubility- 6 x10-4
Solubility in Methanol- 3x10-2
Solubility in Benzene- 1.8
Vapor Pressure- 2x10-7
Henry’s Law constant (Pa m3 mol-1)- 3.34
Melting point (K) 578
Decomposition Temperature (K)- >973
 Synthesis of 2,3,8-trichlorodibenzofuran

Properties of dioxins is almost similar to

Cl Cl
PCBs; logKow ranges from 4.20-8.20
Cl Cl

Cl heat 2,3,7,8-TCDD- most toxic , has low Kow of

Cl
O2 6.80 close to DDT (6.20)
ClCl O
2,3,8-trichlorodibenzofuran
Toxicity of PCBs
Acute (single dose) oral LD50 for Arochlor
mixture with rats: 10g/kg body weight
Thermal events such as fires and
Chronic effects: chloracne, cancer
explosions with PCB-containing oils
promoter
can result in the formation of PCDFs in
any remaining oil, in combustion Biochemical changes: vitA depletion,
effluent and in soot that is formed. alteration to lipid metabolism and
hormonal changes
2,3,4,7,8-PCDF- most toxic
Individual congeners of PCBs demonstrate a range of toxicities. The most toxic have
chlorine substituents in the non-ortho positions (3,3’,4,4’,5,5’) positions. Why?

Toxicity of Dioxins
Acute Effects: chloracne, headaches
Chronic Effects: induction of microsomal
enzymes; altered liver metabolism;
immunotoxicity; strongly implicated in
carcinogenicity

2,3,7,8-TCDD and
3,3’,4,4’,5,5’-hexachlorobiphenyl; there
is a close correspondence in molecular
structure between the planar
conformations of the two molecules-
share the same receptor site.
Properties of PAHs
Boiling Pt- very high Concentration of PAHs Produced by
Aq. Solubility- 10-4 – 10-10 M Cigarette smoke:
Log Kow – 3.36-6.04 (benzo(a) pyrene ng/m3
Kow – a measure of the tendency of the Fluoranthene 99
compound to dissolve in biota fat and Pyrene 66
other lipoidal substances such as
Benzo(a)anthracene100
humic acid in soil and sediments
Benzo(a)pyrene 22
Log Kow range of 2-6.5 is considered as
the range for lipophilic compounds. Perylene 11
Thus the PAHs would be expected to
bioaccumulate and concentrate in Cancer inducing effects of tobacco
sediments and soils in the environment smoking is not due to exposure to
to an extent depending on their nicotine but due to PAH
persistence in the media.
Properties of PAHs Toxicity of PAHs to various aquatic organism
Behavior of PAHs in the environment PAH Organism LC50 (96 hr)
t1/2 Naphthal fish 0.1-8 (mg/L)
Clear water sediment w/water Acenaph
Exp to sunlight microcosm (weeks) thene fish 0.6-3.0
0.75 34-70 (Pyrene) Phe-
0.034 200-300 (benz(a)pyrene Nanthrene fish 0.04-0.6

The major degradation pathway involves Benzo (a)pyrene- induces

chemical, photolytic and metabolic
processes. chromosomal aberration in fish
PAHs in water where oxygen is available -fish develope liver cancer
dissolved within the water mass when
exposed to sunlight can exhibit rapid rate of
photolytic decomposition but in turbid water-
degradation decreases
Pesticides
“…a pesticide is any substance or mixture of
substances intended for preventing,
destroying, repelling, or mitigating any pest.”

“…a pest is any harmful, destructive, or

troublesome animal, plant or microorganism.”

US Environmental Protection Agency (EPA)

 Pesticides
-chemicals designed to control agricultural and public
health pests

>Insecticides- organophosphates, carbamates, organochlorines, pyrethrines

>herbicides-carbamates, phenoxyacetic acids, phenylureas
>fungicides- dithiocarbamates, copper, mercurials
Chlorinated Hydrocarbon Pesticides
e. DDT b. Heptachlor c. Lindane d. Chlordane
f. Aldrin f. Endrin g. Mirex

Cyclodiene group (heptachlor, dieldrin, chlordane and alrin) are produced by

Diels-Alder reaction of hexachlorocyclopentadiene with cyclopentadiene
or with other substances containing at least one C-C double bond.
Another compound often included in their group is endosulfan.
Endosulfan is not a chlorohydrocarbon and not a member of the cyclodiene
group; its property is influenced by the presence of sulfur-containing
group.
 Cl Cl Cl
Cl Cl
Cl Cl
Cl Cl Cl Cl

O Cl Cl
Cl Cl Cl Cl Cl
Cl
heptachlor dieldrin lindane

Cl Cl
Cl Cl
Cl Cl
Cl Cl Cl
O
Cl Cl Cl S
Cl Cl O
O
Endosulfan
chlordane aldrin
Properties of Chlorohydrocarbon Pesticides

Solubility in Lipid Aq. Solubility Log Kow

(g/L) (mg/L)
4,4’-DDT 330 3.36 6.36
Heptachlor 1000 50 4.11
Dieldrin 3700 200 3.88
Lindane 800 130 2.67

Toxicity and Persistence of Various Chlorohydrocarbon Pesticides

Compound LD50 LC50 EC50 t1/2 range
(estuarine fish) (Daphnia) (soil, yrs)
(mg/kg body rats) (ug/L; 96 hr) (ug/L; 48 hr)
4,4’-DDT 115 0.4-89 0.36 2.0-15.6
Dieldrin 50 0.9-34 250 0.5-3.0
Lindane 125 9-66 460 0.04-0.7
Aldrin 50 5-100 28 0.06-1.6
Ecological effects: major reduction in the reproductive success of carnivorous birds such
as the Perigrine falcon with DDT- this is due to interference of the enzyme system
which causes thinning of egg shell.
EPA's First 12 Priority PBT Pollutants
From the Canada-US Binational Toxics Strategy

 aldrin/dieldrin  DDT, DDP, DDE

 mercury and its compounds
 PCBs
 benzo(a)pyrene  hexachlorobenzene
 mirex  dioxins and furans
 chlordane  alkyl-lead
 octachlorostyrene  toxaphene
Ecological Effect

 Major reduction in the reproductive success of carnivorous birds

such as the Perigrine falcon with DDT. This is due to the
interference of the enzyme system causes thinning of egg shell.

Organophosphate Insecticides
- Used during WWII as military gases
- Exhibit high mammalian toxicity compared to chlorohydrocarbon
pesticide but due to environmental problem of chrinated
hydrocarbon, a great deal of attention has been focused onto the
organophosphate groups as pesticides
 General Structure

O (S) R = CH3 or CH3CH2-

RO P OX
O can be replaced by S
RO
X = see examples
S
S OC2H5
MeO
P
MeO S
S NO2
O C2H5O
P
OC2H5 C2H5O
Malathion Parathion

Cl
O NO2
S O Cl S
MeO MeO
P P S OMe
MeO MeO
Dichlorvos Dimethoate
Physical Property, Environmental Property, and Toxicity of
Organophosphates
Physical Property
-greater water solubility
Log Kow = 2.71-3.81
T1/2 = 3-7 days
LC50 = 2,500 ng/kg body weight
LC50 (estuarine fish)= 27-3250
ng/L/96 hrs.
Environmental Property
-does not persist in soil
-lack of bioaccumulation capacity
 Toxic Activity
-the organophsphate pesticides
exhibit strong toxic activity with a
wide range of biota.
-active in inhibiting
acetylcholinesterase, an important
enzyme that facilitates the
transmission of nerve impulses. It
operates by hydrolyzing the
substance acetylcholine which is
generated in the transmission of
nerve impulses.
Inorganic pollutants
 Heavy metals (trace
metals) and
metalloids
 Organometals
 Radionuclides
Carbamates
Environmental Properties
-polar, water soluble, limited
persistence in the environment
because of hydrolysis
- toxic, readily absorbed through the General Structure
skin
R' = H or other groups
- -principal biodegradation pathway- O R = variety of groups
hydrolysis and oxidation R'
R O N

O
 Mechanism of Toxic Action O N
H
N
H
- Anticholinesterase O O
- -only distinction against
organophosphate- not deactivated
Propoxur or Baygon Carbamyl
for a long time
Pyrethrum and Pyrethroids
 Pyrethrum – natural insecticide
found in the flowers of cetain
plants belonging to the genus
chrysanthemum

General Structure

R'
R O
 Physical Property O
- Have polar groups, but large non- O
Natural Constituent
polar groups so poorly soluble in
water soluble in acetone and R R'

alcohol Pyrithrin I CH3 CH2=CH

- Low vapor pressure except Pyrithrin II -COOCH3 CH3

allethrin; sufficiently volatile -COOCH3 CH3CH2
Cinerin II
- -constituent of mosquito coils
- Natural pyrethroids eaily
hydrolyzed in water
 Mechanism of Toxic Action
 Neurotoxic but do not interact with
acetylcholinesterase. The toxic
action is due to the loose chemical
binding of the pyrethrin to a neural
receptor that alters the Na and K Synthetic Pyrethroids
ion conductance.
 In small doses, the pyrethrins
exhibit a knockdown effect- O
induction of temporary paralysis.
 Knockdown tends to be
Allethrin O
associated with the more polar
pyrethroids, while lethality seems
related to the more lipophilic O
O
pyrethroid Cl O
 In domestic formulations; CN
pyrethrins are used with synergist-
this compound inhibits the MFO so Fenvalerate
as to prevent deactivation of
Pyrethrin
 Synergist – piperonyl butoxide
Inorganic Pollutants
Reactive Intermediates in the
Atmosphere
Regions of the Atmosphere
Troposphere: 0-15 km; T- 280-300 K;
region of intense convection
mixing; contains 85% by mass of
entire atmosphere; Tropopause-
temperature change occurs

Stratosphere – 15 -50 km; T- 200-275

K; stable region; less convective
mixing (due to inc in T and
decrease density of gases)
Strapopause – T inversion at -2 oC
and 50 km,
Mesosphere: 50-85 km; 180-275 oC
Temperature dec. with altitude to -90
o
C at 85 km, called the
mesopause
Thermosphere: 85-500 km; T 180-
1473 oC
Chemical Compositions of the Atmosphere

1. Thermosphere: region near vacuum; concentration of species very low;

principal species are ions (ionosphere)
N2 + hν (126 nm)-- 2N ∆Ho = 945 kJ/mol
O2 + hν (240 nm) - 2O ∆Ho = 498 kJ/mol
N2 + hν (80 nm) -- N2+ + 1e ∆Ho = 1500 kJ/mol
O + hν (91 nm) -- O+ + 1e ∆Ho = 1310 kJ/mol

E = hν; N = 6.6 x 1023; H = 6.67 x10-34J.s; c = 3 x 108 m/s

2. Mesosphere: small concentration of O3 detected

Photochemical decomposition: O3 + hv (200-300 nm)-- O2* + O*

3. Troposphere: T- warmer, lighter air at the earth’s surgace; cooler, denser at

high altitude; convection currents and winds cause constant movement of
the air; region with homogeneous composition of gases
Stratospheric Chemistry
Characteristic: T inversion
Principal constituent: O2 and N2
Most important reaction: Synthesis and Decomposition of O3
O3 is an effective filter capable of absorbing uv radiation with l 200- 300 nm
uv A – 315 – 400 nm; 7% of the total flux
uv B – 280 – 315 nm; 1.5% of the total flux (harmful to plants and animals)
uv C- <280 nm; 0.5% of the total flux (damage biota of all types)

Ozone hole – thinning of the O3 layer over the Antarctic (October) and the Arctic (March)
Synthesis and Decomposition of O3 may be described in terms of Chemistry involving
only O2-containing species.
Synthesis of O3

 O2 + hv -- O + O slow
 O + O2-- O3 + M fast

Decomposition of O3:

 O3 + hv -- O + O2 fast
 O + O3-- 2O2 slow
The Ozone Layer
 In the upper stratosphere, the intensity of solar radiation is very high so
O/O2 is very high and production of O3 is limited by reaction (b). At low
altitude, the O/O2 ratio is very low since there is high concentration of O2 but
little radiation to cause dissociation and so the limitation is reaction (a).

 Catalytic Decomposition Process of O3

 -oxygen-only chemistry cannot adequately explain the concentration of O3
in the atmosphere. Other chemical species also play a role in determining
actual concentration and can lead to enhanced O3 destruction.
General Mechanism for O3 Destruction
X + O3 -- XO + O2 X: Free Radical, 3 types:
XO + O - X + O2 a. Hydroxy Radical: HOX: H. ,HO., HOO.
O + O3 -- 2 O2 b. Nitiric Oxide Radical: NOx (NO., NO2.)
c. Chlorine Radicals: Cl., ClO.
 Near the stratosphere, the HOX  The HOX Cycle:
accounts for as much as 70% of
the total mechanism of O3 Generation of HO and H
destruction including the O2-only O + H2O - 2OH
processes. Lower in the
stratosphere (about 30 km, the H2O + hv  H + OH
NOX Cycle dominates the removal
mechanism of O3)
 The NOx Cycle- major
Decomposition of O3 by contributur in the lower
OH and H region of the stratosphere
OH + O3 - HOO + O2 Catalytic Cycle:
HOO + O  HO + O2 NO + O3  NO2 + O2
O + O3  2 O2 NO2 + O  NO + O2
O + O 3  2 O2
H + O3 -- HO + O2
HO + O --- H + O2
 Sources of NO:  The ClOx Cycle
Photochemical
b.
Decomposition at Altitude
-the natural contribution of O 3

greater than 30 km destruction accounts to only 10%

of the total
N2 + hv  2N
-the precursor of Cl in CH3Cl
N + O2  NO + O
produced biogenically from
b. Reaction of N2O with O oceans, burning of vegetation and
volcanic emissions.
N2O + O  2NO
NO + OH +M HNO2 + M (this
CH3Cl + hv  CH3 + Cl
process induces O3 depletion)
Mechanism for O3 Depletion by ClOx
A.  B.
Cl + O3  ClO + O2  ClO + HOO  HOCl + O2
ClO + O  Cl + O2 HOCl + hv  HO + Cl
O + O3  2 O 2 Cl + O3  ClO + O2
HO + O3  HOO + O2
2 O3  3O2
 C.
 Cl + O3  ClO + O2
 Catalytic Cycle Involving Br
 Br + O3  BrO + O2
 ClO + NO  Cl + NO2  BrO + ClO  Br + Cl + O2
 NO2 + O  NO + O2  Cl + O3  ClO + O2
 O + O3  2O2  2O3  3O2
 Depletion of O3 by halogens from natural sources accounts for 60% of the routes by which O3 is
depleted, the rest is due to anthropogenic sources, the CFC’s
 Bromine compounds (CH3Br) can also lead to O3 destruction. It can also produce HBr and
BrONO2 which are easily photolyzed . Br2 is more destructive agent than Cl2
 CFCs
 Properties: low viscosity; low surface tension; low Bpt
 Chemical and Biological inertness: nontoxic, nonflammable
 Applications: refrigerants, solvents for cleaning electronic materials, blowing agents for polymer
foams; replacement for NH3 and SO2 regrigerants
 Nomenclature of CFCs
 CFC- xyz
X = number of C atoms – 1 (usually emitted if X = 0)
Y = number of H atoms + 1
Z = number of F atoms
CFCs are indicated by 3 digit nos, x, y, and z
-The ‘hundred’ is the no. of C atoms minus 1
-The tens is the no. of H atoms + 1
-The units is the no. of F atoms
-The remainder is the Cl atoms
Example: CFCl3 is CFC-11
CF3CF2Cl is CFC-115
-To determine the chemical formula for the chemical symbol, add 90 to the 3-digit number. The
modified 3-digit number gives the number of C, H, and F in sequence.
Example:
CFC-115 = 115 + 90 = 205
The structure contains 2C, 0 H and 5 F; the rest is Cl
Structure: CF3CF2Cl
Photochemical Decomposition of CFC
 CFCl3 + hv - CFCl2 + Cl
 Catalytic Cycle:
Cl + O3 - ClO + O2
ClO + O - Cl + O2
O3 + O  2O2

The degree of O3 destruction by CFCs is measured in terms of ODP (Ozone

depletion potential) defined as the ratio of the impact on O3 from a
specific chemical to the impact from an equivalent mass of CFC-11, the
standard by which all other CFCs are calculated
The greater the number of Cl atoms in CFCs the higher the ODP values. Most
CFCs have ODP values between 0.1 and 1.0 while
hydrochlorofluorocarbons (HCFCs) have ODP values of about 0.01.
HCFCs which have no chlorine atoms have ODP values of zero.
Montreal Protocol of 1989 – legislative body created for the reduction of CFCs
Current Research on Modification of CFCs
k. Incorporation of H in the structure of HCFCs
 Increase in H reduces inertness of CFCs meaning it is destroyed in the troposphere;
however, the H radical is also destructive in the troposphere (carcinogen);second,
the compounds becomes flammable
 Increasing F atoms and replacing C make the molecule more stable even in the
stratosphere; however, HFCs are excellent greenhouse gases.
 New Replacement Compounds:
d. HFC – 1340 (CF3CH2F) = no O3 depletion but difficult to manufacture, also produce
H radical; easily decomposed by OH in the troposphere.
e. HCFC-123 (CF3CHCl2)- less effect on O3 depletion

Halons, the bromine analogues of CFCs (used as extinguisher because of its high
density); it smothers a fire at ground level and because the Br atom terminates the
radical chain reactions which propagate the combustion process
-ODP values> CFCs
Nomenclature for the Halons is straightforward
-first digit indicates the no. of C atom
-second digit indicates the no. of F atom
-third digit indicates the no. of Cl atom
-fourth digit indicates the no. of Br atom

Example:
CF2ClBr-1211
CF3Br- 1301
CBrF2CCBrF2-2404
Null and Holding Cycle
 -Two cycles that prevent  Null Cycle Rxn (1)
species from taking part  NO + O3  NO2 + O2
in catalytic process
 NO2 + hv  NO + O
 Null (do nothing) cycles
interconvert the species X  O3 + hv  O2 + O
and XO while effecting no
net odd oxygen removal
 The null cycle with the catalytic  Catalytic Cycle
cycle is important only during
daytime as it requires radiation in  NO + O3  NO2 + O2
the near uv region
 While the net effect is O3
 NO2 + O  NO + O2
photolysis, O3 is rapidly and  O3 + O  2 O 2
stoichiometrically resynthesized by
reaction, O + O2 + M  O3 + M
 HNO3: reservoir for O3 depleting NO
 NO2 + OH + M  HNO3 + M
 HCl: reservoir for O3 depleting Cl
 Cl + CH4  HCl + CH3
 Almost 50% of NOx is stored in the HNO3
reservoir, while 70% of the stratospheric
chlorine is present as HCl
 HNO3 – photolysis in daylight releasing
NO2
 HCl- releases Cl after reacting with OH
 HOCl: ClO + HOO  HOCl + O2
 HO2NO2 (pernitric acid)
 HOO + NO2 + M HO2NO2 + M
 ClONO2 (Chlorine nitrate)
 ClO + NO2 + M  ClONO2 + M
 These compounds serve to store reactive
species until they are released as active catalyst
or leak back into the troposphere. A
consequence of their release is the development
in recent years of the Antarctic and Arctic Hole
 Antarctic O3 Hole
 During the long dark winter in the Antarctic, a stream of air is drawn toward the South
Pole creating a giant vortex. Inside this vortex, Polar Stratospheric Clouds (PSC) are
formed.
 Type 1 PSC – formed at 193 K ; consists of about 1 um diameter particles of HNO3
and water
 Type 2 PSC – formed when T dropped to 187 K; made up of particles of ice-water up
to 10 um in size; HCl, HOCl, and ClNO3 are also present
 During the winter season, on the surface of PSC, species take part in heterogeneous
reactions which release Cl2 and HOCl.
 HCl + ClONO2 + PSC - Cl2 + HNO3
 HCl + N2O5  ClNO2 + HNO3
 H2O + ClONO2 + PSC  HOCl + HNO3

This situation is stable until the onset of sunlight in October. At that time, the light
provides energy for photolysis,
Cl2 + hv  2Cl
HOCl + hv  Cl + OH
ClNO2 + hv  Cl + NO2 or ClO + NO
Other heterogeneous reactions also occur that lead to photolytically labile species:
ClONO2 + H2O  HOCl + HNO3
N2O5 + HCl  ClNO2 + HNO3
 The Cl depletes the O3 by the catalytic cycle
 2Cl + 2O3  2ClO + 2O3
 ClO + ClO  Cl2O2
 Cl2O2 + hv  ClOO + Cl
 ClOO - Cl + O2
 2O3 + hv  3 O2

The situation persists until the air temperature rises causing the vortex to break
up and the polar stratospheric clouds to dissipate. When this occurs, the Cl
will be tied up again as HCl and ClNO3 and the O3 begins to recover the
pre-hole levels
Arctic Region
 O3 depletion is enhanced due to eruption of Mt.
Pinatubo in the Philippines in 1991; SO4-2 was
found at higher concentration than usual; SO4-2
acts as a catalyst for the removal of N2O5, the
species associated with holding up cycle that
ties up ClO
 N2O5  NO2 + NO3
 ClO + NO2  ClONO2
 N2O5 + H2O (SO-4cat)  2HNO3
 This reaction decreases the convertion of ClO to
ClONO2 and increases the concentration of Cl
which leads to O3 depletion.
Smog – a form of air pollution in which atmospheric visibility is partially
observed by a haze consisting of solid particulates and/ or liquid
aerosols. Smog consists of a mixture of partially oxidized HC, O3, and
other oxidants- observable from midday to late afternoon.

 Two Types:
 1. Classical Smog or London Smog – characterized by a high
concentration of unburned carbon soot as well as elevated levels of
atmospheric SO2.
 -occurs if a source of fuel is coal and emissions from vehicles.
 SO2 – mild reducing agent and precursor of weak acid carbon
particles which serve as nuclei for condensation of water droplets,
forming an irritated fog.
 2. Photochemical Smog – based on emissions from petroleum
combustion; principally from motor vehicles, followed by a sequence
of chemical and photochemical reactions occurring under specific
conditions.
 - the smog contains high levels of oxidants and carbon-containing
reaction products
 Synthesis: N2 + O2 ↔ 2 NO,
combustion engine
 NO + ROO  NO2 + RO
 NO2 (400 nm) NO + O
 O + O2 + M  O3 + M
 O3 – (315 nm) O2 + O
 O + H2O - 2 OH
 OH + RCH3  RCH2 + H2O
 RCH2 + O2 + M  RCH2OO + NO2
 RCH2OO + NO  RCH2O + NO2
 RCH2O + O2  RCHO + HOO
 HOO + NO  NO2 + OH
 RCH3 + 2 O2 + 2 NO  RCHO +
2NO2 + H2O
Process of removing OH and its
precursor, HOO and NO2
OH + NO2 + M  HNO3 + M
2 HOO  H2O2 + O2
OH + HOO  H2O + O2
Secondary reactions which occur with
the oxidation of HC
CH3CO + O2 + M  CH3COO
CH3COOO + NO2  CH3CO2NO3
(peroxyacetic nitric anhydride
(PAN)
PAN – eye irritant in photochemical
smog
-reservoir for NOx species
-stalbe at low T; at high T breaks
down via the reverse process
producing NO2 (potential for
producing O3 and OH
General Principles of VOCs Oxidation
 1. H abstraction or HO addition
 2. Addition of O2 forming a peroxy species or in the case
of aromatics, the O2 abstracts H
 3. Peroxy species transfer an O atom to NO2
 4. The product loses H atom to another O2 or it splits into
2 smaller species. In either case, aldehyde (or ketone)
are formed. The HOO is another product.
 5. The aldehyde reacts with NO2 to form PAN; undergo
further hydroxyl-initiated oxidation or photochemically
decompose
 6. The decomposition products are again subject to
oxidation and the ultimate stable products are CO2 and
H2O.
1. Toxic Effect of O3
O3 - respiratory toxin, causes edema (results from damage to the cell membrane; this damage
affects membrane permeability and causes release of cellular fluid; swelling of the tissues,
constriction of the airways, difficulty with breathing and increased sensitivity to infection are
manifestations of edema).
Chronic exposure to O3 may lead to emphysema- a condition characterized by
decompartmentalization of alveoli. The surface area available for gas exchange is decreased
which causes difficulties in breathing. O3 is also toxic to plants; inbits photosynthesis.
2. Toxicity of Nitrogen Oxides
NO – less toxic than NO2
- Attaches to hemoglobin and reduces oxygen transport

NO2 – exposure for 1 h at 50 – 100 ppm causes inflammation of lung tissue; develop bronhiolitis
obliterans fibroes; death results within 2 -10 days at 500 ppm; disrupts Lactic Acid
Dehydrogenase
3. CO – intermediates in the oxidation of methane; interacts with hemoglobin
Fate in the atmosphere:
CO + OH  CO2 + H
O2 + H + M  HOO + M
HOO + NO  HO + NO2

HOO + HOO  H2O2 + O2

4. SO2 – anthropogenic = combustion of coal and oil
Non-anthropogenic – from H2S produced by biological process and volcanic eruption
Fate in the Atmosphere:
Addition of HO, H2O2, and NH3
HO + SO2  HSO3  SO4
H2O2 + SO2  H2SO4
NH3 + SO2 + H2O  NH4+ + HSO4-
Toxicity: attaches at the upper respiratory tract causing irritation and increases airway resistance, can kill human at
500 ppm
5. H2S: TLV: 10 ppm
-colorless, flammable gas
-rotten-egg odor
-heavier than air
-by product of petroleum refineries, pulp-making factories
-inhibits cytochrome oxidase system resulting in cellular asphyxia
-damages the central nervous system

5. HCN: TLV, 4.7 ppm

-colorless, flammable gas
-smells like bitter almond
-used in the production of resins, fibers, and plastics
-by products in electroplating, metallurgy, and photographic development
• All cyanides are chemial asphyxiants that inhibit the utilization of oxygen by tissue cells.
• Ten grams of tobacco may yield 2 mL of HCN in cigarette smoke.
• Initially it produces an increased respiratory rate due to the effect of CN on chemoreceptors in the carotid bodies
and on the respiratory center in the brain.

• The carotid body is a chemical receptor in the carotid artery that is stimulated by lack of oxygen, excess CO2, or
increased concentration of hydrogen ions which correspond to a lower pH in the blood.
Gaseous Organic Pollutant

1 Chlorofluorocarbons
2. Peroxyacetylnitrie (PAN)
3. Warfare Gases- nerve gases,
acetylcholinesterase inhibitors Cl OH O
Cl
S Cl P F
Cl As
Cl
Mustard Gas Lewisite Sarin

O O
N P P
CN F
OH
OEt
Tabun Sarran
Heavy Metals
-electronegative metals
-do not form ions with ease
- Resist oxidation: Au, Pt, Ag

- Effect of Heavy Metals on Life

- Element Sources Health Effects
Hg coal, electrical kidney damage
batteries nerve damage
Pb autoexhausts brain, liver, kidney
paints
Cd coal, tobacco smoke high blood and
burning plastics and cardiovascular
diseases
interferes with Cu and Zn
metabolism
 Ni  As
 -diesel oil, steel, tobacco  Coal, petroleum, detergent,
smoke pesticides
 Health Effect: Lung cancer  Health Effect: cancer

 Hg: TLV = 0.01 mg/m3

 RHg+ = absorption in
gastrointestinal tract> 90%
-forms a covalent bond with alkyl group forming
the toxic
compared to its neutral Hg
compound
compound
-used as electrodes in batteries, gold  Very soluble in lipids and has a
refining
tendency to bioaccumulate
-organometallic mercury is used as  Usually accumulates in muscles
fungicide and antiseptic
and tissues
• In soil and sediment, Hg  Alkylmercury- volatile so uptake
undergoes methylation with
will also occur through pulmonary
methylcobalamin and S-
route
adenosylmethionine forming
CH3HgCH3
• The cation forms RHg+, very toxic
due to its high affinity with SH
group on protein and enzyme
 Sn
 Organotin, Me3Sn
 Stabilizers of polymers
(e.g. PVC)
 Catalysts in polymer
manufacture; biocides
 Less toxic than Hg and
Pb
 Toxicity is due to its
interaction with the
mitochondria
 Inhibits the conversion of
ADP to ATP
 Pb: TLV = 0.05 mg/m3
Tetramethyl lead = TLV: 0.15 mg/m3
The primary use of Pb in the
manufacture of Pb acid batteries
Tetramethyl and tetraethyl lead =
gasoline additive
Exposure to lead is the result of either
inhalation or ingestion of Pb
contaminated substances
• The most studied effects of Pb
exposure are those associated
with the nervous system.
Exposure also results in
decreased mental development
• -Causes encephalopathy
(dysfunction of the brain)
characterized by fluid
accumulation in the brain, damage
to blood vessels in the brain and
structural changes in the neurons
(loss of the myelin sheath)
 Anemia is often associated with Pb exposure. The causes of anemia are
twofold:
 a) inhibition of heme synthesis
 b) accelerated destruction of red blood cells by inhibiting enzymes
responsible for maintaining the integrity of the red blood cell membranes.
 In the atmosphere, organolead compounds react with OH and eventually
form R3Pb+ or R3Pb+2 (very toxic)
Chromium- oxidation state: +2, +6
Primarily used in electroplating and chromium pigments
+2, +4, and +5 = unstable and pose little health risk
+6 = very toxic
+3 = less toxic; the hexavalent form is easily absorbed by the skin
TLV (+6) = 0.01 mg/m3
+6 Cr = extremely corrosive to the skin and to the mucuous membrane of the
nose; lung carcinogen
 Acids and Bases
 HNO3, TLV: 2 ppm
 Uses: fertilizer, dyes, and plastics
 A strong oxidizing agent, decomposes to NO2 in
the presence of light
 Causes irritation of the eyes, mucuous
membrane and skin
 HF, TLV: 3 ppm
 Uses: manufacture of semiconductors, silicon
chips, glass etching
 Can cause demineralization and systematic
hypocalcemia
 H2SO4, TLV: 1 mg/m3
 Uses: products of alcohol processing,
manufacture of fertilizers, batteries,
 Toxic effect: impairment of the respiratory
system, characterized by increase
respiratory rate
 NaOH/KOH, TLV: 2 mg/m3
 Uses: manufacture of soap
 Toxic effect: gives the same effect as
H2SO4
 Heavy Metals

-is a general collective term applying to the group of metals

and metalloids with an atomic density greater than
6g/mL.
Examples: Cd,Cr, Cu, Hg, Ni, and Pb
 Heavy Metals- Sources

 In general: Worldwide-associated with mining industry

 Sources for food:
 -Environmental pollution
 -Accidental inclusion in processing
 -Contamination from containers
 Entry into Environment:
 -Natural weathering- low levels
 -Extraction and concentration-high levels
 Discarding of products after use
Heavy Metal Behavior in the Environment
1. Atmospheric aerosol particulates
2. Aqueous and Marine Environments
3. Accumulation of Heavy Metals in Marine Invertebrates
4. Heavy Metals in Drinking Water
5. Heavy Metal Ions in soils
6. Methylation of Heavy Metals in the Environment
7. The Uptake of Heavy metals by plants
8. Phytotoxicity
 Relative mammalian toxicity of elements in
injected doses and diets

Element LD50 (mg/kg bdy wt.)Dose in human

diet (mg/day)
Toxic Lethal

As 6 5-50 50-340
Cd 1.3 3-330 1.5k-9k
Cr 90 200 3k-8k
Hg 1.5 0.4 150-300
Pb 70 1 10k
 Lead

Properties: low melting point, high density, acid resistance,

chemical stability, and ease of fabrication
Uses: Storage batteries, pigments, electroplating,
electronics equipment, gasoline additive
Toxic Effect:
- Inhibition of heme synthesis- anemia
- -Neurotoxin – cerebral edema
- Kidney damage
- Critical concentration in blood: 35ug/dl
 Mercury
 Uses:
 -Chlor-alkali process, pulp and paper, antiseptics and
fungicides, batteries
 Toxic Effect:
 -severe gastrointiritis
 -sensory disturbance
 Incoordination
 -Minimata disease
 -Serious mental retardation
 -Nervous System Disorder
 Cadmium
 Uses:
 -Industrial processes
 -Batteries, electroplating
 -Contaminant of Zn in metal alloys

Toxic Effect:
Kidney damage, skeletal deformities, emphysema,
gastrointeritis
Itai-Itai (Ouch, Ouch)- Japan
Biological Half-Life: < 30 years
 Chromium
 Uses:
-electroplating,chromium pigments, tanning, wood
preservations, catalysts
Toxic Effect: respiratory cancer
Cr (VI)- most toxic
 Arsenic

Uses:
Herbicides, insecticides, wood
preservatives, semiconductor industry,
manufacture of glass
Toxic Effects:
-Respiratory and skin cancers
 Radioactive Substances
 Radioactivity- emission of ionizing radiation by some
heavier elements
 Radionuclides or radioactive isotopes – produced as (a)
fission products of heavy nuclei such as Uranium and
Plotonium; (b) reaction of neutrons with stable nuclei
 Ionizing Radiations:
 1. alpha particle
 -similar to He
 -slowest and least penetrating
 -damage occurs only when ingested or inhaled
 2. Beta particle
 -similar to electron
- Travels up to 90% of the speed of light
- -penetration of tissue can be 1 cm or more
- Cl-38 = β − emitter

- 3. Gamma Ray
- -electromagnetic radiation similar to X-ray
- -can penetrate light through a human being
• All known nuclide beyond Bi-209 are radioactive
• U-238 = α − emitter
• Th-234 = β − emitter
• Pa-234 = β emitter
• K-40, V-50, La-138 = β emitter
 Dosage and Biological Damage
-Radiation damages living organisms by initiating (a) bond
breaking in macromolecules, and (b) destruction of
bone marrow
-The study of the ecological and health effects of
radionuclides involves consideration of the following:
3. Type and energy of radiation
4. Half-life of the sources
5. Degree to which the particular element is absorbed by
living system
6. Chemical reactions and transport of elements
* Radionuclide with intermediate t1/2 is the most dangerous
–persist long enough to enter living system while still
retaining high reactivity
 1. Sr-90
 -common waste product of nuclear testing
 -interchangeable with Ca in bone-causes leukemia
 -ingested by cattle and enters the body of infant by way
of cow’s milk
 2. Ra-226 = also goes to the bone
 3. Rn-222 = produced from U-238 decay
 4. I-131 = causes thyroid cancer
 5. Cs-137 = radioactive
Absorption, Excretion and Concentration of
Radioisotopes in Mammals
Radioisotope t1/2 Ease of Speed Place of
absorption of Excrtion Concn.
Sr-90 28 yrs. Good slow bone
I-131 3 days Good months Thyroid
Cs-137 30 yrs. Good months All tissues
C-14 5,600 yrs Good slow “
Zr-95 65 days Fair slow bone
Doses of Various Substances Having the Stated
Biological Effects
Substances Injction(mg/kg bdy wt) Effect Cause by Dose
Sr-90 0.0014 14% incidence of bone
cancer in mice
Ra-226 0.003 30% bone cancer in man
Pu-239 0.00026 33% bone cancer in beagles
LSD 0.003 hallucinogenic dose
MeHg 10 100% death in mice
Parathion 8 50% death in mammals