Concerns on water pollutants

 (1) highly biodegradation-resistant compounds,

 (2) known or probable carcinogens,
 (3) toxicants with adverse reproductive or
developmental effects,
 (4) neurotoxins including cholinesterase inhibitors,
 (5) substances with high acute toxicities,
 (6) known groundwater contaminants.
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
 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
 Surfactants/Detergents
Polychlorinated Biphenyls (PCBs) and Dioxins

 PCBs – Arochlor, Chlophen, Kanechlor and

Fenchlor

 Dioxins or PCDDs (Polychlorinated dibenzo

[1,4]dioxins

TCDD (2,3,7,8-tetrachlorodibenzo [1,4]dioxin)-

most toxic dioxin
 Nomenclature of PCBs

3' 2' 2 3
1' 1
4' 4

5' 6' 6 5

Cl Cl

Cl

Cl Cl

2,2’,4,5,5’-pentachlorobiphenyl
Nomenclature of Dioxins

1
f Oa
e b
O c
d
4

9
9a O 10a
8 2
3
7 5a O 4a
6 5 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.
5. Food – main source of contamination
Usage Categories of PCBs (90% PCB usage in 1971, US)
a. Controllable Closed System
b. Noncontrollable Closed System
c. Open Uses
 Sources of Contamination of Dioxins

1.Chemical processes involving chlorine

-manufacture of organochlorine, bleaching of pulp and paper mills
Industrial processes: melting of scrap metals contaminated with PVC
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.
- Vehicle exhaust emissions-leaded gasoline, dichloroethane additives

* 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
NaOH Cl OH 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
MCPA and 2,4-D-has Dioxin residue

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.
Arochlor 1221, 1232, 1242, and 1248 are colorless
Arochlor 1254- viscous yellow
Arochlor 1260 and 1262- sticky resins
PCBs settle to the bottom compared to mineral oil when mixed with water
Physico-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 L-1)
Vapor pressure 9.4x10-1 1.1x10-3 6.9x10-9
(Pa, 25 oC)
Melting Pt (K) 344 349.5 578.5

Dibenzo[1,4]dioxin = Kow, 4.20

Physico-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 Less toxic compared to DDT and PCDF
explosions with PCB-containing oils Chronic effects: chloracne, cancer promoter
can result in the formation of PCDFs in Biochemical changes: vitA depletion, alteration
any remaining oil, in combustion to lipid metabolism and hormonal changes
effluent and in soot that is formed.
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.
Effect: delayed lethality, main target: liver
Accumulate in adipose tissue and breast milk of
nursing mothers- found in
breastmilk:octachlorodibenzo[1,4]dioxin
Possible Mechanism of Toxic Action of 2,3,7,8-
TCDD

Octachlorodibenzo[1,4]dioxine

Present in breast
milk
Polyaromatic hydrocarbons
Nomenclature
Nomenclature
Properties of PAHs Toxicity of PAHs to various aquatic organism
Behavior of PAHs in the environment PAH Organism LC50 (96 hr)
t1/2 Naphthalene fish 0.1-8 (mg/L)
Clear water sediment w/water Acenaphthene fish 0.6-3.0
Exp to sunlight (hr) microcosm (weeks) Phenanthrene fish 0.04-0.6
0.75 34-70 (Pyrene)
0.034 200-300 (benz(a)pyrene

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
Properties of PAHs
Boiling Pt- very high Concentration of PAHs Produced by Cigarette
Aq. Solubility- 10-4 – 10-10 M smoke:
Log Kow – 3.36-6.04 (benzo(a) pyrene ng/m3
Kow – a measure of the tendency of the compound to Fluoranthene 99
dissolve in biota fat and other lipoidal substances Pyrene 66
such as humic acid in soil and sediments
Benzo(a)anthracene100
Log Kow range of 2-6.5 is considered as the range for
lipophilic compounds. Thus the PAHs would be Benzo(a)pyrene 22
expected to bioaccumulate and concentrate in Perylene 11
sediments and soils in the environment to an
extent depending on their persistence in the Cancer inducing effects of tobacco smoking is not
media. due to exposure to nicotine but due to PAH
Surfactants and Detergents
Surface Active Agent
Types of Micelles
Surfactants
Classes of Surfactants
Synthesis
Detergent Formulation
Detergent Action
Builders
Bleach Booster and Bleaching Agent
Cationic Surfactant as
Germicide/Conditioner
Toxicity
 Pesticides
 Insecticides
 Molluscicides
 Nematicides
 Avicides
 Piscicides
 Herbicides
 Fungicides
 bactericides
 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
a. DDT b. Heptachlor c. Lindane d. Chlordane
e. 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.
Classes of Pesticides
Common Herbicides
 Phenoxyacetic acid Herbicides

O OH O O OH
OH
O O O O
OH Cl Cl

N Cl
Cl Cl Cl
indole-3-acetic acid 2,4D 2,4,5T MCPA
Common Herbicides
Chlorinated Pesticides
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
By-Products of Pesticides
Manufacture
 1. Polychlorinated dibenzodioxines
Emerging Water Pollutants,
Pharmaceuticals and Household Wastes

 1. Nanomaterials
 2. Siloxanes or Silicones
 3. Trihalomethanes (CHCl3,
CHCl2Br,CHClBr2)- disinfection by-
products
 4. Household waste products
Pharmaceuticals found as
Water Pollutants
EPA's First 12 Priority Pollutants
From the Canada-US Binational Toxics Strategy

1. Aldrin/Dieldrin
2. Mercury and its compounds
3. Benzo(a)pyrene
4. Mirex
5. Chlordane
6. Octachlorostyrene
7. DDT, DDP,DDE
8. PCBs
9. Hexachlorobenzene
10. Dioxins and Furans
11. Alkyl lead
12. Toxaphene
ORGANOPHOSPHATES

Organophosphate Insecticides
- Used during WWII as military gases
- Exhibit high mammalian toxicity compared to chlorohydrocarbon
pesticide but due to environmental problem of chlorinated
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
 Toxic Activity
-the organophosphate pesticides exhibit strong toxic
-greater water solubility activity with a wide range of biota.
Log Kow = 2.71-3.81 -active in inhibiting acetylcholinesterase, an
T1/2 = 3-7 days important enzyme that facilitates the
transmission of nerve impulses. It operates by
LC50 = 2,500 ng/kg body weight hydrolyzing the substance acetylcholine which is
LC50 (estuarine fish)= 27-3250 ng/L/96 hrs. generated in the transmission of nerve impulses.

Environmental Property
-does not persist in soil
-lack of bioaccumulation capacity
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
Natural Product Insecticides, Pyrethrins, and
Pyrethroids
 Pyrethrum – natural insecticide
found in the flowers of cetain
plants belonging to the genus
chrysanthemum

General Structure

R O R'

 Physical Property O
- Have polar groups, but large non- O
polar groups so poorly soluble in Natural Constituent

water soluble in acetone and alcohol R R'

- Low vapor pressure except allethrin; Pyrithrin I CH3 CH2=CH
sufficiently volatile Pyrithrin II -COOCH3 CH3
- -constituent of mosquito coils
Cinerin II -COOCH3 CH3CH2
- Natural pyrethroids easily
hydrolyzed in water
 Synthetic Pyrethroids

Allethrin O

O
O
Cl O
CN

Fenvalerate
Estrogenic Substances in
Wastewater Effluents
 Aquatic organisms including fish, frogs,
and reptiles such as alligators exposed to
such substances may exhibit reproductive
 dysfunction, alterations in secondary sex
characteristics, and abnormal serum
steroid levels
Estrogenic Substances
 17α-ethynyl estradiol,
 Diethylstilbestrol
 Mestranol
 Levonorgestrel
 norethindrone used in oral contraceptives,
treatment of hormonal disorders, and
cancer treatment.
Biorefractory Organic Pollutants
 These are poorly biodegradable
substances and are sometimes referred to
as persistent organic pollutants (POP),
prominent among which are aromatic or
chlorinated hydrocarbons.
Biorefractory Organic pollutants
Inorganic pollutants

 .Reactive Intermediates
in the Atmosphere(OHx,
NOx, and ClOx Radicals)
 2.Gases, Acids, and
Bases
 3.Heavy Metals
 4.Radioactive
Substances
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
oC 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 + h (126 nm)-- 2N Ho = 945 kJ/mol
O2 + h (240 nm) - 2O Ho = 498 kJ/mol
N2 + h (80 nm) -- N2+ + 1e Ho = 1500 kJ/mol
O + h (91 nm) -- O+ + 1e Ho = 1310 kJ/mol

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 surface; 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 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 dHo/kJ

(a) O2 + hv( <240 nm) -- O + O slow -E (hv) +498.4

(b) O + O2-- O3 + M fast -106.5

Decomposition of O3:

(a) O3 + hv( = 230-320 nm) -- O* + O2* fast -E(hv) +386.5

(b) O + O3-- 2O2 slow -391.9

dHf O = 249.2 kJ/mol E(e) = O* = 90 kJ/mol E(e) O2* = 190 kJ/mol

dHf O3 = 142.7 kJ/mol
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 OH contributure in the lower
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
O + O3 -- 2 O2
 Sources of NO:  The ClOx Cycle
Photochemical
a.
Decomposition at Altitude
-the natural contribution to O 3

destruction accounts to only 10%

greater than 30 km
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
N2O + O  2NO
volcanic emissions.
NO + OH +M HNO2 + M (this
process induces O3 depletion)
CH3Cl + hv  CH3 + Cl
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 O2 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 O 3 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 O 3 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. HFCs
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
a. Incorporation of H in the structure of HCFCs
b. Replacement of Cl to produce HFCs
 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 become flammable.
 Increasing F atoms and replacing Cl make the molecule more stable even in the
stratosphere; however, HFCs are excellent greenhouse gases.
 New Replacement Compounds:
a. HFC – 134a (CF3CH2F) = no O3 depletion but difficult to manufacture, also produce H
radical; easily decomposed by OH in the troposphere.
b. HCFC-123 (CF3CHCl2)- less effect on O3 depletion, short tropospheric lifetime

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
-remaining is H to attain saturation of C

Example:
CF2ClBr-1211 ODP = 3
CF3Br- 1301 ODP= 10
CBrF2CBrF2-2402 ODP = 6
Null and Holding Cycle
 -Two cycles that prevent  Null Cycle Rxn (1)
species from taking part  NO + O3  NO2 + O2
in catalytic processes
 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 competes with the catalytic

cycle; is important only during daytime as
 Catalytic Cycle
it requires radiation in the near uv region  NO + O3  NO2 + O2
 While the net effect is O3 photolysis, O3 is
rapidly and stoichiometrically  NO2 + O  NO + O2
resynthesized by reaction, O + O2 + M 
O3 + M  O3 + O  2 O 2
 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
Holding Cycle

Second type of null cycle

 Reaction(a) acts as a
NO2 + O3 ---- > NO3 + O2 holding cycle temporarily
NO3 + hv ---- > NO2 + O limiting the availability of
NOx.(depletes O3)
O3 + hv ---- > O2 + O
Side Reaction:
 Eventually:
(a)NO3 + NO2 + M -- > N2O5 + M N2O5 --- > NO2 + NO3


N2O5- not a catalyst for O3

destruction
unreactive reservoir of NOx
Other reservoirs of NOx and Cl

 HOCl: ClO + HOO  HOCl + O2 (Hypochlorous acid)

 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
 The Cl depletes the O3 by the catalytic cycle
 2Cl + 2O3  2ClO + 2O2
 ClO + ClO  Cl2O2
 Cl2O2 + hv  ClO2 + Cl
 ClO2 - 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.
 Tropospheric Chemistry- Smog Formation
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
 The Chemistry of Hydroxyl Radical Production

Three routes for NO2 production

NO + O2 -- > NO2
NO + O3 - NO2 + O2
NO + ROO. - RO + NO2

Three routes for OH

O + H2O - 2OH
NO2 + H2O - NO + 2OH
NO + NO2 + H2O - HONO
HONO -----(<400 nm) 2NO + 2OH
 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
 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
CH3CHO + OH - CH3CO + H2O
CH3CO + O2 + M  CH3C(O)OO
CH3(C=O)O2 + NO2  CH3C(O)O2NO3
(peroxyacetic nitric anhydride (PAN)
PAN – eye irritant in photochemical smog
-reservoir for NOx species
-stable at low T; at high T breaks down via the
reverse process producing NO2 (potential
for producing O3 and OH
Composition of Photochemical Smog: CO,
NO2, HC, O3, PAN
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 OH to form acetyl and H2O and
then the acetyl reacts O2 generating acetylperoxy which
finally interacts with NO2 to form PAN or 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.
 Gaseous Pollutants
1. O3
-causes edema
-chronic exposure leads to emphysema
2. NO
- Less toxic than NO2, reduces O2 transport
3. NO2- exposure for 1 h at 50-100 ppm, causes inflammation of lung tissue
-disrupts Lactic Acid Dehydrogenase; death results within 2-10 days at 500 ppm
4. 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
5. 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
 Hydrogen Cyanide

. a deadly poisonous substance which can exist in water as

HCN
HCN: TLV, 4.7 ppm
-colorless, flammable gas
-smells like bitter almond
-All cyanides are chemical asphyxiants that inhibit the
utilization of oxygen by tissue cells.
 Industrial Uses
1.Metalcleaning and electroplating
2.Gas and coke scrubber
3.Mineral processing (e.g. gold extraction)
4.Production of resins, fibers, and plastics
Hydrogen Sulfide
H2S: TLV: 10 ppm
-colorless, flammable gas
-rotten-egg odor
-heavier than air
 H2S- product of anoxic decay of organic matter
 -reduction of sulfate by microorganisms
 -evolved as gaseous pollutant from geothermal waters.
 - wastes from chemical plants, paper mills, textile mills, and
tanneries
-inhibits cytochrome oxidase system resulting in cellular asphyxia
-damages the central nervous system


Carbon Dioxide
 Present in water due to organic matter
decomposition
 -used to soften water by recarbonation
 -excessive carbon dioxide levels may
make water more corrosive and may
be harmful to aquatic life.
 Nitrite ion, NO2
 − added to some industrial process water
as a corrosion inhibitor.
 - rarely occurs in drinking water at levels
over 0.1 mg/L.
 Sulfite ion, SO3
 −,found in some industrial wastewaters. Sodium sulfite is commonly
added to
boiler feedwaters as an oxygen scavenger:
-ClO4-1
 an oxidizer for use in solid rocket propellants,
 -advanced chromatography
Asbestos in Water
 The fibers scar lung tissue and cancer
eventually develops, often 20 or 30 years
after exposure.
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
 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
-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
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 1.5-9
Cr 90 200 3-8
Hg 1.5 0.4 150-300
Pb 70 1 10
 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
 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/m 3
Tetramethyl lead = TLV: 0.15 mg/m 3
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)
• Lead line of the gums is another well
known symptoms of lead exposure. It
appears as a dark line on the border of
the gums and is formed by pption of
PbS
 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
 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
 Mercury
 Hg: TLV = 0.01 mg/m3
the toxic compound
-forms a covalent bond with alkyl group forming

-used as electrodes in batteries, gold refining

-organometallic mercury is used as fungicide and antiseptic
• In soil and sediment, Hg undergoes methylation with
methylcobalamin and S-adenosylmethionine forming
CH3HgCH3
• The cation forms RHg+, very toxic due to its high affinity
with SH group on protein and enzyme
 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
Biofouling
 microfouling, in which microorganism
biofilms formon surfaces, and
 (2) macrofouling, which involves the
attachment of larger organisms including
 barnacles, bryozoans, mussels,
polychaete worms, and seaweeds.2
Organically Bound Metals
 The interaction of trace metals with organic compounds in
natural waters and wastewaters is an
 important aspect of water pollution. It may be noted that
metal–organic interactions may involve
 organic species of both pollutant (such as EDTA) and natural
origin.
 and dissolution of precipitates, colloid formation and stability,
acid-base reactions, and
 microorganism-mediated reactions in water
Organotin Compounds
Organotin Compounds
 Major industrial uses of organotin compounds in the past
included applications of tin compounds
 in fungicides, acaricides, disinfectants, antifouling paints,
stabilizers to lessen the effects of heat
 and light in PVC plastics, catalysts, and precursors for
the formation of films of SnO2 on glass.
 The greatest environmental and toxicological concern
with
 organotin compounds has been their uses as antifouling
agents, especially TBT compounds used
 as ingredients in coatings on ship hulls and other
structures in contact with seawater.
 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 =  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 =  emitter
• Th-234 =  emitter
• Pa-234 = – emitter
• K-40, V-50, La-138 =  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:
1. Type and energy of radiation
2. Half-life of the sources
3. Degree to which the particular element is absorbed by
living system
4. 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