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No universal classification
(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://
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
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 such a way that the chlorine substituents are attached to carbon atoms with the lowest possible number Arochlor from Monsanto Corp. has four digit code; the first 2 digits indicate the number of carbon atoms; the last 2 digits indicate the percentage of chlorine in the structure of the biphenyl.
3' 4' 5'
2 2' 1' 1 6' ClCl 6
3 4 5
Cl Cl Cl
Nomenclature of Dioxins
-The [1,4] dioxin portion of the name refers to the middle ring of the tricyclic structure. -The [b,e] denotes the sides of the [1,4] dioxin ring to which the phenyl rings are fused.
1 f Oa e d O c 4 b
9a O 10a
O 6 5a 5 4a 4
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 Cl NaOH ethylene glycol Cl Cl OH Cl OCH2CO2H NaOH ethylene glycol Cl Cl OCl
Cl Cl 2,4,5- T (2,4,5-trichlorophenoxyacetic acid Side-Product
Physical Chemical Properties of PCBs and Dioxins
1. 2. 3. 4. 5.
Low aqueous solubility Nonflammability Resistance to Oxidation Resistance to Hydrolysis 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 Log Kow Aq.Solubility (mol m-1) Vapor pressure (Pa, 25 oC) Melting Pt (K) 3.76 4.4 x 10-2 9.4x10-1 344 2,2’,4,5,5’-PCB 6.38 4.7x10-5 1.1x10-3 349.5 Decachloro-BP 8.20 1.3x10-9 6.9x10-9 578.5
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 PCBs; logKow ranges from 4.20-8.20 2,3,7,8-TCDD- most toxic , has low Kow of 6.80 close to DDT (6.20) Toxicity of PCBs Acute (single dose) oral LD50 for Arochlor mixture with rats: 10g/kg body weight Chronic effects: chloracne, cancer promoter Biochemical changes: vitA depletion, alteration to lipid metabolism and hormonal changes
Cl Cl ClCl
Cl heat O2 Cl
Thermal events such as fires and explosions with PCB-containing oils can result in the formation of PCDFs in any remaining oil, in combustion 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 moleculesshare the same receptor site.
Properties of PAHs
Boiling Pt- very high Aq. Solubility- 10-4 – 10-10 M Log Kow – 3.36-6.04 (benzo(a) pyrene Kow – a measure of the tendency of the compound to dissolve in biota fat and other lipoidal substances such as humic acid in soil and sediments Log Kow range of 2-6.5 is considered as the range for lipophilic compounds. Thus the PAHs would be expected to bioaccumulate and concentrate in sediments and soils in the environment to an extent depending on their persistence in the media. Concentration of PAHs Produced by Cigarette smoke: ng/m3 Fluoranthene 99 Pyrene 66 Benzo(a)anthracene100 Benzo(a)pyrene 22 Perylene 11 Cancer inducing effects of tobacco smoking is not due to exposure to nicotine but due to PAH
Properties of PAHs
Behavior of PAHs in the environment t1/2 Clear water sediment w/water Exp to sunlight microcosm (weeks) 0.75 34-70 (Pyrene) 0.034 200-300 (benz(a)pyrene
Toxicity of PAHs to various aquatic organism PAH Organism LC50 (96 hr) Naphthal fish Acenaph thene fish PheNanthrene fish 0.1-8 (mg/L) 0.6-3.0 0.04-0.6
The major degradation pathway involves chemical, photolytic and metabolic processes. PAHs in water where oxygen is available dissolved within the water mass when exposed to sunlight can exhibit rapid rate of photolytic decomposition but in turbid waterdegradation decreases
Benzo (a)pyrene- induces chromosomal aberration in fish -fish develope liver cancer
“…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 heptachlor Cl Cl Cl Cl Cl chlordane Cl Cl Cl Cl Cl
Cl Cl Cl Cl Cl dieldrin Cl Cl Cl Cl Cl Cl aldrin O
Cl Cl Cl Cl lindane Cl Cl
Properties of Chlorohydrocarbon Pesticides
Solubility in Lipid (g/L) 4,4’-DDT Heptachlor Dieldrin Lindane 330 1000 3700 800
Aq. Solubility (mg/L) 3.36 50 200 130
Log Kow 6.36 4.11 3.88 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
DDT, DDP, DDE aldrin/dieldrin PCBs mercury and its compounds hexachlorobenzene benzo(a)pyrene dioxins and furans mirex alkyl-lead chlordane toxaphene octachlorostyrene
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
O (S) RO P OX RO S OC2H5 S C2H5O P C2H5O S NO2 Parathion Cl S MeO P MeO O O Cl S MeO P S MeO NO2 OMe R = CH3 or CH3CH2O can be replaced by S X = see examples S MeO P MeO O OC2H5 Malathion
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.
-does not persist in soil -lack of bioaccumulation capacity
-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.
Heavy metals (trace metals) and metalloids Organometals Radionuclides
Environmental Properties -polar, water soluble, limited persistence in the environment because of hydrolysis toxic, readily absorbed through the skin -principal biodegradation pathwayhydrolysis and oxidation
General Structure O R O N R' R' = H or other groups R = variety of groups
Mechanism of Toxic Action Anticholinesterase -only distinction against organophosphate- not deactivated for a long time
O H O
Propoxur or Baygon
Pyrethrum and Pyrethroids
Pyrethrum – natural insecticide found in the flowers of cetain plants belonging to the genus chrysanthemum
General Structure R O O Natural Constituent R Pyrithrin I Pyrithrin II Cinerin II CH3 -COOCH3 -COOCH3 O R' CH2=CH CH3 CH3CH2 R'
Have polar groups, but large nonpolar groups so poorly soluble in water soluble in acetone and alcohol Low vapor pressure except allethrin; sufficiently volatile -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 ion conductance. In small doses, the pyrethrins exhibit a knockdown effectinduction of temporary paralysis. Knockdown tends to be associated with the more polar pyrethroids, while lethality seems related to the more lipophilic pyrethroid In domestic formulations; pyrethrins are used with synergistthis compound inhibits the MFO so as to prevent deactivation of Pyrethrin Synergist – piperonyl butoxide
Synthetic Pyrethroids O
Allethrin O Cl O CN
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; Tropopausetemperature 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 1801473 oC
Chemical Compositions of the Atmosphere
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 N2 + hν (80 nm) -- N2+ + 1e O + hν (91 nm) -- O+ + 1e
∆Ho = 498 kJ/mol ∆Ho = 1500 kJ/mol ∆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
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 XO + O - X + O2 O + O3 -- 2 O2 X: Free Radical, 3 types: a. Hydroxy Radical: HOX: H. ,HO., HOO. b. Nitiric Oxide Radical: NOx (NO., NO2.) c. Chlorine Radicals: Cl., ClO.
Near the stratosphere, the HOX accounts for as much as 70% of the total mechanism of O3 destruction including the O2-only processes. Lower in the stratosphere (about 30 km, the NOX Cycle dominates the removal mechanism of O3)
The HOX Cycle: Generation of HO and H O + H2O - 2OH
H2O + hv H + OH The NOx Cycle- major contributur in the lower region of the stratosphere Catalytic Cycle: NO + O3 NO2 + O2
Decomposition of O3 by OH and H OH + O3 - HOO + O2
HOO + O HO + 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 Decomposition at Altitude greater than 30 km N2 + hv 2N N + O2 NO + O b. Reaction of N2O with O N2O + O 2NO NO + OH +M HNO2 + M (this process induces O3 depletion)
-the natural contribution of O
destruction accounts to only 10% of the total -the precursor of Cl in CH3Cl produced biogenically from oceans, burning of vegetation and volcanic emissions.
CH3Cl + hv CH3 + Cl
Mechanism for O3 Depletion by ClOx A. Cl + O3 ClO + O2 ClO + O Cl + O2 O + O3 2 O 2
B. ClO + HOO HOCl + O2 HOCl + hv HO + Cl Cl + O3 ClO + O2 HO + O3 HOO + O2 2 O3 3O2
C. Cl + O3 ClO + O2 ClO + NO Cl + NO2 NO2 + O NO + O2 O + O3 2O2
Catalytic Cycle Involving Br Br + O3 BrO + O2 BrO + ClO Br + Cl + O2 Cl + O3 ClO + O2 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: HFC – 1340 (CF3CH2F) = no O3 depletion but difficult to manufacture, also produce H radical; easily decomposed by OH in the troposphere. 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 species from taking part in catalytic process Null (do nothing) cycles interconvert the species X and XO while effecting no net odd oxygen removal
The null cycle with the catalytic cycle is important only during daytime as it requires radiation in the near uv region While the net effect is O3 photolysis, O3 is rapidly and stoichiometrically resynthesized by reaction, O + O2 + M O3 + M
Null Cycle Rxn (1) NO + O3 NO2 + O2 NO2 + hv NO + O O3 + hv O2 + O
Catalytic Cycle NO + O3 NO2 + O2 NO2 + O NO + O2 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
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
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+ + HSO4Toxicity: 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 As Cl
OH O P F Sarin
Mustard Gas O N P CN OEt Tabun
Lewisite O P F OH Sarran
-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 -diesel oil, steel, tobacco smoke Health Effect: Lung cancer
Hg: TLV = 0.01 mg/m3 the toxic
As Coal, petroleum, detergent, pesticides Health Effect: cancer
RHg+ = absorption in gastrointestinal tract> 90% compared to its neutral Hg compound Very soluble in lipids and has a tendency to bioaccumulate Usually accumulates in muscles and tissues Alkylmercury- volatile so uptake will also occur through pulmonary route
-forms a covalent bond with alkyl group forming
compound -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 Sadenosylmethionine 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
-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. 2. 3. 4. 5. 6. 7. 8.
Atmospheric aerosol particulates Aqueous and Marine Environments Accumulation of Heavy Metals in Marine Invertebrates Heavy Metals in Drinking Water Heavy Metal Ions in soils Methylation of Heavy Metals in the Environment The Uptake of Heavy metals by plants 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 6 1.3 90 1.5 70 5-50 3-330 200 0.4 1 50-340 1.5k-9k 3k-8k 150-300 10k
As Cd Cr Hg Pb
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
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
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
Uses: -electroplating,chromium pigments, tanning, wood preservations, catalysts Toxic Effect: respiratory cancer Cr (VI)- most toxic
Uses: Herbicides, insecticides, wood preservatives, semiconductor industry, manufacture of glass Toxic Effects: -Respiratory and skin cancers
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 Sr-90 I-131 Cs-137 C-14 Zr-95 t1/2 28 yrs. 3 days 30 yrs. 5,600 yrs 65 days Ease of Speed Place of absorption of Excrtion Concn. Good slow bone Good months Thyroid Good months All tissues Good slow “ 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
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