CHARACTERISATION OF POLLUTANTS

Sources of Pollutants

Common Air Pollutants

The air pollution problem is encountered in both indoor as well as outdoor.
Indoor
 Radon
 Combustion by-products
 CO, CO2, SO2, Hydrocarbons, NOx
 Particulates, Polyaromatic hydrocarbons
 Environmental Tobacco Smoke (ETS)
 Volatile organic compounds
 Asbestos
 Formaldehyde
 Biological contaminants
 Pesticides
Outdoor
 SO2
 CO, CO2
 Oxides of Nitrogen
 Ozone
 Total Suspended particles
 Lead
 Particulates
 Volatile organic compounds
 Toxic Air pollutants
Particulate matter pollution
 Properties - varied
Mixture of solid phase and absorbed materials (organic, inorganic and biological)
Carbonaceous core 40-60%, C 7%
 Sources
 Combustion - oil and coal
 Industry
 Automobiles
 Tobacco smoke
 Biomass burning
 Metal smelters
 Properties - varied
Tiny fragments of solid or liquid nature suspended in the air (aerosols).
  Particles may be primary – when emitted directly into the atmosphere by sources, or
 secondary – when particles are formed in the atmosphere through the interaction of
primary emissions.
 Solid particles between 1 and 100 μm (micrometres) in diameter are called dust particles,
 solid particles less than 1 μm in diameter are called fumes, or smoke.

Determinants of PM Concentration
 Weather patterns
 Wind
 Stability (vertical movement of air)
 Turbulence
 Precipitation
 Topography
 Smokestack height and temperature of gases
 Nearby natural and built structures may lead to downward moving currents causing
aerodynamic or building downwash of smokestack emissions.
 Particulates Interchangeable terms:
 Aerosol,
 Particle,
 Particulate (matter).
 Primary PM
 • Emitted directly to the atmosphere
 1. Geologic material
 2. Organic carbon
 3. Elemental carbon (soot)
 4. Metals released into air from combustion

Natural Sources of Airborne Particles

Main natural sources of particles are:
 Erosion of soil by wind which generates dust particles that travel around the globe
 Evaporation of droplets of sea water resulting in sea salt crystals being suspended in the
air
 Volcanoes
 Forest fires
 Living vegetation
Classification according to size
 Total Suspended Particulate (TSP)
 PM10 – 10 microns or less
 PM2.5 - 2.5 microns or less
Visualize PM10 & PM2.5
 Fine = PM2.5
 “Coarse” means between 2.5 and 10 microns
 Supercoarse is greater than 10 microns
Distinction
 PM10 = Coarse + Fine
 TSP = Supercoarse + Coarse + Fine

Particulates – features
 Physical size
 Large
 Small ~10um
 Fine ~2.5um
 Aerodynamic diameter (size equivalent of density=1)
 Large - local irritation (>100um)
 Inhalable (<100um)
 Thoracic fraction (<20um)
 Coarse PM10 (<10um)
 Fine PM2.5 (<2.5um)
 Ultrafine (<0.1um)
 Chemical reactivity
 Shape (fibers)
 Water content
 When measured often referred to as total suspended particles (TSPs)
 Tend to be highest in large cities in developing countries
 Recent studies estimate that 2 to 9% of human mortality in cites is associated PM
 Linked to both lung cancer and bronchitis
 Especially hazardous to elderly and those w/ asthma
 Dust can be deposited on plants
 Interferes absorption of CO2 and O2 and transpiration
 Block sunlight and may cause climate change
 Global dimming
 Gradual reduction in the solar energy that reaches the surface of Earth
 Cools the atmosphere
 Lessens global warming
 PM10 is made up of particles less than 10μm in diameter
  Present everywhere but high concentrations and/or specific types dangerous
 Much particulate matter easily visible as smoke, soot, or dust
 Includes airborne asbestos and heavy metals
 Of particular concern are very fine pollutants
 PM 2.5- less than 2.5 μm in diameter
 Easily inhaled into the lungs, then absorbed into the bloodstream
 Ultrafine particles- <0.18 μm released by automobiles.
 Related to heart disease
 particles of the size PM 2.5- less than 2.5 μm in diameter have very low gravity-related
sedimentation rates and may therefore remain in the atmosphere for days before being
washed out by rain or attached to vegetation or buildings.
Airborne particles may cause:
 Asthma
 Lung cancer
 Cardiovascular problems

Gaseous pollutant features

 Chemical reactivity (ozone)
 Solubility in water
 Soluble
 Ambient (NOx, SOx)
Occupational (Hydrochloric acid, Ammonia)
 Less soluble
 H2S, ozone
 Sulfur dioxide and nitric oxide (NO) are the primary air pollutants
 Nitrogen dioxide (NO2) is both a primary and secondary air pollutant.
Gas pollutants - SO2
 Properties
 Reacts with H2O and forms sulfurous acid (H2SO3), which oxidizes to sulfuric
acid (H2SO4)
 Chemical transformation of other pollutants
 Responsible for acid rain effect
 A colorless gas with a pungent, suffocating odor.
 Dangerous air pollutant because it is corrosive to organic materials and it irritates the
eyes, nose and lungs.
 Sources
 Biomass and fossil fuel combustion
 coal power plants, Industrial emissions, smelters
 Contained within all fossil fuels, and is released in the form of sulfur dioxide (SO2)
during fossil fuel combustion.
 Sulfur contents in fossil fuels range between 0.1% and 4% in oil, oil by-products and
coal, and up to 40% in natural gas
 Adverse effects depend on dose and concentration present
 Injury or death to animals and plants
 Corrosion of paint and metals
 Important precursor to acid rain
 Controls
 Low-S fossil fuels (clean coal)
 Emission control devices
 London fog episode (acute)
 The biggest sulfur dioxide emitters: US, China and Russia

Gas pollutants -NO2

 Properties
 Oxidant, less potent than O3
 Sources
 NO oxidation
 High To combustion (automobiles, power plants)
 Indoor - kerosene, gas stoves, ETS
 Silos (grain store) in farming (75-100ppm)
 Road transport (motor vehicles) is by far the largest contributor of nitrogen
emissions
 Other Transport
 Energy Production

 Electric power generation
 Petroleum refining
 Other combustion
 Combustion for industry use
 Production processes
 Extraction and distribution of fossil fuels.
Nitrogen Oxides
 Occur in many forms in the atmosphere but largely emitted in two forms:
 Nitric oxide or nitrogen monoxide NO
 is a colorless gas
 Nitrogen dioxide- NO2
 A yellow-brown to reddish-brown gas with a distinct sharp, biting odor
 May be converted to NO32-
 the sum of which is equal to NOx.
 Both subject to emissions regulation and contribute to smog
 NO2 major contributor to acid rain
 Combustion of fuels always produces both NO2 and NO.
 But almost 90% of the NOX combustion product is in the form of NO which is then
oxidized to nitrogen dioxide (NO2) in the air.
 only a small percentage of NO2 found in the atmosphere is directly emitted there in this
form.
 The rest has been formed as a result of chemical reactions in the atmosphere itself.
 Nearly all NO2 emitted from human sources
 Automobiles and power plants that burn fossil fuels
 Environmental effects
 Irritate eyes and mucous membranes
 Suppress plant growth
 However when convert to nitrate may promote plant growth
Gas pollutants -NO2
Health effects - starting at 1.5-2ppm
 Deep lung irritant - terminal bronchioles Alveolar cells, ciliated epithelia, Clara
cells
 Similar to ozone but less inflammatory (if < 2-5ppm)
 Enhanced infection, suppression of macrophage action (a large cell that is present
in blood, lymph, and connective tissues, removing waste products, harmful
microorganisms, and foreign material from the bloodstream)Peaks more

Gas pollutants – CO
 Properties
 Colourless, Odorless, heavier than air, stronger binder to Hb than O2
 Sources
 Incomplete combustion
 combustion of carbon-based fuels
 Traffic (inside the car, parking garages, tunnels is highest)
 Inside cars = 3x urban streets, and = 5x residential streets
 90% of CO in atmosphere comes from natural sources
 10% comes from fires, cars, and incomplete burning of organic compounds
 Motor vehicles and industry are among the largest anthropogenic sources of
carbon monoxide emissions.
 Health effects
 Asphyxiant
 Fatigue, confusion, headaches, dizziness, cardiac function (arrhythmias, angina)
  Start at 2.5% COHb (0.5% baseline) (air level 50ppm for 90min)
2ppm COHb, no effect
>5ppm COHb, cardiovascular
effects
40ppm COHb, is fatal
Exposures to carbon monoxide may lead to :
 Toxicity of the central nervous system and heart
 Severe effects on the baby of a pregnant woman
 Problems with getting oxygen supplied to some body parts which may be life-
threatening.

Gas pollutants - O3
Good O3 - stratosphere
Bad O3 - troposphere
 Properties
 Short lived, highly reactive, water soluble
 Colorless gas w/ slightly sweet odor
 Very active chemically, oxidizes or burns
 Beneficial in the upper atmosphere
 Ozone can be found in:
 stratosphere, one of the upper layers of the atmosphere, where it occurs naturally,
 troposphere, the lowest layer of the atmosphere, where it occurs both naturally
and as a result of human-generated emissions.
 Sources
 Photochemical reactions
 formed in the troposphere as a result of anthropogenic emissions of primary pollutants
 A secondary pollutant (reaction of primary pollutants, nitrogen oxides and
hydrocarbons [including VOCs], in the presence of sunlight)
 The tropospheric ozone is the main component of the photochemical smog.
 A photochemical smog (of brown-yellow color) is a product of the chemical reaction
between sunlight, nitrogen oxides and VOCs, which results in the formation of ozone and
airborne particles.
Effects of Ozone as an Air Pollutant
 Irritation of the respiratory system causing coughing, throat irritation and an
uncomfortable sensation in the chest
 Susceptibility to respiratory infections
 Compromised lung function harming the breathing process which may become more
rapid and more shallow than normal
 Inflammation and damage to the lining of the lungs
 Aggravation of asthma
 Reduction in agricultural yields
 Interference with photosynthesis and suppression of growth of some plant species

Air Pollutants: Ammonia

 Ammonia is a colorless, pungent, hazardous caustic gas composed of nitrogen and
hydrogen.
  Ammonia emissions are also grouped as NHy which is a sum of NH3 and NH4.

Sources of Ammonia Emissions

 Agriculture is the biggest source of ammonia emissions.
 Livestock farming and animal waste account for the biggest percentage of total ammonia
emissions which are due to the decomposition of urea from large animal wastes and uric
acid from poultry wastes.
 Based on Jeremy Colls’ table of global ammonia emissions, below is a breakdown of
their major sources:
 Livestock – contributes more than 50% of all emissions
 Fertilizer application
 Oceans
 Vegetation
 Biomass burning

Effects of Ammonia Emissions

 Exposure to very high concentrations of gaseous ammonia in the air may result in lung
damage and even death.

Volatile Organic Compounds (VOCs)

 Defined as organic compounds which easily evaporate and enter the atmosphere
 VOCs may include a wide range of organic air pollutants, from pure hydrocarbons to
partially oxidized hydrocarbons to organic compounds containing chlorine, sulfur, or
nitrogen
 Thousands of hydrocarbon compounds exist, including natural gas, or methane
(CH4); butane (C4H10); and propane (C3H8).
Sources
 Sources: Petroleum emissions, fuel combustion, incineration, biomass burning
 Account for ~14% of all air pollution
 Important factor of indoor air pollution
 Types
 Aliphatic
 Alcohols (ethylene glycol, MTBE)
 Aldehydes (formaldehyde)
 Aromatic (benzene, toluene, xylene)
 Halogenated (TCE, PERC, Methylene Chloride)
 Polycyclic (PAHs)
 Other (Carbon disulfide)
 Earlier, Definition of VOCs did not include methane compounds (non-methane VOCs:
NMVOCs) since the atmospheric concentration of methane was considered to be a stable
natural background.
 But it was ultimately recognized that methane is also an anthropogenic air pollutant that
comes from intensive animal and rice production.
 Though some of these compounds can have direct toxic effects, they have been grouped
together because of their role in ozone formation.
Anthropogenic Sources of Volatile Organic Compounds
 The major anthropogenic sources of VOCs include:
 Solvent Use (including paints, adhesives, aerosols, metal cleaning and printing)
 Road transport (emissions from fuel / petroleum use- Gasoline, diesel, ethanol, etc)
 Production processes
 Extraction and distribution of fossil fuels
 dry cleaning
 Cigarettes, forest fires, etc.
Jeremy Colls points out that substantial NMVOC emissions occur during the following processes
 Painting (evaporation of solvents)

 Oil production (flaring and venting of gas)

 Oil refining (flaring and fugitive emissions)
 Distribution of oil or refinery products (evaporation from storage, displacement losses
when venting tanks)
 Dry cleaning (final drying of clothes)
 Production of alcoholic drinks (breweries and distilleries)
 Arable farming (crop growing, silage manufacture, sludge spreading)

Natural Sources of Volatile Organic Compounds

 Not a lot is known about the natural emissions of VOCs.
 Forests are the primary natural sources of VOC emissions.
 Tropical forests are estimated to produce about half of all global natural non-methane
VOC emissions.
 Plants synthesize many organic molecules and release some VOCs (including a range of
terpenes) into the atmosphere
 In total, around 1000 different compounds (with some of which themselves being
families with thousands of their own members) are known to be emitted by natural
sources
 VOCs are not criteria pollutants

Effects of Volatile Organic Compounds

 Some aromatic compounds such as benzene, toluene and xylene are potential carcinogens
and may cause leukemia
 Contribute to sick building syndrome indoors (a group of symptoms typically including
headaches, skin rashes, and respiratory problems that affect workers in office buildings
and are attributed to toxic building materials or poor ventilation)
 As facilitators in ozone formation, VOCs may indirectly contribute to respiratory
problems and other ozone-related problems
 Alkanes (solvents, varnishes, lacquers)
 Irritants, lung and skin
 neuron degeneration, paralysis
 Pulmonary edema
 React with OH radical in photochemical pollution
 Alkenes (gasoline and aviation fuel) more reactive than alkanes - chains, oxides,
halogenated HC
  cramps, tremor
 nausea, vomiting
Aldehydes
 Formaldehyde H2C=O
 50% of total aldehydes Water soluble
 Steep dose-effect:
0.5-1ppm: odor
2-3ppm: mild irritation
4-5ppm: intolerable
 Scrubbed in upper respiratory tract, but can also reach deeper
 Nasal cancer? (rodents but not humans)
 Acrolein H2C=CHCH=O
 5% of total but more irritating
Aromatic hydrocarbons (stable, persistent) - Low water solubility, volatile, flammable - Priority
pollutants (EPA)
Benzene - most basic
 Additive in gasoline and an important industrial solvent.
 Produced when gasoline and coal undergo incomplete combustion.
 Also component of cigarette smoke
 Major environmental source on and off road vehicles
 Carcinogen (epoxide, phenol metabolites)
 CNS toxicity - narcosis
 Irritation (skin, lung)
 Toluene (more lipCNS depressant (narcosis, impaired coordination, headaches)
 ophilic, but faster metabolism)
 Xylene (o-, p-, m-) (very lipophilic)
 CNS depressant (as above)
 Blood cell damage, anemia
 Irritant (skin)
Polycyclic aromatic hydrocarbons (PAH) incomplete combustion of organic materials,
incineration, industry, natural processes
 16 of 126 priority pollutants
 Environmental transport, accumulation
 Photo - bio- degradation
 Carcinogens exposure* (metabolic activation) -
 Air exposure 0.02-3ug/day
 Cigarette smoke 0.1-0.25ug/cig
 Unfiltered cigarettes 2-5ug/day
 Vegetarian diet 3-9ug/day
 Drinking water 0.2-120ng/day
 Soil (urban) 0.003-0.4ug/day
(* Menzie et.al. 1992, Env. Sci and Technol. Vol. 26: p.1278)

Arcolein
 A volatile hydrocarbon that is extremely irritating to nose, eyes, and respiratory system.
 Produced from
  Manufacturing processes that involve combustion of petroleum fuels
 Component of cigarette smoke

Lead
 Lead is constituent of auto batteries and used to be added to gasoline.
 Lead in gas emitted into air w/ exhaust
 Spread widely around world in soils and water along roadways
 Once in soil can enter the food chain
 Lead now removed from gas in US, CAN, EU
 98% reduction in emissions since 1970s
Air Toxics
 Among pollutants that are known or suspected to cause cancer or other serious health
problems.
 Associated w/ long-term and short-term exposures
 Gases, metals, and organic chemicals that are emitted in relatively small volumes
 Cause respiratory, neurological, reproductive, or immune diseases
 Standards have been set for more than 150 air toxics
 E.g. hydrogen sulfide, hydrogen fluoride, chlorine gases, benzene, methanol,
ammonia
 EPA estimates that the average risk for cancer from exposure to air toxics is about
1 in 21,000

Hydrogen sulfide
 Highly toxic corrosive gas easily identified by its rotten egg odor.
 Produced from
 Natural sources such as geysers, swamps, and bogs
 Human sources such as industrial plants that produce petroleum or that smelt
metals.
 Effects of hydrogen sulfide include
 Functional damage to plants
 Health problems ranging from toxicity to death for humans and other animals.

Hydrogen Fluoride
 Extremely toxic gaseous pollutant
 Released by some industrial activities
 Such as production of aluminum, coal gasification, and burning of coal in power
plants.
 Even a small concentration (as low as 1 ppb) of HF may cause problems for plants and
animals.
 Potentially dangerous to grazing animals because forage plants can become toxic
when exposed to this gas.

Methyl Isocyanate
 An ingredient of a common pesticide
 known in the United States as Sevin.
 Colorless gas
  Causes severe irritation (burns on contact) to eyes, nose, throat, and lungs.
 Breathing the gas in concentrations of only a few ppm causes violent coughing,
swelling of the lungs, bleeding, and death.
 Less exposure can cause a variety of problems, including loss of sight.

Other air pollutants – HAPs

 Hazardous air pollutants
 Not included in the criteria air pollutants
 Include
 Organic chemicals (acrolein, benzene)
 Minerals (asbestos)
 PAH (benzo[a]pyrene)
 Metals (Hg, Be)
 Pesticides (carbaryl, parathion)
 Some are carcinogenic

Persistent Organic Pollutants (POPs)

 Persistent organic pollutants are compounds which are resistant to degradation and
persistent in the environment, with half lives of years in the soil or sediment and days in
the atmosphere.
 Such compounds may include dioxins, furans, polychlorinated biphenyls (PCBs) and
organochlorine pesticides such as DDT.
 They enter the food chains via the process of biomagnification, get accumulated in
human and animal tissue, and are capable of long range transport through being attached
to airborne particles.
Sources of Persistent Organic Pollutants
 Some POPs are used as pesticides.
 Others are used in industrial processes as well as in the production of goods such as
solvents, polyvinyl chloride and medicines.

Effects of Persistent Organic Pollutants

 Exposure to persistent organic pollutants takes place through diet (specifically,
consumption of animal fats), environmental exposure or accidents.
 POPs may lead to :
 Death and illness including disruption of endocrine, reproductive and immune systems
 Neurobehavioral disorders
 Cancers
 When POPs are present in the atmosphere in the form of aerosols, they may be classified
as airborne particles rather than gaseous pollutants.
 They enter the food chains via the process of biomagnification, get accumulated in
human and animal tissue, and are capable of long range transport through being attached
to airborne particles.
  Over 1995-2008, average nationwide levels of major air pollutants have dropped by
between 25-45 percent in India.
Air quality, trends over 1995-2008, averaged for India
Air quality
India India India
indicator[49]
1995 2005 2008
Pollutant, PM10
(micrograms per 109 67 59
cubic meter)
Pollutant, CO2
emissions (kg
0.7 0.6 0.5
per 2005 PPP$
of GDP)
Health,
mortality rate
100 73 67
(under 5, per
1000)
Pollutant,
methane,
Agriculture 68.8 64.4 n.a.
emissions (%
total)
Pollutant,
nitrous oxide,
Agriculture 75.2 73.4 n.a.
emissions (%
total)