Effects of Air Pollutants Effects on Materials Five mechanism: Abrasion, deposition and removal, direct chemical attack, indirect

chemical attack and electrochemical corrosion.

Solids particle travelling at high speed causes abrasion but most air pollutants are too small to cause this effect. Small particles causes aesthetic deterioration.

Chemical attack Solubilization and oxidation/reduction are examples of direct chemical attack . SO2 and SO3 in presence of water react with limestone to form calcium sulfate and gypsum which are soluble in water and are leached way when it rains. Tarnishing of silver is an example of

oxidation/reduction reaction.

Indirect chemical attack Pollutants are absorbed and then react with some components of the absorbent to form a destructive compound. Leather becomes brittle when it absorbs SO2.

Electrochemical corrosion occurs when microscopic anodes and cathodes are formed on the surfaces of metals

.Moisture, temperature and position of exposed material are factors that influence the rate of deterioration.

Effects on Vegetation

Ozone damages the palisade cells resulting in collapse of cell walls and formation of brown spots and finally white spots.

Plant growth may be inhibited by continuous exposure to 0.5 ppm NO2. NO2 in excess of 2.5 ppm for four hours or more will produce necrosis (loss of protoplasm). SO2 concentration of 0.3 ppm for eight hours can cause necrosis.

Effects on Health

Difficult to assesss because humans may be exposed to chemicals from smoking and indoor air pollutants that are much higher than ambient air pollutants.

Upper Respiratory Track nose, pharynx, larynx and trachea forms the URT. Aggravation of sense of smell and inactivation of sweeping mechanism of cilia (which removes and trap particles and mucus).

Lower Respiratory Tract Consists of the bronchi, lung (consists of alveolus, about 300 um in diameter). Wall of alveolus lined with capillaries for gas exchange. Degree of penetration of particles into LRT is a function of the size of the particles and rate of breathing. Particles greater than 5 to 10 um are screened out by the hairs in

the nose. Particles 1 to 2 um penetrate to the alveolus.

Carbon Monoxide

Colourless and odourless , lethal in a few minutes at concentration above 5,000 ppm. CO reacts with Hb to form COHb. Hb has higher affinity for CO than for O2. Thus the formation of COHb deprives body of oxygen.

Hazardous Air Pollutants.

Asbestos, arsenic, benzene, radionuclides may cause cancer. Berrylium cause lung disease and also effects liver, spleen, kidneys. Mercury released during combustion of coal.

Lead A cumulative poison. It can be ingested in food, water and also inhaled. Lead can be measured in urine and blood for evidence of lead poisoning. Acute anemia, fatigue, irritability and headache may result from acute exposure. In excess may cause brain damage abdominal cramp. Chronic exposure lead to brain damage such as seizures, mental incompetence and acute aggressive behaviour.

Nitrogen dioxide.

Exposure to NOx conc above 5 ppm for 15 minutes results in cough and irritation of the respiratory tract, Continuous exposure lead to accumulation of fluid in lung. Gas is reddish brown in high concentration and brownish

yellow at lower concentration. At 5 ppm it has pungent sweetish odour Average NO2 in tobacco is about 5 ppm.

Origin and Fate of Air Pollutants

Carbon Monoxide

Incomplete oxidation of carbon, natural anaerobic decomposition of carbonaceous material by microorganisms

The hydroxyl radical serves as the oxidizing agent. It combines with CH4 to form an alkyl radical

Hazardous Air Pollutants

Lead

Volcanic activity and airborne soil are the primary natural sources of atmospheric lead. Smelters and refining processes as well as incineration of lead containing wastes are major point sources of lead. Approximately 70 to 80 percent of the lead added to gasoline was discharged to the atmosphere.

Nitrogen Dioxide

Bacterial action in the soil releases nitrous oxide to the atmosphere. In the upper troposphere and stratosphere, atomic oxygen reacts with the nitrous oxide to form

nitric oxide (NO)

The atomic oxygen results from the dissociation of ozone. The nitric oxide further reacts with ozone to form nitrogen dioxide.

Combustion processes account for 96 percent of the anthropogenic sources of nitrogen oxides

Nitrogen and oxygen is reactive at Temp above 1600 K. Forms NO and further react with ozone or oxygen to fom NO2. 40 - 45 percent of NOx comes from transportation, 30 -35 percent from power plants and 20 percent from industrial sources.

NO2 is converted to NO2- or NO3- in particulate form

and may be washed off by precipitation.

Photochemical Oxidants

Result from atmospheric reaction and not due to people or nature. Called secondary pollutants. Formed through a series of reactions that are initiated by the absorption of a photon by an atom, molecule, free radicals or ion. Ozone is the principal photochemical oxidants. Formed from nitrogen dioxide photolytic cycle. Hydrocarbons modify the cycle by reacting with atomic oxygen to form free radical. The HC, nitrogen oxides and ozone react and interact to produce more nitrogen dioxide and ozone. The whole reaction depends on the abundance of

sunshine.

Sulfur oxides

Both primary and secondary pollutants. Power plants, industry, volcanoes, and the oceans emit SO2 SO3 and SO4 directly as primary pollutants. Some biological decay and industrial sources emit H2S which is oxidized to form secondary pollutants.

Important sulfur rxn

H2S + O2

H20 + SO2

The ultimate fate of most SO2 in the atmosphere is

conversion into sulfate salts which are removed by sedimentation or by washout with precipitation.

Acid Rain Unpolluted rain is naturally acidic because CO2 from the atmosphere dissolves to a sufficient extent to form carbonic acid. The pH for rain is about 5.6.

Chemical reactions in the atmosphere convert SO2, NO2 and volatile organic compounds to acidic compounds and associated oxidants. Nitric acid is formed by the reaction of NO2 with OH radicals formed photochemically. Ozone is formed and

then protected by a series of reactions involving both NOx and VOC.

Concern with acid rain is its potential effects on aquatic life, damage to crops and forests and damage to building materials. Lower pH effect fish directly by interfering with its reproductive cycle or by releasing insoluble aluminium which is toxic.

About 70% of SO2 emissions in the USA are attributable to electric utilities.

Ozone Depletion Without ozone everything on the earths surface would be incinerated. The presence of ozone in the upper atmosphere (20 to 40 km up) provides a barrier to UV radiation.

Too much UV can cause skin cancer. In 1974 scientists revealed a potential air pollution threat to the ozone shield. They showed that chlorofluocarbons (CF2Cl2 and CFCL3) abbreviated as CFC) which are used as aerosol propellants and refrigerants react with ozone.

Chlorine atom removes ozone from the system and that the chlorine atom is continually recycled to convert more ozone to oxygen.

CFC which is inert in the lower atmosphere becomes serious air pollution at higher elevations.

CF2Cl2 has a lifetime of 110 years. This causes the chlorine content in the atmosphere to continue to grow

Research confirmed that the ozone layer has shrunk about 2.5 % in the preceding decade

Replacement to CFC are: HFC (hydroflurocarbon) and HCFC (Hydrochlorofluorocarbon). HFC do not contain chlorine and therefore do not deplete ozone. HCFC although contain chlorine it is not transported to the stratosphere because of OH scavenging in the troposphere.

Global Warming

The average global surface temp has been increasing for the last 100 years and was higher in 2000 than in any time in the past 2,000 years.

Increasing level of green house gases (ghg) leads to global warming.

Unlike ozone the greenhouse gases are relatively transparent to shortwave UV from the sun. They absorb and emit long wave radiation at wavelength typical of the earths and atmosphere.

GHG act like the glass on greenhouse, they let in shortwave radiation from the sun that heats the ground surface but restricts the loss of heat by radiation from the ground surface. The more GHG in the atmosphere the more effective it is in restricting the outflow of long wave radiation. CO2 is the major GHG because of its

abundance and its strong absorption spectrum in the region where the earth emits most of its radiation.

Other GHG are methane, nitrous oxide and CFC but CO2 is the most prevalent and most absorptive of all.

Air Pollution Meteorology The atmosphere is like an e2222ngine, continuously expanding and compressing gases. The driving energy is the sun. The difference in heat input between the equator and the pole causes the overall circulation of the earths atmosphere. The rotation of the earth coupled with the different heat conductivities of the oceans and land produce weather.

Turbulence Mechanical turbulence is the addition of random

fluctuations of wind velocity to the overall average wind velocity.

Thermal turbulence Heating of the ground surface causes thermal turbulence.

Stability

The tendency of the atmosphere to resist or enhance vertical motion is termed stability. It is related to both wind speed and the change of air temperature with height (lapse rate). For our purpose lapse rate is an indicator of stability condition of the atmosphere.

There are three stability categories.

Unstable: mechanical turbulence is enhanced by the thermal structure

Neutral : the thermal structure neither enhances nor resists mechanical turbulence

Stable atmosphere is when the thermal structure inhibits mechanical turbulence. Anticyclone are associated with stable air.

Neutral stability

The lapse rate for a neutral atmosphere is defined by the rate of temperature increase by a parcel of air that expands or contracts adiabatically as it is raised through the atmosphere. This rate of temperature decrease is called dry adiabatic

lapse rate (T). It has a value of -1.000 C /100 m. When the ambient lapse rate is the same as T, the atmosphere is said to have a neutral stability.

Unstable atmosphere If the temp of the atmosphere falls at a rate greater than T the lapse rate is said to be superadiabatic and the atmosphere is unstable. Mechanical turbulence is enhanced.

Stable Atmosphere

If the temperature of the atmosphere falls at a rate less than T, it is called subadiabatic, and the atmosphere is

stable.

There are 2 special cases of subadiabatic lapse rate. When there is no change of temp change with elevation the lapse rate is called isothermal. When the temperature increases with elevation, the lapse rate is called an inversion. Inversion is the most severe form of a stable temperature profile.

Plume Types

The plume from a tall stack located on a flat terrain has been found to show a characteristic shape that is dependent on the stability of the atmosphere.

Terrain Effects Heat Islands

Results from a mass of material either natural or anthropogenic that absorbs and reradiates heat at a greater rate than the surrounding area. This causes moderate to strong vertical convection currents above the heat island. Large industrial complex and small or large cities are examples of a heat island.

Because of the heat island atmospheric stability will be less over a city than it is over the surrounding countryside..

Land/Sea Breezes

During night land cools more rapidly than the water. Cooler air moves from the land toward the water forming land breeze. During the morning the land heats up faster

than the water. Air above land rise and is replaced by air from the water body forming the sea breeze.

Effect of lake breeze on stability is to cause a surface based inversion on the temp profile. For stacks originating near the shoreline the stable lapse rate causes a fanning plume close to the stack .

Atmospheric Dispersion Factors affect transport, dilution, and dispersion of air pollutants Emission point characteristics, nature of pollutant material, meteorological conditions, and effects of terrain and anthropogenic sources

Pollutants discharged vertically through stack. Plume expand and mix with the ambient air. Horizontal air movement will bend the discharge towards downwind direction.

At some distance the plume will level off. While the plume is rising, bending and move in horizontal direction the gaseous pollutants are being diluted by the ambient air surrounding the plume. They are eventually dispersed towards the ground. The plume rise is affected by both the inertia of the discharge gas stream and by its buoyancy. The vertical inertia is related to the exit gas velocity and mass. The plumes buoyancy is related to the exit gas mass relative to the surrounding air mass. Increasing the exit velocity or the exit gas temperature will generally increase the plume rise. The plume rise together with the physical stack height is called the effective stack height.

The greater the downwind distance between the point of discharge and the ground level receptor downwind, the greater will be the volume of air available for diluting the discharge Wind direction and speed. The wind direction determines the direction in which the contaminated gas stream will move across the local terrain. Wind speed affect the plume rise and the rate of mixing or dilution of the contaminated gases as they leave.

Stability The more unstable the atmosphere the greater the diluting power. An inversion may restrict vertical movement.

Dispersion Modelling A mathematical description of the meteorological transport and dispersion process that is quantified in terms of source and meteorological parameters during a particular time. The resultant numerical calculations yields estimates of concentrations of the particular pollutant for specific locations and times.

Basic Point Source Gaussian Dispersion Model Basic Gaussian diffusion equation assumes that atmospheric stability is uniform throughout the atmosphere. Dilution of gas stream on horizontal and vertical direction can be described by the Gussian or normal equation.

Contaminated gas is released into the atmosphere at a distance above ground level that is equal to the physical stack height plus the plume rise . Model also assumes that the degree of dilution of the effluent is inversely proportional to the wind speed.

AIR POLLUTION CONTROL OF STATIONARY SOURCES Gaseous Pollutants Absorption Transfer the pollutant from a gas phase to a liquid phase. Mass transfer process in which the gas dissolves in the liquid.

Mass transfer is a diffusion process wherein the pollutant gas moves from the point of higher concentration to points of lower concentration. The removal of the pollutant gas takes place in three steps: 1. Dissolution of the pollutant gas to the surface of the liquid 2. Transfer across the gas/liquid interface 3. Diffusion of the dissolved gas away from the interface into the liquid Structure such as spray chambers and towers or column are two classes of devices employed to absorb pollutant gas. In scrubbers which is a type of spray chambers liquid droplet are used to absorb the gas. In towers a thin film of liquid is used as the absortion medium. Solubility of pollutant must be high. If water is the solute, absorption limited to inorganic gases such as NH3, Cl2, and SO2. Scrubbers are generally inefficient absorbers but have the advantage of being able to also remove particulates. Towers are much more efficient absorbers but they can be plugged by particulate matter.

Amount of pollutant absorption that can take place by a

nonreactive solutions is governed by the partial pressure of the pollutants. For dilute solutions the relation between partial pressure and the concentration of the gas solution is given by Henrys Law.

Run the gas and liquid in counter current flow. In this manner the high concentration gas is absorbed into a liquid with a low pollutant concentration. 3 variables in the design of a packed tower are: the gas flow rate, the liquid flow rate, and the height of the tower.

Adsorption This is a mass transfer process in which the gas is bonded to a solid. It is a surface phenomena. The gas (adsorbate) penetrated into the pores of the solid but not into the lattice itself. The bond may be physical or chemical.

Electrostatic forces hold the pollutant gas when the physical bonding is significant. Chemical bonding is the reaction with the surface. Pressure vessels with fixed bed are used to hold the absorbent. Activated carbon, molecular sieves, silica gel and activated alumina are the most common adsorbent. These materials have a large active surface area per unit volume . Very effective for organic pollutants. They can also capture H2S and SO2. Drawbacks (except activated carbon) is that they select water before any other pollutants Thus water must be removed beforehand.

Combustion Used when the gaseous pollutant in the gas stream can be oxidized to an inert gas. Typically used for CO and HC. Both direct flame combustion by afterburners and catalyst combustion have been used. Direct flame combustion is the method of choice if 2 criteria exists: 1) the gas stream have a net heating value NHV greater

than 37 MJ/m3. At this NHV, the gas flame will be autogenous (self supporting after ignition). Below this point supplementary fuel is required. 2) none of the byproducts of combustion be toxic. In some cases the byproducts may be more dangerous than the original pollutant gas. For exp combustion of trichloroethylene produces phosgene. Some catalytic materials enable oxidation to be carried out in gases that have an NHV value of less than 3.7 MJ/m3. Catalyst may be platinum or palladium compounds.

Flue Gas Desulfurization 2 categories: nonregenerative and regenerative. Nonregenerative means that the reagent used to remove the sulfur oxides from the gas stream is used and discarded. Regenerative mean that the reagent is recovered and reused. Nonregenerative systems All have reaction chemistries based on lime (CaO), caustic soda (NaOH), soda ash (Na2CO3), or ammonia (NH3).

The SO2 removed in a lime/limestone FGD system is converted to sulfite. The overall rxn are: Part of the sulfite is oxidized with the oxygen content in the flue gas to form sulfate:

Spray drier based FGD systems consist of one or more spray driers and a particulate collector. The reagent material is typically slaked lime slurry. The reagent is injected in droplet form into the flue gas in the spray drier. The reagent droplets absorb SO2 while simultaneously being dried.

Control Technologies for Nitrogen Oxides Almost all nitrogen oxides air pollution results from combustion processes. They are produced from the oxidation of nitrogen bound in the fuel, from the reaction of molecular oxygen and nitrogen in the combustion air at temp above 1600 K and from the reaction of nitrogen in the combustion air with hydrocarbon radicals Control technologies for NOx are grouped into two

categories : Those that prevent the formation of NOx during the combustion process and those that convert the NOx formed during combustion into nitrogen and oxygen. Prevention: Reducing the peak flame temp in the combust zone reduces NOx formation. Nine alternatives developed are: 1) minimizing operating temperature 2) fuel switching 3) low excess air 4) flue gas recirculation 5) lean combustion 6) staged combustion 7) low NO2 burners 8) secondary combustion and 9) water/steam injection Post Combustion 3 processes may be used to convert NOx to nitrogen gas: 1) selective catalytic reduction (SCR) 2) selective noncatalytic reduction (SNCR), and 3) nonselective catalytic reduction (NSCR). The SCR process uses a catalyst bed (usually vanadium-titanium,\or platinum based or zeolite) and anhydrous ammonia.

After the combustion process ammonia is injected upstream of the catalyst bed. The NOx reacts with ammonia in the catalyst bed to form N2 and water. In the SNCR process ammonia or urea is injected into the flue gas at an appropriate temp. The urea is converted to ammonia which reacts to reduce the NOx to N2 and water. NSCR uses three way catalyst similar to that used in cars. Requires a reducing agent similar to CO and HC upstream of the catalyst.

Particulate Pollutants Cyclones: Good for particles greater than 10 u. Inertial collector with no moving parts. Particulate laden gas is accelerated in a spiral motion which imparts a centrifugal force to the particles. The particles are hurled out of the spinning gas and impact on

the cylinder wall of the cyclone. They then slide to the bottom of the cone. The efficiency of collection of various sizes n can be determined from an empirical expression and graph:

As the diameter of the cyclone is reduced, the efficiency of the cyclone is increased. However pressure drop also increases. This increases the power requirements Efficiency can be increased without increasing the power consumption by using multiple cyclones in parallel (multicyclones). Cyclone are efficient for particles larger than 10 u but it is not very efficient for particles 1 u or less in diameter. Application: Controlling emissions of wood dust, paper fibres. Multicyclones are used for precleaners for fly ash control devices in power plants. Filters Used for high efficiency control of particles smaller than 5 um.

2 types Deep bed filter and baghouse. Deep bed filter resembles a furnace filter. In deep bed filter a packing of fibre is used to intercept particles in the gas stream. Quite effective for clean gases and low volumes such as air conditioning systems For dirty industrial gas with high volumes, the baghouse is better. Fundamental mechanism of collection include screening or sieving where the particles are larger than the openings between the fibers. Interception by filter themselves and electrostatic attraction. Once dust cake formed on the fabric, sieving is the dominant mechanism. A particles collects on the bag, collection efficiency increases. But buildup of the dust cake also increases the resistance to gas flow. When the pressure drop across the filter bags reduces flow rate to unacceptable level, the filter must be cleaned. Three methods used to clean the bags are mechanical shaking, reverse air flow, and pulse jet cleaning. Baghouse.

Pulse jet baghouses are designed with frame structures called cages that support the bag. The particulate matter is collected on the outside of the bag instead of the inside. The dust cake is collected by directing a pulsed jet of compressed air into the bag. Electrostatic Precipitation (ESP) Constructed of alternating plates and wires. Large direct current potential between plates and wires. Results in creation of ion field between the wire and plate. As particle laden gas passes through ions attach to the particle giving a negative charge. This charge then migrate towards charged plate (+ charge). The plates are shaked and the particles falls down to a hopper. Gas particle between the plates are kept low to allow particle migration

Liquid Scrubbing If particulate is wet, corrosive or very hot fabric filter may not work. Instead liquid scrubbing is used. Applications of liquid scrubbing:

control of talc dust, phosphoric acid mist, steel furnace fumes. Simple spray chambers for coarse particle sizes. For high efficiency removal of fine particulates, combination of venturi scrubber followed by cyclones would be selected. Removal mechanism: Particle impinge on the droplet. Droplet particle combination suspended in gas stream, then removed by inertial collection device placed downstream. Because the size of the droplet and particle is increased collection efficiency of the inertial device is higher. ESP (Electrostatic Precipitator) High efficiency, dry collection of particulates from hot gas streams can be obtained by electrostatic precipitator. Consists of alternating plates and wires. A large direct current is supplied between the plate and wire creating an ion field . As particles pass through the plate and wire, ions attach to the particle giving it net negative charge. These particles then migrate toward the positively

charged plate where they stick. The plates are rapped at interval and particles fall to a hopper. Used to control air pollution from electric power plants, Portland cement kilns, metallurgical processes, and mist from acid production facilities.

Adiabatic Expansion and Compression

Adiabatic process is a process that takes place with no addition or removal of heat and with sufficient slowness so that the gas can be considered to be in equilibrium, at all times.

Increase in thermal energy resulted in an increase in the temperature of the gas. If gas is expanded adiabatically the temperature will decrease.

Units of measure

Microgram per meter cube, parts per million, and the micron (micrometer)

Ug/m3 or ppm for gas, ug/m3 for particulate.

Ppm = volume to volume ratio. Change in temp and pressure does not change this ratio.