A.P.

Environmental Science
Mr. Lindsey
Student Notes – Unit 7, Atmospheric Pollution

Greenhouse effect –

Most common greenhouse gasses: H2O, CO2, CH4,

N2O, O3, CFC’s

Air pollutants are found throughout the entire global

system. Some are natural, some are anthropogenic.

Aerosols – tiny particles of liquids or solids suspended

in the atmosphere. “Aerosol,” “particulate,” and
“particulate matter” are pretty much the same thing.
The black or gray color of smoke comes from
particulates.

Developing Countries: As developing countries

develop, they use more fossil fuels. Air emissions initially are not usually subject to governmental regulation or controls.
China has 7 of the world’s 10 most air polluted cities.

Many air pollutants are the result of combustion. Combustion is never perfect. Fossil fuels can burn at very high
temperatures, and molecules that naturally occur in the air can turn into pollutants. Natural air is made up of: N2, O2,
CO2, and H2O

Typical combustion reaction: CH4 + O2  CO2 + H2O + heat

This reaction above is perfect (note that even in perfect reactions, combustion always releases CO2). But this
hydrocarbon is naturally surrounded by N2, O2, CO2, and H2O molecules when it burns, so “incomplete combustion” may
result in a remix of atoms/molecules, and the resulting pollutants NOx and CO. And if the hydrocarbon molecule doesn’t
burn at all, it is released into the air and is called an “unburned hydrocarbon,” and classified as a VOC (pollutant). Wood
is also made of hydrocarbons which release energy when burned. When wood is burned, the main byproduct (aside
from CO2) is particulates/aerosols. These are molecules and particles that the tree used to live its life, and are
considered impurities in terms of combustion.

Criteria Pollutants –

Arnold says to criteria pollutants: “You have No CLOSS!”

Nitrogen Oxides (NOx)- (NO, NO2, N2O etc.) -

Nitric oxide (NO) forms when nitrogen and oxygen gas in air react at the high-combustion temperatures in automobile
engines and coal-burning power plants. NO can also form from lightning and certain soil bacteria. NO reacts with air to
form nitrogen dioxide (NO2). NO2 reacts with water vapor in the air to form nitric acid (HNO3) which is a component of
acid deposition.

Carbon monoxide (CO) –

Most CO in the U.S. is released by internal combustion engines (vehicles). CO readily bonds with hemoglobin, so red
blood cells think they are getting oxygen to deliver to body cells, but they’re not (and that’s bad)

Lead (Pb) –

Neurotoxin, causes brain damage, bioaccumulates in bones

Ozone (O3) –

Ground-level (tropospheric ozone) is bad. Stratospheric ozone is good – this ozone layer protects the Earth from
ultraviolet radiation. At ground level, ozone breaks down most organic molecules that it comes in contact with, including
lung and eye tissue in humans (and animals), and plant stems/leaves. Prolonged ozone exposure in humans can cause
and aggravate respiratory illness, can aggravate heart disease, can inhibit photosynthesis in plants, and can damage
rubber in tires, fabrics, and paints.

Sulfur dioxide (SO2) –

(You may also see it as SOx, which refers to all sulfur-oxygen compounds. If you see SOx, just think SO2) About one-third
of SO2 in the troposphere occurs naturally through the sulfur cycle. Two-thirds come from human sources, mostly
combustion (S + O2  SO2) of sulfur-containing coal (electricity and smelting process), oil refining, smelting of sulfide
ores, and burning diesel fuel in trucks. SO2 in the atmosphere can be converted to sulfuric acid (H2SO4).

SO2 can actually have a global cooling effect by increasing albedo of the atmosphere (remember volcanoes?)

Suspended Particulate Matter (SPM) –

The most harmful are fine particles (PM10, with an average diameter < 10 micrometers) and ultrafine particles (PM2.5).

According to the EPA, SPM is responsible for about 60,000 premature deaths a year in the U.S.

Volatile Organic Compounds (VOCs) –

Most things that have a fragrance are VOCs. Not all VOCs are toxic. Harmful VOCs include solvents such as
formaldehyde, trichlorethylene (TCE), benzene, and vinyl chloride. Long-term exposure to benzene can cause cancer,
blood disorders, and immune system damage. Gaseous hydrocarbons (methane, butane, propane) are VOCs which are
largely emitted through automobile pollution. Levels of these has decreased some since the 1970s due to technology.

Aldehydes - Aldehydes are reactive compounds that harm humans and animals; they are carcinogens. Aldehydes are
VOCs. Two major examples are formaldehyde and acetaldehyde. Aldehydes enter the atmosphere (outdoor pollution)
from the incomplete combustion of biomass or fossil fuels, especially from automobiles; tobacco smoke also contains
many aldehydes. Formaldehyde is a common indoor air pollutant (more on that later).

Mercury: Released naturally by volcanoes, the weathering of rock and evaporation of sea water. Released
anthropogenically by coal combustion, incineration of trash, and smelting.

Natural Sources of Air Pollution: Volcanoes – release particulates, SO2, COx, H2S, sometimes Hg. Forests – release VOCs
that may form O3. Sea Spray – can release sulfur compounds into atmosphere.
Primary Pollutant –

Can be natural or anthropogenic

Secondary Pollutant –

It is much easier to regulate (or even ban)

primary pollutants. The sources and
formation of secondary pollutants are often
very complex.

Smog: Smoke + Fog

There are two main types of smog. The word

smog originally referred to “industrial
smog” (aka London smog, pea soup smog, sulfurous smog). This first appeared in London because it’s naturally foggy
there, and industrialization brought the burning of fossil fuels (mainly coal), and the smoke/soot that results. Formation
of industrial smog: Coal or oil is burned, releasing smoky particulates, CO, CO2, and sulfur. Sulfur reacts with oxygen to
form SO2 and then H2SO4. The water vapor helps the smog stay in one place for a long time, and people continue to
breath in the pollutants. In 1952 industrial smog killed 4,000 people in London due to respiratory tract infections (“The
Great Smog”). So, be aware that this is a thing. However, when we talk about smog we are usually talking about…

Photochemical smog (aka brown air smog) –

The formation of photochemical smog is complex and still not well

understood. A number of pollutants are involved and they undergo a series
of complex transformations in the atmosphere.

Ground-level Ozone – (O3) and other photochemical oxidants irritate the

reparatory tract and eyes of animals and damage plant tissues, inhibiting
photosynthesis. The EPA monitors ozone levels (NO CLOSS!) and will
declare an “Ozone Action Day” if levels get too high – this means that old
people and babies should stay indoors.

Nitrogen dioxide (NO2) – a highly toxic

secondary pollutant and component of
photochemical smog; usually
responsible for the translucent reddish-
brown color of photochemical smog
(Note: NO2 can be a primary pollutant
as part of NOx or a secondary pollutant
as part of photochemical smog).
Photochemical smog is a mixture of air
pollutants formed by the reaction of
volatile organic hydrocarbons (VOCs)
and nitrogen oxides (NOx) under the
influence of sunlight. Photochemical
smog often occurs in urban areas because the large number of motor vehicles there emit NOx and VOCs (unburned
hydrocarbons).

NOx is produced early in the day by automobiles. O3 concentrations peak in the afternoon and are higher in the summer
because of the increased sunlight. If photochemical smog occurs along with a temperature inversion, the result is
especially toxic. Health Effects: Photochemical smog is capable of inflicting irreversible damage on the lungs and heart.
It causes painful irritation of the eyes, respiratory system, reduced lung function and difficulty breathing; this is more
evident while exercising or working outdoors. High levels of smog also trigger asthma attacks because the smog causes
increased sensitivity to allergens, which are triggers for asthma. Children, the elderly, and people with poor lung
function carry a far greater risk of developing respiratory illness from photochemical smog.

Application: Rush-hour traffic, vehicle exhaust. Analyze this graph

of air pollutants and how their concentrations change throughout
the day.

Which of these gases are directly produced by rush hour traffic

(vehicle exhaust)?

Around 7am, NO begins to decrease, but NO2 continues to

increase for a while. Why do you think this is? (hint, the “peak” of
NO2 is higher than the peak of NO)

If technology that reduces the hydrocarbon concentration had

been better utilized, what be the most likely result?

NO and NO2 begin their rise at 3am, but O3 begins to rise at 7am. Why?

Thermal Inversion (aka temperature inversion) –

During a temperature inversion, normal convection and pollution

dissipation are not allowed to occur (dilution…is…). Usually found in
cities surrounded by mountains like Los Angeles, Denver, Mexico
City. This is especially bad when combined with photochemical smog
and automobile exhaust, because ozone and particulates are trapped
at ground level and can cause an increase in respiratory irritation.
They are more common in winter than summer, and can occur from
close to ground level up to thousands of feet high. Areas with sunny
climate, no/light winds, mountains on three sides and an ocean on
the other are susceptible to inversions. Temperature inversions are
considered “localized” events, not part of an area’s overall climate.
Carbon Dioxide: In 2009, the EPA declared carbon dioxide to be a pollutant. 93% of carbon dioxide (CO2) in the
troposphere occurs as a result of the carbon cycle through cell respiration. 7% of CO2 in the troposphere occurs as a
result of human activities (mostly burning fossil fuels). CO2 in the atmosphere is increasing because of deforestation and
the combustion of fossil fuels.

Indoor air pollution in developing countries: Developing countries mainly burn biomass for heating and cooking. There
can be very little ventilation in homes. Indoor air pollution from burning biomass includes: Carbon dioxide, Carbon
monoxide, Particulates, NOx, and VOCs (the smoky smell). Indoor burning of coal releases SO2

In developed countries, materials in the home can become

sources of indoor air pollution. The major indoor air
pollutants in developed countries are tobacco smoke,
formaldehyde, asbestos, carbon monoxide, radon, and
VOCs. Indoor air pollution often is a greater threat to
human health than outdoor air pollution. According to the
EPA, the four most dangerous indoor air pollutants in
developed countries are: (1) Tobacco smoke, (2)
Formaldehyde, (3) Radioactive Radon-222 gas, and (4) Very
small superfine and ultrafine particles.

Environmental Tobacco Smoke (ETS) – The leading cause of

lung cancer, classified as particulates

Formaldehyde - Released from building materials such as plywood, particleboard, textiles, furniture stuffing and carpets

Asbestos – A naturally-occurring mineral fiber (a form of silicate). It was used as noise-insulation and fire-insulation. It is
strong and cheap. The EPA began regulating its use and phased out in
1977 (no buildings after 1977 were built with asbestos). Asbestos
fibers (particulates) can get loose, breathed in, and can cause lung
cancer or mesothelioma. If old asbestos is discovered in buildings, it
needs to be sealed or replaced by professionals.

Radon – a radioactive gas naturally produced by the decay of uranium

in soil and/or bedrock (especially granite). As a gas, it can move up
through the soil and enter homes via the basement or cracks in the
walls or foundation. Radon can be dissolved in groundwater that
enters homes through a well. It is the second-leading cause of lung
cancer in the US. Ways to prevent breathing in radon in your home:
(1) make sure that floors and basements are completely sealed from
surrounding rock and soil, (2) increase ventilation of basements and
rooms so that radon that enters can then escape.

Why are particulates considered more dangerous as they get

smaller? First, they more easily bypass our respiratory filters
(cilia, mucous). Second, smaller particles have greater total
surface area – there are exponentially more opportunities to
come into contact with cells and do harm.

Carbon Monoxide - Comes from only partially combusted fuels.

In the home it can come from the fireplace or from natural-gas-
burning appliances. CO prevents O2 from combining with hemoglobin and asphyxiates (chokes) organisms, including
humans. CO is taken up in the blood 250x faster than O2. 90 percent of CO in the world is natural.

Household dust is considered a particulate pollutant. Household dust mites that feed on human skin and dust live in
materials such as bedding and furniture fabrics. They can cause asthma attacks and allergic reactions in some people.

BFRs (brominated flame retardants) are used in many products such as furniture, paint, and carpet. BFRs are
neurotoxins, endocrine disruptors, and carcinogens.

Mold - Molds are fungi that produce microscopic cells called spores. Mold spores are present everywhere both outdoors
and indoors and spread easily through the air. About 10 percent of the population is severely allergic to some type of
mold. Symptoms include respiratory problems, nasal and sinus congestion, watery eyes, sore throat, coughing and skin
irritations. Mold also can trigger asthma attacks. To grow, mold needs a food source, moisture, and warm temperatures.
The food source can be any organic material such as dust, books, papers, animal dander, soap scum, wood, particle
board, paint, wallpaper, carpet and upholstery. When such materials stay damp (especially in dark areas with poor air
circulation) mold will grow. Flooding, pipe leaks, leaky roofs, moisture in walls, high indoor humidity, condensation, and
poor heating/air-conditioning system design and operation can create the damp environment that mold needs to grow.
The only way to prevent mold growth is to keep things dry. Fix leaks in plumbing and keep the relative humidity indoors
as low as possible.

Methods to Reduce Air Pollutants

Regulatory practices – laws that prohibit dangerous practices or require technology to remove pollutants

Conservation practices – preventing fuels from being leaked into the environment and volatizing into the atmosphere

Alternative fuels that do not have air pollution byproducts

The best way to decrease air pollution emissions is to avoid them in the first place. There are a lot of ways to prevent
and control air pollution from coal-burning facilities.

Electrostatic Precipitator –

Can remove 99% of particulate matter, but does not remove hazardous ultrafine particles. Collects toxic dust that must
then be safely disposed of. It uses large amounts of electricity (energy).

Wet Scrubber –

Can remove 98% of SO2 and particulate matter, but not very effective in removing hazardous fine and ultrafine particles.

Baghouse (aka baghouse filter, bag filter, fabric filter) - an air pollution control device and dust collector that removes
particulates or gas released from commercial processes. Power plants, steel mills, pharmaceutical producers, food
manufacturers, chemical producers and other industrial companies often use baghouses to control emission of air
pollutants. Baghouses came into widespread use in the late 1970s after the invention of high-temperature fabrics
capable of withstanding high temperatures of exhaust gasses. Baghouses typically have a particulate collection efficiency
of 99% or better, even when particle size is very small.

Fluidized bed combustion –

The limestone “captures” sulfur impurities of coal, lowering SO2 emissions. The burning of coal also becomes more
efficient and less heat is wasted. Less NOx is produced too. Oxygen is shot upwards from the bottom, resulting in a mix
of limestone particles and coal particles which bounces around like a fluid. The tumbling action allows more effective
combustion, heat transfer, and pollution is absorbed into the limestone.

Catalytic Converters –

Reduces CO to CO2. Reduces NOx to N2 and O2. Reduces unburned hydrocarbons (VOCs) to CO2 and H2O.

Vapor recovery nozzle –

Prevention of Air Pollution – Much air pollution comes from burning fossil fuels for generation of electricity and
transportation. We can: Burn less fossil fuels; Get better automobile efficiency to use less gasoline; Use more efficient
home appliances to save energy; Have better insulated homes to save energy; Use natural gas over coal

Alternative fuels – By using renewable forms of energy to generate electricity we avoid the air pollutants that come
from burning coal. Renewable electricity comes from: Hydroelectric, Geothermal, Solar, and Wind.

Clean Air Act of 1963 (amended 1970 and 1990) – the original act was
designed to help states decrease air pollution. Amendments created the list
of criteria pollutants and the National Ambient Air Quality Standards. To
help reduce SO2 emissions, the Clean Air Act authorized an emission trading
(cap-and-trade, aka “offset allowances,” “permit trading,” “market
permits”) program. This enables the 110 most polluting power plants to
buy and sell SO2 pollution rights/credits. So, power plants that spend
money to reduce their pollution will pollute less than they are allowed to,
and will have leftover pollution rights/credits. They can then sell these
credits to power plants that have not invested in pollution control.
Hypothetically it should economially reward the non-polluters and punish
the polluters. Cap and trade is common in the United States for SO2, and
the concept has been adopted in Europe for CO2

Acid Rain

Quick, what would you guess the pH of pure, normal rainfall is? Rainwater is naturally_______, with a pH of about ____.
CO2 forms ___________________ naturally.

Acid deposition, mainly from burning fossil fuels, can fall as rain, snow, gases, and particles and harms plants, soil, and
water. Acids are solutions that contain more H+ ions than OH- ions. pH means “power of hydrogen” (or, exponent of
hydrogen). Air molecules react with water vapor in the atmosphere to form acid aerosols. Anthropogenic SO2, NOx, and
Cl form sulfuric, nitric, and hydrochloric acids. “Acid rain” is anthropogenic and has a pH of around 4. Acid rain is a
problem for organisms that cannot tolerate acidic environments. Acid rain may damage crops, trees, animals, and
aquatic organisms. Naturally alkaline materials like limestone (calcium carbonate, CaCO3) and gypsum may buffer or
neutralize acid rain. FYI, salts have no effect on the pH of water (the ocean is not more basic or acidic because of salt).

Sulfur dioxide (SO2), nitrogen oxides (NOx), and particulates can react in the atmosphere to produce acidic chemicals
that can travel long distances before returning to the earth’s surface. Acid deposition is much less of a problem than it
used to be.
Sulfuric acid (H2SO4) – responsible for about 2/3 of the damage done
by acid rain, and SO2 comes primarily from coal burning power plants.
Nitric acid (HNO3) – responsible for about 1/3 of the damage done by
acid rain, and is primarily from automobile exhaust. If we want to
reduce acid rain, we need to reduce the burning of fossil fuels (burning
of coal for SO2, burning of petroleum for NOx).

Acid deposition usually does not kill plants directly: Cuticles (the
protective coating on leaves) may become damaged, making the plant
more susceptible to infection. Acid deposition can dissolve base-like
nutrients like calcium, potassium, and magnesium, and then wash
these away or leach them downward, out of reach of the plants. Acid
deposition can dissolve solid heavy metals and make these toxins
available to plants. Runoff of acid rain can make bodies of water more
acidic, and the pH may be outside the range of tolerance of aquatic
organisms.

Acid rain can corrode structures and statues made of limestone,

marble, steel and brass

Cation-Exchange: In cation exchange, positive ions of calcium, magnesium, potassium, etc (trace elements needed for
healthy organisms) are attached to negatively-charged soil molecules - the metal ions are then held in place and
available to plants despite water moving around
through the soil.

Effects of Acid: Hydrogen ions from acid rain trade

places with the metal ions. Calcium, potassium, and
magnesium ions are then free and are leached down
or washed out as runoff. Either way, they’re no
longer available to organisms.
Aluminum ions: Acids can also free up aluminum ions which are normally present in an insoluble, nontoxic form. When
the soil pH dips to 5 or lower, aluminum ions are dissolved into the water and then become toxic to plants. Lower soil pH
and free aluminum ions can reduce populations of soil bacteria, slowing down decomposition which further slows the
release of nutrients into the ecosystem. Acids can free up other toxic metals (lead, mercury, zinc, copper, cadmium,
chromium, manganese) from their insoluble to their soluble ion forms in the same way as aluminum. These metals in
their toxic form may all slow the growth of trees, soil bacteria, and other organisms. These metals can also harm aquatic
life if they runoff into surface water.

Acid deposition contributes to chronic respiratory disease and can leach toxic metals (such as lead and mercury) from
soils and rocks into acidic lakes used as sources for drinking water.

Noise pollution – sound at levels high enough to cause physiological stress and hearing loss. Affects animals that use
sounds to communicate. There were mysterious deaths of squid, whales, and dolphins after naval exercises / sonar (UK
in 2008, US East Coast 2013, San Diego 2011). Sources of noise include transportation, construction, and domestic and
industrial activity. Effects on animals include stress, impaired communication or hunting, damaged hearing, and changes
to migratory routes.
Appendix - Why was lead added to gasoline in the first place?

• For a more detailed explanation of why lead used to be added to gasoline, it’s necessary to understand a little
bit more about gasoline and what properties make it a good combustion material in car engines. Gasoline itself
is a product of crude oil that is made of carbon atoms joined together into carbon chains. The different length of
the chains creates different fuels. For example, methane has one carbon atom, propane has three, and octane
has eight carbon atoms chained together. These chains have characteristics that behave differently under
various circumstances; characteristics like boiling point and ignition temperature, for instance, can vary greatly
between them. As fuel is compressed in a motor’s cylinder, it heats up. Should the fuel reach its ignition
temperature during compression, it will auto-ignite at the wrong time. This causes loss of power and damage to
the engine. Fuels such as heptane (which has 7 carbon atoms chained together) can ignite under very little
compression. Octane, however, tends to handle compression extremely well.

• The higher the compression in the cylinders a car’s motor can produce, the greater the power it can get out of
each stroke of the piston. This makes it necessary to have fuels that can handle higher compression without
auto-igniting. The higher the octane rating, the more compression the fuel can handle. An octane rating of 87
means the fuel is a mixture of 87% octane and 13 percent heptane, or any mixture of fuels or additives that have
the same performance of 87/13.

• Over time, other manufacturers found that by adding lead to fuel they could significantly improve the octane
rating of the gas. This allowed them to produce much cheaper grades of fuel and still maintain the needed
octane ratings that a car’s engine required.

• Production of leaded gasoline began in 1923. It didn’t take long for workers to begin succumbing to lead
poisoning. At DuPont’s manufacturing plant in Deepwater New Jersey workers began to fall like dominoes. One
worker died in the fall of 1923. Three died in the summer of 1924 and four more in the winter of 1925. Despite
this, public controversy didn’t begin until five workers died and forty-four were hospitalized in Oct. of 1924 at
Standard Oils plant in Bayway, NJ.

• The Public Health Service held a conference in 1925 to address the problem of leaded gasoline. As you would
expect, Kettering testified for the use of lead. Alice Hamilton of Harvard University countered proponents of
leaded gasoline and testified that this type of fuel was dangerous to people and the environment. In the end,
the Public Health Service allowed leaded gasoline to remain on the market.

• In 1974, after environmental hazards began to become overwhelmingly apparent, the EPA (Environmental
Protection Agency) announced a scheduled phase out of lead content in gasoline. One way manufacturers met
these and other emission standards was to use catalytic converters. Catalytic converters use a chemical reaction
to change pollutants, like carbon monoxide and other harmful hydrocarbons, to carbon dioxide, nitrogen and
water. Tetraethyl lead would tend to clog up these converters making them inoperable. Thus, unleaded gasoline
became the fuel of choice for any car with a catalytic converter.

• On January 1, 1996, the Clean Air Act completely banned the use of leaded fuel for any on road vehicle. Should
you be found to possess leaded gasoline in your car you can be subject to a $10,000 fine.

• This hasn’t completely gotten rid of leaded gasoline. You are still permitted to use it for off road vehicles,
aircraft, racing cars, farm equipment, and marine engines, in the United States.