Professional Documents
Culture Documents
AirPoll Ch2
AirPoll Ch2
AirPoll Ch2
• Fanning Plumes
– Require stable air and slow vertical movement of the
emission
– common after calm clear nights
– temperature inversion limits the rise of the plume into
the upper atmosphere
The Fanning Plume
• Looping plumes
– Require windy conditions which cause the plume can
swirl up and down
– common in the afternoon.
– Moderate and strong winds are formed on sunny days
creating unstable conditions
– Exists for several hours.
Coning plumes
• Coning plumes
– Require moderate winds and overcast days
– wider than it is deep, and is elliptical in shape
– exists for several hours.
Fumigating plume
• Fumigating plume
– Is short-lived (fraction of an hour), but reaches the earth's
surface.
– occur when the conditions move from stable to unstable
– A fanning plume develops overnight under stable
conditions but as the day heats up, unstable air is
produced
Fumigating Plume
• Lofting plume
– When plume is above the inversion layer (or there is
no inversion), it becomes a lofting plume.
– Normal wind direction and speed will disperse the
plume into the atmosphere without effect from ground
warming or cooling.
Stack emissions
• factors used to establish the amount of stack
emission allowed, and its conc. to the
atmosphere include:
– smoke stack (chimney) height,
– local topography,
– temperature,
– emission rates,
– chemical reactivity, and
– existing air pollution problems
– wind allow rapid dispersal of pollutants.
Fugitive Emissions
• Fugitive emissions are emissions which
escape from a process rather than being
discharged
• They often have serious consequences
because their levels are not monitored and
they are untreated when entering the
atmosphere
Fugitive Emissions
• There are many sources of fugitive emissions
including:
– industrial sources (particulate fluorides from
aluminium smelters)
– small business (e.g. dry cleaning solvents)
– agriculture (e.g. dust from ploughing)
– natural sources (e.g. volcanoes, forest fires)
Fugitive emissions
• Often the result of poor maintenance of
plant and equipment
• Can be eliminated by SOP’s that involve
timed maintenance and quality control
checks
• Some are almost impossible to control
(e.g. natural sources)
Types of air pollutants
• There are four types of air pollutants;
– particulate pollutants and
– gaseous pollutants,
– odour and
– noise.
Primary vs Secondary pollutants
• Not all of the pollutants found in the
atmosphere are the direct result of
emissions.
• Many pollutants arise from chemical
reactions in the atmosphere with other
substances or light (photochemical
reactions).
1° vs 2° pollutants
• Pollutant substances that are directly
emitted into the atmosphere = primary
pollutants.
• Substances not directly emitted into the
atmosphere, formed by chemical reactions
in the atmosphere = secondary pollutants.
Particulate Pollutants
• Very small solid or liquid particles
• Individual particles may vary in size,
geometry, chemical composition and
physical properties
• May be of natural origin (pollen or sea
spray) or man made (dust, fume and soot)
Particulate Pollutants
• Provide a reactive surface for gases and
vapours in the formation of secondary
pollutants
• Particles also diffuse light reducing
visibility
• Come from stack emissions, dusty
processes, unsealed roads, construction
work and many other sources
Particulate Pollutants
• Dusts
– large solid particles
• Fume
– solid particles (metallic oxides) formed by
condensation of vapours from a chemical
reaction process or physical separation
process
• Mist
Particulate Pollutants
– liquid particles formed by condensation of vapours or
chemical reaction.
SO3 + H2O H2SO4
• Smoke
– solid particles formed as a result of incomplete
combustion of carbonaceous materials.
• Spray
– a liquid particle formed by the atomisation of a parent
liquid.
Particle Size
• Particles range in size from 0.005 - 500m.
• Smallest of these are clusters of molecules
whilst the largest are easily visible with the
naked eye.
• Sizes given are not the physical size, but
rather the aerodynamic equivalent diameter
which relates the particle to the behaviour
of an equivalent spherical particle.
Particle Size
• Particles less than 1m in diameter behave like
gases (remain suspended, may coalesce, move
in fluid streams),
• Larger particles act like solids (affected by
gravity, don’t stay suspended long, don’t
coalesce).
• Smaller particles generally derive from chemical
reactions, whereas the larger particles (10m or
greater) are usually generated mechanically and
tend to be basic.
Particle Size
• Smaller particles most dangerous to health,
• In urban areas there is an approx. even
distribution between fine and coarse particles,
this is weather dependent.
• Calm conditions more fine particles than coarse,
• Fine particulate matter spread over much
greater distances
Particle behaviour in the atmosphere
N 2 + O2 2NO
Nitrogen Dioxide (NO2)
• light yellow to orange colour at low conc’s
and brown at high conc’s.
• pungent, irritating odour , and extremely
corrosive especially in wet environments
• toxic - can cause anoxia
Nitrogen Dioxide (NO2)
• Some of the NO2 in air produced by direct
oxidation of NO
2NO + O2 2NO2
Nitrogen Dioxide (NO2)
• At low atmospheric NO levels, oxidation is
slow, accounts for <25% of NO conversion
NO2 + O3 NO3 + O2
NO2+ NO3 N2O5
N2O5 + H2O 2HNO3
Nitrogen Oxides (NOx)
• NO3 is nitrate free radical
• key factor in night-time chemistry
• reaction product of NO2 and NO3 is
dinitrogen pentoxide (N2O5) - reacts with
water rapidly to produce HNO3
Nitrogen Oxides (NOx)
• Some of the HNO3 in the atmosphere
reacts with ammonia (NH3) or other
alkaline species to form salts such as
NH4NO3
• Nitrate aerosol is generally removed by
the dry and wet deposition processes in
much the same way as sulfate aerosol
Ammonia (NH3)
• relatively unimportant man made pollutant
• Most comes from biological decomposition
• Background conc's vary from 1 to 20ppb
• The avg. atmospheric residence time is
approx. 7 days
Organic Nitrates
• produced in the atmosphere by reaction of
NOx and hydrocarbons
• Examples are peroxyacyl nitrates (PAN’s)
and peroxybutylnitrates (PBN’s).
• discussed in detail in photochemical smog
section
Hydrocarbons
• organic materials in the atmosphere.
• In the atmosphere simple hydrocarbons react
with substances containing
– oxygen,
– nitrogen,
– sulfur,
– chlorine
– bromine
– even some metals (Pb)
Hydrocarbons
• Atmospheric hydrocarbons exist in gas,
liquid and solid phases
• gases and volatile liquids the most
significant pollutants
• Solid hydrocarbons generally of higher
MW and exist as condensed particles in
atmospheric aerosols
Hydrocarbons
• Methane (CH4) most common
hydrocarbon in the atmosphere - formed
from many natural sources;
– termites,
– cows
– decomposition of organic matter
• It and the other alkanes found in the
atmosphere are fairly un-reactive
Hydrocarbons
• atmospheric hydrocarbons of most
significance in terms of chemical reactivity
are the alkenes
• highly reactive alkene hydrocarbons are
formed naturally by plants (e.g. terpenes
from citrus plants and eucalyptus haze)
Hydrocarbons
• greatest source of non-methane
hydrocarbons are motor vehicles and
petroleum processing
• Alkenes are the major air pollutant
responsible for photochemical smog and
other gross oxidants in the atmosphere
Hydrocarbons
• Once in the atmosphere non-methane
H/C’s combine with O2 to form many
different oxygenated H/C’s including;
– alkanones
– alkanals
– alkanoic acids
– alkanols
– ethers
Hydrocarbons
• Aromatic H/C’s not very reactive, but can
react with other very reactive chemical
oxidants to form toxic substances, such
as;
– benzo[]pyrene
– poly-aromatic hydrocarbons (PAH’s)
Benzo[]pyrene
Hydrocarbons
• H/C’s emitted from a variety of natural and
man made sources
• important pollutants because of their role
in atmospheric photochemistry
• biological and geological processes
release hydrocarbon compounds naturally
Hydrocarbons
Sources include;
– plant and animal metabolism
– vaporisation of volatile oils from plant surfaces
– biological decomposition
– emission of volatiles from fossil fuel deposits
Hydrocarbons
Sinks
• most important sink processes are;
– photochemical conversion of hydrocarbons to CO2
and H2O or
– to soluble or condensable products such as
dicarboxylic acids - a major component of
photochemical aerosol.
• aerosols are removed from the atmosphere by
both dry and wet deposition processes.
Methane
• was initially considered an unimportant
H/C
• Measurements of total H/C subtracted the
conc. of CH4
• Hence ambient air quality standard for
H/C’s is a non-methane hydrocarbons
standard
Methane
• recognised as one of the trace gases that
may have significant greenhouse effect on
global climate
Methane
• by far the most abundant H/C in the
atmosphere, with a 1980 conc. of
1.65ppm.
NO2 + h NO + O*
• The reaction of O* with O2 produces O3, which reacts immediately with NO
to regenerate NO2.
NO + O3 NO2 + O2
Ozone
• All reactions proceed rapidly with approx.
conc. of 20ppb
• atmospheric NO2/NO conc. ratios can be
equal to 1
• Hence conc's of ozone remain low unless
imbalances in the levels of NO2 or other
alternate chemical reactants are available
Oh dear! The chemistry!
• We need to look closely at the chemistry
we have seen thus far.
•
Photochemical Smog
• refers to an atmosphere laden with
secondary pollutants that form in the
presence of sunlight as a result of
chemical reactions in the atmosphere
• arises in urban areas, where there is a
heavy build-up of vehicle exhausts
• greatly exacerbated by weather conditions
Photochemical Smog
• normally primary air pollutants are dispersed
over a large region or to the upper atmosphere
• A good prevailing wind is important for cities and
large urban areas to reduce smog
• At certain times of the year, when wind is very
still, primary pollutants build up over cities.
• Autumn worst for photochemical smog
Photochemical Smog
Photochemical Smog
• In autumn, days are sunny and warm, with cool
nights
• Under still conditions, a warm inversion layer
forms under a layer of higher cooler ai
• Large urban areas store heat, which provides
the warmth for the inversion layer
• The inversion layer limits air mixing and
dispersal trapping primary pollutants at lower
altitudes over urban areas
Photochemical Smog
Photochemical Smog
• primary pollutants (NOx), and H/C’s
trapped in the lower atmosphere are
subjected to UV radiation from the sun –
photochemical smog forms.
Photochemical Smog
• products called gross photochemical oxidants,
defined by their ability to oxidise I- to I2.
• They include
– ozone (O3)
– hydrogen peroxide (H2O2)
– organic peroxides (ROOR')
– organic hydroperoxides (ROOH) and
– by far the most serious to health, peroxyacyl nitrates
(RCO3NO2), known as PAN's.
Photochemical Smog
• The key chemical reactants in the
formation of photochemical smog are NOx
and hydrocarbons.
• The reactions undergone by these
substances in the atmosphere are many
and varied.
• Many of the reaction mechanisms are not
well understood.
Photochemical Smog
• In the lower atmosphere O3 conc's are often
much higher than those that occur from NO2
photolysis alone.
• This is because there are chemical reactions
that convert NO to NO2 without consuming O3.
• In polluted atmospheres, these changes in O3
chemistry can be attributed to peroxy radicals
(RO2) and other species produced by the
oxidation of hydrocarbons as shown in the
reactions below.
Photochemical Smog
RO2 + NO NO 2 + RO
NO2 + h NO + O*
O* + O2 + M O3 + M
Net: RO2 + O2 + h RO + O 3
Photochemical Smog
Photochemical Smog
• The rate of O3 formation is closely related
to the conc. of RO2.
• Peroxy radicals are produced when
hydroxy radicals OH and HOx react with
hydrocarbons.
• Hydroxy radicals are produced by
reactions involving the photolysis of O3,
carbonyl compounds (mostly alkanals),
and nitrous acid.
Photochemical Smog
• In polluted atmospheres, O3 conc's are directly
related to;
– the intensity of sunlight,
– NO2/NO ratios,
– the hydrocarbon type and conc's,
– and other pollutants, such as alkanals and CO, which
react photochemically to produce RO2.
• The increase in NO2/NO ratios caused by
atmospheric reactions involving RO2 results in
significant increases in lower atmosphere O3 levels.
Photochemical Smog
• summary of reactions in smog formation
can be compressed into 4 stages.
• At night no O3 produced
Photochemical Smog
• Under inversion layer, O3 may persist for
80 hrs.
• allows O3 to be transported over long
distances
• At sunrise, inversion breaks up, bringing
O3 and other products to the ground,
where they mix with the pollutants held in
by the inversion layer, and begin cycle all
over again
Photochemical Smog
• In unpolluted atmospheres O3 conc's near
ground are 10-20ppb (0.01-0.02ppm)
during the warm months
• O3 conc's over landmasses with large
motor vehicle numbers often well above
this even at remote sites
• Los Angeles basin 1 hour conc's are 0.20-
0.40ppm
Photochemical Smog
• warm, sunny NSW central coast means
Sydney Basin has high photochemical
smog production