Particles in the

Atmosphere
10. Particles in the Atmosphere

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◍ Particles in the atmosphere are
made up of a variety of
materials and discrete objects
that may consist of either
solids or liquid droplets.

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Add table 10.1

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 Particulates
◍ Term for particles in the atmosphere
◍ Particulate matter or particles
◍ Makes up the most visible and obvious form of air
pollution
◍ Atmospheric aerosols are solid or liquid
particles smaller than 100um in diameter
◍ Particulate matter may be organic or inorganic

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◍ Some particles are of biological origin:
bacteria, bacterial spores, fungal spores, pollen
◍ Organisms may contribute to sulfate particulate
matter in the atmosphere
◍ Marine biological sources may contribute to
atmospheric aerosol

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10.2 Physical Behavior of Particles
in the Atmosphere

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◍ Atmospheric particles undergo a number of processes in
the atmosphere
◍ Small colloidal particles are subject to diffusion
processes
◍ Smaller particles coagulate together to form larger
particles
◍ Two major mechanisms for particle removal from the
atmosphere
◌ Sedimentation or dry deposition of particles
◌ Scavenging by raindrops and other forms of
precipitation 8
Figure 10.2

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◍ Particles size – expresses the diameter of a
particles
◍ The settling rate is important in determining the
effect of the particle in the atmosphere
◍ Add equation 10.2.1

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 Size and Settling of Atmospheric Particles

◍ Mass Median Diameter – used to describe

aerodynamically equivalent spheres having an assigned
density

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10.4 Physical Processes for Particle
Formation

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◍ Dispersion Aerosols formed from disintegration of
larger particles are usually above 1um in size.
◍ Typical processes for forming dispersion:
◌ Evolution of dust from coal grinding
◌ Formation of spray in cooling towes
◌ Blowing of dirt from dry soil
◍ Many dispersion aerosols originate from natural
sources: sea spray, windblown dust, volcanic dust

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◍ ‘All terrain’ vehicles churn across desert lands,
coating desert plants with layers of dispersed dust
◍ Quarries and rock crushers spew out plumes of ground
rock
◍ Cultivation of land has made it more susceptible to
dust-producing wind erosion.

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◍ Most dispersion aerosols are relatively large
◍ Larger particles tend to have fewer harmful
effect than smaller ones
◌ Larger particles are less respirable
◌ Larger particles are easier to remove from
air pollution effluent sources

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◍ Huge volcanic eruptions can cause
highly elevated levels of particles in
the atmosphere
◌ Physical process of simply blowing
volcanic dust as high as the
stratosphere
◌ Chemical process involving the
production of sulfuric acid and
sulfates from volcanic SO2 and H2S

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10.4 Chemical Processes for
Particle Formation

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◍ Chemical processes in the atmosphere
convert large quantities of atmospheric
gases to particulate matter.
◍ Organic pollutants and nitrogen oxides
cause the formation of ozone and
photochemical smog in the troposphere

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 Chemical Processes that produce particles

◍ Combustion processes ◍ Particles from combustion

◌ Fossil-fuel-fired power
occur in a size range below
plants 1um
◍ Incinerators ◌ Most readily carries into
◍ Home furnaces, fireplaces and the alveoli of lungs
stoves ◌ Likely to be enriched in
◍ Cement kilns more hazardous
constituents (heavy
◍ Internal Combustion engines metals and arsenic)
◍ Forest, brush and grass fires
◍ Active volcanoes

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 Inorganic Particles

◍ Aerosol mists involving the

◍ Particulate iron oxide formed
oxidation of atmospheric sulfur
during combustion of pyrite-
dioxide to sulfuric acid
containing coal

◍ In the presence of basic air

◍ Calcium carbonated in the ash
pollutants (NH3 or CaO),
fraction is converted to
sulfuric acid reacts to form
calcium oxide
salts

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 Organic Particles
◍ Internal combustion engines
◌ Process involves
pyrosynthesis and
nitrogenous compounds
◌ Products are nitrogen-
containing compounds and
oxidized hydrocarbon
polymer
◍ Lubricating oil and its
additives
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◍ Emission from gasoline auto
engines and diesel trucks
◌ N-alkanes, n-alkanoic
acids, benzaldehyde,
benzoic acids,
azanapthalenes, PAHs,
oxygenated PAHs,
pentacyclic triterpanes
and steranes
 PAH Synthesis

◍ PAH hydrocarbons – consists of

condensed ring aromatic (aryl)
molecules
◍ Benzo(a)pyrene – a compound that the
body can metabolize to a carcinogenic
form

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 PAH Synthesis

◍ PAHs may be synthesized from ◍ PAHs may be formed from higher

saturated hydrocarbons under alkanes present in fuels and
oxygen-deficient conditions plant materials by the
◍ Low-molar mass hydrocarbons form pyrolysis
PAHs by pyrosynthesis ◍ Pyrolysis is the ‘cracking’ of
◍ Pyrosynthesis happens at organic compounds to form
temperatures exceeding 500°C at smaller and less stable
which C-H bonds and C-C bonds molecules and radicals
are broken to form free
radicals.
◍ Radicals undergo dehydrogenation
to from aryl ring structures
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PAHs Synthesis

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10.5 The Composition of Inorganic
Particles

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◍ The proportions of elements in the
atmospheric particulate matter reflect
relative abundance of elements in the
parent material
◍ The source of particulate matter is
reflected in its elemental composition

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◍ Inorganic matter found in
polluted atmosphere are: salts,
oxides, nitrogen compounds,
sulfur compounds, various
metals and radionuclides.
◍ In coastal areas, sodium and
chlorine get into atmosphere
particles as sodium chloride
from sea spray
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◍ Major trace elements that
typically occur at levels
above 1ug/m3 in particulate
matter are: aluminum, calcium,
carbon, iron, potassium,
sodium and silicon.
Likely sources of copper, lead, titanium and zinc, antimony, beryllium, bismuth,
cadmium, cobalt, chromium, cesium, lithium, manganese, nickel, rubidium, selenium,
strontium, vanadium
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◍ Particulate carbon as soot,
carbon black, coke and graphite
from auto and truck exhaust,
heating furnaces, incinerator,
power plants and steel and
foundry operations
◍ Particulate carbon composes one
of the more visible and
troublesome particulate air
pollutants
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◍ Carbon can be a carrier of
gaseous and other particulate
pollutants
◍ Particulate carbon surfaces may
catalyze some heterogenous
atmospheric reactions,
including the conversion of
sulfur dioxide to sulfate.
 Fly Ash

◍ A byproduct from burning

pulverized coal in electric
power generating plants.
◍ Ash produced in small dark
flecks, typically from a
furnace and carried into the
air.

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 Fly Ash
◍ Mineral particulate matter is
in the form of oxides and other
compounds produced during the
combustion of high-ash fossil
fuel
◍ Coal or lignite is converted
during combustion to a fused,
glassy bottom ash
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◍ Some particles of fly ash enter
furnace flues and are
efficiently collected in a
properly equipped stack system.
◍ Some fly ash escapes through
the stack and enters the
atmosphere
◍ Fly ash tends to consist of
smaller particles that do the
most damage to human health,
plants and visibility
 Fly Ash
◍ Size of fly ash particles is a
very important factor in
determining their removal from
stack gas and their ability to
enter the body through the
respiratory tract.
◍ Fly ash from coal-fired utility
boilers have a shown a bimodal
distribution of size
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◍ Submicrometer particles
probably result from a
volatilization-condensation
process during combustion
◍ The very small particles are
the most difficult to remove by
electrostatic precipitators and
bag houses.
 Asbestos

◍ Asbestos is a group of fibrous

silicate minerals, typically
those of the serpentine group
◍ Tensile strength, flexible,
nonflammable
◍ Uses in structural materials,
brake linings, insulation and
pipe manufacturer

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 Asbestos

◍ When inhaled it may cause

◌ Asbestosis (a pneumonia condition)
◌ Mesothelioma (tumor of the mesothelial
tissue lining the chest cavity adjacent to
the lungs)
◌ Bronchogenic carcinoma (cancer originating
with the air passages in the lungs)

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10.6 Toxic Metals

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◍ Some of the metals found predominantly
as particulate matter in polluted
atmospheres are known to be hazardous
to human health
◍ Beryllium , Cadmium, Chromium, Mercury,
Lead, Vanadium, Nickel and Arsenic

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 Atmospheric Mercury

◍ Toxic, volatile and mobile

◍ Mercury in the atmosphere exists as
elemental mercury from coal combustion
and volcanoes
◍ Dimethymercury
◍ Monomethylmercury salts

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 Atmospheric Lead

◍ Particulate lead halides

◍ Occurs through the action of dichloroethane and
dibromoethane added as halogenated scavengers to prevent
the accumulation of lead oxides inside engines
◍ Lead halides exit through the exhaust system but condense
in the air to form particles

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 Atmospheric Beryllium

◍ Used for the formation of specialty alloys used in

electrical equipment, electronic instrument, space gear
and nuclear reactor components
◍ One of the main results of the recognition of beryllium
toxicity hazards was the elimination of this element from
phosphors in fluorescent lamps.

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10.7 Radioactive Particles

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◍ Some of the radioactivity
detected in atmospheric
particles is of natural origin
◍ A significant source of
radionuclide in the atmosphere
is radon, a noble-gas product of
radium decay
◍ Radioactivity originating from
uranium mine tailings that have
been used in some areas as
backfill, soil conditioner, base
for building foundation
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◍ Combustion of fossil fuels
introduces radioactivity into
the atmosphere in the form of
radionuclides contained in fly
ash
◍ Large coal-fired powerplants
lacking ash-control equipment
may introduce up to 700
millicuries of radionuclides
into the atmosphere
◍ Radioactive noble gas Kr is emitted
into the atmosphere by the operation of
the nuclear reactors and the processing
of spent reactor fuels
◍ Above ground detonation of nuclear
weapons can add large amounts of
radioactive particulate matter to the
atmosphere

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10.8 The Composition of Organic
Particles

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◍ Particles can be collected onto a
filter
◍ Extracted with organic solvents
◍ Fractionated into neutral, acid and
basic groups
◍ Analyzed for specific constituents by
chromatography and mass spectometry

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◍ Neutral group contains ◍ Aldehyde fraction contains
hydrocarbons, including aldehydes, ketones, epoxides,
aliphatic, aromatic and peroxide, esters, quinones and
oxygenated fractions lactones. Some can be mutagenic
◍ Aliphatic fraction contains high or carinogenic.
percentage of long-chain
hydrocarbons, those with 16-28
carbons atoms
◍ The aromatic fraction contains
carcinogenic polycyclic aromatic
hydrocarbons

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 Polycyclic Aromatic Hydrocarbons

◍ PAHs in atmospheric particles ◍ Atmospheric PAHs are found

have known carcinogenic effects almost exclusively in the solid
in some compounds. phase, largely sorbed to soot
◍ Levels of PAHs compounds of up particles.
to 20ug/m3 ◍ Soot is a highly condensed
◍ Elevated levels of PAHs are most product of PAHs
likely to be encountered in
polluted urban atmospheres and
in the vicinity of natural fires
such as forest and prairie fires

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 Carbonaceous Particles from Diesel Engines

◍ Diesel engines emit significant levels

of carbonaceous particles.
◍ Consists largely of elemental carbon

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10.9 Effects of Particles

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◍ Reduction and distortion of
visibility
◍ Provide active surfaces upon
chemical reactions can occur
◍ Nucleation bodies for the
condensation of atmospheric
water vapor
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◍ Most visible effects of
aerosol particles result
from their optical effects
◍ Particulates inhaled
through the respiratory
tract may damage health
◍ Respiratory system may be ◍ High levels or particulate
damaged directly by particulate matter are accompanied by
matter that enters the blood or elevated concentrations of SO2
lymph system through the lungs
◍ Particulate material or soluble
components of it may be
transported to organs some
distance from the lungs and have
detrimental effect on these
organs

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10.10 Water as Particulate Matter

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 Droplets can have significant and sometimes
harmful effects

◍ Reduction of visibility ◍ pH of water in acidic mist

◌ Effects on driving, flying droplets
and boat navigation
◍ Acidic mist can be especially
◍ Water droplets in fog act as damaging to the respiratory
carriers of pollutants tract
◌ Corrosive salts like
ammonium nitrates and
sulfates and solutions of
strong acids

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◍ Waters as aquatic media in
which many atmospheric
processes occur
◌ Oxidation of S(IV) species
to sulfuric acid and
sulfate salts
◌ Oxidation of aldehydes to
organic carboxylic salts
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◍ Hydroxyl radical HO·
◌ Can enter water droplets
from the gas phase
atmosphere
◌ Can be produced in water
droplets photochemically
◌ Can be generated from H2O2
and ·O2 radical ion
◍ Nitrite or nitrate and
Fe(III) can also react
photochemically in
aqueous solution
◍ UV radiation at 313nm
and simulated sunlight

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10.11 Control of Particulate
Emissions

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◍ Removal of particulate matter from gas
streams is the most widely practiced
means of air pollution control
◍ Selection of a particles system for a
gaseous waste stream depends upon
◌ The particle loading
◌ Nature of particles (Size
distribution)
◌ Type of gas-scrubbing system used

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 Particle Removal by Sedimentation and Inertia

◍ Inertial Mechanisms
◍ Sedimentation
◍ Depend upon the radius of the
◍ Gravitational settling chambers
path of a particle rapidly
are used to remove particles
moving, curbing air stream is
from gas streams by settling
larger than the path of the
under the influence of gravity
stream as a whole
◍ Gravitational settling is
◍ When a gas stream is spun by
enhanced by increased particle
vanes, the particulates matter
size
may be collected on a separator
wall because the particles are
forced outward by centrifugal
force
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 Particle Filtration

◍ Fabric Filters
◍ Fabrics that allow the
passage of gas but retain
particulate matter
◍ Used to collect dust in bags
contained in structure called
baghouses

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Scrubbers

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