Chapter 1 Part 2

- Air pollution and air quality

- Fate of airborne chemicals and impacts of air pollutants

on health and the environment
 Air pollution and air quality

Ambient air quality index

The concentrations of pollutants are converted

to dimensionless index scales to convey the air
quality to the general public.
 Air Quality Index (AQI)
originally developed by USEPA
• AQI is an index for reporting daily air quality
– Based on five criteria air pollutants regulated by the US
Clean Air Act: (CO SO2 NO2 PM2.5/PM10 O3)
– An indicator of air quality, and what health effects might
be a concern for you.

• AQI focuses on health effects one may experience

within a few hours or days after breathing polluted air.
• The AIRNow website provides the public with easy access to
national air quality information, which includes daily AQI
forecasts and real-time AQI conditions for many cities across
the US.
AQI is divided into six categories
• AQI =100 generally corresponds to the national air quality standard for
the pollutant - the level USEPA has set to protect public health.
• AQI < 100 is generally considered satisfactory
 Relationship between AQI and
the individual air pollutant concentrations
For each category, a linear relationship is assumed between index
values and the concentrations of the sub-index pollutants.
At the end of each hour, the concentration of each pollutant
(measured at a particular AQI site) is converted into a number
ranging from zero upwards using a common scale or index.
Sub-index AQI(X) = a1C + a2
where C is the concentration of pollutant “X”
At a given site, the highest sub-index AQI(X) will be taken as the
AQI reading for that hour

AQI Calculator
[Link]
 Air Quality Health Index (AQHI) – Canada
Before 2009, Environment Canada used the Air Quality Index
(AQI) in the day-to-day forecast. The Air Quality Health Index
(AQHI) has been used by Environment Canada since then.

AQHI is a public information tool developed by Health Canada

and Environment Canada in collaboration with the provinces
and key health and environment stakeholders .
[Link]
Primarily, the AQHI communicates the following:
• The scale for the AQHI An integer number from 1 to 10+
indicating the quality of the air. Health risk associated with the
air quality (1-3 Low, 4-6 Moderate, 7-10 High, 10+ Very High).

• Health messages customized to each category for both the

general population and the ‘at risk’ population.

• Current hourly AQHI readings

• Maximum forecasted values for today, tonight and tomorrow
AQHI is calculated based on the measurements of three specific air
pollutants, chosen as indicators of the overall mixture, which are
known to harm human health:
• ground-level ozone (O3)
• particulate matter (PM2.5 )
• nitrogen dioxide (NO2)

AQHI = K (eaX + ebY + ecZ – 3)

where K = 96.2 (a, b, c) = (8.71, 5.37, 4.87) x 10-4
X: NO2 concentration, ppb
Y: O3 concentration, ppb
Z: PM2.5 concentration, μg/m3
Here, “ppb” is the same as “ppbv” or “ppb (vol.)”
All three pollutants can have effects on human health even as a result of
short-term exposure; and pose health risks at low levels of exposure,
especially among those with pre-existing health problem.
AQHI vs. AQI

• AQI is based on the highest value of only one pollutant.

• AQHI is based on the combined health risks from each of
the pollutants in the index.

• AQHI reflects current knowledge of the health effects

associated with air pollution.
• AQI is based on air quality standards and takes into
consideration both environmental and human health
concerns.
Fate of airborne chemicals and impacts of
air pollutants on health and the environment
 PM and O3
• Can cause coughing, difficult or painful breathing, asthma,
bronchitis…

• Long term exposure to PM2.5 can result in Chronic Obstructive

Pulmonary Disease (COPD) – progressive lung diseases including
emphysema, chronic bronchitis, refractory (non-reversible)
asthma… could lead to permanently decreased lung function,
heart disease, cancer, and even premature death of those with
compromised lung or heart function

• O3 can have some of these effects

• Most particles larger than 5 m can be removed by the nasal
passage (hairs and moist surfaces).

• The body cannot efficiently remove the fine particles (PM2.5) and
ultrafine particles (PM1) that attack the bronchioles and alveoli
and find passage to the cardiovascular system.

For particles larger than 0.5 μm,

deposition increases with increasing
particle size because of increased
gravitational and inertial transport,
while for particles smaller than 0.5 μm in
diameter, deposition increases with
decreasing particle size because of
increased Brownian diffusive transport.
 CO
• Human and other species rely on hemoglobin to transfer O2 from
the air to the cellular tissue of the organism.
• Hemoglobin is a component of blood which, under normal
conditions, receives O2 from the air in the lungs and transfers it,
via the blood, to various tissues.
• In turn it picks up and releases CO2 in the lungs.
• Hemoglobin has a stronger affinity for CO than it does for O2.
In the presence of sufficiently high CO concentration the ability
of hemoglobin to transfer O2 is impaired.
 mechanism similar to CO: forming a complex bond
H2S with iron in blood; and preventing cellular respiration
Concentration, ppm Symptom

0.0005 (0.5 ppb) Odor threshold

> 0.0005 Nausea in sensitive individuals

50 Severe eye irritation

100-150 Paralysis of olfactory senses

700-800 Death by paralysis of the

respiratory system
[Link]
Definition of odor (odour):

The “property of a substance that is perceptible to the

sense of smell”.

→There can be numerous constituent components that

make up an odor, but “odor” itself is not a substance.
• Emissions of malodours from a variety of industries (such as
rendering plant, composting, refinery, pulp mill, fish processing),
farms, landfills, and wastewater treatment facilities etc. can cause
impact to neighbouring communities in terms of odour nuisance
and possible health problems.

• Odour emissions have resulted in an increasing number of

complaints being made by the exposed population.

• Health impact: Even when the individual chemical constituents of

the odour are not toxic per se, the human response to malodours
can activate stress mechanisms.

Metro Vancouver Air Quality Department receives more complaints

than any other type of air emission.

16
Examples of target compounds designated as main offensive malodours
Odorous chemical Characteristic smell Average* odor detection
compounds threshold value (OTV), ppb
Reduced sulfurs
hydrogen sulfide rotten egg 0.5
dimethyl sulfide rotten cabbage, sour, sulfide 3.0
dimethyl disulfide sulfide 2.2
methyl mercaptan garlic, sulfide 0.07
Amines and ammonia
ammonia pungent 1500
trimethylamine fishy 0.032
Aldehydes
acetaldehyde ripen fruit, sweet 1.5
butyraldehyde 0.67
isovaleraldehyde 0.1
propionaldehyde 1.0
valeraldehyde 0.41
VOC
styrene 35
* OTV of some compounds such as methyl mercaptan can have large variability
Odorous chemical compounds Characteristic smell Average odor detection
threshold value (OTV), ppb
Amines
cadaverine rotten fish, fishy 0.04
skatole fecal 0.006
indole fecal, burnt coffee 0.3

Volatile fatty acids

acetic acid vinegar, sour 400
butyric acid rancid, spoiled butter 0.6
propionic acid rancid 15
isovaleric acid foul sweat, dirty socks 0.008
& valeric acid

Alcohols sweet, medicinal 5.6

phenol

The term Pervasive compounds refers to those with very low OTV values
that generally need a large amount of dilution to reach thresholds
 (eg. H2S, mercaptans, amines, VFAs)

(eg. NH3)
For individual compounds,

Dilution-to-threshold (D/T)
= Ci/OTVi

where

Ci is the initial concentration of the compound

OTVi is its odor detection threshold value

Possible symptoms

sleep disturbance, nausea, difficulty breathing,

dizziness, headache, irritated eyes, coughing, sore
throat

→ eventually leading to adverse health outcomes

[Link]
POP
eg. Methoxychlor (a pesticide)

Other names: Methoxcide (trade name); Dimethoxy-DDT

Abbreviation: DMDT (vs. DDT: Dichlorodiphenyltrichloroethane)

• A synthetic organochloride insecticide that is used to protect crops,

ornamentals, livestock, and pets against fleas, mosquitoes,
cockroaches, and other insects

• It was intended to be a replacement for DDT but has since been

banned for use as a pesticide based on its acute toxicity,
bioaccumulation, and endocrine disruption activity.

• 2004 Stockholm Convention for persistent organic pollutants (POPs)

[Link]
 Smog formation
• Nitrogen dioxide NO2 is a light absorbing gas, which
converts the light energy (photons) into its internal energy,
leading to the formation of excited monatomic oxygen,
and the formation of ozone and smog in the troposphere
due to photochemical reactions.

• Reactions in the atmosphere involve hydrocarbons (VOCs)

that enhance the production of NO 2.
 London-type smog
• Caused mainly by air pollution due to combustion of
coal and emission of SO2 and PM (smoke).

• Such pollution mixed with fog can produce droplets of

sulfuric acid (H2SO4) suspended in the air.

1952 London, England

• A 5-day temperature inversion in December trapped deadly acid
aerosols in the atmosphere
• Over 4000 people succumbed to respiratory and cardiac diseases
• Continued air pollution problems resulted in the passage of the Clean
Air Act in 1956

25
 Los Angeles-type smog
(Photochemical smog)
• Occurs on sunny days due to intense traffic
• Main component is O3, a secondary pollutant
• The primary pollutants involved in O3 formation are:
NOx and VOC (both are Common Air Contaminants in Canada)

• In the presence of UV solar radiation, they react to produce a

mixture of aerosols and gases.

• Particulates created from gaseous primary pollutants and

compounds in photochemical smog are secondary pollutants →
photochemical smog contains primary and secondary pollutants
26
• Photochemical reactions:
Typically, nitric oxide (NO) is released by stationary and mobile
sources, and it tends to oxidize to NO2 in the atmosphere.

a) Photolytic NO2 cycle (a simplified model)

k1: NO2 + h (~0.42 m) → NO + O*
k2: O* + O2 + M → O3 + M (energy acceptor e.g. N2)
k3: O3 + NO → NO2 + O2 O 2

h
NO2 O* O3

NO
O2

d[NO]/dt = k1 I [NO2] – k3[NO][O3]

generation consumption
• Under steady state: d[NO]/dt=0
k1 [ I ][ NO2 ]
[O3 ] =
k 3 [ NO ]

• This equation is the photo-stationary state expression for O3.

• The intensity of the photon, I, depends on the latitude, time of the
year, time of the day.

• Most of the NO must be converted to NO2, i.e. NO2:NO ratio ≥ 10

for O3 to build up in the lower atmosphere.
– But for typical values of (k1, k3 and I), O3 accumulation cannot be
explained by the kinetics of the photolytic NO2 cycle alone.
b) The role of hydrocarbons
In the presence of organic gases “RH” (that represents the
reactive VOCs),

O* + H2O → 2OH (ydroxyl radical) (4)

OH + RH → H2O + R (organic radical) (5)
R + O2 + M → RO2 (peroxy radical) (6)
RO2 + NO → RO + NO2 (Enhanced NO2 production) (7)

NO2 + h (~0.42 m) → NO + O* (1)

O* + O2 + M → O3 + M (h ~0.32 m) (Enhanced O3 production) (2)
O3 + NO → NO2 + O2 (3)
O3 + NO2 → NO3 + O2
The RHs are primarily olefin hydrocarbons, aromatic compounds
and aldehydes emitted from many sources .
▪ Although this scheme does not show the overall complexity of
the actual system, it can explain qualitatively the buildup of NO 2
and O3 levels.

• The reactions involving hydrocarbons enhance the production of

NO2 beyond that due to the NO 2 photolytic cycle.

• NO is known to preferentially reacts with the RO 2* radical

(reaction 7) versus O3 (reaction 3)
→ less O3 is consumed while more NO2 is formed
→ both NO2 and O3 can accumulate
▪ The reactions involving hydrocarbons also lead to the
formation of carbonyl compounds such as aldehydes and
ketones, organic acids and organic nitrates, which are
photochemically active.
e.g. the RO radical (from reaction 7) will react with O2 to form aldehydes

▪ The acyl radical formed from the hydrolysis of aldehydes and

the peroxy radical react with NO and NO2 to form peroxyacyl
nitrates
e.g. peroxyacetyl nitrate (PAN), peroxybenzoyl nitrate (PBN)
Both are strong eye irritants
(PBN ~ 100 times more so than PAN)

Ref.
De Nevers 2017: Appendix D Elementary chemistry of ozone production
Cooper and Alley 2011: Chapter 19 Air pollution and meteorology
 Acid rain formation
• SO2 (sulfur dioxide), SO3 (sulfur trioxide) and SO42-
(solid sulfates) are important contributors to the
generation of acid rain.

• SO3 readily reacts with water to form H2SO4

(sulfuric acid).

• NOx (i.e. NO + NO2) can be converted to HNO3

(nitric acid) in the presence of oxygen and water.
Greenhouse gases GHG

Atmospheric Absorption

Solar radiation passes rather freely through

earth's atmosphere.

The earth re-emits long wavelength energy.

Some gases like CO2, CH4 , N2O, H2O, O3
and CFCs absorb long wavelengths in the
spectrum window of earth’s radiation.
Effects of climate change/global warming
• More extreme weather events (temperature, storms, floods,
droughts, etc.)
• Length of seasons
• Raised sea level → threatening coastal resources and
wetlands…
• Reducing biodiversity via degradation of natural ecosystems
• Increased risk of wildfires
• Increased risk of certain diseases by producing new breeding
sites for pests and pathogens
• Impact on agricultural regions and woodlands – increased
insect populations and plant disease
• Reducing biodiversity via degradation of natural ecosystems
 Effect on visibility

• Light scattering involves interaction of light with

molecules or particles in such a way that the direction
or frequency of the light is changed.

• Visible solar radiation has wavelengths in the range of

0.4 to 0.8 m, with maximum intensity at 0.52 m.

Visible light and UV light spectrum (unit: m)

UV Violet Blue Green Yellow Orange Red Infrared

0.02- 0.390- 0.455- 0.492- 0.577- 0.597- 0.622- 0.770-500

• An object, a distance d from an observer, is illuminated by a
light beam of intensity I. Light passing through a differential
distance dx is reduced by scattering and absorption by an
amount dI which is proportional to I,

dI/dx = - I (1)
→ I = Io exp (- d) (2)

• The extinction or attenuation coefficient () includes

contributions from gaseous molecular scattering, gaseous
molecular absorption, particulate scattering and particulate
absorption.
 = sg + ag + sp + ap (3)

• All of the coefficients are wavelength dependent.

Light scattering also depends on the scattering angle.
 Scattering and Absorption by gases (sg, ag)

• Light scattering by air molecules

without the presence of particles
and gaseous pollutant is called
Rayleigh scattering. The extinction
coefficient is dependent on the
wavelength.

• Light is absorbed by NO2 due to

photochemical reactions. The
extinction coefficient ag is
proportional to the concentration of
NO2 (Beer-Lambert law).
Scattering by particles (Mie scattering), sp

Light scattering by particulates and aerosols of sizes that are

similar to the visible wavelength
Factors that affect sp include:
• Particle size
• particle density
• concentration of the particles
• refractive index of the particles
 Absorption by particles, ap
• Light absorption by particles in the atmosphere is
mostly confined to absorption by black soot.

• Other particulate matters scatter but do not absorb

significantly.
 Visibility limit Lv
• In general, it is assumed that the lower limit of
visibility for most people occurs when the light
intensity is reduced to 2-6 percent of the un-
attenuated light beam.

• If the visibility limit Lv is obtained with

I/Io = 0.02 (i.e. 2 percent of the un-attenuated light
beam) and substitute into Eqn. (2), then we get
I / Io= exp (- Lv) = 0.02
→ Lv = 3.9/ (4)
Example

If the limit of visibility is defined as the distance when I/I o

reaches a value of 0.04, determine the percent extinction
that occurs in the first: a) 10%, b) 20%, c) 50% of the path
length (i.e. the visibility limit).
• Note: percent extinction is conceptually the same as
plume opacity