University of San Carlos - Department of Chemical Engineering

University of San Carlos - Department of Chemical Engineering

Air Pollution

The presence in the outdoor atmosphere of one or more air contaminants

(i.e., dust, fumes, gas, mist, odor, smoke, or vapor) in sufficient quantities,
of such characteristics, and of such duration as to be or to threaten to be
injurious to human, plant, or animal life or to property, or which reasonably
interferes with the comfortable enjoyment of life or property.
 Historical Overview
University of San Carlos - Department of Chemical Engineering

61 A.D.: the Philosopher Seneca describe “the heavy air of

Rome” and “the stink of the smoky chimneys thereof”

1273: King Edward I was bothered enough by the smoke and

fog mixture that brooded over London to prohibit the burning of
“sea coal”.

Queen Elizabeth I passed law prohibiting the burning of coal

when the Parliament was sitting.

1661: compliance to the law was still not obtained based from
John Evelyn’s pamphlet, Fumifugium: or the Inconvenience of
the Aer and Smoake of London Dissipated, together with some
Remedies Humbly Proposed.
University of San Carlos - Department of Chemical Engineering

1930: an inversion trapped smog in Belgium’s highly

industrialized Meuse Valley.

1952: the London smog disaster made it impossible to ignore ay

longer the serious consequences of air pollution.

1955: the Air Pollution Control Act was introduced in the

United States.
 Air Quality Standards
University of San Carlos - Department of Chemical Engineering

• Those for ambient air quality

• Those for industrial emission

The key references for both ambient and emission standards are:

• WHO (1987) – Air Quality Guidelines for Europe

• TA Luft (1987) – Technical Instructions on Quality Control,
Germany
• EC (European Community) Directives(1987)
• USEPA (1990) – National Air Quality Standards
 Air Pollution System
University of San Carlos - Department of Chemical Engineering

Detector

Atmosphere Response
Emission Source
Source Control
Response
Humans,
Receptor animals,
flora,
materials

Figure 1. Air Pollution System (adapted from Seinfeld, 1986).

 Table 1. Major Air pollutants and their sources.
University of San Carlos - Department of Chemical Engineering

Pollutant Sources of Activity

Power Traffic Domesti Oil Quarrying, Chemical, Manufacturin Waste Agricultur
Statio c refinin mining Pharmaceut g metals, etc. Incinerati e
n heating g ical on
Particulates √ √ √ √ √ √ √

CO √ √ √ √

CO2 √ √ √ √

SOx √ √ √ √ √

NOx √ √ √ √ √

VOCs √ √ √ √ √

O3 √

HC √ √ √ √ √ √

Heavy
Metals
Pb √ √ √ √

Hg √ √ √ √ √ √

Cu √ √ √

Cd √ √ √ √ √ √

Zn √ √ √

Radionuclide √
s
CFCs √ √
 Air Pollutants
University of San Carlos - Department of Chemical Engineering

Primary Pollutants – those emitted by an identifiable source

SO2, CO, NOx, SOx, particulates, hydrocarbons, and metals

Secondary Pollutants – those formed in the atmosphere by

chemical reaction
O3, other photochemical oxidants (peroxyacetyl nitrate)
and oxidized hydrocarbons

Criteria Pollutants – those defined by the USA, EC and WHO

CO, NO2, O3, SO3, PM- 10 (particulate matter of

diameter < 10μm and lead
 Table 2. Properties and pollution significant of criteria pollutants.
University of San Carlos - Department of Chemical Engineering

Pollutant Properties Pollution Significance

Formed during incomplete combustion of
Carbon Monoxide Colorless, odorless gas hydrocarbons. Causes greenhouse effects
ad climatic change.
Significant component of photochemical
Nitrogen dioxide Brown-orange gas
smog and acid deposition.
A secondary pollutant, produced during
Ozone Highly reactive formation of photochemical smog.
Damages flora and materials.
Colorless, choking gas, soluble in Principal component of acid deposition.
Sulfur dioxide H2O to produce sulfurous acid, Damages humans, flora, fauna and
H2SO3 materials.
Coal burning power station, traffic,
Particulate matter < 10 μm in domestic coals, quarrying, and
PM - 10
diameter incineration. Can cause respiratory
problems
Principal source leaded petrol. Also from
lead pipes, quarrying, incineration.
Lead Heavy metal, bioaccumulative
Damages humans and fauna when in
excess.
 Units of Concentration
University of San Carlos - Department of Chemical Engineering

Different ways of expressing concentrations of air pollutants

· ppm (v/v)
· ppb (v/v)
· mg/m3
·mg/Nm3 (Nm3 = normal dry m3 at STP)

At STP (00C and 101.3 kPa), 1 mole of an ideal gas occupies 22.4L

T 101.3kPa
At NSTP (non standard), 1 mole = 22.4
273K P
 Criteria Pollutants
University of San Carlos - Department of Chemical Engineering

Carbon Monoxide, CO
- most abundant of the criteria pollutants
- a product of incomplete combustion of carbonaceous fuel
- about 70% of all CO comes from mobile sources
- can replace oxygen in the bloodstream and forming carboxyhemoglobin (COHb)

Nitrogen Oxides, NOx

The oxides of gaseous nitrogen include: The acids of nitrogen include:

- NO - nitric oxide - HNO2 - nitrous acid
- NO2 - nitrogen dioxide - HNO3 - nitric acid
- NO3 - nitrogen trioxide
- N2O - nitrous oxide
- N2O5 - nitrogen pentoxide
 Nitrogen Oxides, NOx
University of San Carlos - Department of Chemical Engineering

- produced during the combustion of fossil fuels

Fuel NOx - produced in the oxidation of nitrogen containing compounds in the fuel
Thermal NOx - produced in the oxidation of atmospheric molecular N2 at high
temperatures of combustion in the presence of oxygen

Oxidation of NOx
Respiratory problems
2 NO +O2 ⇔2 NO2
NO +O3 →NO2 +O2 Smog

2 NO2 + H 2O → HNO3 + HNO2

3 NO2 + H 2O → 2 HNO2 + NO + O2
Reaction with organic compounds or hydrocarbons

HC + NOx + sunlight → photochemical smog

 Sulfur Oxides, SOx
University of San Carlos - Department of Chemical Engineering

- the product of fossil fuel combustion

- dominant gaseous emission of sulfur is as sulfur dioxide with a small amount of
sulfur trioxide

Sulfuric acid formation from SO2

−
SO2 +OH − →HOSO2
− −
HOSO2 +O2 →SO3 +HO2−
−
SO3− +H 2O →H 2 SO4

Negative Impact of SO2 levels.

25 mg/m3 for 10 min exposures - can impaired bronchial functioning
50 μg/m3 - forest growth is inhibited
 Particulate Matter - PM - 10
University of San Carlos - Department of Chemical Engineering

- emitted in the urban areas from power plants, industrial processes,

vehicular traffic, domestic coal burning and industrial incineration

Table 3. Particulate Matter Size

Group Description Composition Particle Size
WHO USEPA (PM – 10)
Coarse Dust, earth, crust matter > 2.5 μm = 10 μm

Fine Aerosols, combustion particles, < 2.5 μm = 10 μm

recondensed organic and metal
vapors (primary and secondary
pollutants)
 Table 4. Typical values of black smoke and PM concentration
University of San Carlos - Department of Chemical Engineering

Location Annual Concentrations

Black Smoke (μg/m3) Suspended particles by
gravimetry (μg/m3)
Rural 0 –10 0 – 50
Urban 10 – 40 50 – 150
Maxima 100 – 150 200 – 400

Volatile Organic Compounds, VOCs

- comprise hydrocarbons and other substances
- methane is the most abundant
- less abundant but more reactive VOCs include:
ethylene oxide, formaldehyde, phenol, benzene, carbon tetrachloride and CFCs
 Hydrocarbons, HC
University of San Carlos - Department of Chemical Engineering

- one species of VOC emission

- petroleum products
- major sources include traffic, organic chemical production, transport and
processing of crude oil and distribution of natural gas

Ozone, O3

- most abundant oxidant

The irradiation of air containing hydrocarbons and oxides of

nitrogen leads to:
- Oxidation of NO to NO2
- Oxidation of HCs
- Formation of O3
Lead, Pb
- bluish-gray soft metal
- bioaccumulative