PHOTOCHEMICAL SMOG

Industrial Ecology

Dr. Alessandro Tugnoli

a.tugnoli@unibo.it
 Urban Smog

The word smog was initially coined in the 19th century England referring to the
pollution from the industrial activity (smoke + fog).
Today the term to a mixture of numerous gaseous and particulate pollutants
found in the atmosphere as result of human activities.

– London smog (winter smog): is the

result of the combination of extended fog
periods and high concentrations of
particle pollutants (smoke from coal
burning). The adverse health effects from
the inhalation of the particles and of
substances dissolved in the fog droplets
(e.g. sulfuric acid). The formation of
London smog requires stagnant air and
high emissions of particulate matter.
Today is typical of cities like Moscow,
Sofia, Bombay, Beijing

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 2
Earth Resources Engineering
 Urban Smog

– Los Angeles smog (summer

smog or photochemical smog):
it is the consequence of
photochemical reactions among
the pollutants released by human
activity. In the process secondary
pollutants are formed, which are
often more dangerous than the
primary ones (e.g. ozone). The
phenomenon may became
apparent because of the
formation of secondary
particulate matter. The formation
requires stagnant air, pollution
(NOx, VOC, etc.) and as well as
intense sunlight.

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 3
Earth Resources Engineering
 Damage from the tropospheric ozone

In the troposphere ozone is an harmful gas, both for people and the ecosystem
Immediate health effects of ozone include:
• shortness of breath and pain
• coughing and sore or scratchy throat, inflammation and damage the airways
• aggravation of lung diseases (asthma, emphysema, chronic bronchitis, etc.)
• make the lungs more susceptible to infection, scar lung tissues.
Particularly sensitive population: people with lung disease, children, older adults,
Societal consequences: increased school absences, medication use, visits to
doctors and emergency rooms, and hospital admissions. Increase the risk of
premature death from heart or lung disease.
Ozone harms sensitive vegetation (e.g. trees during the growing
season). It can:
• interfere with the ability to produce and store food
• visibly damage the leaves
• increase the susceptibility to disease, damage from insects,
effects of other pollutants, harm from severe weather.
ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA
Industrial Ecology – L04B 4
Earth Resources Engineering
 Formation of tropospheric ozone

Ozone is formed in the troposphere by a photochemical cycle involving NOx

NO2 + h  NO + O Reaction 1 NO is transformed to

NO2 and back, but the
O + O2  O3 Reaction 2
overall concentration
O3 + NO  NO2 + O2 Reaction 3 of NOx is constant
Nitrogen oxides are naturally present in small amounts in the atmosphere, but
large quantities are released in exhausts from combustion processes

O  H 2 O  2 OH  The Volatile Organic Compounds (VOCs) take

part in a complex system of radical reactions,
RH  OH  R  H2O where they get oxidized

R  O2  ROO  The oxidation of the VOC contributes

to the conversion of NO into NO2
ROO   NO  RO   NO2 fueling ozone formation

RO  O2  R' CHO  HO2  And several other ….

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 5
Earth Resources Engineering
 The photochemical cycle of ozone formation

In urban smog
episodes
consternations of
ozone exceeds
120 ppb

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 6
Earth Resources Engineering
 Chain radical reactions: other products

Formation of free organic radicals Organic chain reactions

 
  
R + O 2  RO O
O  R + R C O
 
  
R C O + O 2  R (CO) O O
Olefines + O 3  R C O + R O+ aldehyde
   
O H  R  H 2 O R O+ O 2  aldehyde + HO O

 
  
RO O+ NO  R O+ NO 2
 O  R + O H
 
Aromatics + O 3  non significan t R (CO) O O + NO  R (CO) O+ NO 2
 
 
O H  R  H 2 O R (CO) O  R + CO 2
    
O  R + O H R O+ aldehyde  R C O + ROH
Alchanes + O 3  non significan t
 
O H  R  H 2 O Termination of free organic radicals
 
  
R O+ R C O  chetone + aldehyde
 O  R C O + O H

Aldehydes + O 3  non significan t R O+ NO 2  RONO 2 alchyl nitrate
  
O H  R C O  H 2 O R (CO) O O + NO 2  R(CO)OONO2 PAN = peroxyacetyl nitrate
ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA
Industrial Ecology – L04B 7
Earth Resources Engineering
 ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA
Industrial Ecology – L04B 8
Earth Resources Engineering
 Ozone isopleth diagrams

These diagrams are specific

for each urban region
(different sources of emission,
meteorology, etc.)

NOx-limited regime: in this

region NOx control O3
formation since they are the
limiting reagent

VOC-limited regime: in this

region VOC is a limiting
reagent. An increase in NOx
concentration may lead to a
reduction of O3 concertation,
as NO reacts with O3

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 9
Earth Resources Engineering
 Time evolution of smog pollutants

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 10
Earth Resources Engineering
 Time evolution of smog pollutants

Smog is both a local and regional problem

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 11
Earth Resources Engineering
 Weather conditions promoting smog formation

The atmospheric mixing height is

the height at up to which we can
consider the air to be well mixed
(i.e. uniform concentrations of
pollutants)
Typical values::
- urban areas: 1 km
- in case of temperature
inversion: 500 m

Temperature inversion conditions are possible

with high-pressure systems, where usually
wind speeds are low and skies are clear
When the mixing height is low, we experience
higher concentrations of pollutants in air for
the same emission rates.
ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA
Industrial Ecology – L04B 12
Earth Resources Engineering
 Measuring VOC emissions

The evaluation can be based again ozone formation from i

on the concept of benchmarking of CF 
ozone formation potentials ozone formation from Rif .

Incremental reactivity approach: the incremental reactivity is the incremental

amount of ozone formed per unit mass of a specific VOC added (or subtracted)
from the overall VOC mixture in a given air mass.
[O3 ]
IR  ( for [VOC ]  0)
[VOC ]
The IR value depends on a number of factors (reference VOC mixture,
conditions of the atmosphere, NOx concentration, etc.); different assumptions
lead to the proposal of different scales. The most used one are:
– The maximum incremental reactivity (MIR) scale
– The photochemical ozone creation potential (POCP) scale

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 13
Earth Resources Engineering
 Measuring VOC emissions

– The maximum incremental reactivity (MIR) scale: it evaluates the value of

IR for conditions where it is at the maximum point (e.g. adjusting NOx
concentration) with reference to background conditions typical of USA and
time horizons of about 1 day
– The photochemical ozone creation potential (POCP) scale: it evaluates
the value of IR accounting for a trajectory model (transpiration of the
reactive system across the territory) based on European scenarios and
considering a time horizon of 5 days

In both cases the indicator is calculated from the inventories of VOCs

emissions as:

I MIR  i MIRi  mi I POCP  i POCPi  mi

mi mass of release material i

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Industrial Ecology – L04B 14
Earth Resources Engineering
 MIR values

https://www3.epa.gov/region9/CA-Air-
SIP/California%20Code%20of%20Regulations/Title%2017,%20Division%203,%20Chapter
%201,%20Subchapter%208.6,%20Article%201,%20Sections%2094700%20-%2094701.pdf

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 15
Earth Resources Engineering
 POCP values

Warning: different scales

lead to different evaluations

MIR m-xylene
= 6.28
MIR ethanol

POCP m-xylene
= 2.77
POCP ethanol

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 16
Earth Resources Engineering
 POCP
Example
Compare two products (A and B) from the point of view of photochemical ozone
formation emissions caused by their overall lifecycle.
The analysis of the system produced the flowing lifecycle inventory:
Product A Product B POCP Product A Product B
Emissions kg kg kgEthylene/kg kgEthylene kgEhtylene
CH4 3.36E-03 8.10E-06 6.00E-03 2.02E-05 4.86E-08
NO2 8.78E-04 3.71E-03 2.8E-02 2.46E-05 1.04E-04
NO 6.97E-06 3.38E-05 -4.27E-01 -2.98E-06 -1.44E-05
CO 4.16E-04 1.69E-03 2.70E-02 1.12E-05 4.56E-05
Propane 3.30E-04 2.97E-06 1.76E-01 5.81E-05 5.23E-07
Ethane 1.83E-04 3.29E-04 1.23E-01 2.24E-05 4.04E-05
TOTAL 1.34E-04 1.76E-04

Data form the analysis POCP Calculate the kg ethylene

of the inventory values equivalent for each material
(kg emitted) and sum
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Industrial Ecology – L04B
Earth Resources Engineering
 Further readings

• General information on ozone pollution (EPA website):

https://www.epa.gov/ozone-pollution
• Standard of air quality (WHO website):
http://whqlibdoc.who.int/hq/2006/WHO_SDE_PHE_OEH_06.02_eng.pdf
• Mechanism of ozone formation:
http://www.shodor.org/master/environmental/air/photochem/smogapplication.html

• Collection of MIR values:

https://www3.epa.gov/region9/CA-Air-
SIP/California%20Code%20of%20Regulations/Title%2017,%20Division%203,%20Chapter%201,%20Subchapter%208.6,%20
Article%201,%20Sections%2094700%20-%2094701.pdf

• Collection of POCP values:

https://eippcb.jrc.ec.europa.eu/sites/default/files/2019-11/ecm_bref_0706.pdf

ALMA MATER STUDIORUM – UNIVERSITA’ DI BOLOGNA

Industrial Ecology – L04B 18
Earth Resources Engineering