Air pollution measurements

and emission estimates

Dr. M.A. Elangasinghe

ChE 663 Environmental monitoring
EPC Eng PG Programme

Why do we need to know concentration of pollutants

in ambient air ?
To know the ambient concentrations
To identify emission sources
To see if the concentrations exceed NAAQS (National Air
Quality Standards)
Use this information to come up with solutions to control
emissions
To make the authority aware about the severity of the air
quality issue
For air quality modelling and forecasting

Ambient air quality is monitored in different ways

Fixed air quality monitoring stations (measuring concentrations 24
hours a day)
Mobile monitoring stations not measuring continuously in one
place.
Personal samplers (measuring personal exposure indoor/outdoor)
Passive sampling covering special scale but limited temporal scale.
Temporal coverage
Spatial coverage

Two kinds of air pollution measurements

Ambient measurements- ambient monitoringConcentrations of pollutants in the air the public
breathes
Source measurements- source testingConcentration and or emission rates from air
pollution sources

Source measurements
Flue gas from a stack concentrations of gaseous
pollutants and particulate matter
Emissions from vehicle tail pipe- concentrations of
gaseous emissions and particulate matter

Air pollutant measuring device

A representative ambient air sample

Generally the ambient air monitoring station is located where public has free access
and pollutant concentrations are highest

Other factors influencing an air sampling site

Access to power
Shelter from rain/snow
Constant temperature environment
Easy access for monitoring personals
Protection from vandalism
Free rent

Measurement of stack emissions

Sample inlet- should have a device to exclude
unwanted matter
Gases particle filter
Particles size segregation - PM10, PM2.5
Avoid condensing of gases heating the sampling
probe

Isokinetic Sampling
in
stack sampling of particulates
ISOKINETIC

Iso similar or the same

Kinetic Moving energy, motion

Isokinetic Sampling
in
stack sampling of particulates

Isokinetic Sampling
in
stack sampling of particulates

Gaseous Sampling Principles

Homogenous nature of gases - therefore not necessary to
sample isokinetically
This is because flue gases are presumed to mix thoroughly
Very small molecules therefore not adversely affected by
gravity
Properties of gases are such that a sample can be taken at
several predetermined points along the diameter of the duct
and still be representative with out having to sample
isokinetically

US EPA Standard Sampling methods for

different air pollutants
Reference methods test method that is considered the standard
against which other methods can be tested
Equivalent methods methods that have been tested against
reference method and found to give similar results
Equivalent methods can be easier, simpler and cheaper than
reference method

US EPA Reference Sampling methods for different

air pollutants
Particulate matter (TSP, PM10, PM2.5)
A sample of ambient air is drawn through an inlet designed
to exclude particles larger than a certain size (50 mm,
10mm, 2.5 mm)
These particles are collected on a filter paper for a certain
period ( 3 hr, 8 hr, 24 hr)
The filters gain in weight is divided by measured
cumulative air flow through the filter to determine the
particle concentration.

Sulfur Dioxide
Method 1: West-Gaeke method
A known volume of air is bubbled through a solution of sodium
tetrachloromercurate which forms a complex with SO2.
After several intermediate reactions, the solution is treated with pararosaniline to
form the intensely coloured pararosaniline methyl sulfonic acid.
Concentration is determined in a colorimetric method.
Method 2: Reaction with Dilute NaOH
A known volume of air is bubbled through a dilute solution of NaOH to form
Na2SO3.
Change in NaOH is determined by simple acid base titration.
However , CO2 will cause a interference by reacting with NaOH to form Na2CO3

Ozone

The air is mixed with ethylene, which reacts with ozone in a lightemitting (chemiluminescent) reaction.
The light is measured with a photomultiplier tube.

Carbon monoxide
The concentration is measured by non-dispersive infrared (NDIR)
absorption
Filters are used to obtain a wavelength band at which CO strongly
absorbs.

Hydrocarbon (Non-methane)
The air sample is passed through a flame ionization detector (FID),
where the hydrocarbons burn in hydrogen flame.
Hydrocarbons cause more ionization than hydrogen.
This ionization is detected electronically.

Nitrogen dioxide (NO2)

NO2 is converted to NO, which is then reacted with ozone.
Light from this chemiluminescent reaction is measured.
Since ambient air also contain NO, a parallel sample is run without
conversion of the NO2 to NO, and the resulting NO reading is
substracted from the combined NO and NO2 reading to give the NO2
value
The instrument normally gives NO concentration as well.

Lead
A TSP filter is extracted with nitric and hydrochloric acid to dissolve
lead.
Atomic Absorption spectroscopy is used to determine the amount of
Lead in the sample

Some equivalent methods

Miniature chromatographic systems (mGC) (lab on-a-chip type (LOC)) and

portable analyzers

GC method for CO
A more sensitive method for measuring low background levels is gas chromatography
(GC).
This technique is an automated, semi-continuous method where CO is separated from
water, CO2, and hydrocarbons other than methane (CH4) by a stripper column.
Carbon monoxide and CH4 then are separated on an analytical column, and the CO is
passed through a catalytic reduction tube, where it is converted to CH4.
The CO (converted to CH4) passes through a flame ionization detector (FID), and the
resulting signal is proportional to the concentration of CO in the air.

This method have no known interferences and can be used to measure levels from 0.02 to
45 ppm.

Electrochemical sensors for air pollution measurement

Importance in measuring in special and temporal scales
Precision of measurement / number of measuring sties: compromise
Need of a dense network.

Low cost sensors?

At both ppm and ppb level

Electrochemical sensors principle of operation

Electrochemical sensors principle of

operation
Each sensor contains a cell which incorporates three electrodes
separated by so-called wetting filters.
These filters are hydrophilic separators which enable ionic contact
between the electrodes by allowing transport of the electrolyte via
capillary action.
The electrodes are termed the working, reference and counter
electrodes.

Electrochemical sensors principle of

operation
The working electrode is the site for either reduction or oxidation of
the chosen gas species.

It is generally coated with a catalyst selected to provide a high surface

area and optimized to promote.
reaction with the gas-phase species of choice, which for these devices
enters the sensor by diffusion.

Electrochemical sensors principle of

operation
Electronic charge generated by the reaction at the
surface of the working electrode is balanced by a
reaction at the so-called counter electrode, thereby
forming a redox pair of chemical reactions.
Consequently, the current output by the sensor is
directly proportional to the concentration of the
target gas

Electrochemical sensors principle of

operation
During operation, the working electrode is maintained
at a fixed potential while the potential of the counter
electrode is allowed to float (i.e. it does not have a
fixed potential).
In clean air, the counter electrode has the same
potential as the working electrode
This changes as a current between the electrodes is
generated in the presence of the sensed gas.

Electrochemical sensors principle of

operation
To ensure linearity and sensitivity, the working
electrode potential is set and maintained relative to
an internal reference electrode, which is set at a
constant and stable potential.
The potential difference between the working and
counter electrodes then generates an electric current
which is the output signal of the sensor.

Electrochemical sensors principle of

operation
The current generated by these types of electrochemical sensors is
typically in the range 10s to 100s of nA per ppm of the sensed gas,
and is measured using suitable electronics.

Source measurements
Flue gas from a stack concentrations of gaseous pollutants and
particulate matter
Emissions from vehicle tail pipe- concentrations of gaseous emissions
and particulate matter
A well defined source (eg. Power plant stack is easy to measure)
Poorly defined sources (eg road dust from an unpaved road, CO from
a forest fire) difficult to measure.
EPA has produced a Emission Factors Library

Emission Factors
Pollutants produced per kg of fuel
Vehicles eg: kg pollutant/l or kg pollutants/km

Example 1
The sampling train for SO2 indicates the concentration of SO2 in a stack
is 600 ppm. The pitot tube and manometer in the same figure indicates
that the flow velocity is 12 m/s. The stack diameter is 1.5 m. The stack
gas temperature and pressure are 232 0Cand 1 atm. What is the SO2
flow rate?

Example 2
The emission factor for CO for coal combustion in large furnace is 0.25
kg/tonne.
What is the corresponding emission factor for automobiles in kg
CO/tonne of fuel burned? The permitted CO emissions for new cars is
2.1 g/km. Assume that the fuel economy is 11km/l and the gasoline
density is 0.72 kg/l.

Example 3
We wish to design a rapid response, portable PM10 sampler. The
specifications call for an air flow rate of 1 l/min and a 10 min sampling
time.
(a) If the ambient concentration of PM10 is 25 mg/m3, what is the eight
of the sample you would collect on the filter paper?
(b) What should be the accuracy of the balance that you must use?

Example 4
In a source test, the stack was divided into four sectors, each of which
had the same cross-sectional area. The following velocities and
pollutant concentrations were measured in these sectors.
Section number

Velocity V m/s

Concentration c (mg/m3)

10

500

12

600

14

650

15

675

What is the average concentration in the gas flowing in this stack?

Biomonitoring
Find what is biomonitoring

References
Noel De Nevers, 2000. Air Pollution Control Engineering. McGraw- Hill
Higher Education
Mariusz Marc, Marek Tobiszewski, Bo_zena Zabiegaa, Miguel de la
Guardia and Jacek Namiesnik, 2015. Current air quality analytics and
monitoring: A review. Analytica Chimica Acta 853 (2015) 116126
Jacek Gebicki, 2016. Application of electrochemical sensors and
sensor matrixes for measurement of odorous chemical compounds.
Trends in Analytical Chemistry 77 (2016) 113