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ENVE509/611 ENS 509/611
Air Pollution Measurements
The principal basis of air pollution law in Air Quality Standard
philosophy:
Concentration in the ambient air must be measured to determine
whether that air is indeed safe to breathe.
This means that air quality should meet the NAAQS.
To achieve that: Control and Monitoring of Air pollutants
should be implemented.
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To control pollutant concentrations:
The time, the place, and the amount of emissions
should be regulated.
The emission rates of various sources of air pollutants
must be measured.
Why measurements are needed?
1) Legal Requirements
2) Evaluation of air pollution control devices
Air Quality Measurement
• Measurements of air quality generally fall into three classes:
• Measurements of Emissions - also called source sampling -
Concentrations and/or emission rates from air pollution sources are
measured
• Ambient air measurement, or Ambient Monitoring
Concentrations of pollutants in the air the public breathes. Almost all the
evidence of health effects is based on these measurements
Meteorological Measurement - Measures meteorological factors that
show how pollutants are transferred from source to recipient
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Air Quality Measurement
• Also have:
• Industrial Hygiene sampling - for testing the air
quality inside of factories and places of work
• Residential Indoor sampling - to evaluate the quality
of air in living spaces
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The Ambient Air Quality
Monitoring Program of the
Bureau of Air Quality Planning,
Nevada
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Sampling System
• In a sampling system;
• principle requirments is to obtain a sample that is representative of
the atmosphere at a particular place and time and that can be
evaluated as a mass or volume concentration.
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The major components of most sampling
systems and devices are:
1) An inlet manifold
2) A collection medium
3) An air mover
4 ) Flow measurement device
(1) The inlet manifold transports the material from the
ambient atmosphere to the collection medium or
analytical device in an unaltered condition, all inlets for
ambient sampling must be rainproof.
Inlet manifolds are made out of glass, teflon,
stainless steel, or other inert materials
(2) The collecting medium, may be solid or liquid
sorbent for dissolving gases, a filter surface for collecting
particles, or a chamber to contain an aliquot of air for
analysis.
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(3) The air mover provides the force to create a vacuum
or lower pressure at the end of the sampling system
(pumps).
(4)The flow device measures the volume of air associated
with the sampling system.
Examples of flow devices are mass flow meters (measures the mass flow
rate of a fluid), rotameters (measures flow rate of fluid in closed tube), etc
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Getting the representative sample to the detector:
Many sampling instruments have some kind of devices on the
inlet to exclude unwanted materials.
i.e.: Insects sucked into a particulate sampler nozzle lead to
erroneously high readings.
- Bug screen will exclude all but the smallest of these.
In sampling device, gases
• may condense in the sampling device, or
• Many combustion stack gases have a high water content and will
condense on the walls of an unheated sampling probe. In such cases,
probes are normally heated to prevent this.
• react with the solids they encounter there.
• Acid gases, like SO2 will react with alkaline solids on a filter, thus
increasing the weight of solids on the filter.
A grab sample should be taken in the sample container from appropriate
material that not react with or modify its content. Glass react with
some air pollutants.
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Sampling method:
• Passive sampling
• Active sampling
• Automatic methods
• Remote methods
Passive (static) sampling
• Passive samplers does not involve any pumping. Instead
the flow of air is controlled by a physical process, such as
diffusion (diffusive sampling).
• Passive sampling methods provide reliable, cost-effective air
quality analysis, which gives a good indication of average
pollution concentrations over a period of weeks or months.
• Diffusion tubes are simple passive samplers, which provide
very useful information regarding ambient air quality.
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Diffusion tubes
They are available for a number of pollutants, but are
most commonly and reliably used for nitrogen dioxide
and benzene.
The tubes, which are 71mm long with an internal diameter of 11mm,
contain two stainless steel gauzes placed at one end of a short cylinder.
The steel gauzes contain a coating of triethanolamine, which converts the
nitrogen dioxide to nitrite.
The accumulating nitrates are trapped within the steel gauze, ready for
laboratory analysis.
The tubes are manually distributed and collected, and are analyzed in a
laboratory.
Active sampling
• Active sampling methods use physical or chemical methods to
collect polluted air, and analysis is carried out later in the
laboratory.
• Typically, a known volume of air is pumped through a collector
(such as a filter, or a chemical solution) for a known period of
time. The collector is later removed for analysis.
• Samples can be collected daily, providing measurements for
short time periods, but at a lower cost than automatic
monitoring methods.
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Automatic methods
• The samples are analyzed using a variety of methods including
spectroscopy and gas chromatography . The sample, once
analyzed is downloaded in real-time, providing very accurate
information.
• Automatic methods produce high-resolution measurements of
hourly pollutant concentrations or better, at a single point.
Pollutants analyzed include ozone, NOx, SO2, CO and
particulates.
Remote methods
• Remote optical / long path-analysers use spectroscopic techniques,
make real-time measurements of the concentrations of a range of
pollutants including nitrogen dioxide and sulphur dioxide.
• Lidar or sodar (radar technologies)
• Colorimetry, in which a sample absorbs visible light, is one example of a spectroscopic
method of analysis
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A Representative Sample
In air measurements there are two important problems
1) To obtain the suitable representative sample, (is harder)
2) The determination of the concentration of the pollutant of
interest in it correctly.
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The representative ambient air sample has been the topic of
legal and technical controversy.
Some of the problems:
1. If the sample was taken from inside parking structure, the
result will show great violation of NAAQS, specially CO.
2. If the sample is taken directly across the street from such a
structure, in most cases the concentration will be of magnitude
less than inside the structure.
3. A block away, the concentration will be even less.
4. On the side walk directly adjacent to the structure, the
concentration will be may twice as high as on the opposite side
of the street.
Which of these locations is suitable for obtaining a
sample of ambient air?
•Generally the ambient air sampler should be located
at the place to which the public has free access
where the pollutant concentration is highest.
•This means that all indoor spaces and plant sites,
which the public has no access are excluded.
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•In the previous case, the suitable place is (the traditional place
has been) the roof of county health building or of the county
courthouse.
•However the concentration of the auto-related pollutants
measured there is much lower than at street level at the busiest
intersection downtown.
•There are EPA guidelines for the proper placement of intakes
for air samplers that are to represent ambient air, i.e. CO
measurements must be made at street level, downtown.
In Source Testing: The representative sample problem is
equally difficult
Gas flow in large industrial flue or smokestack may be
steady and well-mixed across the diameter of the stack
representative sample can be taken any time and any place in the stack.
But, most of such stacks have variation in velocities and
concentrations from point to point, and from time to time.
Many seperate measurements must be made and averaged
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Measured local velocities and concentrations in a duct carrying a particle-bearing gas stream.
Ratio of the observed value to the average value.
There are substantial differences in velocity and
particle concentration from place to place in the duct.
Clearly if one had measured the velocities
Uniformity and concentrations at only one point, for example,
increase near the bend on the inside, one would have
computed a much lower overall gas flow rate and
emission rate than the true values.
Even 36 feet farther downstream, the velocity and
concentration data do not indicate that the flow has
become uniform, although the nonuniformity is
much less than it was close to the bend.
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In newer plants, designers sometimes considered the problems of
obtaining a uniform gas flow and have provided access and a
suitable location for the source sampler to place the required
instruments.
In older plants such convenience is rarely the case, and in many
newer plants it is more economical to make the plant efficient,
Procedures adopted by the EPA attempt to standardize the number
and location of the samples on a technically sound basis.
Concentration determination
• Concentration of the pollutant must be determined after
representative sampling.
• For some pollutants this measurement can be done fairly easily by
real-time instruments.
• Most of these operate optically;
• the sample passes through a cell in which a light beam of a suitable
wavelength is absorbed by the pollutant of interest, or the pollutant is
allowed to enter a fast, light-producing chemical reaction with some
reagent and the resulting light emission is measured.
• However, some other pollutant called an interference also absorbs or
emits at the wavelength of interest.
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The interferences problem in air pollutants measurements is not trivial.
• I.e: Measuring SO2 gas in nitrogen gas is easy, due to the reaction
• SO2 + 2NaOH → Na2SO3 + H2O
• And measuring the change in NaOH (sodium hydroxide) concentration by simple acid
base titration. (Na2SO3 sodium sulphate)
• However, if the problem is to measure SO2 in air, CO2 in the air will also react as the
following reaction (Na2CO3 sodium carbonate):
• CO2 + 2NaOH → Na2CO3 + H2O
• the measured change in NaOH concentration will be due partly to the S02 and partly
to the C02. In this case, the C02 concentration in the air is known, so a correction
could be made in principle;
• in the case of concentration of interfering component not known, uncertainty in the
measurement is also unknown.
Averaging
• We are measuring ambient air quality with real time instruments,
the average concentration over some period of time should be calculated
Compare with standards
1
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 = 𝑐𝑎𝑣𝑒 = 𝑐 𝑑𝑡
∆𝑡
c=the instantaneous concentration indicated by the instrument
t= the time of measurement
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• Most of real-time instruments present their results as an
electronic signal that can be easily averaged by built-in
electronics for any suitable chosen averaging time.
• The older instruments for gases as well as the current
instruments for particulates are not real time instruments,
but rather are averaging instruments.
• For example:
In EPA-required method for PM2.5 sampling is PM2,5 sampler, it
consists of:
• Special inlet that exclude particles >2.5 micron in diameter,
• A filter
• A fan
• A flow measuring device
• Suitable housing
Preweighted filter is placed in the filter holder and
• Air is sucked through the filter for 24 hours at a measured rate
increase in filter weight
Average Concentration =𝑐𝑎𝑣𝑒 =
air flow rate x ∆t
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Example 4.2. (page 69)
• A PM2.5 sampler ran for 24 hours at an average flow rate of 16.7 L/min.
The tare weight of the fresh filter was 0.1400 g, and the gross weight of
the filter, dried to the same humidity as the fresh filter, was 0.1405 g.
What was the average PM2.5 concentration in the air drawn through the
sampler?
Some older measuring schemes for gas pollutants have the principles
of:
• 1- A measured volume of gas passing through a bubbler that
contained solution that react specifically (no interference) with the
gas to be measured.
• 2- Titration of the solution to determine the concentration of the
gas
• 3- Or measuring the color of the solution, spectrophotometrically.
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• For the calculation of concentration:
Weight change of the filter is replaced by the
(change in number of equivalents of reagents reacted) X (the molecular weigth ratio)
or
(color of the solution) x(some suitable weigth conversion factor)
Standard Analytical Methods
EPA has standard sampling methods for various
pollutants. (often one for source sampling and other for
ambient air sampling)
These methods define the pollutant.
i.e. in ambient SO2 is defined as that material which is detected
by the SO2 method shown in Table 4.1 (text book: ), The West-
Gaeke method.
However, in powerplant stack SO2 is defined as that material
that is detected by (Method 6, Fig. 4.5) which is chemically quite
different from the West Gaeke method.
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In EPA terminology, for each air pollutant, there is a
•Reference methods, is considered the standard and other
methods are tested against it .
•Equivalent methods, which have been checked against the
reference method and found to give similar results.
• State and local ambient monitoring agencies mostly use
the equivalent methods, which are generally simpler,
cheaper, and easier to use than the reference methods
Pollutant Reference method – for ambient air
Particulate matter Filter-based mass masurements
SO2 Waste-Gaeke method
Ozone Ultraviolet photometry
CO NDIR
NO2 chemioluminscence
HC Flame ionization
Lead Atomic absorption spectroscopy
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Reference methods from Table 4.1
• Particulate Matter, TSP, PM10, PM2.5
• 3 standard methods,
• differ in the excluding in the inlet designed to exclude particles larger
than a certain size, 50 µm, 10 µm, 2.5 µm .
• Then particles are collected on a filter for 24 hours.
• The filters gain in weight is divided by the measured cumulative
air flow through the filter to determine the particle
concentration. (example 4.2, Averaging the results (weight
difference))
SO2: West-Gaeke Method
•Known volume of air bubbled through a solution of sodium
tetrachloro mercurate (TCM), which forms a complex with SO2.
• After several reactions, solution treated with pararosaniline to
form intensity colored pararosaniline methyl sulfonic acid.
•The concentration is determined colorimetric, at wavelength
548 nm.
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Ozone (chemioluminscence by etheylene)
•The air is mixed with ethylene, which reacts with ozone in a
light-emitting reaction (chemioluminscence reaction).
• Chemiluminescence is the emission of light with limited
emission of heat (luminescence), as the result of a chemical
reaction.
•The light is measured with a photomultiplier tube related to
concentration of the Ozone reacted.
CO
•It is measured by non-dispersive infrared absorption (NDIR).
•Non-dispersive mean that the IR is not dispersed by a prism or
grating into specific wavelengths; rather filters are used to
obtain a wavelength band at which CO strongly absorbs.
•Absorption of IR radiation by CO
•Detection due to energy difference signal
Note:
•This method is sensitive for water vapor interferences.
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NDIR analyzer
NO2
• NO2 is converted to NO which is then reacted with O3
•The light from chemioluminscence reaction is measured.
• Ambient air contains NO (often more than NO2), so a parallel
sample is run without convertion of the NO2 to NO.
• The resulting NO reading is subtracted from the combined NO
and NO2 reading to give NO2 value.
•The instrument normally reports the NO concentration as well
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Hydrocarbons (non methane)
•Gas is passed through FID (Flame Ionization
Detector), where HCs is burned in a hydrogen flame.
•HC cause more ionization than H2 (Dihydrogen) and this
ionization is detected electronically.
•Part of the sample is diverted to gas chromatograph
(GC) where methane CH4 is seperated from the other
gases and then quantified.
•Its concentration is substracted from the total HC value
from the FID.
Note:
•HC determination is important even it is not NAAQS, for ozone control program.
Lead
• A TSP filter extracted with HNO3 (Nitric acid) and HCL (Hydrolic acid) to
dissolve the lead.
• Atomic absorption spectroscopy (AAS) used to determine the
amount of lead in the extract.
• AAS: is a spectro-analytical procedure for the qualitative and
quantitative determination of chemical elements employing the absorption
of optical radiation (light) by free atoms in the gaseous state.
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Determining pollutant flow rate
• The mass flow rate of pollutant is the product of the
concentration in the gas and the molar or mass flow rate of the
gas
Pollutant molar flow rate= (molar flow rate of gas)X(pollutant molar concentration in gas)
Pollutant flow rate= (molar flow rate of gas)X(pollutant mass (or molar) concentration in gas)
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Isokinetic sampling
•In stack sampling for particulates, one must maintain isokinetic flow into the sampling probe.
If the velocity in the nozzle exceeds that in the stack
then the gas stream lines will bend into the nozzle, and
the inertia of the particles will carry some of them past the
nozzle even though the gas they were in will be collected,
and thus the measured concentration will be less than the
true concentration.
If the velocity in the nozzle is less than the velocity in the
stack then the gas streamlines will bend away from the
nozzle and their inertia will carry some particles into the
nozzle, away from the gas that accompanied them. The
measured concentration will then be larger than the true
one
If the gas velocity inside the sampling probe is the same
as the gas velocity in the stack from which the sample is
being taken, the sampling condition is isokinetic
measured concentration (cm) will equal the true concentration (ct).
Emission factors
• Emission testing is expensive.
• For a simple, well-defined sources (e.g., a powerplant stack), it
can be tedious, but it is not difficult
• For a poorly defined sources (e.g., road dust from an unpaved
road or from a forest fire), reliable results are difficult to get.
• Furthermore, such testing is only possible after the facility is in
place; often we may want to know what the emission
from a new facility will be before it is built.
• To meet these needs, the EPA has produced a very useful set of
emission factor document (AP-42).
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Emission Factors
?
An emissions factor is a representative value
that attempts to relate the quantity of a pollutant
released to the atmosphere with an activity
associated with the release of that pollutant
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EPA Chief (Clearinghouse for Inventories and Emissions
Factors)
https://www.epa.gov/chief
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• Emission factors
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• Often we want to know what the emissions from a new facility
will be before it is built.
• Emission testing is expensive
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