EVT 714

ENVIRONMENTAL SAMPLING AND

ANALYSIS

EMISSION MONITORING AND

SAMPLING
EMISSION MONITORING AND SAMPLING
OUTLINE OF CONTENTS
1. INTRODUCTION

2. EMISSION STANDARD

3. DRY STANDARD CUBIC METER (dscm)

4. GAS FLOW MEASUREMENT

5. MONITORING OF EMISSION

6. IN-SITU CONTINUOUS EMISSION MONITORING

(CEMs)
7. EXTRACTED CEMs.

2
INTRODUCTION
 Generally the detection of air pollutants emit from
plants performed on-line by in-situ continuous
emission monitoring (PM, SO2, NOX and CO).
 However stack sampling and monitoring extracted
continuous monitoring need to be done in order to:
 Confirm that the on-line measurement is correct.
 To examine applicability of new detector or facilities
functioned as design.
 To examine any release of pollutants in case of
public complain.
 To determine pollutants not measured on-line such
as mercury, Ammonia, HCl etc. 3
EMISSION STANDARD

Emission Standards

Emission standards for stationary sources are as

prescribed in the Environmental Quality Act (EQA), 1974
under the Environmental Quality (Clean Air) Regulations
1978 and its subsequent revisions.

4
EMISSION STANDARD

5
6
7
EMISSION STANDARD AND REQUIREMENT

 Emission control governed by Environmental

Quality Clean Air Regulation 2014
• Understanding terms and unit describing
emission from stationery sources.
• Emission monitoring normally based on US-
EPA reference method.
 First let understand term and standard
condition used to describe the concentration of
pollutants emission.

8
EMISSION REGULATION – DRY STANDARD
CUBIC METER (DSCM)

 EPA standardized most of its emission at 25oC

for stack sampling and pressure at 1 atm (760
mmHg).
 Emission standard show emission standard that
are written in terms of a concentration include
the phrase, “corrected to 7% O2”.

• DSCM - dry standard cubic meter – volume at

standard temperature and pressure without
moisture.
9
EMISSION REGULATION – CORRECTED TO 7%
OXYGEN

10
EXAMPLE CALCULATION OF DSCM AND
CORRECTED TO 7% O2

 Example
 A source must meet a standard for PM of 30 mg/dscm
corrected to 7% O2 . An in situ stack monitor measures 22
mg/m3 at stack conditions. The stack gas is at 1 atm and
200oC, and contain 12% moisture and 4% O2 (note
measurement technique for O2 automatically reports the O2
at dry conditions). Is this source meeting the standard.

11
EXAMPLE CALCULATION OF DSCM AND
CORRECTED TO 7% O2 (CONTINUED)

12
GAS FLOW MEASUREMENT
Device used – Pitot tube
Based on designed by Henri Pitot 1732

1/2
2∆𝑃
V = ρ

P1

L-shaped Pitot Tube
Where ∆P pressure
difference in unit N/m2
, v is velocity in unit
m/s and ρ is density of
the flu gas. In unit
kg/m3 .
13
GAS FLOW MEASUREMENT
STANDARD AND ACTUAL AIR VOLUME

THE gas volume is temperature and pressure

dependence. Therefore in expressing the emission
concentration one need to apply Ideal Gas Law to do
correction on the gas volume as the temperature or
pressure change.
Rational
Stack temperature about 200 – 250oC
Standard temperature 25oC or 298K

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GAS FLOW MEASUREMENT
APPLICATION OF IDEAL GAS LAW

PV = nRT
Unit???
P = absolute pressure, unit in atm.
V = volume in liters
n = in gmol
R = ideal gas law constant, for this set of unit 0.08206 L-
atm/gmol-K (list of various values of R given in the
Table)
T = absolute temperature

15
GAS FLOW MEASUREMENT - APPLICATION
OF IDEAL GAS LAW (CONTINUED)
For gas flow measurement
A fixed number of moles of gas a certain
temperature and pressure occupies a certain
volume. If the pressure and temperature of this
fixed number of moles of gas are changed, then
the new volume can be easily calculated.

𝑃𝑉
= nR
𝑅𝑇
Since n is constant in this case, the new volume
can be calculated:
𝑃1 𝑉1 𝑃2 𝑉2
=
𝑇1 𝑇2
𝑃1 𝑇2
V2 = V1
𝑃2 𝑇1
GAS FLOW MEASUREMENT - APPLICATION OF
IDEAL GAS LAW

EXAMPLE
A sample stream of dry gas is being withdrawn from a
stack. The stack gases are at 200oC and 730 mm Hg. The
stream flows through a heated filter, a set of cooled
impingers, a small air pump, and then through a flow
meter. The rate of flow is determined to be 30.0
liters/minute at 20oC and 790 mm Hg.
(a) Calculate the actual volumetric flow rate through the
filter (at 200oC and P = 730mm Hg.
(b) If 1.42 mg of solid particles are collected on the filter
in 30 min., calculate the concentration of particles in
the stack gas ( in µg/m3). 17
GAS- FLOW MEASUREMENT - EXAMPLE
APPLICATION OF IDEAL GAS LAW

790 473
(a) Qfilter = (30.0) = 52.4 liters/min
730 293
(b) Total volume of gas sampled (at stack
condition)

𝐿 1𝑚3
52.4 𝑥 𝑥30 𝑚𝑖𝑛 = 1.572 m3
𝑚𝑖𝑛 1,000𝐿

1.42 𝑚𝑔 103 µ𝑔
Cpart. = 𝑥 = 903 µg/m3
1.572𝑚3 1𝑚𝑔
GAS FLOW MEASUREMENT
Gas flow rate can be measured by various method.
Such devices need to be calibrated, then the actual
flow rate can be measured.

𝑇𝑎 𝑃 𝑀𝑊
Qa = Qi x 𝑥 𝑐 𝑐 where Qi indicated flow
𝑃𝑎 𝑀𝑊𝑎 𝑇𝑐
rate
a= actual conditions and
c= calibration
condition

Example application of the equation:

QUESTION
You have an orifice meter that was calibrated for air
at 70oF and 1 atm. You are using it to measure air
flow, and you get an indicated reading of 25.0 ACFM
at 100oF and 1.1 atm. What is the true gas flow rate in
SCFM?
GAS FLOW RATE
SOLUTION

Substituting into the equation to correct the

indicated flow rate to an actual flow rate, and
then convert the actual flow rate (using ideal
gas law) to an equivalent standard flow rate,
we get;
Qa = 25.0CFM 560𝑅/1.1 1.0 𝑎𝑡𝑚/530𝑅 0.5
= 24.5 CFM

1.1
Qs =24.5 CFM x 537𝑅/560𝑅 𝑥 = 25.8 SCFM
1.0
MONITORING OF EMISSION
There are two types of continuous emission
monitoring to be perform at the stationary
sources:

i) In-situ CEMs
ii) Extracted CEMs
MONITORING OF EMISSION
In-situ CEMs
 In situ systems have at least some part of their
analysis subsystem mounted in the stack in direct
contact with the flue gas. Because they perform
analysis at the stack, in-situ systems neither condition
the sample gas nor transport it to a remote analytical
unit.
 The lack of conditioning and transport subsystem
indicates that in-situ CEMs design require
substantially less equipment than do extractive CEMs
design.
 However the analytical subsystem of these CEMs 22
generally expected to a more harsh environment than
those of extractive system.
 MONITORING OF EMISSION
In-situ CEMs
There are generally two approaches taken for in-
situ system design:
• Path analyzer – the approach that is to monitor
across a certain path of stack gas. EPA
distinguish between path and point monitoring
by the percentage of the stack diameter ( or
equivalent diameter for non-circular duct)
represented by the measurement path. An
instrument that measures gas concentrations
along a path which is greater than 10% of the
diameter is said to be path analyzer.
• Point analyzer – If the measurement path is less
or equal to 10% of the diameter, the instrument
is considered a point analyzer.
CONTINUOUS EMISSION MONITORING
The in-situ-CEM system shall comprise of the following:
a) Instrumentations and programs that will determine & analyze
and quantify the concentration of the specified pollutants in the
gas stream.
b) Instrumentations and/or programs that will determine the flow
rate of the gas stream.
c) Instrumentations and programs that will record and process
the information produced and produce electronic and printed
reports showing the emission rate of the specified pollutant with
the time resolution.
d) Quality Assurance programs and Quality Control procedures
to ensure that all pollutant measurement, instrument verification
and reporting activities are performed adequately.
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IN-SITU CEMS REQUIREMENT

The in-situ CEMs requirement specified in the

following documents:

1. Volume 1 – Guideline for the Continuous

Emission Monitoring System for industrial
premises and facilities
2. Volume II - Guideline for the Continuous
Emission Monitoring System – Data interface
System (CEM-DIS) for industrial premise and
facilities
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TYPE OF EMISSION MONITOR IN-SITU
Type of gases monitor in-situ include:
 NOx

 SO2

 CO

 O2

 Total particulate

 Opacity

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 NOX IN-SITU CEMS
• Nitrogen oxides continuous emission monitors (CEMs)
provide a direct indication of the performance of the NOX
control techniques being used. Chemiluminescence analyzers
are the most common type of NOX monitors presently used in
CEM systems.
• Other major components of the CEM system include the
sample acquisition and conditioning equipment, the
calibration equipment, and the data acquisition system.
• To ensure that the NOx emission data are accurate and
representative, the CEM system should be installed in
accordance with U.S. EPA specifications in 40 CFR Part 60.
The CEM system should be routinely calibrated and tested in
accordance with Appendix F of Part 60.
NOX IN-SITU CEMS
The NOxCEM system should have the capability to compile the
following data necessary to confirm proper system operation.
Analyzer and Data Acquisition System
• Daily zero and span checks
• Fault lamps on the analyzer panel and/or codes on the
data acquisition system
• Data acquisition system operation

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31
CO IN-SITU CEMS

 Carbon monoxide (CO) concentrations can be monitored by

CEMs. Non-dispersive infrared (NDIR) type instruments are
usually used for CO monitoring. These extract a sample gas
stream in a manner similar to that described for NOx monitors.
The installation and design requirements for CO CEMs is also
similar to NOx monitors. The applicable design specification
for CO CEMs is in EPA Performance Specification

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CO IN-SITU CEMS

 The use of CO CEMs provides a means to detect high carbon

monoxide concentrations caused by combustion upsets and/or
overly aggressive attempts to reduce NOxemissions.
 CO instruments are useful because they often provide an early
warning concerning conditions that could cause increased
emissions of partially oxidized organic compounds.
 The poor combustion conditions that cause CO formation can
also contribute to fireside fouling of heat exchange surfaces in
the boiler or incinerator.

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O2 IN-SITU CEMS
 Most combustion systems limit oxygen concentrations in order
to avoid localized high concentrations in the peak temperature
zones where thermal where thermal and fuel NOX can form.
 However, air infiltration into the combustion system can
increase to substantial levels due, in part, to the frequent
thermal expansion and contraction of the combustion system
during start-up, shut down, and operating rate changes. The
oxygen entering with the infiltrating air can increase the
thermal NOX formation rates.

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O2 IN-SITU CEMS
 Improperly adjusted burners can have oxygen levels above the
intended levels causing high NOx formation rates because of
the availability of the oxygen in the peak temperature zones.
 In reviewing the oxygen concentration data, it is also important
to note that the oxygen concentrations are often not spatially
uniform at the measurement location. Problems caused by air
infiltration or burner adjustment can create stratified gas
streams with substantial differences in oxygen concentrations.
 Oxygen monitors sampling gas at only one or two locations in
the duct or breeching might not accurately characterize the
variations in the oxygen concentration across the gas stream.
Accordingly, to the extent possible, the the entire breeching or
duct should be sampled with an oxygen monitor.
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OPACITY IN-SITU CEM
 Particles entrained in a gas stream scatter visible light. The extent to
which the intensity of the light beam is reduced is described by the
Beer-Lambert law.
 The most convenient way to express the reduction in light intensity is
the opacity.
Opacity = 100 - Transmittance (%)
 If there is no reduction in light intensity, the transmittance is 100%
and the opacity is zero.
 If all the light is scattered, the transmittance is zero and the opacity is
100%.
 High opacity is generally associated with high particulate matter
concentrations.
 Accordingly, opacity is used as an indirect indicator of particulate
emissions in some regulations and as a separately enforceable
requirement in other regulations.
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PARTICULATE MATTER IN-SITU CEM

 There are a variety of instruments that are being

developed and used to provide a continuous
measurement of the particulate matter mass emissions
(Particulate CEMs).
 There are four different types of instruments being
evaluated for possible application in future emission
monitoring applications.
• Light scattering instruments
• Beta gauge instruments
• Scintillation monitors
• Oscillating microbalance instruments
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PARTICULATE MATTER IN-SITU CEMS
Light Scattering
 The light scattering instruments operate on entirely
different principles than opacity monitors used to
measure opacity. The light scattering particulate matter
CEMs measure the quantity of light that is scattered in
specific directions from the surfaces of particles
passing through the detection area. The detection area
is a small zone located several feet within the stack or
duct being monitored. Unlike transmissiometers used
to measure opacity, light scattering particulate matter
CEMs do not use a light beam passing across the
entire stack or duct.

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PARTICULATE MATTER IN-SITU CEMS
 The scattered light energy received at the detector is
amplified to provide a signal proportional to the
particulate matter mass in the sensor zone.

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PARTICULATE MATTER IN-SITU CEM
Scintillation
• Scintillation particulate CEMs operate in a
manner that is conceptually similar to
transmissometers.
• The scintillation monitors generate a light beam
that is projected across the stack or duct being
monitored.
• Like all light scattering instruments, the
scintillation instrument is moderately sensitive to
the particle size distribution.
• It also can not distinguish between solid
particles and droplets of uncombined water. All
particles and droplets that are capable of
scattering light are detected with this instrument.
PARTICULATE MATTER IN-SITU CEM

41
PARTICULATE IN-SITU CEM
 However, unlike transmissimeters, the wavelength of the
scintillation instrument light source is modulated at a high
frequency. The instrument detector obtains a frequency
dependent light signal that is proportional to the mass
concentration of particulate matter passing through the
light beam.
 Like all light scattering instruments, the scintillation
instrument is moderately sensitive to the particle size
distribution. It also can not distinguish between solid
particles and droplets of uncombined water. All particles
and droplets that are capable of scattering light are
detected with this instrument.
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PARTICULATE MATTER IN-SITU CEM
Beta Gauge
 A beta gauge instrument collects a sample of particulate
matter on a filter and exposes the sample to low levels of
beta radiation.
 The amount of radiation absorbed by the sample is
proportional to the mass of solids on the filter.
 All beta gauge instruments extract the sample from one
or more points in the stack or duct being monitored. The
samples are accumulated on the filter surface for periods
ranging from 1minute to more than twenty minutes
depending on the concentration of solids in the gas
stream.
 Once there is sufficient sample, the sample gas stream is
interruped and the sample and filter are exposed to beta
radiation. 43
PARTICULATE MATTER IN-SITU CEM
Beta Gauge
 A beta ray detector below the filter is used to compare
the energy levels with the collected solids with a baseline
energy level obtained when the filter was clean.

44
 MONITORING OF EMISSION

Extracted CEMs
• Extracted systems withdraw flue gas from the
stack, condition it and transport the gas to
the analysis section which is usually at some
convenient site within the plant.
• It is carried out on periodic basis in order to
examine applicability of in-situ CEM.
• To examine emission of pollutants not
monitored in-situ CEM such as mercury.
• US-EPA are the common method as reference
method for the extracted CEM program.
EMISSION MONITORING

 Mostly done by In – Situ Continuous Emission

Monitoring (CEM) technique.
 However in certain circumstances – should be done by
non-in situ method – in order to examine the
applicability of the in-situ CEM method.
 Normally performed based on US EPA standard
method.

46
SAMPLING LOCATIONS

Air in stack is not uniform, it is turbulent , therefore it is

very difficult for a practitioner to determine one
sampling point that can represent the average velocity of
the entire stack. The practice is to collect samples at
more than one sampling point.

There are two type of duct formation

i. Circular
ii. Rectangular duct.

47
US-EPA REFERENCE METHOD FOR
EMISSION MEASUREMENT
All the method listed in 40CFR Part 60 Appendix A
Examples of the method are as below:
Method 1--Sample and velocity traverses for stationary sources
Method 1A--Sample and velocity traverses for stationary sources with small
stacks or ducts
Method 2--Determination of stack gas velocity and volumetric flow rate (Type S
pitot tube)
Method 2A--Direct measurement of gas volume through pipes and small ducts
Method 2B--Determination of exhaust gas volume flow rate from gasoline vapor
incinerators
Method 2C--Determination of stack gas velocity and volumetric flow rate in small
stacks or ducts (standard
pitot tube)
Method 2D--Measurement of gas volumetric flow rates in small pipes and ducts
Method 3--Gas analysis for carbon dioxide, oxygen, excess air, and dry molecular
weight
PARTICULATE MATTER (PM) EMISSION
There are two main test procedures used for
measuring total particulate emissions:
• U.S. EPA Methods 5
• U.S. EPA Method 17.

They differ with respect to the means used to filter

the particulate from the sample gas stream.

IMPORTANT NOTES ON PM SAMPLING

The procedure has to be performed iso-kinetically

METHOD 5

50
Method 17
PARTICULATE MATTER EMISSION
Method 5
• The U.S. EPA Method 5 sampling train is shown in Figure
8-15. The filter is kept in a hot box which must be
maintained at 248 ± 25°F. The probe is also heated to this
temperature.
• The total quantity of particulate matter captured during
the emission measurement run is determined by adding
the weight gain of the filter and the quantity of solids
washed from the nozzle, the probe, and the front half of
the filter holder.
• Only pollutants that are in a solid and/or liquid form at
248 ± 25°F are captured in these areas. Vapor phase
materials that can pass through the probe and filter at
this temperature are captured in the impingers. The
impinger "catch" is not usually counted as particulate
matter.
PARTICULATE MATTER EMISSION
Method 17
• The U.S. EPA Method 17 sampling train is shown in
Figure after Method 5. In this case, the particulate
matter filter is mounted in a holder that is inserted
in the stack. With this approach, the filter is at
approximately the same temperature as the stack
gases being tested.
• The particulate matter concentration measured
using U.S. EPA Method 17 can be different than
that measured by U.S. EPA Method 5 since
particulate matter can both condense and vaporize
depending on the temperature.
PARTICULATE MATTER EMISSION

 The total particulate matter emissions calculated from

U.S. EPA Method 5 and Method 17 data are based on
measurements from U.S. EPA Methods 2 through 4,
which are conducted simultaneously.
 Method 2 for example developed for determination of
stack gas velocity and volumetric flow rate (type S pitot
tube).
 Method 4 developed for determination of moisture
content in stack gas.

54
ISOKINETIC SAMPLING FOR PM
• The sample gas flow rate through the particulate
matter sampling train must be adjusted as the
probe is moved from point to point during
traversing of the sampling location.
• Due to the inertial properties of the particulate
matter, the velocity of the sample gas entering the
end of the probe must be approximately equal to
the velocity of the gas stream at the sampling point.
• When the velocity of the gas entering the sampling
nozzle is exactly equal to the velocity of the gas
stream, isokinetic sampling is achieved.
 ISOKINETIC SAMPLING FOR PM
• If the velocity into the nozzle is too high, the gas will be
pulled in from too large of an area.
• This is called overisokinetic sampling - It leads to lower-
than-actual particulate matter measurements since many of
the large particles fly past the sample probe as the gas is
drawn into the probe.
• Gas velocities into the nozzle that are too low can also
cause significant errors. This is termed under-isokinetic
sampling.
• Under-isokinetic sampling results in greater-than-actual
particulate matter concentrations since large particles fly
into the probe as part of the gas stream flows around the
probe.
• During most particulate matter emission tests, the sampling
velocities must be maintained at an average of 90% to 110%
of the isokinetic rate in order to avoid these errors.
ISOKINETIC SAMPLING

57
PARTICULATE MATTER PM10 EMISSION
 The PM10 is determined based on the US-EPA Method
201 and Method 201A . The following picture show the
sampling train for the PM10 determination.

58
PARTICULATE MATTER PM10 EMISSION

• The gas stream enters through a nozzle, which

is identical to that used in Methods 5 and 17. The
sample gas then enters a cyclone which
removes the particulate matter larger than 10
mm.
• The performance of the cyclone is strongly
dependent on the gas flow rate. Accordingly,
Method 201A includes specifications concerning
the acceptable minimum and maximum gas flow
rates for the sampling train.
• During a Method 201A test, the isokinetic range
is 80% to 120%.
 PARTICULATE MATTER PM10
EMISSION
• It is important to note that the TSP or SPM
no more in the list of criteria air pollutant of
US-EPA in favor of PM 10. This is known as
PM10 standard.
• In 1996 the US-EPA again revise the
standard to include the PM2.5.
PARTICULATE MATTER PM2.5 EMISSION
 In 1997, the U.S. EPA promulgated new NAAQS
concerning PM2.5 PM.
 The test procedure being developed for PM2.5 is an
extension of Method 201A used for the measurement of
PM10 PM.
 This sampling system consists of a nozzle, a PM10 cut
size cyclone identical to the one used in U.S. EPA
Method 201A, a PM2.5 cut size cyclone, and a filter.
Using this sampling system, the PM captured in the gas
stream is separated into the following size fractions.
• Super coarse PM larger than 10 µm
• Coarse PM >2.5 µm and equal or less 10 µm.
• Fine PM equal to or < 2.5 µm
62
PARTICULATE MATTER PM2.5 EMISSION

 One of the advantages of this sampling approach is that it

is possible to obtain emissions data in the PM10 and PM2.5
size categories simultaneously.
 Furthermore, separate emission measurements are
obtained for the fine and coarse fractions of PM . The10

sampling train can be used to acquire sufficiently large

sample quantities to facilitate detailed chemical analyses.
 This is important because there is increasing interest in the
specific chemical species present in the fine particulate
matter fraction.

63
SO2 AND OTHER SULFUR COMPOUND FROM
STATIONERY SOURCES

• Generally the SO2 measured by in-situ

CEM. However, extracted sample need to
be collected for laboratory analysis one a
while in order to examine the effectiveness
of the in-situ CEM.
• Method employed for the measurement
can be:
Method 6 – determination of sulfur
oxide from stationary sources.
Method 8 - Determination of sulfuric acid mist
and sulfur dioxide emissions from stationary sources
SO2 AND OTHER SULFUR COMPOUND FROM
STATIONERY SOURCES

Principle

A gas sample is extracted from the sampling point in the

stack. The sulfuric acid mist (including sulfur trioxide) and
the sulfur dioxide (SO2) are separated. The SO2 fraction is
measured by the barium-thorin titration method.

65
SO2 AND OTHER SULFUR COMPOUND FROM
STATIONERY SOURCES

Applicability

• This method is applicable for the determination of

SO2 emissions from stationary sources. The
minimum detectable limit of the method has been
determined to be 3.4 milligrams (mg) of SO2/m3 .
Although no upper limit has been established, tests
have shown that concentrations as high as 80,000
mg/m3 of SO2 can be collected efficiently in two
midget impingers, each containing 15 milliliters of 3
percent hydrogen peroxide, at a rate of 1.0 liter/min
for 20 minutes. Based on theoretical calculations,
the upper concentration limit in a 20-liter sample is
about 93,300 mg/m3.
SO2 AND OTHER SULFUR COMPOUND FROM
STATIONERY SOURCES

Applicability
• Possible interferents are free ammonia, water-
soluble cations, and fluorides. The cations and
fluorides are removed by glass wool filters and
an isopropanol bubbler, and hence do not
affect the SO2 analysis. When samples are
being taken from a gas stream with high
concentrations of very fine metallic fumes
(such as found in inlets to control devices), a
high-efficiency glass-fiber filter must be used
in place of the glass wool plug (i.e., the one in
the probe) to remove the cation interferents.
SO2 AND OTHER SULFUR COMPOUND FROM
STATIONERY SOURCES

68
NOX FROM STATIONARY SOURCES
Similar to SO2 determination the NOx normally
performed by in-situ CEMs but a need may arise for
extracted determination.

Reference method applied

Method 7 – Determination of NOx from stationary

sources

69
NOX FROM STATIONARY SOURCES
Method 7
Principle
A grab sample is collected in an evacuated flask
containing a dilute sulfuric acid-hydrogen
peroxide absorbing solution, and the nitrogen
oxides, except nitrous oxide, are measured
colorimeterically using the phenoldisulfonic acid
(PDS) procedure.
NOX DETERMINATION FROM STATIONARY
SOURCES

Applicability
 This method is applicable to the measurement of
nitrogen oxides emitted from stationary sources. The
range of the method has been determined to be 2 to
400 milligrams NO (as NOx ) per dry standard cubic
meter (dscm), without having to dilute the sample.
 Absorbing Solution. Cautiously add 2.8 ml
concentrated H2 SO4 to 1 liter of water. Mix well and
add 6 ml of 3 percent hydrogen peroxide, freshly
prepared from 30 percent hydrogen peroxide solution.
The absorbing solution should be used within 1 week
of its preparation. Do not expose to extreme heat or
direct sunlight.
71
NOX DETERMINATION FROM STATIONARY
SOURCE

72
METHOD 29 – DETERMINATION OF METALS
EMISSIONS
FROM STATIONARY SOURCES

73
METHOD 29
Applicability
This method is applicable to the determination of metals
emissions from stationary sources.

Principle
 A stack sample is withdrawn isokinetically from the source,
particulate emissions are collected in the probe and on a heated
filter, and gaseous emissions are then collected in an aqueous
acidic solution of hydrogen peroxide (analyzed for all metals
including Hg) and an aqueous acidic solution of potassium
permanganate (analyzed only for Hg).
 The recovered samples are digested, and appropriate fractions
are analyzed using an analytical method with a sufficient
detection limit to demonstrate compliance
74
METHOD 29
Sample Train & Recovery Components & Supplies
 A schematic of the sampling train is shown in Figure 29-1 of
the method. It has general similarities to that of EPA Method 5.
 Specifically, the sampling train will be constructed with
components specified under EPA Method 29.

75
METHOD 29
 The impinger train (for condensing and collecting gaseous metals
and determining the moisture content of the stack gas) will consist of
four to seven impingers connected in series with leak-free ground
glass fittings or other leakfree, non-contaminating fittings.
 The first impinger is used as a moisture trap. The second impinger
(which is the first HNO3/H2O2, 5 Percent HNO3/10 Percent H2O2,
impinger) will be identical to the first impinger in Method 5. The
third impinger (which is the second HNO3/H2O2 impinger) will be a
Greenburg Smith impinger with the standard tip as described for the
second impinger in Method 5, Section 6.1.1.8. The fourth (empty)
impinger and the fifth and sixth (both containing acidified KMnO4, 4
Percent KMnO4 (W/V), 10 Percent H2SO4 (V/V)) impingers are the
same as the first impinger in Method 5.
 A temperature sensor capable of measuring to within 1oC (2oF) will
be placed at the outlet of the last impinger. If no Hg analysis is
planned, then the fourth, fifth, and sixth impingers are not used.
76
 CONCLUDING REMARKS

• The criteria air pollutants from stationary

sources normally measured on-line – in-situ
CEM.
• However for a valid reasons, extracted CEM
are performed to measure those pollutants not
measured by in-situ CEM; for example heavy
metals and mercury, naturally occuring
radioactive materials.
• Other gases pollutants such as NH3, HCl and
etc.