Guidelines For Source Emission Monitoring CPCB PDF

Laboratory Analytical Techniqes
Series: LATS / 80 / 2013-2014
GUIDELINES ON METHODOLOGIES FOR

SOURCE EMISSION MONITORING
Central Pollution Control Board

(Ministry of Environment & Forests)
Parivesh Bhawan, East Arjun Nagar, Delhi - 110 032
Website: www.cpcb.nic.in
CPCB, 200 Copies, 2012
Prepared & Published byy P R Division, Central Pollution Control Board on behalf of
Sh. J. S. Kamyotra, Member Secretary, CPCB
Printing Supervision:- Shri G. Ganesh, Ms Anamika Sagar and Shri Satish Kumar
Printed at :- Aravali Printer & Publishers Pvt. Ltd.
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Central Pollution Control Board
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Phone : 22304948/22307233
MIRA MEHRISHI
Chairman
FOREWORD
To harmonize the methodologies adopted by the State Pollution Control Boards/ Pollution
Control Committees, Central Pollution Control Board has taken up the task to collate and
compile the techno-feasible and internationally compatible source emission monitoring
methodologies for all the criteria pollutants (PM, SO2, NOX) and including special parameters
like HCI, HF. This exercise has been an ongoing actiity of CPCB catering to the continuous
need of standard development and harmonizing protocols for emission measurements being
done by regulatory authorities. The first effort was made by CPCB in 1985 with the publication
of Emission Regulation (Part III) - a document on lsokinetic sampling of Particulate Matter. The
present document is an updated version based on enhanced need with the inclusion of new
parameters in emission regulation.
The effort of Shri Abhijit Pathak, ‘B’, air Laboratory in compilation and collation of information
is appreciated. The exercise was possible under the encouraging supervision of Dr. D. Saha,
Scientist ‘D’ and the guidance of Shri J.S. Kamyotra, Member Secretary, CPCB.
I trust and believe that the SPCBS / PCCS, industries and other stakeholders will find this
document useful for improving their technical competence to adjudge industrial compliance
status.
August, 2012 MIRA MEHRISHI

Chairman CPCB
'Parivesh Bhawan' C.B.D-cum Office Complex, East Arjun Nagar, Delhi-110 032
Fax : 22304948 / 22307078 e-mail : [email protected] Website : http//www.cpcb.nic.in
iii
CONTENTS
Chapter – 1 Material and Methodology for Isokinetic Sampling 1-25

Part I 1-18
1.0 Source Emission Monitoring 1
2.0 References 18
Chapter – 1 Determination of particulate matter emissions
Part II 19-25
1.0 Principle 19
2.0 Applicability 19
3.0 Interferences 19
4.0 Sampling 19
5.0 Procedure for Particulate Matter Determination 19
6.0 Sample Recovery 22
7.0 Calculation 22
8.0 References 25
Chapter – 2 Standard Operating Procedure for Determination of Particulate Matter 26-34
1.0 Pre Sampling Activity 26
2.0 Traverse Point Calculation 26
3.0 Determination of Composition of Flue Gas 26
4.0 Measure ambient temperature (ºC) and Barometric pressure in mm Hg 26
5.0 Check the Leak in Sampling Train 26
6.0 Moisture Determination 27
7.0 Wet Molecular Weight Determination 27
8.0 Determine Stack Gas Velocity Pressure(Δ P) And Stack Temperature (Ts) 28
9.0 Determination Of Static Pressure (Absolute Stack Gas Pressure) 28
10.0 Stack Gas Velocity Determination (Us) 28
11.0 Determination of Volumetric Flow Rate/ Discharge 29
12.0 Determination of Flow at Nozzle 29
13.0 Determination of Sampling Rate at the Gas Meter 30
14.0 Sampling 30
15.0 Determination of Volume of Gas Sampled 31
iv
17.0 Determination of Dust Concentration 31
18.0 Correction of the result at 11 % Oxygen 32
19.0 Determination of Emission Rate 32
Chapter – 3 Determination of Hydrogen Halides (Hx) and Halogens in Emission 35-48
Part (i) Sampling of Hydrogen Halides(Hx) and Halogens 35-40
1.0 Principle 35
4.0 Reagents 36
5.0 Sampling 36
6.0 Sample Analysis 39
7.0 Calculation 39
Part (ii) Analysis of Hx and Halogens 41-48
1.0 Purpose and Applicability 41
2.0 Summary of Method 41
4.0 Apparatus and Materials 41
5.0 Sample Handling 43
6.0 Calculation and Data Reduction 45
7.0 Quality Assurance and Quality Control 46
8.0 References 47
Chapter – 4 Standard Operating Procedure for Sampling of Hydrogen Halides and Halogens 49-53
2.0 Pre Sampling Activities 49
3.0 Preparation of Reagents 49
4.0 Field Activities and Isokinetic Sampling 50
5.0 Preparation of the Sampling Train 50
6.0 Sample Collection 50
Chapter – 5 Determination of Metals and Non Metals in Emissions 54-69
1.0 Principle 54
4.0 Reagents 56
v
5.0 Procedure 58
6.0 Calculation 64
7.0 References 69
Chapter – 6 Standard Operating Procedure (SOP) for Sampling, Sample Preparation and
Analysis of Metals and Non Metals 70-84
Part I Standard Operating Procedure (SOP) for Sampling 71-80
2.0 Pre-sampling Activities 72
3.0 Preparation of Reagents 72
4.0 Preparation of sampling train 73
5.0 Field Activity 74
Part II Standard Operating Procedure (SOP) of Sample Preparation and analysis 81-84
1.0 Sample Preparation 81
2.0 Sample Digestion / Extraction 81
3.0 Sample Analysis 83
4.0 Calculation 83
Chapter – 7 Determination of Sulfur Dioxide in Emissions 85-95
1.0 Principle and Applicability 85
2.0 Apparatus 85
3.0 Reagents 89
4.0 Procedure 90
5.0 Calibration 92
6.0 Calculation 93
7.0 Bibliography 95
Chapter – 8 Determination of Nitrogen Oxides in Emissions 96-106
1.0 Principle and Applicability 96
2.0 Apparatus 96
3.0 Reagents 99
4.0 Procedure 101
5.0 Calibration 103
6.0 Calculation 105
7.0 Bibliography 106
vi
CHAPTER - 1
Method-1
(Part- I)
Stack Monitoring – Material and Methodology for Isokinetic Sampling
1.0 SOURCE EMISSION MONITORING
This section deals with the method of source emission monitoring. It also gives the minimum
requirement of a stack monitoring equipment.
1.1 Specifications of Stack Monitoring Equipment
Table 1.1: Specifications of Stack Monitoring Equipment
S.N. Item/Equipment Specifications / Applicable ranges
General Requirements
1 Stack Velocity Range: 0 to 30 m /sec

For low velocity range differential pressure determination
should be done by differential manometer
Stack Temperature: 0 to 600 ºC)
Range Particulate At 10 to 60 lpm
Sampling:
Filter Paper (Thimble): Collection of particulates down to 0.3 micron
Gaseous sampling: At 1 to 2 LPM collection on a set of impingers containing
selective reagents.
2 Pitot tube i. Pitot tube shall be modified “S- type” fabricated from SS
304 or equivalent grade. The construction feature should be
as per United States Environmental Protection Agency (EPA)
regulation, Method 2, Given in Figures 1.1 and 1.2 (A)
ii. The construction feature shall be such that the coefficient
of the pitot tube is above 0.95.
3 Sampling probe Sampling probe shall be fabricated from SS 304 tube of
suitable diameter (not less than 15 mm Internal diameter
(ID). The SS probe should have inner glass liner to facilitate
sampling for metals, acids (HCl) and PCDDs and PCDFs.
Length of pitot tube and the sampling probe may correspond
to user requirement.
1
4 Nozzles Nozzles shall be fabricated with SS 304 or equivalent material

with internal diameters suitable to cover the full range of stack
velocities. The leading edge of the nozzle should be sharp
and tapered. The minimum internal diameter of the nozzle
shall not be less than 4 mm. Glass nozzles are recommended
for Hx and halogens, metals and PCDDs/PCDFs sampling
5 Heated filter box Heated filter box upto 200 oC with filter holder made of glass
is recommended
6 Sample transfer line Heated sample transfer line (upto 200 oC) made of nonreactive,
non corrosive material is recommended to eliminate artifacts
due to condensation
7 Thermocouple Thermocouple sensor shall be provided with digital dial gauge
capable of measuring temperature from 0 to 600 oC covered
with stainless steel or mild steel casing with acid resistant
treatment.
8 Mounting flange A pair of male/female flanges fabricated with mild steel with
proper hole for mounting thermocouple sensor, sampling
tube and pitot tube.
9 Panel box sides Panel box shall be fabricated with aluminium/mild steel/
fiber glass sheets with oven-baked stove–enamel finish. It
should have suitable arrangement for housing stop- watch,
manometer, rotameter, dry gas meter etc.
10 Back panel Back panel shall be hinged door panel of mild steel to contain
cold box with 8-10 impingers.
11 Inclined - cum – Inclined- cum – vertical manometer shall be fabricated with

Vertical Manometer soild acrylic sheets. It shall be provided with Inlet and outlet
for filling in gauge fluid and spirit level for leveling. Velocity
range of the manometer shall be 0 to 30 m/sec.
12 Rotameters 0 to 60 lpm for particulate monitoring and 0 to 3 lpm for
gaseous monitoring
2
13 Stop-watch 0 to 60 minutes, one second readout with hold facility.
14 Impinger Four number 100 ml and four to six number 225 ml capacity.
Facility should be there for keeping ice at the bottom of
impinge box. Electrical cooling is desirable
15 Connectors Push and close type quick connector to ensure better leak
proofness
16 Vacuum pump Vaccum pump shall be of rotary design, with a capacity of to

0 to 120 lpm gas flow with single phase motor, 220 V. The
pump shall also have a moisture trap and air inlet valve. It
shall be mounted inside pump housing and shall be portable
17 Dry gas meter The sampling train shall have a dry gas meter. The capacity
of the meter should be adequate to record upto 60 lpm of
airflow and a minimum readout of 0.001 cubic meters.
18 Pump housing Mild steel case with oven- baked stove enamel finish and
ON/OFF switch with indicator lights.
19 Tools A Kit containing the essential tools for connecting various

components shall be provided with the equipment.
20 Isokineticity The kit shall be capable to perform continuous monitoring of

isokinetic condition throughout the sampling period
21 Temperature at Temperature measuring device at metering point shall

metering point beprovided (0-50 oC)
22 Vaccum Digital/analog vaccum pressure drop measurement device in

measurement mm Hg should be provided in stack kit.
23 Train leakages The sampling train shall be tested for leakage by plugging the
inlet. The rotameter shalll not give a reading beyond 5 lpm
when the flow has been set at 100 lpm. The dry gas meter
shall also give a reading of less than 5 percent of the airflow.
3
Properly constructed Type S pitot tube shown in: a) Top view; face opening planes parallel to
longitudinal axis; b) side view; both legs of equal length and central lines coincident, when
viewed from both sides. Baselines coefficient values of 0.84 may be assigned to pitot tubes
constructed this way.
FIGURE 1.1 “S – TYPE” pitot tube construction
4
5
1.2 Method of Testing
1.2.1 Molecular weight determination
Dry and wet molecular weights
Equation 1 is used to calculate the dry molecular weight of flue gas. This equation
may be modified with terms if other gaseous constituents that will influence the molecular
weight if present. Equation 2 is used to calculate the molecular weight of the sample is used
to calculate the molecular weight of the gas on a wet basis.
Calibrated multiple combustion gas analyzer may be used to know the percentile composition
of flue. Orset analysis may also serve the same purpose.
Md = 0.44 (%CO2)+0.32 (% O2) +0.28(% N2+ % CO) +………… Eq - 1
Ms = Md (1 – BWO) + 18 BWO ………………………………. Eq - 2
Where,
0.44 – molecular weight of carbon dioxide divided by 100, kg/kg-mole
0.32 – molecular weight of oxygen divided by 100, kg/kg –mole
0.28 – molecular weight of nitrogen and carbon monoxide divided by 100, kg kg-mole
BWO – proportion by volume of water vapour in stack gas.
18 - molecular weight of water, Kg / Kg -mole
Note: % N2 is calculated by difference. In the majority of cases the following equation may be
used:
% N2 = 100 – ( % CO2 avg + % O2 avg + % CO avg. )
Where,
Md = molecular weight of stack gas on dry basis, kg / kg –mole.
Ms = molecular weight of stack gas on wet basis, kg / kg –mole
% CO2 = Percent CO2 by volume, dry basis
% O2 = Percent oxygen by volume, dry basis
% N2 = percent nitrogen by volume, dry basis
6
1.2.2 Static pressure determination
For the static pressure determination requires first to disconnect the positive end of
the pitot tube then take the reading of velocity pressure. Use the following formula for the
alculation. For measurement of static gas pressure pitot tube Should be rotated by 90o from
the position of actual Δ P measurement. This would provide better accuracy.
Ps may be calculated as
Ps = P bar ± (Δ Ps / 13.6)
Where:
P bar = Barometric pressure in mm mercury column
Ps = Stack gas velocity pressure, mm water column
Ps = Static pressure mm Hg column.
Density of Hg = 13.6
1.2.3 Stack gas velocity determination
For velocity determination connect pitot tube to the stack as given in Fig 1.2 (B). The
dynamic and a static pressure are measured by using the manometer. The temperature inside
the duct is also measured. The velocity of gas in the duct and the air quantity are determined
usingg tthee following
o o g formula.
o u a.
7
1.2.3.1 Preliminary determination
Preliminary determination requires for the parameters like Temperature (Stack & ambient
temperature ºC), velocity pressure Head ΔP, Barometric pressure, Static pressure as mentioned
in the above paragraph.
Us = Kp X Cp X ( Δ P ) 1/2 [Ts / (Ps × Ms)] 1/2
Where
Us = Stack gas velocity, m/s
Kp = Constant, 33.5
Cp = S- type pitot tube coefficient.
Ts = absolute stack gas temperature, °K
P = Stack gas velocity pressure, mm water column
Ps = Absolute stack gas pressure, mm Hg
Ms = Molecular weight of stack gas on wet basis, Kg / Kg –mole
1.2.3.2Stack gas volumetric flow Rate
The following equation is used to calculate the stack gas volumetric flow rate, Qs (m3 hr).
Qs = 3600 (Us) × As (1 – BWO) X ( Tref / Ts) X (Ps / Pref)
As = Area of the stack (duct), m2
BWo = Proportion by volume of water vapour in stack gas.
Tref = 298 °K
Pref = 760 mm of Hg
Ts = Absolute stack gas temperature, °K
Ps = Absolute stack gas pressure
1.2.4 Moisture determination
The moisture content may be determined either by condenser method or by wet / dry
bulb method temperature and then referring to a suitable psychrometric chart. Latter should
be limited to non-acid gas streams with moisture content of less than 15 percent and dew
point less than 52o C. The condenser method works well for most gas streams and also relative
easy to perform.
8
1.2.4.1 Condenser method
The condenser method, in principle, involves extracting a sample of the stack gases
through a filter for removal of the particulate matter, then through a condensor, accumulating
the condensate formed in process. The object of the test is to collect and measure the volume
of all the condensate formed at the condensing temperature from a measured amount of
gas.
Apparatus – The apparatus necessary for determination of moisture content by the

condensate method is given below.
S.No Apparatus Description
1 Particulate Sampling Apparatus Consisting of a probe of stainless steel or pyrex

glass sufficiently heated to prevent condensation
and equipped with a filter to remove particulate
matter.
2 Condenser It is equipped with temperature gauge. This
may be substituted with two condenser bottles
in an ice bucket each with 30 ml capacity or
equivalent. The condenser /condenser bottles
are ﬁlled with chilled water.
3 Dry Gas Meter To measure within 5 percent of the total sample
volume
4 Gauges Two thermometers (range 0 – 100 OC),
two calibrated vacuum gauges or U- tube
manometers (range 0 – 500 mm mercury).
5 Gas Pump Leak free diaphragm type or equivalent, for
sucking gas through sampling apparatus
6 Fittings Tubing (rubber, neoprene, etc.), rubber stoppers
and flow control (needle- valve and shut –off
ball valve).
Procedure – Except in unusual circumstances, the water vapour is uniformly dispersed

in the gas stream and therefore sampling for moisture determination need not be isokinetic
and is not sensitive to position in the duct. The sampling nozzles may be positioned down
–stream to minimize the build up of pressure drop across the thimble due to particulates
catch. Sample the gas at a rate of about 500 ml/ sec. Run the test until enough condensate has
been collected to enable an accurate measurement. Measure the temperature and pressure
9
of condenser close to the meter, as an insignificant pressure loss in the line between them is
expected. The meter pressure may be substituted for condensate pressure also in order to
calculate the moisture content. Measure the volume of condensate collected in a graduated
measuring cylinder.
Calculations
Calculate the volume of water vapour collected using the following equation:
(Vc x 22.4) Tm 760

Vv = x x
1000 x 18 273 Pbar - Pm
Vv = Equivalent vapour of condensate under sampling condition, m3
Vc = Volume of condensate in condensor, ml
Tm = Temperature at metering condition, °K
Pm = Suction at meter, mm mercury column
Pbar = Barometer pressure, mm mercury column
Calculate the moisture content of the gases using the following equation:
Vv
BWO =
Vv + Vm
Vv
M = x 100
Vv + Vm
Where
M = Moisture in the flue gases, perent
Vv = Equivalent vapour volume of condensate under sammling condition.
Vm = Volume of gas sampled (m3)
1.2.4.2 Wet / dry bulb method
The equilibrium temperature attained by water, which is vapourizing adiabatically into

gas of composition and constant dry bulb or actual temperature, is termed as wet bulb
temperature. The amount of depression of the wet bulb temperature below the dry
10
bulb temperature is a function of the degree of saturation of the humidity of the gas.
Therefore, the moisture content of the gas can be determined from the wet and dry bulb
temperature.
Calculations – the moisture content may be determined from the test data using a
psychrometric chart.The percentage water vapour by volume is found directly. Inputs
are the dry bulb temperature and wet bulb temperature.
1.3 Selection of Sampling Site and Minimum Number of Traverse Points
Select the sampling site at any cross section of the stack or duct that is at least eight stack
or duct diameters downstream and two diameters upstream from any flow disturbance
such as bend, expansion, contraction, visible flame, or stack exit (see inlet, Figure 1.3).
For rectangular cross section, the larger dimension shall be used to represent the stack
diameter.
1.3.1 When the above sampling site criteria can be met, determine the minimum number of
traverse points required, from Table 1.3. The minimum required number of traverse
points is a direct function of stack or duct diameter.
1.3.2 When a sampling site such as described in 1.3 is not accessible, choose a convenient
sampling location and use Table 1. 3 and Figure 1.3 to determine the minimum required
number of traverse location to the nearest upstream and downstream disturbance. First,
measure the distance from the chosen sampling location to the nearest upstream and
downstream disturbance.
1.3.3 Then, from Figure 1.3 determine the corresponding sample points multiples for both
distances and select the greater of these. Multiply it by the number obtained from Table
1.3. The result of this calculation is the minimum number of traverse points required.
This number may have to be increased such that for circular stacks the number is a
multiple of 4 and for rectangular stack the number follows the criteria given in1.3.4.
1.3.3 Cross- section layout and location of traverse points For circular stack divide the cross
section into equal parts by two right- angle diameters. Locate half the traverse points
symmetrically along each diameter according to Figure 1.4 and Table 1.4.
1.3.4 For rectangular areas as there are traverse points as many equal rectangular areas traverse
points such that the ratio of the elements/ area is between one and two. Locate the
traverse points at the centroid of each area according to Figure 1.4.
1.3.5 Under no condition shall sampling points be selected within 3 cm of the stack wall.
11
Table 1.3 : Minimum required number of traverse points for sampling sites which
meet specified criteria
Inside diameter of stock of duct (m) Number of points
I.D. < 0.3 4
0.3 < I.D. < 0.6 8
0.6 < I.D. < 1.2 12
1.2 < I.D. < 2.4 20
2.4 < I.D. < 5 32
FIGURE 1.3 Travers point multiples to determine minimum number

of traverse points requirement when a <2 dia or b <8 dia
12
FIGURE 1.4 Location of traverse points on circular and rectangular cross section divided
into twelve equal areas
13
TABLE-1.4 Location of traverse points on diameters of cross section of circular stacks
1.4 Location of Sampling Port
To ensure laminar flow, sampling ports shall be located atleast 8 times chimney diameter
downstream and 2 times upstream from any flow disturbance. For a rectangular cross section
the equivalent diameter (De) shall be calculated by using following equation to determine up
stream, downstream distances.
De = (2 L X W) / (L+W)
Where, L = Length in m, W= width in m.
14
Sometimes it may so happen for existing chimneys that sufficient physical chimney
height is not available for desired sampling locations. In such cases additional traverse points
shall be taken as explained at section 1.3.
1.4.1 Number of sampling ports
The pitot tubes commercially available in the country generally do not exceed 2 meter
in length. Any points on the horizontal cross- section of a stack (chimney) along any diameter
can be measured for flow by the pitot tube, if the point is approachable. Inserted pitot tube
through the sampling port (hole) for stacks with diameter less than 2m. Minimum two (mutually
orthogonal) sampling ports are required in a circular chimney, so that full stack cross-sectional
area can be covered for measurements. For stacks having diameter between 2 and 4 meters,
two mutually orthogonal sampling ports are to be increased to four by providing additional
sampling ports at diametrically opposite position, to the first two sampling ports (Fig 1.5)
1.4.2 Dimensions of sampling port
Port Type: Pitot tube, temperature and sampling probe are to be inserted together into
the sampling port for monitoring purposes. Sampling port should be a standard flanged pipe
of 0.10 m inside diameter (ID) with 0.15 m bolt circle diameter. An easily removable blind
flange should be provided to close the port when not in use. Port Installation: Flanged pipe
used as port should be installed with the interior stack wall. Port should extend outward from
the exterior stack wall not less than 50 mm and not more than 200 mm only when additional
length is required for gate valve installation. Ports should be installed at a height between 0.90
and 1.2 m above the floor of the working platform. Port Loading: The port installation should
be capable of supporting the following loads:
Vertical shear of 91 Kg
Horizontal Shear of 23 Kg and
Radial tension of 23 Kg (along stack diameter)
1.4.3 Features of platform for stack sampling
Size and extent of platform for sampling: If two ports are required at 90 degree the
work platform should serve that half of the stack circumference between the ports and extend
at least 1.2 meters beyond each port. If four ports are required at 90 degree, the work platform
should serve the entire circumference of the stack. Minimum platform width shall always be
1.2 meters regardless of diameter of stack and number of sampling ports. A typical platform
for sampling is shown in Figure1.6.
15
FIGURE 1.5 Position of sampling ports in a circular chimney
16
1.4.4 Platform access
Safe and easy access to the work platform should be provided via caged ladder, stairway,
or other suitable means.
Guardrails, Ladder wells and Stairwells: A safe guardrail should be provided on the
platform. Angular rail is preferable than round rail member. No ladder well, stairwell, or other
such openings should be located within 1 meter of any port. Ladderwells should be covered
at the platform. Any stairwell leading directly to the platform should be equipped with a safety
bar at the opening.
1.4.5 Platform loading
The work platform should be able to support at least three men (Average 80 Kg each)
and 91 Kg of test equipment (stack monitoring kit, etc.). If the stack exists through a building
roof, the roof may suffice as the work platform, provided the minimum test sites required are
complied with.
1.4.6 Clearance zone
A three- dimensional, obstruction free clearance zone should be provided around each
port. The zone should extend 0.6 m above, below, to either side of the port. The zone should
extend outward from the exterior wall of the stack to a distance of at least 3 meters. The
clearance zone is illustrated in Figure 1.6.
1.4.7 Power Supply
Power supply shall be as follows:
A. Platform- one 220 volts, 15 amp, single phase AC circuit with a grounded, two receptacle
weatherproof outlets.
B. Stack base- one 220 volts, 15 amp, single phase AC circuit with a grounded, two
receptacle weatherproof outlet.
1.4.8 Vehicle access and parking
Except for situations in which sampling operation must be conducted from a rooftop or
similar structure, stack sampling is sometimes coordinated and controlled from a monitoring
van, which is usually parked near the base of the stack for the duration of the sampling period.
Vehicle access and parking space must be provided, since various equipment transport lines
will be strung from the monitoring van to the stack platform and will remain in position during
the sampling.
1.4.9 Additional requirements
In addition to above aspects, the sampling platform, guardrails etc. should also be
regularly painted and checked for corrosion. There should be no leakage around the sampling
17
port (specially needed for stacks emitting corrosive chemicals). If anticorrosive lining is done
inside the chimney, the same should be extended to the projected portion of the sampling
port, monolithically. Improper lining at the port reduces chimney life considerably. Sampling
port should be air tight and moist air should not be allowed to enter the chimney
FIGURE 1.6 Typical sampling provision
2.0 REFERENCES
1. Comprehensive Industry Document Series: COINDS/ 20/ 1984 - 85, Central Pollution
Control Board
18
Method – 1
(Part- II)
Determination of particulate matter emissions from stationary sources
1.0 PRINCIPLE
Determination of particulate concentration consists of isokinetic sampling of a

measured amount of gas from the flue gases and separating the particles from the gas and
hence determining the particulate concentration. To ensure representative sample, the kinetic
energy of the gas stream in the stack should be equal to kinetic energy of the gas stream
through the sampling nozzle.
2.0 APPLICABILITY
This method is applicable for determination of particulate matter (PM) emissions from
stationary sources. This is for sampling of particulate matter in a moving gas stream in a duct
or a stack. These procedures utilize particulate filtering systems, which are located within the
stack. If properly used, these systems are satisfactory for determining the mass concentration
of particulate matter in the gas stream at stack condition. The use of collection systems located
outside the stack for collecting samples at other than in-stack condition is an alternative.
3.0 INTERFERENCES
It has been observed that, if sampling velocity is greater than the isokinetic rate, the
sampling will have a lower mass concentration of particulate material than the main stream
because of greater percentage of fine particles. However, if the sampling velocity is less
than the isokinetic rate, the particulate sample has a higher mass concentration than actually
present, with lower concentration of fine particles.
4.0 SAMPLING
Sampling at other than isokinetic velocities induces errors for two reasons. First, sampling
at greater or less than isokinetic rates tend to cause respectively a larger or a smaller volume to
be withdrawn from the flue gases than accounted for by the cross section area of the probe.
Secondly, particles greater than 3.5 micron in size have sufficient inertia so that particle motion
may deviate significantly from the gas flow streamline pattern.
4.1 The Sampling Consists of Several Distinct Steps. Refer 1.2 of Stack monitoring –
Material and Methodology for Isokinetic Sampling (Method1)
5.0 PROCEDURE FOR PARTICULATE MATTER DETERMINATION
5.1 Selection of Location of Sampling
Sample for particulate concentration shall be done at the same be traverse points where
velocity measurements were carried out.
19
5.2 Calculation of Proper Sampling rate
The meter for measuring the gas sample measures the gas at conditions of temperature,
pressure and moisture content which are different than those in the flue. Therefore, calculate
the sampling rate at the gas meter for each sampling points before starting the test and record
on the log the required rate (Table-2).
Calculate the sampling rate at the gas meter as follows:

Tm Pbar - Ps Vm
Vv = Rs x x x
Ts Pbar - Pm Vm + Vv
Where
Rm = flow rate through meter, m3/s
Rs = Sampling rate at nozzle, LPM
Tm = Absolute temperature in metering conditions, °K
Ps = Absolute stack gas pressure, mm mercury column
Pm = (Pm1 - Pm0) / 2 Suction at meter, mm mercury column
Vm = Volume of gas sampled at meter conditions, m3
Vv = equivalent vapour volume of condensate at meter conditions, m3
Note: Take initial reading of vacuum gauge (Pm0) in mm Hg at the staring of sampling and
final vacuum pressure (Pm1) in mm Hg just before putting off the pump, when sampling is
complete. Calculate average difference in suction pressure, referred as Pm
5.3 Select the nozzle size, which provide a meter-sampling rate between 40 to 60 lit /
min. Charts relating sampling rate with stack and meter condition may be prepared for
the range of condition expected. Duration of Sampling- Deem the run to be of
sufficient length if one of the following criteria has been obtained:
a. A minimum of 1 m3 of dry gas has been withdrawn for sampling.
b. The mass of particulate matter amounts to atleast 20 percent of the mass of the filtering
medium in the sampler.
20
Experience and intelligent judgment should be applied in determining the sampling time.
Too short a time, may give unreliable result and too long a time may cause the resistance
of the sampling train to exceed the pump’s limits.
5.4 Preparation of the Sampling Train
• After proper nozzle and filtering medium have been selected assemble the sampling
train as shown in Figure 2
• Mark the sampling probe (including nozzle and filter holder) with the same traverse
points used for conducting the velocity traverse.
• Place a clean, pre-weighted thimble/filter in the filter holder and tighten securely.
• Start the test after sampling rates have been calculated and train assembled & checked
for leakages. When the equipment is ready in all respects, record the initial dry gas
meter reading and push the sampling probe carefully into the duct to the point nearest
to the back wall. This will allow the probe to cool in hot stack as it comes out, shortening
the time required for cooling after the sample is taken. It is advisable to allow the nozzle
and filter holder to preheat so that moisture present in the gases does not condense in
the filter initial part of the sampling.
• When starting the test, the nozzle should be facing in the upstream direction, start
operating the suction source, open the control valve and start the stop watch. Note the
time and record it in the log sheet. Adjust the flow rate with the help of rotameter and
control valve until the desired flow rate for isokinetic condition is obtained. As the test
proceeds, dust collected in the thimble/ filter increases the amount of suction required to
maintain proper meter rate. Valve should be adjusted accordingly. This suction should
not exceed 150 mm of mercury for paper thimble / filter. In case it exceeds this value
before the completion of sampling, replace the same with a new thimble and restart
sampling. During the test, if the mercury suction pressure at the meter drops suddenly it
indicates that a leak has developed in the equipment or that thimble/filter has cracked.
Record the initial gas meter reading and pressure and temperature in the sampling train
as well as condensor temperature at half – minute’s interval during the test.
• When sampling at one point has been completed, move the sampling probe to the next
point as quickly as possible. At the completion of test, close the control valve, turn the
direction of the probe so that the sampling nozzle is facing downstream and record
the final gas volume and time. Remove the sampler carefully from the flue and plug the
nozzle to prevent the loss of sample.
21
6.0 SAMPLE RECOVERY
After the sampler has cooled, brush down the dust on the inside of the nozzle carefully
into the thimble using a small brush. Then, remove the thimble and place it in a dust tight
container for transportation to the weighing room. In case the filter holder is kept outside
during the sampling, the dust from the sampling probe before the filter holder should be
brushed down into the filter.
Determine the mass of dust collected in the thimble by difference in weighing, that is,
by weighing the thimble before and after the run. Dry the thimble in an oven for about 2 hours
at 120 oC prior to sampling. After sampling, cool it and dry again for weighing the thimble
along with dust maintaining the same condition as prior to sampling.
7.0 CALCULATIONS
Calculate the volume of gas sampled using the following equation: Volume of dry gas
through the sampling train (25 oC 760 mm Hg )
22
Pbar - Pm 273 + 25 °C
Vstd = Vm Y x
760 mm Hg Tm + 273
Where
Tm = Temperature of gas at dry meter condition, °C

Vm = Volume of gas sampled at dry gas meter conditions, m3
(Pbar-Pm) = Actual pressure in sampling train, mm mercury column.
Pm = Suction at meter , mm mercury column
Pbar = Barometeric pressure in sampling train, mm mercury column.
Y = Cali bration factor of dry gas meter.
7.1 Dust Concentration
Calculate the dust concentration using the following equation:

(W2 - W)m) grm x 1000
EM =
Vstd
Dust Concentration in mg / Nm3,
(25°C, 760 mm Hg, dry basis)
Where
Vstd = Volume of dry gas through the meter

(25°C, 760 mm Hg), Nm3
W1 = Initial weight of filter paper
W2 = Final weight of filter paper
O2 correction is only carried out, if O2 corrections > 11%. For O 2 < 11%. No correction is
allowed.
It’s require to correct the value for the 11% O2 by following formula
21 - OS
ES = x EM
21 - OM
Similarly in case of CO2 (12%) correction

12
ES = Em
%CO2 observed
No correction for CO2 > 12%
23
ES = calculated emission concentration at the standard percentage oxygen concentration
EM = measured emission concentration
OS = standard oxygen concentration
OM = measured oxygen concentration
7.3 Emission Rate
Calculate the dust emission rate as follows:
EM x QS
Dust Emission Rate =
106
Where
QS = flue gas flow rate ( 25 °C, 760 Hg mm Hg), Nm3 / hr.
All stack emission test results shall be given in dry basis as in 7.1 above, i.e. at zero percent
moisture.
Note : Report the concentration as corrected at 11% O2
24
Table - 2
Field Data Sheet
Name & Address
Date & time of sampling
Ambient temperature °C
Barometric Pressure (mm mercury column)
Moisture in the flue gas (%) flue gas composition (CO2 %, O2 %,N2)
Filter No and weight ( Initial as well as Final)
Travers ΔP Ts Ps Us Qs Rs Pm Rm Time DGM (M3) Vstd
Point (mm) (°K) (m/s) (m3/hr) (LPM) (LPM) (min) (Nm3)
Pm0 Pm1 Initial Final
ΔP = Stack Gas Velocity Pressure, (mm water column), Ts = Stack temperature (°K)
Ps = Static pressure (mm water column), Us = Velocity of stack gas (m/s),
Qs = Volumetric Flow rate / discharge, Rs = Flow at nozzle (LPM),
Pm = Vaccum Pressure Drop (mm mercury column),
Rm = Determination of sampling rate at gas meter. (LPM),
Vstd = Determination of volume of gas sampled
Other required information:
o Feed rate of hazardous waste
o The nature, composition and quantity of the material being incinerated during monitoring
o Installed and operating capacity of the incinerator
o No of sampling ports
o Internal diameter of the stack
o Nozzle size selected for sampling
o Pitot tube constant
o ID fan capacity
o Pollution control equipment installed and its status
o House keeping
Signature of sample collector Verified by Approved by Occupier/

Representative of
the incinerator facility
8.0 REFERENCES
1. Comprehensive Industry Document Series, COINDS/ 20/ 1984 – 85, Central Pollution
Control Board
2. EPA Method 5 and Method 17.
25
CHAPTER - 2
Standard Operating Procedure for Particulate Matter Determination
1.0 Pre Sampling Activity
Weigh the properly conditioned thimble/filter and place it into the clean, air tight
W
container. Designate appropriate label or ID No. to each thimble/filter container. Follow
section 5.4 of part –II (Determination of particulate matter emission from stationary sources)
of “Stack Monitoring – Material and Methodology for Isokinetic sampling (method-1).”
Field activity starts with the collection of detail information’s from the industry about
the products, raw materials, fuels, and stack dimensions.
2.0 Traverse Point Calculation
Calculate the traverse point and accordingly mark the distance from tip of the nozzle,
on pitot tube and probe. Do not forget to add the collar length of port to the calculated
traverses. For detail calculation see the section 1.3 of “Stack Monitoring Material and
Methodology for Isokinetic Sampling (Method-1).
3.0 Composition of Flue Gas
Determine flue gas composition by orsat apparatus or multi gas analyzer. In case of
Orsat analysis gas sample has to be collected in tedlar bag / non reactive bladder and allowed
to cool before analysis. Gas analysis by multi gas analyser may be performed by direct insertion
of sampling probe inside the stack and simultaneous estimation of all the components in
pre-calibrated gas analyser. At least 3 observations should be taken for average percentile
composition. Use gaseous composition data to calculate dry molecular weight of flue gas
(Md).
Determine the Dry molecular weight (Md) by following equation
Md = 0.44 (%CO2) + 0.32 (% O2) +0.28(% N 2 + % CO) +……
4.0 Measure ambient temperature (o C) and Barometric pressure in mm Hg.
Ambient Temperature and Barometric pressure readings are to be noted
5.0 Check the Leak in Sampling Train
The sampling train after having set up will be tested for leakage by plugging the inlet.
The rotameter shall not give a reading beyond 5 lpm when the flow has been set 100 lpm. Also
the dry gas meter should give a reading of less than 5 percent of the air flow.
26
6.0 Moisture Determination
Moisture can be determined by condenser method , in principle, involves extracting a

sample of the stack gases through a filter for removal of the particulate matter, then through a
condenser accumulating the condensate formed in process, and finally through a gas meter.
The objective of the test is to collect and measure the volume of all the condensate formed
at the condensing temperature from a measured amount of gas. For the detail see the section
1.2 of “Stack Monitoring – Material and Methodology for Isokinetic Sampling (Method-1).
Calculations
Calculate equivalent vapour of condensate under sampling condition, m3
(Vc x 22.4) TM 760

VV = x x
1000 x 18 273 Pbar - Pm
Vv = Equivalent vapour of condensate under sampling condition, m3
Vc = Volume of condensate in condensor, ml
Tm = absolute meter temperature, °K
Pm = suction at meter, mm mercury column
Calculate the moisture content of the gases using the following equation
Vv
BWO =
Vv + Vm
Vv
M = x 100
Vv + Vm
BWO = Proportion by volume of water vapour in stack gas.
M = Moisture in the flue gases, percent
Vv = equivalent vapour volume of condensate under sampling condition.
Vm = Volume of gas sampled (m3)
7.0 Wet Molecular Weight (Ms) Determination
This equation can be used to determine the molecular weight of the stack gas on a wet
basis
Ms = Md (1-Bwo) + 18 Bwo
27
Md = molecular weight of stack gas on dry basis, / kg - mole
8.0 Determine Stack Gas Velocity Pressure (Δ P) And Stack Temperature (Ts)
• Check and adjust the upper miniscus of manometer fluid at zero.
• Connect +ve and –ve end of the pitot tube in respective points.
• Slowly insert the pitot and thermocouple upto the first traverse mark inside the stack.
Keep the positive end towards the direction from which flue is coming. Hold it for
stabilisation. Take the reading of fluid displacement in manometer and temperature.
• Repeat the same in next traverse mark and so on.
• Take average reading for Δ P and Ts
• For measurement of static gas pressure pitot tube should be rotate by 90 °C from the
position of actual Δ P measurement. This would provide better accuracy.
9.0 Determination of Static Pressure (Absolute Stack Gas Pressure)
For the static pressure determination requires first to disconnect the positive end of
the pitot tube then take the reading of velocity pressure at the traverse point in which the
calculated average Δ P matches closely. For measurement of static gas pressure pitot tube
should be rotated by 90° from the position of actual Δ P measurement. This would provide
better accuracy.
Clalculate PS
Ps = P bar + (Δ Ps / 13.6)
P bar = Barometric pressure in mm mercury column
Δ Ps = Stack gas velocity pressure, mm water column
Ps = Static pressure mm Hg column.
Density of Hg = 13.6
10.0 Stack Gas Velocity Determination (Us)
Connect pitot tube to the stack for velocity determination, calculate the stack gas
velocity at all the traverse point by using the following formula. Consider the density factor
for correction of velocity pressure and Δ Ps to convert water column manometer.
Us = Kp Cp (Δ P)1/2 [Ts) / (Ps x Ms) ]

28
Where
Us = stack gas velocity, m/s
Kp = constant
Cp = s-type pitot tube coefficient.
Ts = absolute stack gas temperature, °K
ΔP = stack gas velocity pressure, mm water column
Ps = absolute stack gas pressure, mm Hg
Ms = molecular weight of stack gas on wet basis, Kg / Kg - mole
11.0 Determination of Volumetric Flow Rate/ Discharge
The following equation is used to calculate stack gas volumetric flow rate (m3 /hr).
Tref Ps
Qs = 3600 (Us) x As (1-Bwo) x
Ts Pref
As = area of the stack (duct), m2
Bwo = proportion by volume of water vapour in stack gas.
Tref = 298 °K
Pref = 760 mm
Ts = absolte stack gas temperature,°K
Ps = absolute stack gas pressure
12.0 Determination of Flow at Nozzle
Select the nozzle size, in such away that sampling rate a meter shall not exceed 70 % of pump
capacity in any case. Cross sectional area of nozzle (mm) for different diameter is as follow
S No. Dia of the nozzle (inch) Cross sectional area (m2 )
1. 5/8 1.9783 × 10 - 4
2. 3/4 2.8487 × 10 - 4
3. 1/2 1.2661 × 10 - 4
4. 1/4 3.16531 × 10 - 5
5. 1/8 7.9132 × 10 - 6
29
Rs = (Us* an)* 60* 1000} LPM
Where,
Rs = sampling rate at nozzel, LPM
Us = stack gas velocity, m/sec
An = area of nozzel, m2
60 = conversion factor seconds to minute
1000 = conversion factor m3 to litre
13.0 Determination of Sampling Rate at the Gas Meter
The meter for measuring the gas sample measures the gas at conditions of temperature,
pressure and moisture content which are different than those in the flue. Therefore, calculate
the sampling rate at the gas meter for each sampling points before starting the test and record
on the log the required rate (Table 1). Calculate the sampling rate at the gas meter as follows:
Ts Pbar - Ps Vm
Rm = Rs x x x
Ts Pbar - Pm Vm + Vv
Rm = Flow rate through meter, m3/s

Rs = Sampling rate at nozzle, LPM
Tm = Temperature at metering condition, °K
Ps = Absolute stack gas pressure, mm mercury column
Pm = (Pm1-Pm0) / 2 Suction at meter, mm mercury column
Vm = Volume of gas sampled at meter conditions, m3
Vv = Equivalent vapour volumeof condensate at meter conditions, m3
Note: Take initial reading of vacuum gauge (Pm0) in mm Hg at the staring of sampling and
final vacuum pressure (Pm1) in mm Hg just before putting off the pump when sampling
is complete. Calculate average difference in suction pressure, referred as Pm
14.0 Sampling
Start the test after the sampling rate has been calculated and train assembled and
checked for leakages. When equipment is ready in all respect, record the initial dry gas
30
meter reading and push the sampling probe carefully into the duct to the point nearest to the
back wall. Take the sample appropriately as per the requirement and with all the necessary
precaution.
15.0 Determination of Volume of Gas Sampled
Calculate the volume of gas sampled using the following equation:
Pbar - Pm 273 + 25 °C
Rstd = Vm Y x
760 mm Hg Tm + 273
Tm = Temperature of gas at dry meter condition, °C

Vm = Volume ofa gas sampled at dry gas meter conditions, m3
(Pbar-Pm) = Actual pressure in sampling train,mm mercury column.
Pm = Static pressure in sampling train, mm mercury column.
Pbar = Barometeric pressure in sampling train, mm mercury column.
Y = Calibration factor of dry gas meter.
16.0 Sample Recovery
After the sampler has cooled, brush down the dust on the side of the nozzle carefully
into the thimble using a small brush remove the thimble and replace it in same labeled
container. In the case of filter holder is kept outside during the sampling, the dust from the
sampling probe before the filter holder should be brushed down into the filter.
Note:
See the section 6.0 of part –II (Determination of particulate matter emission from stationary
sources) of “Stack Monitoring – Material and Methodology for Isokinetic Sampling
(method-1).”
17.0 Determination of Dust Concentration
Determine the mass of dust collected in the thimble by difference i.e weighing the
thimble before and after the run. Dry the thimble in an oven for about 2 hours at 120 o C prior
to sampling. After sampling, cool, dry and again weigh the thimble along with dust maintaining
the same condition as prior to sampling.
Calculate thye dust concentration using the following equation:
(W2 - W1) grm x 1000

Em =
Dust Concentration in mg /Nm3’ Vstd
(25 °C, 760 mm Hg, dry basis)
31
Vstd = Volume of dry gas through the meter
(25 °C, 760 mm Hg), Nm3
W1 = Initial weight of filter paper
W2 = Final weight of filter paper
18.0 Correction of the result at 11 % O2
O2 correction is only carried out, if O2 corrections > 11%. For O2 < 11% no correction is
allowed.
It’s require to correct the value for the 11% O2 by following formula
21 - Os
Es = x EM
21 - Om
ES = Calculated emission concentration at the standard percentage oxygen concentration

EM = Measured emission concentration
OS = Standard oxygen concentration
OM = Measured oxygen concentration
19.0 Determination of Emission Rate
Calculate the dust emission rate as following
Em x Qs
Dust Emission Rate =
(Kg/Hr) 106
Qs = Flue gas flow rate (25 °C, 760 Hg mm Hg), Nm3/hr.

Note: Report the concentration as corrected at 11% O2
32
Table - 1
Field Data Sheet
Name & Address

o The nature, composition and quantity of the material being incinerated during
monitoring
o ID fan capacity
o House keeping
33
34
CHAPTER - 3
DETERMINATION OF HYDROGEN HALIDES (Hx) and HALOGENS IN SOURCE

EMISSION
( Part- I)
1.0 PRINCIPLE
Gaseous and particulate pollutants are withdrawn isokinetically from the source and
collected in an optional cyclone, preferably on a PTFE filter, and in absorbing solutions. The
cyclone collects any liquid droplets and is not necessary if the source emissions do not contain
them; however, it is preferable to include the cyclone in the sampling train to protect the filter
from any moisture present. The filter collects other particulate matter including halide salts.
Acidic and alkaline absorbing solutions collect the gaseous hydrogen halides and halogens,
respectively. Following sampling for emissions containing liquid droplets, any halides/
halogens dissolved in the liquid in the cyclone and on the filter are vaporized to gas
and collected in the impingers by pulling conditioned ambient air through the sampling train.
The hydrogen halides are solubilized in the acidic solution and form chloride (Cl-), bromide
(Br-), and fluoride (F-) ions. The halogens have a very low solubility in the acidic solution and
pass through to the alkaline solution where they are hydrolyzed to form a proton (H+), the
halide ion, and the hypohalous acid (HClO or HBrO). Sodium thiosulfate is added in excess to
the alkaline solution to assure reaction with the hypohalous acid to form a second halide ion
such that two halide ions are formed for each molecule of halogen gas. The halide ions in the
separate solutions are measured by ion chromatography (IC).
2.0 APPLICABILITY
This method is applicable for determining emissions of hydrogen halides (HX) [hydrogen
chloride (HCl), hydrogen bromide (HBr), and hydrogen fluoride (HF)] and halogens [chlorine
(Cl2 and bromine (Br)] from stationary sources. Same method may be applicable for those
sources, which are controlled by wet scrubbers and emit acid particulate matter. Due to
corrosive nature of expected flue gas glass lined probe is recommended for this method.
2.1 DETECTION LIMIT
The in-stack detection limit is approximately 0.05 µg per liter of stack gas; the analytical
detection limit is 0.1µg/ml.
3.0 INTERFERENCES
Volatile materials, such as chlorine dioxide (ClO2) and ammonium chloride (NH4Cl),
which produce halide ions upon dissolution during sampling, are potential interferents.
Interferents for the halide measurements are the halogen gases which disproportionate to a
hydrogen halide and a hydrohalous acid upon dissolution in water. However, the use of
acidic rather than neutral or basic solutions for collection of the hydrogen halides greatly reduces
the dissolution of any halogens passing through this solution. The simultaneous presence of
35
HBr and Cl2 may cause a positive bias in the HCl result with a corresponding negative bias in
Cl2 result as well as affecting the HBr / Br split. . High concentrations of nitrogen oxides (NOx)
may produce sufficient nitrate (NO3) to interfere with measurement of very low Br- levels.
4.0 REAGENTS
4.1 Sampling Reagents
Table 1 : Sampling reagents
S.No Reagents Procedure for preparation
1 Deionized, distilled water
2 0.1 N Sulfuric Acid (H2SO4) To prepare 100 ml of the absorbing solution for
the front impinger pair, slowly add 0.28 ml of
concentrated H2SO4 to about 90 ml of water
while stirring, and adjust the final volume to
100 ml using additional water. Shake well to
mix the solution.
3 0.1 N Sodium Hydroxide To prepare 100 ml of the alkaline absorbing
(NaOH. solution for the fourth impinger, dissolve 0.40
g of solid NaOH in about 90 ml of water, and
adjust the finla solution volume to 100 ml
using additional water. Shake well to mix the
solution.
4 Sodium Thiosulfate (Na2S2O3 .
5H2O) powder.
4.2 Analytical Reagents

• Deionised / nano pure distilled water
• Absorbing Solution Blanks
• Stock Standard Solutions
5.0 SAMPLING
5.1 Preparation of Collection Train
Prepare the sampling train as following:
Pour 50 ml of the acidic absorbing solution into each one of the first pair of impingers, and 50
ml of the alkaline absorbing solution into each one of the second pair of impingers. Connect
the impingers in series with the knockout impinger first, if used, followed by the two impingers
containing the acidic absorbing solution and the two impingers containing the alkaline absorbing
solution. Place a fresh charge of silica gel, or equivalent, in the drying tube or impinger (after
36
the one more empty impinger) at the end of the impinger train. Adjust the probe temperature
and the temperature of the filter and the stopcock, i.e., the heated area in Figure – 1 to a
temperature sufficient to prevent water condensation. This temperature should be at least 20
o
C above the source temperature, but not greater than 120 oC. The temperature should be
monitored throughput run to ensure that the desired temperature is maintained.
5.1.1 Leak-check procedure

The sampling train after having set up will be tested for leakage by plugging the inlet. The
rotameter shall not give a reading beyond 5 lpm when the flow has been set 100 lpm. Also the
dry gas meter should give a reading of less than 5 percent of the air flow.
5.1.2 Preliminary determinations and isokinetic sampling
Determine the stack pressure, temperature, leak check, calculation of Isokinetic velocity,
volumetric flow rate, flow at nozzle/ selection of nozzle, adjustment of flow rate at rotameter,
temperature at metering point and volume of gas sampled, pressure drop during sampling.
37
Note:
For the Calculation of isokinetic velocity and collection of the sample refer Method -1 “Stack
monitoring – Material and Methodology for Isokinetic Sampling” or SOP for the particulate
matter determination
5.1.3 Sample collection
Turn on the vacuum pump and make a slight vaccum of 25 mm Hg (1 in. Hg). Set the
sampling rate in gaseous train at 2 LPM & allow rest of the flow for isokinetic sampling rate in
particulate train and maintain this rate to within 10 percent during the entire sampling run.
Take readings of the dry gas meter volume and temperature, rate meter, and vacuum gauge at
least once every five minutes during the run. A sampling time of one hour is recommended.
Shorter sampling times may introduce a significant negative bias in the HCl concentration.
During calculation of volume of air passes through the impinger & filter should be done by
adding both the flow rate multiplied by sampling time. At the conclusion of the sampling run,
remove the train from the stack and cool it.
5.2 Sample Recovery
Collect filter separately. No heating should be done in conditioning of filter

preferably desiccation or use of conditioning room is suggested for Pre- conditioning and
post-conditioning of filter. Disconnect the impingers after sampling. Quantitatively transfer
the contents of the acid impingers and the knockout impinger, if used, to a leak-free storage
bottle. Add the water rinses of each of these impingers and connecting glassware to the storage
bottle. Quantity rinsing water should not be used more than 25ml. Repeat this procedure for
the alkaline impingers and connecting glassware using a separate storage bottle. Add 25 mg
sodium thiosulfate to ensure complete reaction with the hypohalous acid to form a second Cl-
ion in the alkaline solution. Save portions of the absorbing reagents (0.1 N H2SO4 and 0.1 N
NaOH) equivalent to the amount used in the sampling train dilute to the approximate volume
of the corresponding samples using rinse water directly from the wash bottle being used. Add
the same (25 mg) amount of sodium thiosulfate solution to the 0.1 N NaOH absorbing solution
blank. Also, save a portion of the rinse water used to rinse the sampling train. Place each in
a separate, pre-labeled storage bottle. The sample storage bottles should be sealed, shaken to
mix, and labeled. Mark the fluid level.
5.3 Sample Preparation for Analysis
Note the liquid levels in the storage bottles and confirm on the analysis sheet whether
or not leakage occurred during transport. If major leakage is observed make up with DI
water upto the marked level. Quantitatively (the whole sample or aliquot) transfer the sample
solutions to 100-ml volumetric flasks, and dilute to 100 ml with water.
For acid mists extract the ions from thimble with 50 ml distilled water under
ultrasonic bath at 60 oC for 1 hour.
38
6.0 SAMPLE ANALYSIS
• All the samples extracted mists and impingers (first 2 – acidic and last two alkaline)
should be analyzed separately for target ions.
• Analysis of the acid and alkaline absorbing solution samples requires separate standard
calibration curves if test run does not conform proper separation and baseline artifacts.
• Ensure adequate baseline separation of the analyses. Before sample analysis, establish
a stable baseline. Next, inject a sample of water and determine if any Cl-, Br- , or F-
appears in the chromatogram. If any of these ions are present, repeat the load/injection
procedure until they are no longer present.
• Between injections of the appropriate series of calibration standards reagent blanks,
quality control sample, and the field samples should be injected. Duplicate injections
are recommended and use the mean response to determine the concentrations of
the field samples and reagent blanks using the linear calibration curve (forced through
zero or linear quadratic). The values from duplicate injections should agree within 5
percent of their mean for the analysis to be valid. Dilute any sample and the blank with
equal volumes of water if the concentration exceeds that of the highest standard.
7.0 CALCULATIONS
Retain at least one extra decimal figure beyond those contained in the available data in
intermediate calculations, and round off only the final answer appropriately. As the individual
analysis is performed for mist, acidic sample and alkaline sample in this method, individually
calculated concentrations should be sum up to report final concentration of target analytes in
flue gas. The formulae for individual calculation are stated below.
7.1 Sample Volume, Dry Basis, Corrected to Standard Conditions
Tstd Pbar Pbar
Vmstd = Vm Y = K1 Y Vm
Tm Pstd Pm
Where:
K1 = 0.3858 °K/mm Hg for metric units,
= 17.64 °C/in. Hg for English units
Pbar = Barometric pressure at the exit orifice of the DGM, mm Hg (in. Hg).
Pstd = Standard absolute pressure,760 mm Hg (29.92 in.Hg).
Tm = Average DGM absolute temperature, °K (°C).
Tstd = Standard absolute temperature, 293 °K
Y = Dry gas meter calibration factor
Vm(std) = Dry gas volume measured by the dry gas meter, corrected to standard conditions,
Nm3
Vm = {Sampling rate in gas channel (LPM) X duration (Minutes)} / 1000 m3.
39
Table - 1
Field Data Sheet
Name & Address

monitoring
o ID fan capacity
o House keeping

Representative of
40
Analysis of Hx and Halogens
(Part – II)
1.0 PURPOSE AND APPLICABILITY
This document outlines procedures for the filter preparation and extraction, and the
subsequent determination of anions in filter extracts.
2.0 SUMMARY OF METHOD
Teflon filters for collection of anions do not require pretreatment. Exposed filter samples
are extracted by a method appropriate for the analyte(s) of interest. Filters are extracted with
deionized water. Extraction with deionized water makes it possible to analyze for both anions
and cations. Sample extracts are passed through a column of ion chromatographic resin
consisting of polymer beads coated with quaternary ammonium active sites. During passage
through the column, anion separation occurs due to the different affinities of the anions for
the active resin sites. Following separation, the anions pass through a suppressor column which
exchanges all cations for H+ ions. An eluent, which yields a low conducting acid, is used.
Species are detected and quantified as their acids (e.g., HCl) by a conductivity meter
3.0 INTERFERENCES
Large amounts of anions eluting close to the ions of interest will result in interference.
No interferences have been observed in Teflon / nylon filters samples analyzed. If interferences
are observed, several steps to increase separation can be taken, such as reducing eluent strength
and/or flow rate or replacing the columns.
4.0 APPARATUS AND MATERIALS
• Filters (Teflon/Nylon)
• Volumetric flask, 1000 mL, 500 mL, 250 mL, 100 mL and 50 mL
• Tweezers
• Glass rod drying racks
• Tweezers
• Adjustable Eppendorf or equivalent micro-pipettes
• Ultrasonic bath
• Syringe filter with 13 mm Nylon filter holder and filter discs
• 250 mL glass beakers
41
Reagents
Stock Standards:- Use high purity graded chemicals for the preparation of all solutions.
Dry chemicals used for the preparation of calibration standards at 105 ºC for 2 hours and
cool in desiccators immediately before weighing. The stock solutions containing (anion) =
1000 mg/L can also be prepared by dissolving the appropriate amount of a suitable salt (purity
standard.) in ultrapure water. The sample weight required per liter ultrapure water is shown
in the Table 1. To prepare the anion standard, these stock solutions are then diluted to the
desired concentrations with ultrapure water.
Table 1 : Required weight of salts to prepare 1000 ppm stock individual standards
Anions Salt Weights in (g) Final Volume Concentrations
Fluoride NaF 2.2100 1000 mL 1000 mg/L
Chloride NaCl 1.6484 1000 mL 1000 mg/L
Bromide NaBr 1.4998 1000 mL 1000 mg/L
Commercially available high purity individual liquid stock standards (1000 ppm) are
also useful. Mix standards should be chosen carefully considering the difference in responses
of individual ions in a chromatogram.
Calibration Standards preparation:
Prepare Standard Mix - A solution containing 100 ppm each Cl-, from 1000 ppm stock
by diluting the same.
Repare Standard Mix – B solution containing F- (5 ppm) and 20 ppm Br by diluting the
respective stock. Final calibration standards for 6 levels are prepared following the Table given
2. Prepare fresh working calibration standards weekly and refrigerate when not in use. Stock
Standards may be used for 6 months if refrigerated properly.
Table 2 : Calibration Standards preparation guidelines (Final volume 100 ml)

Ions Level I Level II Level III Level IV Level V Level VI
15 ml A
0.5ml A + 1 ml A + 2 ml A + 5 ml A + 10 ml A +
+ 15
0.5 mL B 1 mL B 2 mL B 5 mL B 10 mL B
mL B
Fluoride 0.025 0.05 0.1 0.25 0.5 1.0
Chloride 0.5 1.0 2.0 5.0 15.0 15.0
Bromide 0.1 0.2 0.4 1.0 3.0 3.0
42
Eluent:
It is specific for brand and make to instrument and columns being used. For concentration
and composition of eluent please refer to the application notes. Generally for anion analysis
NaHCO3 - Na2CO3 eluent is used. Eluents are prepared by dissolving prescribed amount of
chemicals in high purity nano-pure distilled water. Eluents are required to be filtered through
0.22 µm nylon filter.
Suppressor:
Dionex system has inbuilt ionic suppressor system but Metrohm system chemical
suppression for anions with 2.8 mL concentrated (98%) pure H2SO4 diluted in 1 litter is used
for regeneration of suppressor cartridges. Pure water (DI) is used for washing of suppressor
during run.
5.0 SAMPLE HANDLING
Laboratory shall provide chain-of-custody documentation with all sample shipments

to track and ensure that filter samples are collected, transferred, stored, and analyzed
by authorized personnel; sample integrity is maintained during all phases of sample handling
and analysis; and an accurate written record is maintained of sample handling and treatment
from the time of its collection, through the laboratory analytical process, to the eventual
relinquishing of all data to the project coordinator.
Filter / Thimble Extraction Procedure
Filters to be analyzed for halides are extracted with water. Extraction with deionized
water makes it possible to analyze for these ions.
i) Remove filters to be extracted from the freezer and allow them to equilibrate
to room temperature.
ii) Using gloved hands and tweezers, place each filter in cleaned glass beakers (250mL) that
has been labeled with the sample I.D.
iii) Add measured 50-100 mL of deionized water. The extraction volume will depend upon
the quantity of dust accumulated on filter paper.
iv) Place the batch of beakers in ultrasonic bath , expose them to ultrasonic energy in a
bath for 60 minutes at 60 oC, and then allow them to sit at room temperature overnight.
Refrigerate at least one additional night prior to analysis.
v) Record the date of extraction on the Sample Filter Processing Form. Allow the samples
to warm to room temperature just prior to analysis.
43
vi) Filter all the samples by syringe filter using 13 mm 6.6 µm nylon filter disc. Ensure no
particle should pass through in samples to be injected. Injection may be done manually
or through auto sampler.
The liquid sample (alkaline and acidic) analysis
The alkaline and acidic samples are injected separately in IC system and analyzed for
all the three halides.
Note: Different calibration curve for acidic and alkaline analysis may be required to get better
baseline separation in IC system. In this case separate set of calibration Standards in two different
absorbing media shall be prepared
IC Procedure:
i) Fill the eluent reservoirs with the eluent.
ii) Fill the supressor reservoir and distilled water reservoir in case of chemical
supression technique (Metrohm instrument)
iii) Start the eluent flow, activate the self-regenerating suppressor in case of (Dionex
instrument), and allow the baseline to stabilize.
iv) In case of Metrohm instrument ensure that all the three supressor cartridge are
recharged. Start baseline determination wait until stable baseline is achieved.
v) Inject two pure distilled water blanks to flush the system and to ensure that the system is
operating properly.
vi) Using the calibration schedule, perform the monthly multipoint calibration over the
range.
vii) Inject middle level calibration standards daily to know the status of performance.
If the observed value for any ion differs by more than 10 percent from the known values,
identify and correct the problem before analyzing samples.
viii) Load the sample extracts into the autosampler vials according to the schedule prepared
for that day. Typically, fifty field samples are analyzed per day. The daily schedule includes,
at a minimum, 3 duplicate samples, 2 spiked samples and 5 QA/QC samples.
ix) Begin the analysis run, occasionally checking to ensure that the system is operating
properly.
x) Examine the data at the end of the run. If the concentration of any ion exceeds the
upper end of the calibration curve, dilute the sample appropriately and include with
the samples to be analyzed the following day.
44
6.0 CALCULATIONS AND DATA REDUCTION
In-built software will always give some results, which may not be acceptable all the time.
Study each and every chromatogram and perform manual integration of peaks if necessary.
Proceed to report format and copy the results in Excel data sheet.
mHX = K (Vs) (Sx-Bx)
Where
mHX = Mass of HCI, HBr,or HF in sample, µg.
Bx = Mass concentration of applicable absorbing solution blank, µg halide ion (CI-, Br -, F -)

/ ml, not to exceed 1 µg/ml which is 10 times the published analytical detection limit
of 0.1 µg / ml.
Sx = Analysis of sample, µg halide ion (CI-, Br -, F -) / ml
Vs = Volume of filtered and diluted sample, ml.
KHCI = 1.028 (µg HCI / µg-mole) / (µg CI-/µg-mole).
KHBr = 1.013 (µg JBr / µg-mole) / (µg Br- /µg-mole).
KHF = 1.053 (µg HF / µg-mole) / (µg F- /µg-mole).
6.2 Total µg CI-, Br-, F- per Sample
Where
Mx2 = Mass of CI-, Br- or in sample, µg.
Bx = Mass concentration of applicable absorbing solution blank, µg halide ion (CI-, Br-,F-) /
ml, not to exceed 1 µg/ml which is 10 times the published analytical detection limit of
0.1µg/ml.
Sx = Analysis of sample, µg halide ion (CI-, Br-, F-) /ml
Vs = Volume of filtered and diluted sample, ml.
Calculated values for all the aliquots (Thimble, Alkaline trap and acidic trap) are sum
up and the total mass is divided by stanadardised Air volume to get respective concentrations
in mg/Nm3.
Hence, for F, CI2 or Br2
Cx = [{mx2(Thimble) + mx2 (Alkaline trap) + mx2 (Acidic Trap)} * 10-3] / V m(std) mg/Nm3
Where,
Cx = Concentration of CI-, Br-, F- in Flue gas
45
mx2 = Mass of CI-, Br-, or F- in sample (µg) in respective aliquot.
Vm(std) = Dry gas volume measured by the DGM, corrected to standard conditions,Nm3
Hence, for HCI, HBr, or HF
CHX = [{mHX (Thimble) + mHX (Alkaline trap) + mHX (Acidic Trap)} * 10-3] / Vm(std) mg/Nm3
Where,
CHX = Concentration of HCI, HBr or HF in flue gas.

mHX = Mass of HCI,HBr or HF in sample (µg) in respective aliquot.
Vm(std) = Dry gas volume measured by the DGM, corrected to standard conditions, Nm3
Note: Report the concentration as corrected at 11% O2 (as mentioned in the method for PM
determination)
7.0 QUALITY ASSURANCE AND QUALITY CONTROL
The analyst should be familiar with the terms and use of following parameters for QA/QC
Blank:
a sample that has not been exposed to the analyzed sample stream in order to monitor
contamination during sampling, transport, storage or analysis. The blank is subjected to the
usual analytical and measurement process to establish a zero baseline or background value
and is sometimes used to adjust or correct routine analytical results.
Field Blanks:
These are filters that are treated in all ways as a normal sample (including installation on
the sampler) except that no air is sampled on them. (These are also referred to as equipment
blanks in LIMS.)
Continuing Calibration Blank (CCB):
A “zero” standard analyzed along with the CCV standard to verify that the lower end of
the calibration curve remains valid during the analysis of the batch of samples. A CCB is
analyzed at the beginning of each batch, at the end of a batch, and at least every 20 samples
during a batch.
Continuing Calibration Verification Standard (CCV):
A standard analyzed after the initial calibration to verify that the instrument calibration
remains valid. The concentration of this standard is varied over the calibration range during
each run. A CCV is analyzed at the beginning of each batch, at the end of a batch, and at least
every 20 samples during a batch.
46
Laboratory Duplicate:
Aliquots of a sample taken from the same container under laboratory conditions and
processed and analyzed independently. In this SOP, laboratory duplicates are created by
extracting equal portions of the loaded filters.
Matrix Spike (spiked sample or fortified sample):
A sample prepared by adding a known mass of target analyte to a specified amount of

matrix sample for which an independent estimate of Target analyte concentration is available.
Matrix spikes are used, for example, to determine the effect of the matrix on a method’s
recovery efficiency. In this SOP, a matrix spike consists of adding a known concentration of
analyte(s) to a separate aliquot of the filter.
Method Detection Limit (MDL):
Tthe minimum concentration of an analyte that can be identified, measured, and

reported with 99% confidence that the analyte concentration is greater than zero.
Method Reporting Limit (MRL):
The minimum concentration of an analyte that is reported. Generally, this will be 3 to

5 times the concentration of the MDL.
If correlation coefficient for all the multipoint calibration curves does not exceed 0.998,
stop the analysis and identify the problem.
Analyze QC samples at the beginning of every analytical run. Compare the results with
those obtained during previous QC tests. If the observed concentration of any ion differs from
the known value by greater than 10%, stop the analysis until the problem is identified and
corrected. Analyze a duplicate sample, a QA/QC sample, and a spiked sample after at least
every 20 field samples.
8.0 REFERENCES
1. DRI Document No. 8068.1F4, Appendix D, Section 4.2
2. Steinsberger, S. C. and J. H. Margeson, “Laboratory and Field Evaluation of a Methodology

for Determination of Hydrogen Chloride Emissions from Municipal and Hazardous
Waste Incinerators,” U.S. Environmental Protection Agency, Office of Research and
Development, Report No. 600/3- 89/064, April 1989. Available from the National
Technical Information Service, Springfield, VA 22161 as PB89220586/AS.
3. State of California, Air Resources Board, Method 421, “Determination of Hydrochloric

Acid Emissions from Stationary Sources,” March 18, 1987. 3. Cheney, J.L. and
47
C.R. Fortune. Improvements in the Methodology for Measuring Hydrochloric Acid in
Combustion Source Emissions. J. Environ. Sci. Health. A19(3): 337-350. 1984.
4. Stern, D. A., B. M. Myatt, J. F. Lachowski, and K. T. McGregor. Speciation of Halogen and

Hydrogen Halide Compounds in Gaseous Emissions. In: Incineration and Treatment
of Hazardous Waste: Proceedings of the 9th Annual Research Symposium, Cincinnati,
Ohio, May 2-4, 1983. Publication No. 600/9- 84-015. July 1984. Available from
National Technical Information Service, Springfield, VA 22161 as PB84-234525.
5. Holm, R. D. and S. A. Barksdale. Analysis of Anions in Combustion Products. In: Ion

Chromatographic Analysis of Environmental Pollutants. E. Sawicki, J. D. Mulik, and E.
Wittgenstein (eds.) Ann Arbor, Michigan, AnnArbor Science Publishers. 1978. pp. 99-
110.
6. Steinsberger, S. C. and J. H. Margeson. Laboratory and Field Evaluation of a Methodology

for Determination of Hydrogen Chloride Emissions from Municipal and Hazardous
Waste Incinerators. U.S. Environmental Protection Agency, Office of Research and
Development. Publication No. 600/3-89/064. April 1989. Available from National
Technical Information Service, Springfield, VA 22161 as PB89220586/AS.
7. State of California Air Resources Board. Method 421 - Determination of Hydrochloric

Acid Emissions from Stationary Sources. March 18, 1987.
8. Cheney, J.L. and C.R. Fortune. Improvements in the Methodology for Measuring
Hydrochloric Acid in Combustion Source Emissions. J. Environ. Sci. Health. A19(3): 337-
350. 1984.
9. Stern, D.A., B.M. Myatt, J.F. Lachowski, and K.T. McGregor. Speciation of Halogen and
Hydrogen Halide Compounds in Gaseous Emissions. In: Incineration and Treatment
of Hazardous Waste: Proceedings of the 9th Annual Research Symposium, Cincinnati,
Ohio, May 2-4, 1983. Publication No. 600/9- 84-015. July 1984. Available from National
Technical Information Service, Springfield, VA 22161 as PB84-234525.
10. Holm, R.D. and S.A. Barksdale. Analysis of Anions in Combustion Products. In: Ion
Chromatographic Analysis of Environmental Pollutants, E. Sawicki, J.D. Mulik, and E.
Wittgenstein (eds.). Ann Arbor, Michigan, Ann Arbor Science Publishers. 1978. pp. 99-
110.
48
CHAPTER - 4
Standard Operating Procedure for the Sampling of Hydrogen Halides (Hx) and Halogens
from Source Emission
1.0 Purpose and Applicability

This method is applicable for determining emissions of hydrogen halides (HX) and
halogens from stationary sources. Same method may be applicable for those sources, which
are controlled by wet scrubbers and emit acidic particulate matter.
1.1 Detection Limit
The in-stack detection limit is approximately 0.05 µg / liter of stack gas; the analytical
detection limit is 0.1 µg / ml.
2.0 Pre sampling activity
• Rinse all sampling train glassware with hot tap water and then wash in hot soapy
water.
• Rinse glassware three times with tap water, followed by three additional rinses with
distilled water.
• Soak all glassware in a 10 percent (V/V) nitric acid solution for a minimum of 2 hours,
• Later rinse three times with distilled water, rinse finally with acetone, and allow to air dry
cover all glassware openings where contamination can occur until the sampling train is
assembled for sampling.
3.0 Preparation of Reagents
3.1 Sampling Reagent
• Deionized, distilled water
• Sulfuric Acid (H2SO4) 0.1 N
• Add 0.28 ml of concentrated H2SO4 to 90 ml of distilled water while stirring.
• Make final volume upto 100 ml for front impinger pair.
• Sodium Hydroxide (NaOH) (0.1 N)
• Dissolve 0.40 g of solid NaOH in 90 ml of water and make final volume up to 100 ml
for third and fourth impinger.
• Sodium Thiosulfate (Na2S2O3 , 5H2O) powder.
3.2 Analytical Reagents
• Deionised / nano pure distilled water
• Absorbing Solution Blanks
49
• Stock Standard Solutions
• Field activities start with the collection of details information from the industry about
products, materials, fuel and stack.
4.0 Field Activities and Isokinetic Sampling
Determine the stack pressure, temperature, leak check, calculation of Isokinetic velocity,
volumetric flow rate, flow at nozzle/ selection of nozzle, adjustment of flow rate at rotameter,
temperature at metering point and volume of gas sampled, pressure drop during sampling as
described in the SOP of the particulate matter.
Note:
For the Calculation of isokinetic velocity and collection of the sample refer Method -1 “Stack
monitoring – Material and Methodology for Isokinetic Sampling” or SOP for the particulate
matter determination
5.0 Preparation of the Sampling Train
• Pour 50 ml of the acidic absorbing solution into each one of the first pair of
impingers
• Pour 50 ml of the alkaline absorbing solution into each one of the second pair of
impingers
• Connect the impinger in series with empty knockout impinger first if used (See Figure
1)
• Place a fresh charge of silica gel, or equivalent, in the drying tube or impinger (after the
one more optional empty impinger) at the end of the impinger train.
• Adjust the probe temperature and the temperature of the filter and the stopcock
temperature sufficient to prevent water condensation. Temperature should be at least 20
o
C above the source temperature, but not greater than 120 oC. The temperature should
be monitored to ensure that the desired temperature is maintained.
6.0 Sample Collection
• Turn on the vacuum pump and make a slight vacuum of 25 mm Hg (1 in. Hg). Set the
sampling rate in gaseous train at 2 LPM & allow rest of the flow for Isokinetic sampling
rate in particulate train.
• Take readings of the dry gas meter volume and temperature, rotameter, and vacuum
gauge at least once every five minutes during the run.
• Sampling should be carried out for 1 hr or for the duration sufficient to collect samples
to be detected above detection limit.
• During calculation of volume of air passes through the impinger & filter should be done
by adding both the flow rate multiplied by sampling time.
• At the completion of sampling remove the train from the stack and cool it.
50
7.0 Sample Recovery
• Collect filter separately. No heating should be done in conditioning of filter preferably
desiccation or use of conditioning room is suggested.
• Disconnect the impingers; quantitatively transfer the contents of the acid impingers and
the first empty impinger, if used, to a leak-free storage bottle.
• Add the water rinses of each of these impingers and connecting glassware to the storage
bottle. Quantity of rinsing should not be used more than 25ml.
• Repeat this procedure for the alkaline impingers and connecting glassware using a
separate storage bottle. Quantity of rinsing water should not be used more than 25ml.
• Add 25 mg sodium thiosulfate to ensure complete reaction with the hypohalous
acid to form second Cl- ion in the alkaline solution.
• Save portions of the absorbing reagents (0.1 N H2SO4 and 0.1 N NaOH) equivalent
to the amount used in the sampling train dilute to the approximate volume of the
corresponding samples using rinse water directly from the wash bottle being used. Add
the same (25mg) amount of sodium thiosulfate solution to the 0.1 N NaOH absorbing
solution blank.
• Also, save a portion of the rinse water used to rinse the sampling train. Place each in a
separate, prelabeled storage bottle. The sample storage bottles should be sealed, shaken
to mix, and labeled. Mark the fluid level.
51
52
Table - 1
Field Data Sheet
Name & Address

monitoring
o ID fan capacity
o House keeping

Representative of
53
CHAPTER - 5
DETERMINATION OF METALS AND NON METALS EMISSIONS FROM
STATIONARY SOURCES
1.0 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 for Hg by cold vapor atomic
absorption spectroscopy (CVAAS) and for Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, P, Se, Ag,
Tl, and Zn by inductively coupled argon plasma emission spectroscopy (ICAP) or atomic
absorption spectroscopy (AAS). Graphite furnace atomic absorption spectroscopy (GFAAS)
is used for analysis of Sb, As,Cd, Co, Pb, Se, and Tl if these elements require greater analytical
sensitivity then can be obtained by ICAP. One can choose AAS for analysis of all listed metals.
Similarly, inductively coupled plasma-mass spectroscopy (ICP-MS) may be used for analysis of
Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, As, Tl and Zn.
2.0 APPLICABILITY
This method is applicable for determination of antimony (Sb), arsenic (As), barium (Ba),
beryllium (Be), cadmium (Cd), chromium (Cr), cobalt (Co),copper (Cu), lead (Pb), manganese
(Mn), mercury (Hg), nickel (Ni), phosphorus (P), selenium (Se), silver (Ag), thallium (Tl),
and zinc (Zn) emissions from stationary sources. This method may be used to determine
particulate emissions in addition to the metals emissions if the prescribed procedures and
precautions are followed.
2.1 Range and sensitivity
Front - half: Back - half: Back - half:

Metal Total Train:
Probe and Filter Impingers 1-3 Impingers 4-6a
1 1 1
Antimony 7.7 (0.7) 3.8(0.4) 11.5(1.1)
1 1 1
Arsenic 12.7 (0.3) 6.4 (0.1) 19.1 (0.4)
Barium 0.5 0.3 0.8

1 1 1
Beryllium 0.07 (0.05) 0.04 (0.03) 0.11 (0.08)
1 1 1
Cadmium 1.0 (0.02) 0.5 (0.01) 1.5 (0.03)
54
1 1 1
Chromium 1.7 (0.2) 0.8 (0.1) 2.5 (0.3)
1 1 1
Cobalt 1.7 (0.2) 0.8 (0.1) 2.5 (0.3)
Copper 1.4 0.7 2.1
1 1 1
Lead 10. (0.2) 5.0 (0.1) 15.1 (0.3)
1 1 1
Manganese 0.5 (0.2) 0.2 (0.1) 0.7 (0.3)
2 2 2 2
Mercury 0.06 0.3 0.2 0.56
Nickel 3.6 1.8 5.4
Phosphorus 18 9 27
1 1 1
Selenium 18 (0.5) 9. (0.3) 27 (0.8)
Silver 1.7 0.9 (0.7) 2.6
1 1 1
Thallium 9.6 (0.2) 4.8 (0.1) 14.4 (0.3)
Zinc 0.5 0.3 0.8
a
Marcury analysis only.
1
Detection limit when analyzed by GFASS.
2
Detection limit when analysed by CVAAS, estimated for Back-half and total train.
Note: Actual method detection limits may vary from these values, because the stack kit,QA/QC,
expertise in sampling and analyses here considered as per USEPA.
3.0 INTERFERENCES
Iron (Fe) can be a spectral interference during the analysis of As, Cr, and Cd by ICAP.
Aluminum (Al) can be a spectral interference during the analysis of As and Pb by ICAP. Generally,
these interferences can be reduced by diluting the analytical sample, but such dilution raises
the in-stack detection limits. Background and overlap corrections may be used to adjust for
spectral interferences.
3.1 Sampling Train
It has general similarities to the particulate sampling train. A schematic of the sampling train
is shown in Figure-1.
55
3.1.1 Condenser
Use the following system for condensing and collecting gaseous metals and
determining the moisture content of the stack gas. The condensing system shall consist of four to
seven impingers connected in series with leak-free ground glass fittings or other leak-free, non-
contaminating fittings. Use the first impinger as a moisture trap. The second impinger (which
is the first HNO3 /H2O2 impinger) shall be identical to the first impinger. The third impinger
(which is the second HNO3 / H2O2 impinger) shall be a Greenburg Smith impinger with the
standard tip. The fourth (empty) impinger and the fifth and sixth (both acidified KMnO4)
impingers. Place a thermometer capable of measuring temperature of 1 oC at the outlet of the
last impinger. If no Hg analysis is planned, then the fourth, fifth, and sixth impingers are not
required.
4.0 REAGENTS
Table 1 : Sampling reagents
S No. Reagent Description
1 Sample Filters without organic The filters shall contain less than 1.3 µg/in. of
binders each of the metals to be measured. However,
if glass fiber filters become available which
meet these requirements, they may be used.
56
2 Ultrapure Distilled Water All target metals should be less than 1 ng/ml.
3 Nitric Acid (HNO3). Concentrated.
4 Hydrochloric Acid (HCL). Concentrated
5 Hydrogen Peroxide (H2O2) 30 Percent (V/V).
6 Potassium Permanganate (KMnO4).
7 Sulfuric Acid (H2SO4). Concentrated
8 Silica Gel and Crushed Ice
4.2 Pretest Preparation of Sampling Reagents

Tabel 2 : Preparation of sampling reagents
S. No. Reagent Procedure for preparation
1 HNO3/H2O2 Absorbing Solution, 5 Add carefully with stirring 50 ml of concentrated
Percent HNO3/10 Percent H2O2 HNO3 to a 1000-ml volumetric flask containing
approximately 500 ml of water, and then add
carefully with stirring 333 ml of 30 percent
H2O2. Dilute to volume with water. Mix well.
This reagent shall contain less than 2 ng/ml of
each target metal.
2 Acidic KMnO4 Absorbing Solution Dissolve, with stirring, 40 g of KMnO4 into 100
ml percent H2SO4 (V/V) and add 10 percent
H2SO4 (V/V) with stirring to make volume of
1 filter. Prepare and store in glass bottles to
prevent degradation. This reagent shall contain
less than 2 ng/ml of Hg.
Precaution: To prevent autocatalytic
decompossition of the permanganate solution,
filter the solution through whatman 541 filter
paper. Also, due to the potential reaction of
the potassium permanganate with the acid,
there could be pressure buildup in the solution
storage bottle. Therefore, these bottles shall
not be fully filled and shall be vented to
reliebe excess pressure and prevent explosion
potentials. Venting is required, but not in a
manner that will allow contamination of the
solution.
57
3 0.1N HNO3 Add with stirring 6.3 ml of concentrated HNO3
(70 Percent) to a flask containing approximately
900 ml of water. Dilute to 1000 ml with water.
Mix well. This reagent shall contain less than 2
ng/ml of each target metal.
4 8 N HCI Carefully add with stirring 690 ml of
concentrated HCI to a flask containing 250 ml
of water. Dilute to 1000 ml with water. Mix
well. This reagent shall contain less than 2 ng/
ml of Hg.
5.0 PROCEDURE
5.1 Sampling
The complexity of this method is such that, to obtain reliable results, both testers and
analysts must be trained and experienced with the test procedures, including source sampling;
reagent preparation and handling; sample handling; safety equipment and procedures;
analytical calculations; reporting; and the specific procedural descriptions throughout this
method.
5.1.1 Pretest preparation
Unless particulate emissions are to be determined, the filter need not be

desiccated or weighed. First, rinse all sampling train glassware with hot tap water and then
wash in hot soapy water. Next, rinse glassware three times with tap water, followed by three
additional rinses with water. Then soak all glassware in a 10 percent (V/V) nitric acid solution for
a minimum of 4 hours, rinse three times with water, rinse a final time with acetone, and allow
to air dry. Cover all glassware openings where contamination can occur until the sampling
train is assembled for sampling.
5.1.2 Preliminary determinations
Perform leak check. Determine the stack pressure, temperature, calculation of Isokinetic
velocity, volumetric flow rate, flow at nozzle/ selection of nozzle, adjustment of flow rate
at rotameter, temperature at metering point and volume of gas sampled, pressure drop during
sampling as described in the SOP of the particulate matter.
Note:
Calculate isokinetic velocity and collect the sample following the SOP prescribed for particulate
monitoring.
5.1.3 Preparation of sampling train:
a. Set up the sampling train as shown in Figure-1.
58
b. Use the first impinger (empty) as a moisture trap.
c. Place 100 ml of the HNO3 /H2O2 solution in each of the second and third impingers as
shown in Figure -1.
d. Keep another Empty impinger in 4th position.
e. Place 100 ml of the acidic KMnO4 absorbing solution in each 5th and 6th impingers as
shown in Figure 1,
f. Transfer approximately 200 to 300 g of pre-weighed silica gel from its container to the
last impinger.
g. If Hg analysis will not be performed, the fourth, fifth, and sixth impingers as shown in
Figure -1 are not required.
h. To insure leak-free sampling train connections and to prevent possible sample

contamination problems, use Teflon tape or other non-contaminating material instead
of silicone grease.
Precaution:
• Exercise extreme care to prevent contamination within the train.
• Prevent the acidic KMnO4 from contacting any glassware that contains sample material
to be analyzed for Mn. Prevent acidic H2O2 from mixing with the acidic KMnO4.
• Leak Check Procedures. Initial and final reading in Hg guage should be noted. If the
pressure drop during sampling is not quantifiable then the whole process shall be
repeated after ensuring there is no leak in sampling train
5.2 Sample Recovery
Begin cleanup procedures as soon as the probe is removed from the stack at the end
of a sampling period. The probe should be allowed to cool prior to sample recovery. When
it can be safely handled, wipe off all external particulate matter near the tip of the probe
nozzle and place a rinsed, non-contaminating cap over the probe nozzle to prevent losing or
gaining particulate matter. Do not cap the probe tip tightly while the sampling train is cooling;
a vacuum can form in the filter holder with the undesired result of drawing liquid from the
impingers onto the filter. Before moving the sampling train to the cleanup site, remove the
probe from the sampling train and cap the open outlet. Be careful not to lose any condensate
that might be present. Cap the filter inlet where the probe was fastened. Remove the umbilical
cord from the last impinger and cap the impinger. Cap the filter holder Outlet and impinger
inlet. Use non contaminating caps, whether ground-glass stoppers, plastic caps, serum caps,
or Teflon tape to close these openings.
59
Transfer the probe and filter-impinger assembly to a cleanup area that is clean and
protected from the wind and other potential causes of contamination or loss of sample.
Inspect the train before and during disassembly and note any abnormal conditions. Take
special precautions to assure that all the items necessary for recovery do not contaminate the
samples.
Container No.1 (Sample Filter)
Carefully remove the filter from the filter holder and place it in its labeled petri dish
container. To handle the filter, use either acid washed polypropylene or Teflon coated tweezers
or clean, disposable surgical gloves rinsed with water and dried. If it is necessary to fold the
filter, make certain the particulate cake is inside the fold. Carefully transfer the filter and any
particulate matter or filter fibers that adhere to the filter holder gasket to the Petri dish by using
a dry (acid cleaned) nylon bristle brush. Do not use any metal- containing materials when
recovering this train. Seal the labeled Petri dish. See the Figure – 2.
Container No. 2 (Probe Rinse)
Keep the probe assembly clean and free from contamination during the probe rinse.
Rinse the probe nozzle and fitting, probe liner, and front-half of the filter holder thoroughly
with a total of 100 ml of 0.1 N HNO3 and place the wash into a sample storage container.
Note:The use of exactly 100 ml is necessary for the subsequent blank correction rocedures.
Record the volume of the rinses Mark the height of the fluid level on the outside of the
Storage container and use this mark to determine if leakage occurs during transport. Seal
the container, and clearly label the contents. Finally, rinse the nozzle, probe liner, and front-half
of the filter holder with water followed by acetone, and discard these rinses. (See figure – 2).
Container No. 3 (Impingers 1 through 3
Moisture Knockout Impinger when used, HNO3 /H2O2 Impingers Contents and Rinses).
Due to the potentially large quantity of liquid involved, the tester may place the impinger
solutions from impingers 1 through 3 in more than one container, if necessary. Measure
the liquid in the first three impingers to within 0.5 ml using a graduated cylinder. Record the
volume. This information is required to calculate the moisture content of the sampled flue gas.
Clean each of the first three impingers, the filter support, the back half of the filter housing,
and connecting glassware by thoroughly rinsing with 100 ml of 0.1 N HNO3
Note: The use of exactly 100 ml of 0.1 N HNO3 rinse is necessary for the subsequent
blank correction procedures. Combine the rinses and impinger solutions, measure and
record the final total volume. Mark the height of the fluid level, seal the container, and clearly
label the contents. (See figure 2.1)
Container Nos.4A (0.1 N HNO3), 4B (KMnO4 /H2SO4 absorbing solution), and 4C (8 N

HCl rinse and dilution).
60
When sampling for Hg, pour the liquid from impinger No. 4 into a graduated cylinder
and measure the volume to within 0.5 ml. This information is required to calculate the moisture
content of the sampled flue gas. Place the liquid in Container No. 4A. Rinse the impinger with
exactly 100 ml of 0.1 N HNO3 and place this rinse in Container No. 4A.
Pour all the liquid from the two permanganate impingers into a graduated cylinder and
measure the volume to within 0.5 ml. This information is required to calculate the moisture
content of the sampled flue gas. Place this acidic KMnO4 solution into Container No. 4B.
Using a total of exactly 100 ml of fresh acidified KMnO4 solution for all rinses (approximately
33 ml per rinse), Similarly, using 100 ml total of water, rinse the permanganate impingers and
connecting glass a minimum of three times, and pour the rinses into Container 4B, carefully
assuring transfer of any loose precipitated material. Mark the height of the fluid level, and
clearly label the contents.
NOTE: Due to the potential reaction of KMnO4 with acid, pressure buildup can occur in the
sample storage bottles. Do not fill these bottles completely and take precautions to relieve
excess pressure.
If deposits remain on the impinger surfaces, wash them with 25 ml of 8 N HCl, and
place the wash in a separate sample Container No. 4C containing 200 ml of water. First, place
200 ml of water in the container. Then wash the impinger walls and stem with the HCl by
turning the impinger on its side and rotating it so that the HCl contacts all inside surfaces. Use
a total of only 25 ml of 8 N HCl for rinsing both permanganate impingers combined. Rinse the
first impinger, then pour the actual rinse used for the first impinger into the second impinger
for its rinse. Finally, pour the 25 ml of 8 N HCl rinse carefully into the container. Mark the
height of the fluid level on the outside of the container to determine if leakage occurs
during transport. See figure 2.2
Container No. 5 (Silica Gel)
Note the color of the indicating silica gel to determine whether it has been completely
spent and make a notation of its condition. Transfer the silica gel from its impinger to its
original container and seal it. The small amount of particles that might adhere to the impinger
wall need not be removed. Do not use water or other liquids to transfer the silica gel since
weight gained in the silica gel impinger is used for moisture calculations. Alternatively, if a
balance is available in the field, record the weight of the spent silica gel (or silica gel plus
impinger) to the nearest 0.5 g.
• Container No. 6A (0.1 N HNO3 Blank).
• Container No. 6B (Water Blank).
• Container No. 7 (5 Percent HNO3 /10 Percent H2O2 Blank).
• Container No. 8 (Acidified KMnO4 Blank).
61
• Container No. 9 (8 N HCl Blank).
• Container No. 10 (Sample Filter Blank)
5.3 Sample Preparation
Note the level of the liquid in each of the containers and determine if any sample was
lost during shipment. A diagram illustrating sample preparation and analysis procedures for
each of the sample train components is shown in Figure –3 and Figure - 3.1
Container No. 1 (Sample Filter)
If particulate emissions are being determined, first desiccate the filter and filter catch
without added heat (do not heat the filters to speed the drying) and weigh to a constant weight
as described in the term “constant weight” means a difference of no more than 0.5 mg or
l percent of total weight less tare weight, whichever is greater, between two consecutive
weighing, with no less than 6 hours of desiccation time between two weighing.
Option I – Microwave digestion
Make pieces of filter papers/thimbles (Do not use metallic scissor). Place the pieces
in the analyst’s choice of either individual microwave pressure relief vessels or ParrR Bombs.
Add 6 ml of concentrated HNO3 and 4 ml of concentrated HF to each vessel. For microwave
heating, microwave the samples for approximately 12 to 15 minutes total heating time as
follows: heat for 2 to 3 minutes, then turn off the microwave for 2 to 3 minutes, then heat for
2 to 3 minutes, etc., continue this alternation until the 12 to 15 minutes total heating
time are completed (this procedure should comprise approximately 24 to 30 minutes at
600 watts). Microwave heating times are approximate and are dependent upon the number
of samples being digested simultaneously. Sufficient heating is evidenced by sorbent reflux
within the vessel. Then cool the samples to room temperature.
Option II – Hot Plate Digestion
Place the pieces of thimbles in acid cleaned beaker add about 50 ml water, add 6 ml
of concentrated HNO3 and 4 ml of concentrated HF to it. Place it on hot plate under fume
extraction hood. Set the Temperature at 70 oC. Continue to digest for 12 hrs.
Verify that the pH of this sample is 2 or lower. If it is not, acidify the sample by careful
addition with stirring of concentrated HNO3 to pH 2. Use water to rinse the sample into
a beaker, and cover the beaker with a ribbed watch glass. Reduce the sample volume to
approximately 20 ml by heating on a hot plate at a temperature below boiling. Add 6 ml
of concentrated HNO3 and 4 ml of concentrated HF to it. Place it on hot plate under fume
extraction hood. Set the Temperature at 70 oC Continue the digestion for 12 hrs. If the
62
sampling train includes an optional glass cyclone in front of the filter, prepare and digest the
cyclone catch by the same way. Then combine the resultant sample directly with the acid
digested portions of the filter prepared previously, acid rinse concentrate and cyclone catch
concentrate (If done). Filter the combined sample using Whatman 41 filter paper. Dilute to
300 ml (or the appropriate volume for the expected metals concentration) with water. This
diluted sample is “Analytical Fraction 1”. Measure and record the volume of Analytical Fraction
1 to within 0.1 ml. Quantitatively remove a 50-ml aliquot and label as “Analytical Fraction
1B”. Label the remaining 250-ml portion as “Analytical Fraction 1A”. Analytical Fraction 1A is
used for ICAP or AAS analysis for all desired metals except Hg. Analytical Fraction 1B is used
for the determination of front-half Hg. This fraction should be treated with acid and KMnO4 at
90oC for 2 hours. Excess KMnO4 should be removed by using Hydroxylamine Hydrochloride
before analysis of Hg.
Container No.3 (Impingers 1-3)
Measure and record the total volume of this sample to within 0.5 ml, if the leakage
found significant make up with fresh distilled water. Remove a 75- to 100-ml aliquot for
Hg analysis and label the aliquot “Analytical Fraction 3B”. Label the remaining portion as
“Sample Fraction 3A”. Verify that the pH of Sample Fraction 3A is 2 or lower. If necessary,
use concentrated HNO3 by careful addition and stirring to lower the pH upto 2. Use water
to rinse Sample Fraction 3A into a beaker and then cover the beaker with a ribbed watch
glass. Reduce Sample to approximately 20 ml by heating on a hot plate at a temperature
just below boiling. Add 30 ml of 50 percent HNO3 and heat for 30 minutes on a hot plate
to just below boiling. Add 10 ml of 3 percent H2O2 and heat for 10 more minutes. Add 50
ml of hot water, and heat the sample for an additional 20 minutes. Cool, filter the sample,
and dilute to 150 ml (or the appropriate volume for the expected metals concentrations) with
water. Analytical Fraction 3A is analyzed for all metals except Hg. Analytical fraction 3B will be
digested separately with HCl and KMnO4 at 90 oC for two hours. Excess Permanganate should
be removed by Hydroxylamine Hydrochloride before analysis in Cold Vapour AAS.
Container No. 4A (Empty impnger washing liquid with 0.1 N HNO3 ), 4B (KMnO4 /
H2 SO4 absorbing solution of impinger 5 and 6), and 4C (8 N HCl rinse of impinger 5
and 6 for scaling of MnO2).
Keep the samples in Containers Nos. 4A, 4B, and 4C separate from each other. Measure
and record the volume of 4A to within 0.5 ml. Concentrate the sample upto 20 ml on hot
plate at below boiling temperature. Keep it separate. To remove any brown MnO2 precipitate
from the contents of Container No. 4B, filter its contents through Whatman 40 filter paper
into a 500 ml volumetric flask, make up the volume with distilled water. This fraction is
analytical fraction 4B. Save the filter for digestion of the brown MnO2 precipitate. Place the
saved filter into an appropriately sized vented container, which will allow release of any gases
including chlorine formed when the filter is digested in a laboratory hood. Add 25 ml of 8 N
63
HCl to the filter and allow to digest for a minimum of 24 hours at room temperature. Filter
the contents of Container No. 4C through a Whatman 40 filter into a 500-ml volumetric flask.
Then filter the result of the digestion of the brown MnO2 from Container No. 4B through a
Whatman 40 filter into the same 500-ml volumetric flask, and dilute and mix well to
volume with water. Discard the Whatman 40 filter. Mark this combined 500-ml dilute HCl
solution as Analytical fraction 4C. So three samples will be generated in this section for Hg
analysis. All these fractions shall be digested and concentrated to desired volume with HCl and
KMnO4 at 90 oC for two hours. Excess Permanganate should be removed by Hydrxylamine
Hydrochloride before analysis in Cold Vapour AAS.
Weigh the spent silica gel (or silica gel plus impinger) to the nearest 0.5 g using a balance.
5.4 Sample Analysis

For each sampling train sample run, seven individual analytical samples are
generated ; two (Analytical fraction 1A and 3A) for all desired metals except Hg, and five
for Hg (Analytical fraction 1B, 3B, 4A, 4B and 4C). A schematic identifying each sample
container and the prescribed analytical preparation and analysis scheme is shown in Figure
3 and Figure 3.1. Blanks for all reagents used should be processed with samples in parallel.
6.0 CALCULATIONS
For Molecular weight determination, Stack gas velocity, Isokinetic Flow rate,
Moisture content and parameters required for particulate emission calculation follow the
formulae mentioned in method prescribed for particulate matter determination.
Dry Gas Volume. Using the data from this test, calculate V , the dry gas sample volume
at standard conditions m(std) as outline Correct the sample volume measured by the
dry gas meter to standard conditions (25 oC, 760 mm Hg or 68 oF, 29.92 inch Hg) by using
following Equation. Where, Y is DGM Calibration Factor.
Tstd Pbar Pbar

Vmstd = Vm Y = K1 Y Vm
Tm Pstd Pm
Where:

Pstd = Standard absolute pressure,760 mm Hg (29.92 in.Hg).
64
Nm3
Calculate all the seven fraction (2 for other metals and 5 for mercury) in mass of
individual elements following the formula
Metals (Except Hg) in Source Sample.
Mx = Cx (ppm) * D * Vds
Where:
Mx = Total mass of each metal in µg.
Cx = Concentration of metal in respective fraction as read from the standard curve in µg/ml
(ppm) after respective blank subtraction
D = dilution Factor
Vds = Totalvolume of digested smaple solution in Analytical fraction ml.
Mx values calculated for fraction 1A and 3A should be added individually to represent

to total mass for each metals except Hg. The concentration emitted from stack would be
calculated as below.
{Mx(1A) + Mx(3A)} * 10-3 / Vm(std) mg/NM3
Similarly for Hg
{Mx(1B) + Mx(3B) + Mx(4A) + Mx(4C)} * 10-3 / Vm(std) mg/NM3
Note: Report concentration as corrected at 11% O2
65
66
67
68
7.0 REFERENCES
1. Method 303F in Standard Methods for the Examination of Water Wastewater, 15th
Edition, 1980. Available from the American Public Health Association, 1015 18th Street
N.W., Washington, D.C. 20036.
2. EPA Methods 6010, 6020, 7000, 7041, 7060, 7131, 7421, 7470, 7740, and 7841, Test
Methods for Evaluating Solid Waste: Physical/Chemical Methods. SW-846, Third Edition,
November 1986, with updates I, II, IIA and IIB. Office of Solid Waste and Emergency
Response, U. S. Environmental Protection Agency, Washington, D.C. 20460.
3. EPA Method 200.7, Code of Federal Regulations, Title 40, Part 136, Appendix C. July 1,
1987.
4. EPA Methods 1 through 5, Code of Federal Regulations, Title 40, Part 60, Appendix A
July 1, 1991.
5. EPA Method 101A, Code of Federal Regulations, Title 40, Part 61, Appendix B, July 1,
1991.
69
CHAPTER - 6
PART I
STANDARD OPERATING PROCEDURE (SOP) FOR SAMPLING OF METALS
AND NON METALS
&
PART II
STANDARD OPERATING PROCEDURE (SOP) OF SAMPLE PREPARATION
FOR ANALYSIS OF METALS AND NON METALS
Disclaimer:
These Standard Operating Procedures (SOPs) are only guidelines for sampling and analysis of
metals and non metals in incinerator stack emissions. Concerned Institutes/ Organizations/
laboratories may modify the analytical part according to their need; infrastructure and men
power training involved maintaining the QA/QC protocol as required by the method.
70
CHAPTER - 6
Part-I
STANDARD OPERATING PROCEDURE FOR SAMPLING OF METALS AND NON METALS
1.0 Purpose and Applicability
This method is applicable for determination of antimony (Sb), arsenic (As), barium (Ba),
beryllium (Be), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), lead (Pb),
manganese (Mn), mercury (Hg), nickel (Ni), phosphorus (P), selenium (Se), silver (Ag), thallium
(Tl), and zinc (Zn) emissions from stationary sources. This method may be used to determine
particulate emissions in addition to the metals emissions if the prescribed procedures and
precautions are followed.
1.1 Range and sensitivity
Front - half: Back - half: Back - half:

Metal Total Train:
Probe and Filter Impingers 1-3 Impingers 4-6a
1 1 1
Antimony 7.7 (0.7) 3.8(0.4) 11.5(1.1)
1 1 1
Arsenic 12.7 (0.3) 6.4 (0.1) 19.1 (0.4)
Barium 0.5 0.3 0.8
1 1 1
Beryllium 0.07 (0.05) 0.04 (0.03) 0.11 (0.08)
1 1 1
Cadmium 1.0 (0.02) 0.5 (0.01) 1.5 (0.03)
1 1 1
Chromium 1.7 (0.2) 0.8 (0.1) 2.5 (0.3)
1 1 1
Cobalt 1.7 (0.2) 0.8 (0.1) 2.5 (0.3)
Copper 1.4 0.7 2.1
1 1 1
Lead 10.1 (0.2) 5.0 (0.1) 15.1 (0.3)
1 1 1
Manganese 0.5 (0.2) 0.2 (0.1) 0.7 (0.3)
2 2 2 2
Mercury 0.06 0.3 0.2 0.56
71
Nickel 3.6 1.8 5.4
Phosphorus 18 9 27
1 1 1
Selenium 18 (0.5) 9. (0.3) 27 (0.8)
Silver 1.7 0.9 (0.7) 2.6
1 1 1
Thallium 9.6 (0.2) 4.8 (0.1) 14.4 (0.3)
Zinc 0.5 0.3 0.8
a
Marcury analysis only.
1
Detection limit when analyzed by GFASS.
2
Detection limit when analysed by CVAAS, estimated for Back-half and total train.
Note: Actual method detection limits may vary from these values, because the stack kit,QA/QC,
expertise in sampling and analyses here considered as per USEPA.
2.0 Pre sampling activity
Rinse all sampling train glassware with hot tap water and then wash in hot soapy water.
Rinse glassware three times with tap water, followed by three additional rinses with distilled
water.
Soak all glassware in a 10 percent (V/V) nitric acid solution for a minimum of 4 hours,
later rinse three times with distilled water, rinse finally with acetone, and allow to air dry. Cover
all glassware openings where contamination can occur until the sampling train is assembled for
sampling.
3.0 Preparation of reagent

• Sample Filters without any organic binders
• Quartz or GF filters shall contain less than 1.3 µg / inch 2 of each of the metals to be
measured.
• Ultrapure distilled water.
• Concentrated Nitric Acid (HNO3)
• Concentrated Hydrochloric Acid (HCl)
72
• Hydrogen Peroxide (H2O2) 30 Percent (V/V)
• Potassium Permanganate (KMnO4)
• Sulfuric Acid (H2SO4)
• Silica Gel
3.2 Preparation of sampling reagents
HNO3 /H2O2 Absorbing Solution, 5 Percent HNO3 /10 Percent H2O2
Add 50 ml of concentrated HNO3 to a 1000-ml volumetric flask containing
approximately 500 ml of water add carefully with stirring 333 ml of 30 percent H2O2,
Make up the volume with distilled water.
Acidic KMnO4 Absorbing Solution (4 % KMnO4 (W/V), in 10 Percent H2SO4 (V/V).
Mix carefully, with stirring, 100 ml of concentrated H2SO4 into approximately 800 ml
of water, and add water with stirring to make a volume of 1 liter: this solution is 10 % H2SO4
(V/V). Dissolve 40 g of KMnO4 into 10 percent H2SO4 (V/V) and add 10 % H2SO4 (V/V) with
stirring to make a volume of 1 liter. Prepare and store in glass bottles to prevent degradation.
Note:
To prevent autocatalytic decomposition of the permanganate solution, filter the solution through
Whatman 41 filter paper. Also, due to the potential reaction of the potassium permanganate
with the acid, there could be pressure buildup in the solution storage bottle. Therefore, these
bottles shall not be fully filled and shall be vented to relieve excess pressure and prevent
explosion potentials. Venting is required, but not in a manner that will allow contamination of
the solution.
0.1N HNO3
Add 6.3 ml of concentrated HNO3 (70 percent) to a flask containing approximately

900 ml of distilled water. Dilute to 1000 ml with distilled water.
8 N HCl
Add stirring 690 ml of concentrated HCl to a flask containing 250 ml of water. Dilute
to 1000 ml with water.
Note: All the reagent shall satisfy at less than 2 ng/ml of each target metals.
4.0 Preparation of sampling train
• Assemble the sampling train as shown in the Figure – 1.
73
• Select First impinger as a moisture trap.
• Put 100 ml of the HNO3 /H2O2 solution in the second and the third impinger.
• Keep fourth impinger empty.
• Place 100 ml of the acidic KMnO4 absorbing solution in each 5th and 6th impingers
• Take 200 to 300 g of pre-weighed silica gel in the last impinger.
If Hg analysis will not be performed, the fourth, fifth, and sixth impingers as shown in
Figure -1 are not required.
Precaution:
• Prevent the acidic KMnO4 from contacting any glassware that contains sample material
to be analyzed for Mn.
• Prevent acidic H2O2 from mixing with the acidic KMnO4.
• Uses of amber glass impinger are recommended for acidic KMnO4 Solution.
5.0 Field activity
Perform leak check. Determine the stack pressure, temperature, calculation of Isokinetic
velocity, volumetric flow rate, flow at nozzle/ selection of nozzle, adjustment of flow rate at
rotameter, temperature at metering point and volume of gas sampled, pressure drop during
sampling as described in the SOP of the particulate matter.
Note:
Calculate isokinetic velocity and collect the sample following the SOP prescribed for Particulate
monitoring.
6.0 Sample Recovery
Cool the probe, Transfer the probe and filter assembly to a clean area, cap all the open
outlet with the non-contaminated glass stoppers or plastic cap.
Take special precautions to assure that all the items necessary for recovery do not contaminate
the samples.
Remove filter from the filter holder; Place it in the labeled petri dish container. Seal the
petri dish. See the Figure – 2
Rinse the probe nozzle and fitting, probe liner, and front-half of the filter holder
74
thoroughly with a total of 100 ml of 0.1 N HNO3, and place the wash into a sample
storage container. Use of a total 100 ml is necessary for the subsequent blank correction
procedures Put the mark on the storage container for the fluid level to determine leakage
during transportation. See the figure – 2
Container No. 3 (Impingers 1 through 3, Moisture Knockout Impinger when used,

HNO3 / H2O2 Impingers Contents and Rinses)
Measure the liquid in the first three impingers to within 0.5 ml using a graduated
cylinder. Record the volume. This information is required to calculate the moisture content of
the sampled flue gas.
Clean each of the first three impingers, the filter support, the back half of the filter
housing, and connecting glassware by thoroughly rinsing with exactly 100 ml of 0.1 N HNO3.
Mark the height of the fluid level, seal and label the contents. See Figure 2.1
Container Nos.4A (0.1 N HNO3)
• Measure the volume of impinger No 4
• Place the liquid in Container No 4A. Rinse the impinger with exactly 100 ml of 0.1 N
• Place this rinse into the same Container No 4A.
4B (KMnO4 /H2SO4 absorbing solution)
• Pour all the solution of 5th & 6th impinger into the container No 4B. Measure the
volume to within 0.5 ml
• Rinse the impingers (5th & 6th ) with exactly 100 ml of fresh acidifying KMNO4 solution
into for all rinses (Approximately 33 ml per rinse).
• Similarly, use 100 ml distilled water for the rinsing of 5th & 6th impingers and connecting
glass minimum three times, pour this rinses into the container No 4B.
• Don’t fill these bottle completely, Take precaution to relive excess pressure.
4C (8 N HCl rinse and dilution)
• Remove the residue of Impinger No 5th & 6th with exactly 25 ml 8N HCl.
• Place this wash into different container ie 4C which contain 200 ml of water.
• Mark the container for fluid level. (See Figure – 2.2)
• Transfer the silica gel from its impinger to its original container and seal it.
75
• If a balance is available in the field, record the weight of the spent silica gel (or silica gel
plus impinger) to the nearest 0.5 g.
Container No. 6A (0.1 N HNO3 Blank)
• Container No. 6B (Water Blank).
• Container No. 7 (5 Percent HNO3 /10 Percent H2O2 Blank).
• Container No. 8 (Acidified KMnO4 Blank).
• Container No. 9 (8 N HCl Blank).
• Container No. 10 (Sample Filter Blank).
76
77
78
Table - 2
Sample detail sheet
Industry Name & Address:
Date & Time of Sampling
Container Sample Information Volume/wight Remartks

No the sample
Container Filter and any particulate matter or filter fiber that adhere to the
No. 1 filter holder gasket keep them into container no 1.
Container Rinse probe nozzle and fitting, liner and nozzle, front half of
No. 2 filter housing by 100 ml of 0.1N HNO3 Place this rinses in
Container no 2
Container Solution of 1 throught 3 impingers pour it in container 3. Clean
No. 3 each of the first three impingers, the filter support, the back half
of the filter housing, and connecting glassware by thoroughly
rinsing with exactly 100 ml of 0.1N HNO3, pour this rinses in
the same container.
Container Liquid of impinger No 4 as well as rinsing solution (100 ml of
No. 4A 0.1N HNO3) of the same impinger keep in the container No
4A.
Container It contains solution of both the 5th & 6th Impingers (Acidifying
No. 4B permanganate impinger) as well as rinsing solution (100 ml
of fresh acidified KMnO4 &100 ml of distilled water) of same
impingers.
Container If deposits remain in the 5th & 6th impingers, wash them with
No. 4C exactly 25 ml 8N HCI & pour this washing liquid into container
No 4C containing 200 ml of water.
Container Note the color of the indicating silica gel and transfer the silica
No. 5 gel from its impinger to container No 5.
Container Keep blank of 0.1N HNO3(used in the sample recovery process)
No. 6A into container No A.
Container Water Blank (water used for the sample recovery): Keep water
No. 6B blank into container No 6B.
Container Keep blank of Nitric acid impinger reagent (5 Percent HNO3/10
No. 7 Percent H2O2) into the container 7
Container Blank of Acidified KMnO4 impinger solution pour in to
No. 8 container No 8
Container Keep blank of 8N HCI (sample recovery reagent) in to Container
No. 9 No. 9
Container Sample Filter Blank i.e. unused filter from the same lot as the
No. 10 sampling filters.
Note: volume of the blank subjected, to be decided according to the volume of sample (to be considered for
the analysis).
79
Table - 3
Field Data Sheet
Name & Address

monitoring
o ID fan capacity
o House keeping

Representative of
80
Part-II
STANDARD OPERATING PROCEDURE (SOP) OF SAMPLE PREPARATION FOR ANALYSIS
OF METALS AND NON METALS
1.0 Sample Preparation

Note the level of the liquid in each of the containers and determine if any sample was
lost during shipment. A diagram illustrating sample preparation and analysis procedures for
each of the sample train components is shown in Figure –3 and Figure – 3.1. By difference in
weight and gas sample volume (Field data) calculates Particulate Matter concentration in mg/
Nm3.
If particulate emissions are being determined, first desiccate the filter and filter catch
without added heat (do not heat the filters to speed the drying) and weigh to a constant
weight.
Option I – Microwave digestion
• Make pieces of filter papers/ thimbles (Do not use metallic scissor).
• Place the pieces of in the analyst’s choice of either individual microwave pressure relief
vessels or Parr R Bombs.
• Add 6 ml of concentrated HNO3 and 4 ml of concentrated HF to each vessel
• In microwave heat the sample for 2- 3 min, then turn off the microwave for 2 to 3
minutes and heat for 2 – 3 minutes again
• Continue this alteration until the 12 to 15 minutes. This procedure should comprise
approximately 24 to 30 minutes at 600 watts.
Option II – Hot Plate Digestion
• Place the pieces of thimbles in acid cleaned Teflon beaker add about 50 ml distilled
water,
• Add 6 ml of concentrated HNO3 and 4 ml of concentrated HF to it.
• Place it on hot plate under fume extraction hood.
• Set the Temperature at 70 oC. Continue to digest for 12 hrs.
• Verify that the pH of this sample is 2 or lower. If it is not, acidify the sample by careful
addition with stirring of concentrated HNO3 to pH 2.
• Use water to rinse the sample into a Teflon beaker, and cover the beaker with a ribbed
watch glass. Reduce the sample volume to approximately 20 ml by heating on a hot
plate at a temperature below boiling.
81
• Add 6 ml of concentrated HNO3 and 4 ml of concentrated HF to it. Place it on hot plate
under fume extraction hood. Set the Temperature at 70 oC continue the digestion for 12
hrs.
• If the sampling train includes an optional glass cyclone in front of the filter, prepare and
digest the cyclone catch by the same way.
• Then combine the resultant sample directly with the acid digested portions of the filter
prepared previously, acid rinse concentrate and cyclone catch concentrate (If done).
• Filter the combined sample using Whatman 41 filter paper. Dilute to 300 ml (or the
appropriate volume for the expected metals concentration) with water.
• This diluted sample is "Analytical Fraction 1". Measure and record the volume of Analytical
Fraction 1 to within 0.1 ml.
• Quantitatively remove a 50-ml aliquot and label as "Analytical Fraction 1B". Label the
remaining 250-ml portion as "Analytical Fraction 1A". Analytical Fraction 1A is used for
ICAP or AAS analysis for all desired metals except Hg.
• Analytical Fraction 1B is used for the determination of front-half Hg. This fraction should
be treated with acid and KMnO4 at 90oC for 2 hours.
• Excess KMnO4 should be removed by using Hydroxylamine Hydrochloride before
analysis of Hg.
Container No.3 (Impingers 1-3)
• Measure and record the total volume of this sample to within 0.5 ml, if the leakage
found significant make up with fresh distilled water.
• Remove a 75- to 100-ml aliquot for Hg analysis and label the aliquot "Analytical
Fraction 3B".
• Label the remaining portion as "Sample Fraction 3A".
• Verify that the pH of Sample Fraction 3A is 2 or lower. If necessary, use concentrated
HNO3 by careful addition and stirring to lower the pH upto 2.
• Use water to rinse Sample Fraction 3A into a beaker and then cover the beaker with a
ribbed watch glass.
• Reduce Sample (3A) to approximately 20 ml by heating on a hot plate at a temperature
just below boiling.
• Add 30 ml of 50 percent HNO3 and heat for 30 minutes on a hot plate to just below
boiling.
• Add 10 ml of 3 percent H2O2 and heat for 10 more minutes. Add 50 ml of hot water,
and heat the sample for an additional 20 minutes.Cool, filter the sample, and dilute to
82
150 ml (or the appropriate volume for the expected metals concentrations) with water.
Analytical Fraction 3A is analyzed for all metals except Hg.
• Analytical fraction 3B will be digested separately with HCl and KMnO4 at 90 oC for
two hours. Excess Permanganate should be removed by Hydrxylamine Hydrochloride
before analysis in Cold Vapour AAS.
Container No. 4A (Empty impnger washing liquid with 0.1 N HNO3 ), 4B (KMnO4 /
H2SO4 absorbing solution of impinger 5 and 6), and 4C (8 N HCl rinse of impinger 5 and 6
for scaling of MnO2) Keep the samples in Containers Nos. 4A, 4B, and 4C separate from each
other. Measure and record the volume of 4A to within 0.5 ml.
Concentrate the sample upto 20 ml on hot plate at below boiling temperature. Keep
it separate.To remove any brown MnO2 precipitate from the contents of Container No. 4B,
filter its contents through Whatman 40 filter paper into a 500 ml volumetric flask, make
up the volume with distilled water. This fraction is anlytical fraction 4B.
Save the filter for digestion of the brown MnO2 precipitate. Place the saved filter into an
appropriately sized vented container, which will allow release of any gases including chlorine
formed when the filter is digested in a laboratory hood. Add 25 ml of 8 N HCl to the filter
and allow to digest for a minimum of 24 hours at room temperature. Filter the contents of
Container No. 4C through a Whatman 40 filter into a 500-ml volumetric flask. Then filter the
resultant solution of the digestion of the brown MnO2 from Container No. 4B through another
Whatman 40 filter into the same 500-ml volumetric flask, finally dilute and mix well to volume
with water. Discard the Whatman 40 filter. Mark this combined 500-ml dilute HCl solution as
Analytical fraction 4C. So three samples will be genertaed in this section for Hg analysis. All
these fractions shall be digested and concentrated to desired volume with HCl and KMnO4 at
90 oC for two hours. Excess Permanganate should beremoved by Hydrxylamine Hydrochloride
before analysis in Cold Vapour AAS.
5.1 Sample Analysis
For each sampling train sample run, seven individual analytical samples are
generated; two (Analytical fraction 1A and 3A) for all desired metals except Hg, and five for Hg
(Analytical fraction 1B, 3B, 4A, 4B and 4C). A schematic identifying each sample container
and the prescribed analytical preparation and analysis scheme is shown in Figure 3 and
Figure 3.1 Blanks for all reagents used should be processed with samples in parallel.
6.0 CALCULATIONS
For Molecular weight determination, Stack gas velocity, Isokinetic Flow rate,
Moisture content and parameters required for particulate emission calculation follow the
formulae mentioned in method prescribed for particulate matter determination.
Dry Gas Volume. Using the data from this test, calculate V , the dry gas sample volume at
standard conditions m(std) as outline Correct the sample volume measured by the dry
gas meter to standard conditions (25 oC, 760 mm Hg or 68 oFF, 29.92in. Hg) by using following
Equation. Where, Y is DGM Calibration Factor.
83
Tstd Pbar Pbar
Vmstd = Vm Y = K 1 Y Vm
Tm Pstd Pm
Where:
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in.Hg).
Nm3
Calculate all the seven fraction (2 for other metals and 5 for mercury) in mass of individual
elements following the formula
Metals (Except Hg) in Source Sample
Mx = Cx (ppm) * D * Vds
Where:
Mx = Total mass of each metal in µg.
Cx = Concentration of metal in respective fraction as read from the standard curve in µg/ml
(ppm) after respective blank subtraction
D = dilution Factor
Vds = Total volume of digested sample solution in Analytical fraction ml.
Mx values calculated for fraction 1A and 3A should be added individually to represent to total
mass for each metals except Hg. The concentration emitted from stack would be calculated
as below.
{Mx(1A) + Mx(3A)} * 10-3 / Vm(std) mg/NM3

Similarly for Hg
{Mx(1B) + Mx(3B) + Mx(4A) + Mx(4C)} * 10-3 / Vm(std) mg/NM3
Note: Report concentration as corrected at 11% O2 (as mentioned in the method for PM
determination)
84
CHAPTER - 7
Determination of Sulfur Dioxide Emissions from Stationary Sources
1. PRINCIPLE AND APPLICABILITY
1.1 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.
1.2 Applicability & Interferences
1.2.1 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 mg of
S02 /m3 (2.12 x 10-7 lb/ft3). Although no upper limit has been established, tests have shown
that concentrations as high as 80,000 mg/m3 of S02 can be collected efficiently in two midget
impingers, each containing 15 ml 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.
1.2.2 Interferences
Possible interferants 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 S02 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 interferants.
Free ammonia interferes by reacting with S02 to form particulate sulfite and by reacting
with the indicator.
2. APPARATUS
2.1 Sampling.
2.1.1 Sampling Train
The sampling train is shown in Figure 6-1, and component parts are discussed below.
The tester has the option of substituting sampling equipment described in Method 8 in place of
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the midget impinger equipment of Method 6. However, the Method 8 train must be modified
to include a heated filter between the probe and isopropanol impinger, and the operation of
the sampling train and sample analysis must be at the flow rates and solution volumes defined
in Method 8.
The tester also has the option of determining S02 simultaneously with particulate matter
and moisture determinations by (1) replacing the water in Method 5 impinger system with 3
percent peroxide solution, or (2) by replacing the Method 5 water impinger system with a
Method 8 isopropanol-filter-peroxide system. The analysis for S02 must be consistent with the
procedure of Method 8.
2.1.1.1 Probe
Borosilicate glass, or stainless steel approximately 6-mm inside diameter, with a heating
system to prevent water condensation and a filter (either in-stack or heated out-stack) to
remove particulate matter, including sulfuric acid mist. A plug of glass wool is a satisfactory
filter.
2.1.1.2 Bubbler and Impingers
One midget bubbler, with medium-coarse glass frit and borosilicate or quartz glass wool
packed in top (see Figure 6-1) to prevent sulfuric acid mist carryover, and three 30-ml midget
86
impingers. The bubbler and midget impingers must be connected in series with leak-free glass
connectors. Silicone grease may be used, if necessary, to prevent leakage.
At the option of the tester, a midget impinger may be used in place of the midget bubbler.
Other collection absorbers and flow rates may be used, but the collection efficiency must be
shown to be at least 99 percent for each test run and must be documented in the report. If
the efficiency is found to be acceptable after a series of three tests, further documentation is
not required. To conduct the efficiency test, an extra absorber must be added and analyzed
separately. This extra absorber must not contain more than 1 percent of the total S02.
2.1.1.2 Glass Wool
Borosilicate or quartz.
2.1.1.3 Stopcock Grease
Acetone-insoluble, heat-stable silicone grease may be used, if necessary.
2.l.1.4 Temperature Gauge
Dial thermometer, or equivalent, to measure temperature of gas leaving impinger train to

within 1º C (2º F).
2.1.1.5 Drying Tube
Tube packed with 6- to 16-mesh indicating-type silica gel, or equivalent, to dry the gas
sample and to protect the meter and pump. See also the note in Method 5, Section 3.1.2.
2.1.1.6 Valve
Needle valve, to regulate sample gas flow rate.
2.1.1.7 Pump
Leak-free diaphragm pump, or equivalent, to pull gas through the train. Install a small
surge tank between the pump and rate meter to eliminate the pulsation effect of the diaphragm
pump on the rotameter.
2.1.1.8 Rate Meter
Rotameter, or equivalent, capable of measuring flow rate to within 2 percent of the

selected flow rate of about 1000 cc/min.
2.1.1.9 Volume Meter
Dry gas meter (DGM), sufficiently accurate to measure the sample volume to within
2 percent, calibrated at the selected flow rate and conditions actually encountered during
sampling, and equipped with a temperature gauge (dial thermometer, or equivalent) capable
of measuring temperature accurately to within 3 oC (5.4 oF).
87
2.1.1.10 Barometer
Mercury, aneroid, or other barometer capable of measuring atmospheric pressure to within

2.5 mm (0.1 in.)Hg.
2.1.1.11 Vacuum Gauge and Rotameter
At least 760-mm (30-in.) Hg gauge and 0— to 40-cc/min rotameter, to be used for leak-check
of the sampling train.
2.2 Materials required for Sample Recovery
2.2.1 Wash Bottles.
Polyethylene or glass, 500-ml, two.
2.2.2 Storage Bottles.
Polyethylene, 100-ml, to store impinger samples (one per sample).
2.3 Materials and instruments required for Analysis.
2.3.1 Pipettes
Volumetric type, 5-ml, 20-ml (one per sample), and 25-ml sizes
2.3.2 Volumetric Flasks
100-ml size (one per sample) and 1000-ml size.
2.3.3 Burettes
5-ml and 50-ml sizes.
2.3.4 Erlenmeyer Flasks
250-ml size (one for each sample, blank, and standard).
2.3.5 Dropping Bottle
125-ml size, to add indicator.
2.3.6 Graduated Cylinder
100-ml size.
2.3.7 Spectrophotometer
To measure absorbance at 352 nanometers.
88
3. REAGENTS
Unless otherwise indicated, all reagents must conform to the specifications established by the
Committee on Analytical Reagents of the American Chemical Society. Where such specifications
are not available, use the best available grade.
3.1 Sampling
3.1.1 Water
Deionized distilled to conform to ASTM Specification D 1193—77, Type 3. At the

option of the analyst, the KMn04 test for oxidizable organic matter may be omitted when high
concentrations of organic matter are not expected to be present.
3.1.2 Isopropanol, 80 Percent
Mix 80 ml of isopropanol with 20 ml of water.
3.1.2.1 Check each lot of isopropanol for peroxide impurities as follows: Shake 10 ml of
isopropanol with 10 ml of freshly prepared 10 percent potassium iodide solution. Prepare
a blank by similarly treating 10 ml of water. After 1 minute, read the absorbance at 352
nanometers on a spectrophotometer, using a 1-cm path length. If absorbance exceeds 0.1,
reject alcohol for use.
3.1.2.2 Peroxides may be removed from isopropanol by redistilling or by passage through a

column of activated alumina; however, reagent grade isopropanol with suitably low peroxide
levels may be obtained from commercial sources. Rejection of contaminated lots may,
therefore, be a more efficient procedure.
3.1.3 Hydrogen Peroxide, 3 Percent

Dilute 30 percent hydrogen peroxide 1:9 (v/v) with water (30 ml is needed per sample).
Prepare fresh daily.
3.1.4 Potassium Iodide Solution, 10 Percent
Dissolve 10.0 g of KI in water, and dilute to 100 ml. Prepare when needed.
3.2 Sample Recovery
3.2.1 Water
Same as in Section 3.1.1.
3.3 Chemicals & Reagent required for Analysis
89
3.3.1 Water
3.3.3 Thorin Indicator
1-(o-arsonophenylazo)-2-naphthol-3,6-disulfonic acid, disodium salt, or equivalent. Dissolve
0.20 g in 100 ml of water.
3.3.4 Barium Standard Solution, 0.0100 N
Dissolve 1.95 g of barium perchlorate trihydrate [Ba(Cl04)2, 3H20] in 200 ml water, and dilute
to 1 liter with isopropanol. Alternatively, 1.22 g of barium chloride dihydrate [BaCl2, 2H20]
may be used instead of the perchlorate. Standardize as in Section 5.5.
3.3.5 Sulfuric Acid Standard, 0.0100 N
Purchase or standardize to ±0.0002 N against 0.0100 N Na0H which has previously been
standardized against potassium acid phthalate (primary standard grade).
4. PROCEDURE
4.1 Sampling.
4.1.1 Preparation of Collection Train
Measure 15 ml of 80 percent isopropanol into the midget bubbler and 15 ml of 3 percent

hydrogen peroxide into each of the first two midget impingers. Leave the final midget impinger
dry. Assemble the train as shown in Figure 6-1. Adjust probe heater to a temperature sufficient
to prevent water condensation. Place crushed ice and water around the impingers.
4.1.2 Leak-Check Procedure
A leak-check prior to the sampling run is optional; however, a leak-check after the sampling
run is mandatory. The leak-check procedure is as follows:
• Temporarily attach a suitable (e.g., 0- to 40-cc/min) rotameter to the outlet of the DGM,
and place a vacuum gauge at or near the probe inlet. Plug the probe inlet, pull a vacuum
of at least 250 mm (10 in.) Hg, and note the flow rate as indicated by the rotameter. A
leakage rate not in excess of 2 percent of the average sampling rate is acceptable. Note:
Carefully release the probe inlet plug before turning off the pump.
• It is suggested (not mandatory) that the pump be leak-checked separately, either prior to
or after the sampling run. If done prior to the sampling run, the pump leak-check shall
precede the leak-check of the sampling train described immediately above; if done after
90
the sampling run, the pump leak check shall follow the train leak-check. To leak-check
the pump, proceed as follows: Disconnect the drying tube from the probe-impinger
assembly. Place a vacuum gauge at the inlet to either the drying tube or the pump, pull a
vacuum of 250 mm (10 in.) Hg, plug or pinch off the outlet of the flow meter, and then
turn off the pump. The vacuum should remain stable for at least 30 seconds.
4.1.3 Sample Collection.
• Record the initial DGM reading and barometric pressure. To begin sampling, position
the tip of the probe at the sampling point, connect the probe to the bubbler, and start
the pump. Adjust the sample flow to a constant rate of approximately 1.0 liter/min as
indicated by the rotameter. Maintain this constant rate (±10 percent) during the entire
sampling run. Take readings (DGM, temperatures at DGM and at impinger outlet, and
rate meter) at least every 5 minutes. Add more ice during the run to keep the temperature
of the gases leaving the last impinger at 20 ºC (68 ºF) or less. At the conclusion of each
run, turn off the pump, remove probe from the stack, and record the final readings.
Conduct a leak-check as in Section 4.1.2. (This leak-check is mandatory.) If a leak is
found, void the test run or use procedures acceptable to the Administrator to adjust the
sample volume for the leakage. Drain the ice bath, and purge the remaining part of the
train by drawing clean ambient air through the system for 15 minutes at the sampling
rate.
• Clean ambient air can be provided by passing air through a charcoal filter or through an
extra midget impinger with 15 ml of 3 percent H202. The tester may opt to use simply
ambient air without purification.
4.2 Sample Recovery
Disconnect the impingers after purging. Discard the contents of the midget bubbler.
Pour the contents of the midget impingers into a leak-free polyethylene bottle for shipment.
Rinse the three midget impingers and the connecting tubes with water, and add the washings
to the same storage container. Mark the fluid level. Seal and identify the sample container.
4.3 Sample Analysis.
• Note level of liquid in container, and confirm whether any sample was lost during
shipment; note this on analytical data sheet.
• Transfer the contents of the storage container to a 100-ml volumetric flask, and dilute
to exactly 100 ml with water. Pipette a 20-ml aliquot of this solution into a 250-ml
Erlenmeyer flask, add 80 ml of 100 percent isopropanol and two to four drops of thorin
indicator, and titrate to a pink endpoint using 0.0100 N barium standard solution. Repeat,
91
and average the titration volumes. Run a blank with each series of samples. Replicate
titrations must agree within 1 percent or 0.2 ml, whichever is larger.
Note: Protect the 0.0100 N barium standard solution from evaporation at all times.
4.4 QC Sample Analysis.
• Concurrently analyze the one/two Control samples in the same manner to evaluate the
technique of the analyst and the standards preparation. (Note: It is recommended that
known quality control samples be analyzed prior to the compliance and audit sample
analysis to optimize the system accuracy and precision. One source of these samples is
the Source Branch listed in Section 3.3.6.)
• Calculate the concentrations in mg/NM3 using the specified sample volume in the audit
instructions.
• The concentrations of the audit samples obtained by the analyst shall agree within 5
percent of the actual concentrations. If the 5-percent specification is not met, reanalyze
the compliance samples and audit samples, and include initial and reanalysis values in
the test report (see Note in first paragraph of this section).
• Failure to meet the 5-percent specification may require retests until the audit problems
are resolved. However, if the audit results do not affect the compliance or noncompliance
status of the affected facility, the Administrator may waive the reanalysis requirement,
further audits, or retests and accept the results of the compliance test. While steps are
being taken to resolve audit analysis problems, the Administrator may also choose to use
the data to determine the compliance or noncompliance status of the affected facility.
5. CALIBRATION
5.1 Metering System.
5.1.1 Initial Calibration.
• Before its initial use in the field, first leak-check the metering system (drying tube, needle
valve, pump, rotameter, and DGM) as follows: Place a vacuum gauge at the inlet to the
drying tube, and pull a vacuum of 250 mm (10 in.) Hg; plug or pinch off the outlet of
the flow meter, and then turn off the pump. The vacuum shall remain stable for at least
30 seconds. Carefully release the vacuum gauge before releasing the flow meter end.
• Next, remove the drying tube, and calibrate the metering system (at the sampling flow rate
specified by the method) as follows: Connect an appropriately sized wet test meter (e.g.,
1 liter per revolution) to the inlet of the drying tube. Make three independent calibrations
runs, using at least five revolutions of the DGM per run. Calculate the calibration factor, Y
92
(wet test meter calibration volume divided by the DGM volume, both volumes adjusted
to the same reference temperature and pressure), for each run, and average the results.
If any Y-value deviates by more than 2 percent from the average, the metering system is
unacceptable for use. Otherwise, use the average as the calibration factor for subsequent
test runs.
5.1.2 Post-Test Calibration Check
After each field test series, conduct a calibration check as in Section 5.1.1 above, except for
the following variations
(a) the leak-check is not to be conducted,
(b) three, or more revolutions of the DGM may be used, and
(c) only two independent runs need be made.
If the calibration factor does not deviate by more than 5 percent from the initial
calibration factor determined in Section 5.1.1), then the DGM volumes obtained during the
test series are acceptable. If the calibration factor deviates by more than 5 percent, recalibrate
the metering system as in Section 5.1.1, and for the calculations, use the calibration factor
(initial or recalibration) that yields the lower gas volume for each test run.
5.2 Thermometers
Calibrate against mercury-in-glass thermometers.
5.3 Rotameter
The rotameter need not be calibrated, but should be cleaned and maintained according
to the manufacturer’s instruction.
5.4 Barometer
Calibrate against a mercury barometer.
5.5 Barium Standard Solution
Standardize the barium perchlorate or chloride solution against 25 ml of standard
sulfuric acid to which 100 ml of 100 percent isopropanol has been added. Run duplicate
analyses. Calculate the normality using the average of a pair of duplicate analyses where the
titrations agree within 1 percent or O.2 ml, whichever is larger.
6. CALCULATIONS
Carry out calculations, retaining at least one extra decimal figure beyond that of the acquired
data. Round off figures after final calculation.
93
CSO2 = Concentration of SO2, dry basis corrected to standard conditions, mg/dsm3 (1b/
dscf).
N = Normality of barium standard titrant, meq./ml.
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Tm = Average DGM absolute temperature, °K (°R).
Tstd = Standard absolute temperature, 293 °K (528 °R).
Va = Volume of sample aliquot titrated, ml.
Vm = Dry gas volume as measured by the DGM, dcm (dcf).
Vm(std) = Dry gas volume measured by the DGM, corrected to standard conditions, dscm
(dscf).
Vsoln = Total volume of solution in which the 2so sample is contained, 100 ml.
Vt = Volume of barium standard titrant used for the sample (average of replicate titrations), ml.
Vtb = Volume of barium standard titrant used for the blank, ml.
Y = DGM calibration factor.
32.03 = Equivalent weight of SO2.
6.2 Dry Sample Gas Volume, Corrected to Standard Conditions.
Tstd Pbar Pbar

Vmstd = Vm Y = K1 Y Vm Eq. 6-1
Tm Pstd Pm
Where:
= 17.64 °R/in. Hg for English units.
6.3 SO2 Concentration.
Vsoln
( )
Vt - Vtb N Va
CSO2 = K2 Eq. 6-1
Vm(std)
K2 = 32.03 mg/meq. for metric units,
= 7.061 x 10-5 lb/meq. for English units.
94
7.0 BIBLIOGRAPHY
1. Atmospheric Emissions from Sulfuric Acid Manufacturing Processes. U.S DHEW, PHS,
Division of Air Pollution. Public Health Service Publication No. 999-AP-13. Cincinnati,
OH. 1965.
2. Corbett, P.F. The Determination of S02 and S03 in Flue Gases. Journal of the Institute of
Fuel. 24:237-243. 1961.
3. Matty, R.E. and E.K. Diehl. Measuring Flue-Gas S02 and S03. Power. 101:94- 7.
November 1957.
4. Patton, W.F. and J.A. Brink, Jr. New Equipment and Techniques for Sampling Chemical
Process Gases. J. Air Pollution Control Association. 13:162. 1963.
5. Rom, J.J. Maintenance, Calibration, and Operation of Isokinetic Source- Sampling
Equipment. Office of Air Programs, Environmental Protection Agency. Research Triangle
Park, NC. APTD-0576. March 1972.
6. Hamil, H.F. and D.E. Camann. Collaborative Study of Method for the Determination of
Sulfur Dioxide Emissions from Stationary Sources (Fossil- Fuel Fired Steam Generators).
Environmental Protection Agency, Research Triangle Park, NC. EPA-650/4-74-024.
December 1973.
7. Annual Book of ASTM Standards. Part 31; Water, Atmospheric Analysis. American Society
for Testing and Materials. Philadelphia, PA. 1974. pp. 40-42.
8. Knoll, J.E. and M.R. Midgett. The Application of EPA Method 6 to High Sulfur Dioxide
Concentrations. Environmental Protection Agency. Research Triangle Park, NC. EPA-
600/4-76-038. July 1976.
9. Westlin, P. R. and R. T. Shigehara. Procedure for Calibrating and Using Dry Gas Volume
Meters as Calibration Standards. Source Evaluation Society Newsletter. 3(1):17-30.
February 1978.
10. Yu, K. K. Evaluation of Moisture Effect on Dry Gas Meter Calibration. Source Evaluation
Society Newsletter. 5(1):24-28. February 1980.
11. Lodge, J.P., Jr., J.B. Pate, B.E. Ammons, and G.A. Swanson. The Use of Hypodermic
Needles as Critical Orifices in Air Sampling. J. Air Pollution Control Association. 16:197-
200. 1966
12. Shigehara, R.T., and Candace B. Sorrell. Using Critical Orifices as Method 5 Calibration
Standards. Source Evaluation Society Newsletter. 10:4-15. August 1985.
95
CHAPTER - 8
Determination of Nitrogen Oxide Emissions from Stationary Sources
1. APPLICABILITY AND PRINCIPLE
1.1 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 N0X (as
N02) per dry standard cubic meter, without having to dilute the sample.
1.2 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 colorimetrically using the phenoldisulfonic acid (PDS) procedure.
2. APPARATUS
2.1 Sampling (see Figure 7-1)
Other grab sampling systems or equipment, capable of measuring sample volume to

within 2.0 percent and collecting a sufficient sample volume to allow analytical reproducibility
to within 5 percent, will be considered acceptable alternatives. The following equipment is
used in sampling:
2.1.1 Probe
Borosilicate glass tubing, sufficiently heated to prevent water condensation and

equipped with an in-stack or out-stack filter to remove particulate matter (a plug of glass wool
is satisfactory for this purpose). Stainless steel or Teflon (Note: Mention of trade names or
specific products does not constitute endorsement by U.S. EPA) tubing may also be used for
the probe. Heating is not necessary if the probe remains dry during the purging period.
2.1.2 Collection Flask
Two-liter borosilicate, round bottom flask, with short neck and 24/40 standard taper
opening, protected against implosion or breakage.
2.1.3 Flask Valve
T-bore stopcock connected to a 24/40 standard taper joint.
96
2.1.4 Temperature Gauge
Dial-type thermometer, or other temperature gauge, capable of measuring 1 ºC (2 ºF) intervals

from -5 to 50 ºC (25 to 125 ºF).
2.1.5 Vacuum Line
Tubing capable of withstanding a vacuum of 75 mm (3 in.) Hg absolute pressure, with "T"

connection and T-bore stopcock.
2.1.6 Vacuum Gauge
U-tube manometer, 1-meter (36-in.), with 1-mm (0.1-in.) divisions, or other gauge capable of
measuring pressure to within 2.5 mm (0.10 in.) Hg.
2.1.7 Pump
Capable of evacuating the collection flask to a pressure equal to or less than 75 mm (3 in.) Hg
absolute.
2.1.8 Squeeze Bulb
One-way
2.1.9 Volumetric Pipette
25-ml.
2.1.10 Stopcock and Ground Joint Grease
A high-vacuum, high-temperature chlorofluorocarbon grease is required. Halocarbon 25-5S

has been found to be effective.
2.1.11 Barometer
Mercury, aneroid, or other barometer capable of measuring atmospheric pressure to within

2.5 mm (0.1 in.) Hg. See Note in Method 5, Section 2.1.9.
2.2 Sample Recovery
The following equipment is required for sample recovery:
50-ml with 1-ml divisions.
2.2.2 Storage Containers
Leak-free polyethylene bottles.
97
2.2.3 Wash Bottle
Polyethylene or glass.
2.2.4 Glass Stirring Rod.
2.2.5 Test Paper for Indicating pH.
To cover the pH range of 7 to 14.
2.3 Analysis.
For the analysis, the following equipment is needed:
2.3.1 Volumetric Pipettes.
Two 1-ml, two 2-ml, one 3-ml, one 4-ml, two 10 ml, and one 25-ml for each sample and
standard.
98
2.3.2 Porcelain Evaporating Dishes
175- to 250-ml capacity with lip for pouring, one for each sample and each standard.
2.3.3 Steam Bath
Low-temperature ovens or thermostatically controlled hot plates kept below 70 ºC (160 ºF)
are acceptable alternatives.
2.3.4 Dropping Pipette or Dropper
Three required.
2.3.5 Polyethylene Policeman
One for each sample and each standard.
100-ml with 1-ml divisions.
2.3.7 Volumetric Flasks
50-ml (one for each sample and each standard),100-ml(one for each sample and each standard,
and one for the working standard KNO3 solution), and 1000-ml one).
2.3.8 Spectrophotometer
To measure at 410 nm.
2.3.9 Graduated Pipette.
10-ml with 0.1-ml divisions.
2.3.10 Test Paper for Indicating pH
To cover the pH range of 7 to 14.
2.3.11 Analytical Balance
To measure to within 0.1 mg.
3. REAGENTS
Unless otherwise indicated, it is intended that all reagents conform to the specifications
established by the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available; otherwise, use the best available grade.
3.1 Sampling
Two reagents are required:
3.1.1 Water
Deionized distilled to conform to ASTM specification D 1193—77, Type 3. At the option
of the analyst, the KMn04 test for oxidizable organic matter may be omitted when high
concentrations of organic matter are not expected to be present.
3.1.2 Absorbing Solution
99
Cautiously add 2.8 ml concentrated H2S04 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.
3.2 Sample Recovery
Two reagents are required for sample recovery:
3.2.1 Water
Same as in 3.1.1.
3.2.2 Sodium Hydroxide, 1 N
Dissolve 40 g NaOH in water, and dilute to 1 liter.
3.3 Analysis
For the analysis, the following reagents are required:
3.3.1 Water
Same as in 3.1.1.
3.3.2 Sulfuric Acid
Concentrated, 95 percent minimum assay. HANDLE WITH CAUTION.
3.3.3 Potassium Nitrate (KN03)
Dried at 105 to 110 ºC (220 to 230 ºF) for a minimum of 2 hours just prior to preparation of
standard solution.
3.3.4 Standard KN03 Solution
Dissolve exactly 2.198 g of dried KN03 in water, and dilute to 1 liter with water in a 1000-ml
volumetric flask.
3.3.5 Working Standard KN03 Solution
Dilute 10 ml of the standard solution to 100 ml with water. One milliliter of the working
standard solution is equivalent to 100 µg nitrogen dioxide (N02).
3.3.6 Phenoldisulfonic Acid Solution
Dissolve 25 g of pure white phenol solid in 150 ml concentrated sulfuric acid on a steam bath.
Cool, add 25 ml fuming sulfuric acid (15 to 18 percent by weight free sulfur trioxide - HANDLE
WITH CAUTION), and heat at 100 ºC (212 ºF) for 2 hours. Store in a dark, stoppered bottle.
3.3.7 Concentrated Ammonium Hydroxide
Analytical Reagent grade or higher
100
3.3.8 Quality Assurance Audit Samples
Nitrate samples prepared from CRM (KNO3)shall be processed in same manner to satisfy audit
criteria.
4. PROCEDURES
4.1 Sampling.
• Pipette 25 ml of absorbing solution into a sample flask, retaining a sufficient quantity
for use in preparing the calibration standards. Insert the flask valve stopper into the
flask with the valve in the "purge" position. Assemble the sampling train as shown in
Figure 7-1, and place the probe at the sampling point. Make sure that all fittings are
tight and leak- free, and that all ground glass joints have been greased properly with
a high-vacuum, high temperature chlorofluorocarbon-based stopcock grease. Turn the
flask valve and the pump valve to their "evacuate" positions. Evacuate the flask to 75
mm (3 in.) Hg absolute pressure, or less. Evacuation to a pressure approaching the vapor
pressure of water at the existing temperature is desirable. Turn the pump valve to its
"vent position, and turn off the pump. Check for leakage by observing the manometer
for any pressure fluctuation. (Any variation greater than 10 mm (0.4 in.) Hg over a period
of 1 minute is not acceptable, and the flask is not to be used until the leakage problem
is corrected. Pressure in the flask is not to exceed 75 mm (3 in.) Hg absolute at the
time sampling is commenced.) Record the volume of the flask and valve (Vf), the flask
temperature (Ti), and the barometric pressure. Turn the flask valve counterclockwise to
its "purge" position, and do the same with pump valve. Purge the probe and the vacuum
tube using the squeeze bulb. If condensation occurs in the probe and the flask valve
area, heat the probe, and purge until the condensation disappears. Next, turn the pump
valve to its "vent" position. Turn the flask valve clockwise to its "evacuate" position, and
record the difference in the mercury levels in the manometer. The absolute internal
pressure in the flask (Pi) is equal to the barometric pressure less the manometer reading.
Immediately turn the flask valve to the "sample" position, and permit the gas to enter
the flask until pressures in the flask and sample line (i.e., duct, stack) are equal. This will
usually require about 15 seconds; a longer period indicates a "plug" in the probe, which
must be corrected before sampling is continued. After collecting the sample, turn the
flask valve to its "purge" position, and disconnect the flask from the sampling train. Shake
the flask for at least 5 minutes.
• If the gas being sampled contains insufficient oxygen for the conversion of N0 to N02
(e.g., an applicable subpart of the standard may require taking a sample of a calibration
gas mixture of N0 in N2), then introduce oxygen into the flask to permit this conversion.
Oxygen may be introduced into the flask by one of three methods: (1) Before evacuating
the sampling flask, flush with pure cylinder oxygen, then evacuate flask to 75 mm (3
in.) Hg absolute pressure or less; or (2) inject oxygen into the flask after sampling; or
(3) terminate sampling with a minimum of 50 mm (2 in.) Hg vacuum remaining in the
flask, record this final pressure, and then vent the flask to the atmosphere until the flask
pressure is almost equal to atmospheric pressure.
101
4.2 Sample Recovery
Let the flask set for a minimum of 16 hours, and then shake the contents for 2 minutes.
Connect the flask to a mercury filled U—tube manometer. Open the valve from the flask to the
manometer, and record the flask temperature (Tf), the barometric pressure, and the difference
between the mercury levels in the manometer. The absolute internal pressure in the flask (Pf)
is the barometric pressure less the manometer reading. Transfer the contents of the flask to a
leak-free polyethylene bottle. Rinse the flask twice with 5-ml portions of water, and add the
rinse water to the bottle. Adjust the pH to between 9 and 12 by adding sodium hydroxide (1
N), dropwise (about 25 to 35 drops). Check the pH by dipping a stirring rod into the solution
and then touching the rod to the pH test paper. Remove as little material as possible during this
step. Mark the height of the liquid level so that the container can be checked for leakage after
transport. Label the container to identify clearly its contents. Seal the container for shipping.
4.3 Analysis.
• Note the level of the liquid in the container, and confirm whether any sample was lost
during shipment; note this on the analytical data sheet. If a noticeable amount of leakage
has occurred, either void the sample or use methods, subject to the approval of the
Administrator, to correct the final results.
• Immediately prior to analysis, transfer the contents of the shipping container to a 50-ml
volumetric flask, and rinse the container twice with 5— ml portions of water. Add the
rinse water to the flask, and dilute to mark with water; mix thoroughly. Pipette a 25-ml
aliquot into the porcelain evaporating dish. Return any unused portion of the sample to
the polyethylene storage bottle. Evaporate the 25-ml aliquot to dryness on a steam bath,
and allow to cool. Add 2 ml phenoldisulfonic acid solution to the dried residue, and
triturate thoroughly with a polyethylene policeman. Make sure the solution contacts all
the residue. Add 1 ml water and 4 drops of concentrated sulfuric acid. Heat the solution on
a steam bath for 3 minutes with occasional stirring. Allow the solution to cool, add 20 ml
water, mix well by stirring, and add concentrated ammonium hydroxide, dropwise, with
constant stirring, until the pH is 10 (as determined by pH paper). If the sample contains
solids, these must be removed by filtration (centrifugation is an acceptable alternative),
as follows: Filter through Whatman No. 41 filter paper into a 100-ml volumetric flask;
rinse the evaporating dish with three 5-ml portions of water; filter these three rinses.
Wash the filter with at least three 15-ml portions of water. Add the filter washings to the
contents of the volumetric flask, and dilute to the mark with water. If solids are absent,
the solution can be transferred directly to the 100-ml volumetric flask and diluted to the
mark with water.
• Mix the contents of the flask thoroughly, and measure the absorbance at the optimum
wavelength used for the standards (Section 5.2.1), using the blank solution as a zero
reference. Dilute the sample and the blank with equal volumes of water if the absorbance
exceeds A4, the absorbance of the 400-µg N02 standard (see Section 5.2.2).
102
4.4 Audit Sample Analysis.
• Concurrently analyze the two audit samples and a set of compliance samples (Section
4.3) in the same manner to evaluate the technique of the analyst and the standards
preparation. (Note: It is recommended that known quality control samples be analyzed
prior to the compliance and audit sample analysis to optimize the system accuracy and
precision. One source of these samples is the Source Branch listed in Section 3.3.9.) The
same analysts, analytical reagents.
• Calculate the concentrations in mg/dsm3 (mg/NM3) using the specified sample volume
in the audit instructions.
• The concentrations of the audit samples obtained by the analyst shall agree within 10
percent of the actual audit concentrations. If the 10—percent specification is not met,
reanalyze the compliance samples and audit samples, and include initial and reanalysis
values in the test report
• Failure to meet the 10-percent specification may require retests until the audit problems
are resolved. However, if the audit results do not affect the compliance or noncompliance
status of the affected facility, the Administrator may waive the reanalysis requirement,
further audits, or retests and accept the results of the compliance test. While steps are
being taken to resolve audit analysis problems,
5. CALIBRATION
5.1 Flask Volume. The volume of the collection flask-flask valve combination must be known
prior to sampling. Assemble the flask and flask valve, and fill with water to the stopcock.
Measure the volume of water to ±10 ml. Record this volume on the flask.
5.2 Spectrophotometer Calibration.
5.2.1 Optimum Wavelength Determination.
• Calibrate the wavelength scale of the spectrophotometer every 6 months. The calibration
may be accomplished by using an energy source with an intense line emission such
as a mercury lamp, or by using a series of glass filters spanning the measuring range
of the spectrophotometer. Calibration materials are available commercially and from
the National Bureau of Standards. Specific details on the use of such materials should
be supplied by the vendor; general information about calibration techniques can be
obtained from general reference books on analytical chemistry. The wavelength scale
of the spectrophotometer must read correctly within 5 nm at all calibration points;
otherwise, repair and recalibrate the spectrophotometer. Once the wavelength scale of
the spectrophotometer is in proper calibration, use 410 nm as the optimum wavelength
for the measurement of the absorbance of the standards and samples.
• Alternatively, a scanning procedure may be employed to determine the proper measuring
wavelength. If the instrument is a double-beam spectrophotometer, scan the spectrum
103
between 400 and 415 nm using a 200 µg N02 standard solution in the sample cell and
a blank solution in the reference cell. If a peak does not occur, the spectrophotometer
is probably malfunctioning and should be repaired. When a peak is obtained within the
400 to 415 nm range, the wavelength at which this peak occurs shall be the optimum
wavelength for the measurement of absorbance of both the standards and the samples.
For a single beam spectrophotometer, follow the scanning procedure described above,
except scan separately the blank and standard solutions. The optimum wavelength
shall be the wavelength at which the maximum difference in absorbance between the
standard and the blank occurs.
5.2.2 Determination of Spectrophotometer Calibration Factor Kc.
Add 0.0 ml, 2.0 ml, 4.0 ml, 6.0 ml, and 8.0 ml of the KN03 working standard solution
(1 ml = 100 µg N02) to a series of five 50-ml volumetric flasks. To each flask, add 25 ml of
absorbing solution, 10 ml water, and sodium hydroxide (1 N) drop wise until the pH is between
9 and 12 (about 25 to 35 drops each). Dilute to the mark with water. Mix thoroughly, and
pipette a 25-ml aliquot of each solution into a separate porcelain evaporating dish. Beginning
with the evaporation step, follow the analysis procedure of Section 4.3 until the solution
has been transferred to the 100-ml volumetric flask and diluted to the mark. Measure the
absorbance of each solution, at the optimum wavelength, as determined in Section 5.2.1. This
calibration procedure must be repeated on each day that samples are analyzed. Calculate the
spectrophotometer calibration factor as follows:
A1 + 2A2 + 3A3 + 4A4
Kc = 100 Eq. 7-1
A12 + A22 + A32 + A42
Where:
Kc = Calibration factor.
A1 = Absorbance of the 100 - µg N02 Standard.
5.2.3 Spectrophotometer Calibration Quality Control
Multiply the absorbance value obtained for each standard by the Kc factor (least squares slope)
to determine the distance each calibration point lies from the theoretical calibration line.
These calculated concentration values should not differ from the actual concentrations (i.e.,
100, 200, 300, and 400 µg NO2) by more than 7 percent for three of the four standards.
5.3 Barometer
Calibrate against a mercury barometer.
5.4 Temperature Gauge
Calibrate dial thermometers against mercury-in-glass thermometers.
104
5.5 Vacuum Gauge.
Calibrate mechanical gauges, if used, against a mercury manometer such as that specified in
2.1.6.
5.6 Analytical Balance. Calibrate against standard weights.
6. CALCULATIONS
Carry out the calculations, retaining at least one extra decimal figure beyond that of the
acquired data. Round off figures after final calculations.
6.1 Nomenclature
A = Absorbance of sample.
C = Concentration of NOx as N2O, dry basis , corrected to standard conditions, mg/dsm3
(1b/dscf).
F = Dolution factor (i.e., 25/5, 25/10, etc., required only if sample dilution was needed
to reduce the absorbance into the range of the calibration).
Kc = Spectrophotometer calibration factor.
m = Mass of NOx as NO2 in gas sample, µg.
Pf = Final absolute pressure of flask, mm Hg (in. Hg).
Pi = Initial absolute pressure of flask, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Tf = Final absolute temperature of flask, °K (°R)
Ti = Initial absolute temperature, of flask, °K (°R).
Tstd = Stamdard absolute temperature, 293 °K (528 °R).
Vsc = Sample volume at standard conditions (dry basis), ml.
Vf = Volume of flask and valve, ml.
Va = Volume of absorbing solution, 25 ml.
2 = 50/25, the aliquot factor. (If other than a 25-ml aliquot was used for analysis, the
corresponding factor must be substituted).
6.2 Sample Volume, Dry Basis, Corrected to Standard Conditions
Tstd [Pf Pi ]
Vsc = (Vf - Va)
Pstd [Tf Ti ]
[Pf Pi ]
= Ki (Vf - 25) Eq. 7-3
[Tf Ti ]
105
Where :
= 17.64 °R/in. Hg for English units.
6.3 Total µg NO2 per sample.
m = 2 Kc A F
Note: If other than 25-ml aliquot is used for analysis , the factor 2 must be replaced by a
corresponding factor.
6.4 Sample concentration, Dry Basis, Corrected to Standard Conditions.
C = K2 (m/Vsc) Eq. 7-4
Where:
K2 = 103 (mg /m3) / (µg /ml) for metric units,
= 6.242 x 10-5 (lb / scf) / (µg / ml) for English units.
6.5 Relative Error (RE) for QA audit Samples, Percent.
RE = 100 (Cd - Ca) / Ca Eq. 7-5
Where:
Cd = Determined audit sample concentration, mg / dsm3.
Ca = Actual audit sample concentration, mg / dsm3.
7.0 BIBLIOGRAPHY
1. Standard Methods of Chemical Analysis. 6th ed. New York, D. Van Nostrand Co., Inc.
1962. Vol. 1, p. 329-330.
2. Standard Method of Test for Oxides of Nitrogen in Gaseous Combustion Products
(Phenoldisulfonic Acid Procedure). In: 1968 Book of ASTM Standards, Part 26.
Philadelphia, PA. 1968. ASTM Designation D 1608—60, p. 725-729.
3. Jacob, M.B. The Chemical Analysis of Air Pollutants. New York. Interscience Publishers,
Inc. 1960. Vol. 10, p. 351-356.
4. Beatty, R.L., L.B. Berger, and H.H. Schrenk. Determination of Oxides of Nitrogen by
the Phenoldisulfonic Acid Method. Bureau of Mines, U.S. Dept. of Interior. R.I. 3687.
February 1943.
5. Hamil, H.F. and D.E. Camann. Collaborative Study of Method for the Determination of
Nitrogen Oxide Emissions from Stationary Sources (Fossil Fuel-Fired Steam Generators).
Southwest Research Institute Report for Environmental Protection Agency. Research
Triangle Park, NC. October 5, 1973.
6. Hamil, H.F. and R.E. Thomas. Collaborative Study of Method for the determination
of Nitrogen Oxide Emissions from Stationary Sources (Nitric Acid Plants). Southwest
Research Institute Report for Environmental Protection Agency. Research Triangle Park,
NC. May 8, 1974.
106

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Laboratory Analytical Techniqes

Series: LATS / 80 / 2013-2014

GUIDELINES ON METHODOLOGIES FOR

Central Pollution Control Board

August, 2012 MIRA MEHRISHI

Chapter – 1 Material and Methodology for Isokinetic Sampling 1-25

1.0 SOURCE EMISSION MONITORING

S.N. Item/Equipment Specifications / Applicable ranges

1 Stack Velocity Range: 0 to 30 m /sec

4 Nozzles Nozzles shall be fabricated with SS 304 or equivalent material

11 Inclined - cum – Inclined- cum – vertical manometer shall be fabricated with

13 Stop-watch 0 to 60 minutes, one second readout with hold facility.

16 Vacuum pump Vaccum pump shall be of rotary design, with a capacity of to

19 Tools A Kit containing the essential tools for connecting various

20 Isokineticity The kit shall be capable to perform continuous monitoring of

21 Temperature at Temperature measuring device at metering point shall

22 Vaccum Digital/analog vaccum pressure drop measurement device in

FIGURE 1.1 “S – TYPE” pitot tube construction

1.2.1 Molecular weight determination

Dry and wet molecular weights

Md = 0.44 (%CO2)+0.32 (% O2) +0.28(% N2+ % CO) +………… Eq - 1

Ms = Md (1 – BWO) + 18 BWO ………………………………. Eq - 2

0.44 – molecular weight of carbon dioxide divided by 100, kg/kg-mole

0.32 – molecular weight of oxygen divided by 100, kg/kg –mole

BWO – proportion by volume of water vapour in stack gas.

18 - molecular weight of water, Kg / Kg -mole

% N2 = 100 – ( % CO2 avg + % O2 avg + % CO avg. )

Md = molecular weight of stack gas on dry basis, kg / kg –mole.

Ms = molecular weight of stack gas on wet basis, kg / kg –mole

% CO2 = Percent CO2 by volume, dry basis

% O2 = Percent oxygen by volume, dry basis

% N2 = percent nitrogen by volume, dry basis

P bar = Barometric pressure in mm mercury column

Ps = Stack gas velocity pressure, mm water column

Ps = Static pressure mm Hg column.

1.2.3 Stack gas velocity determination

Us = Kp X Cp X ( Δ P ) 1/2 [Ts / (Ps × Ms)] 1/2

Us = Stack gas velocity, m/s

Cp = S- type pitot tube coefficient.

Ts = absolute stack gas temperature, °K

P = Stack gas velocity pressure, mm water column

Ps = Absolute stack gas pressure, mm Hg

Ms = Molecular weight of stack gas on wet basis, Kg / Kg –mole

1.2.3.2Stack gas volumetric flow Rate

Qs = 3600 (Us) × As (1 – BWO) X ( Tref / Ts) X (Ps / Pref)

As = Area of the stack (duct), m2

BWo = Proportion by volume of water vapour in stack gas.

Ts = Absolute stack gas temperature, °K

Ps = Absolute stack gas pressure

1.2.4 Moisture determination

Apparatus – The apparatus necessary for determination of moisture content by the

S.No Apparatus Description

1 Particulate Sampling Apparatus Consisting of a probe of stainless steel or pyrex

Procedure – Except in unusual circumstances, the water vapour is uniformly dispersed

(Vc x 22.4) Tm 760

Vv = Equivalent vapour of condensate under sampling condition, m3

Vc = Volume of condensate in condensor, ml

Tm = Temperature at metering condition, °K

Pm = Suction at meter, mm mercury column