Emission Regulations Part-Three

8/3/2019 Emission Regulations Part-Three

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WFCOMPREHENSIVE INDUSTRY DOCUMENTSERIES: COINDS/20/1984 -85

EMISSION REGULATIONSPART-THREE

CENTRAL POLLUTION CONTROL BOARD

July, 1996


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COMPREH ENSIVE INDUSTRY DOCUMENTSERIESOINDS/18/1984-85EMISSION REGULATIONS

PART - THREE

CENTRAL POLLUTION CONTROL BOARD(Ministry of Environment & Forests, Govt. of India)

Parivesh Bhawan, East Arjun Nagar,Delhi -110 032


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CPCB, 1985 (First Edition)CPCB, 200 Copies, 1995 (First Reprint)CPCB, 200 Copies, 1996 (Second Reprint)

ISBN `.81 - 86396-61 -6

Printing Supervision & Layout : Sh. R. N. Jindal, and Sh. Satish Kumar, EN V IS Centre;Published By: Member Secretary, Central Pollution Control Board, Delhi; andPrinted at: M!s Sharma Printers and Stationers, Delhi - 1 1 0 0 9 3 , Phone : 2297265, 2111597


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PREFACE

As an integral part of the emission regulations,it is necessary to hay e standard methods of samplingand analysis of air pollutants. The standards forstack emissions were evolved in July 1984 (Part I)and July 1985 (Part I I). The monitoring requirementsare a sequel to these.

(NILAY CHAUDHURI)Chairman


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CONTENTS

Chapterubjectage1onitoring Requirements for IndustriesStack Monitoring-Equipment27ndTestingProcedureMethod for Measurement of Emission

3fromStationary Sources4Determination of Sulphur Dioxide Emission4fromStationary Sources0Determination of Total Fluoride Emission5fromStationary Sources86mbient Air Quality Monitoring7Determination of Nitrogen Dioxide72nAmen ArDetermination of Total Fluorides2n Ambient Air'


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CHAPTER-1

1.0.0Mon itoring R equirements for IndustriesThe industrial units are required to monitor ambient air qualityand stack emission within industrial premises. The exact locationof ambient air quality monitoring stations and the samplingports in the stacks shall be decided by the concerned industrialunits in consultation with the relevant State Pollution ControlBoard.The new industrial units shall have sampling ports built intothe stack as per Figure 2.5. A permanent sampling platformand approach shall also be provided to the stack sampling station,as given in the section entitled 'Sampling Port', under 2.5.0.The State Board may prescribe more rigorous monitoring re-quirements depending on the location of the industry and speciallyif it is in a protected area.

1.0.1Certification1.0.2 All monitoring equipment and instrument shall be of standard

design approved by the Central Pollution Control Board or anagency like State Pollution Control Board as delegated by CentralPollution Control Board.

1.0.3 The agency or laboratory performing the monitoring of stackemission and ambient air quality tests shall have to be approvedby the State Pollution Control Board in consultation with CentralPollution Control Board. In a case where a dispute occurs, thiswill be resolved by the tests being conducted by the CentralPollution Control Board or its approved laboratory.


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-2-1.1.0General Requirements1.1.1tack monitoring shall be done following the frequency given

for each industry. The report shall be sent to the concernedState Board in a standardized format. Table 3.1 is cited asan example taking particulate matter as the pollutant.

1.1.2n case there is more than one equipment connected to a singlestack then the emission from each equipment must be in-dividually reported. In this case the sampling ports may bemade in the duct and not in the stack.1.1.3he parameters for stack monitoring, in addition to pollutant(s),must include the air flow rate (Nm3 /fir) and the production

during period of sampling.1.1.4mbient air quality sampling shall be done on a24 hour basisevery alternate day. The report for each month shall be sentto the concerned State Board in the format of Table 6.1.1.1.5he parameters for monitoring, in addition to pollutant(s), shall

include micro meteorological data of wind speed and directionand the wet and dry bulb temperatures. In cases where thereis more than one ambient air quality station, the wind andtemperature data may be obtained from only one station.

1.1.6n cases where there are a number of contiguous industries,the State Board would decide on the deviation from the requirednumber of ambient monitoring stations.

1.2.0he maintenance and operation of the required number of ambientmonitoring stations and the frequency of source emission monitor-ing shall be as follows. The stations are to be set up. at theboundary of the manufacturing or processing facility.


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-3-1.2.1ementPlant CapacityTPA

Less than 100,000and including minicement plant100,000 upto300,000300,000 upto600,000600,000 and above

Ambient Air Quality SourcemissionMonitoring StationsonitoringNot requirednce in 8 weeks2 Stationsnce in 4 weeks3 Stationsnce in 2 weeks4 Stationsnce in a weekThe parameter to be monitored shall be suspended particulate

matter in ambient air and total particulates in the stack.1.2.2 Thermal Power

Boiler CapacityM WLess than 200Greater than andincluding 200Greater than andincluding 500

Ambient Air QualityMonitoring Stations2 Stations3 Stations4 Stations

Source EmissionMonitoringOnce in 4 weeksOnce in 2 weeksOnce in I week

The parameters to be monitored shall be suspended particulatematter, sulphur dioxide and nitrogen dioxide in the ambientair and total particulates and sulphur dioxide in the stack. Allstack gas emission results shall be normalized to 12 % CO 2 inthe flue gas.

1.2.3ntegrated Iron and SteelPlantource Emission MonitoringSinteringnce in 2 weeksSteel makingnce in 2 weeks


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-4-There shall be four ambient air quality monitoring stationsfor each steel plant. The -parameters to be monitored shallbe suspended particulate matter, sulphur dioxide and nitrogendioxide in the ambient air and total particulates in the stack.

1.2.4ertilizerPlant typePhosphaticNitrogenousMixed Ambient Air QualityMonitoring StationsThreeThreeThree Source EmissionMonitoringOnce in4 eeksOnce in8 eeksOnce in8 eeksI(the same factory has more than one type of. plant, then thenumber of ambient air quality monitoring stations need notincrease, only the parameters would.The parameter to be monitored in phosphatic fertilizer plantsshall be suspended particulates and total fluorides in the ambientair and total particulates and total fluorides in the stack. Inthe case of nitrogenous and mixed fertilizers, suspended particu-lates shall be monitored in the ambient air and total particulatesin the stack.

1.2.5itric AcidPlant CapacityTPDLess than 15 0Greater than andincluding 15 0 Ambient Air QualityMonitoring Stations2 Stations3 Stations Source EmissionMonitoringOnce in4 eeksOnce in2 eeksThe parameter to be monitored shall be oxides of nitrogen,both in the ambient air and in the stack gases.


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-5-1.2.6ulphuric AcidPlant CapacityTPD

Less than 100Greater than andincluding 10 0

Ambient Air QualityMonitoring Stations2 Stations3 Stations

Source EmissionMonitoringOnce in 4 weeksOnce in 2 weeks

The parameter to be monitored shall be sulphur dioxide bothin the ambient air and in the stack gases.

1.2.7 Primary AluminiumEach facility must have ;four ambient air quality stations formonitoring suspended particulate matter, sulphur dioxide andtotal fluorides. The emissions from the cells shall be monitoredfor total particulates and fluorides every week, while emissionsfrom other stacks shall be monitored once every four weeks.The stacks from the crusher and alumina drying kiln shall bemonitored for total particulates, the boiler stacks for totalparticulates and sulphur dioxide and the stack for anode bakingfor sulphur diocide.

1.2.8 Carbon BlackThe emissions from carbon black manufacturing shall be moni-tored for particulate matter and carbon monoxide once everyeight weeks.

1.2.9 Calcium CarbideEach facility must have three ambient air quality stations formonitoring suspended particulate matter. The emissions fromthe kiln and arc furnance shall be monitored once every fourweeks for particulate matter.


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-6-1.2.10 Oil Refinery

The emissions from the stacks of distillation unit, catalyticcracker and sulphur recovery unit shall be monitored continuouslyfor sulphur dioxide in the oil refineries in Mathura and in Bombay.The schedule for the other refineries shall be as given below:

Refining Capacitymbient Air Quality Source Emissiontonnes crude / dayonitoring StationsonitoringLess than 3000Stationsnce in4weeks3000 and higherStationsnce in2weeksSource emission monitoring for stacks other than distillationand catalytic cracker unit shall be done once in 8 weeks forrefineries processing less than 3000 TPD of crude and oncein4 weeks for the larger units.


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-7-CHAPTER-2

STACK MONITORING-EQUIPMENT AND TESTING PROCEDURE20.0Source Emission Monitoring2.1.0his section deals with the methods of source emission monitoripg.It also gives the minimum requirements of a stack monitoringequipment.2.2.0 Specifications of Stack Monitoring Equipment2.2.1eneral

Stack Velocity Range: 0 to 30 m/secStack Temperature Range: 0 to 600 CParticulate Sampling: At 10 to 100 1pmFilter Paper (Thimble): Collectionf particulatesown to0.3 micronGaseous sampling: At 1 to 2 1pm collection on a set of impingers,containing selective reagents

2.2.2itot Tubei. Modified S-type pitot tube shall be fabricated from SS '304 orequivalent. The construction features should be as per UnitedStates Environmental Protection Agency (EPA) regulations,Method 2, given in Figures 2.1 and 2.2.ii . Standard pitot tube shall be fabricated from SS 304 or equiva-lent. The construction features shall be such that the coeffi-

cient of the pitot tube is above 0.95.223Sampling Probe

Fabricated fromS04ube of suitableiameternotessthan 15 mmID). The lengths of the pitot tube and the samplingprobe shall be decided between the user and the manufacturer.


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TRANSVERSETUBE AXIS

-8-

A

F A C EPENING --^PLANE

' SIDE PLANE

LONGITUDINAL_____TUBE AXIS

IB A SIDE PLANE(bi

OTE:PA __..05 D{


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LONGITUDINATUBE AXISBLOW tU

(d)(t)$i (4A2(+or)

1-or)

(e )

miea11u2 II/T R A N S V E R S E

ITUBE AXIS

(a )b)^J^ z

(f )

(g)Type s of fac e opening m isalignment that ca n result from field useor improper const ru ctruction of Type S picot tube s. These will not effect theba seline va lue of Cp(s) so long as o f and 02


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- 10 -2.2.4ozzlesA set of nozzle's fabricated from SS 304 or equivalent material

with internal diameters suitable to cover the full range of stackvelocities. The leading edge of the nozzle should be sharp andtapered. The minimum internal diameter of the nozzle shouldnot be less than8 mm.

2.2.5 Thimble Holder'Filter paper holders fabricated from SS 316 suitable to holdalundum / cellulose / glass fiber / asbestos thimbles.

2.2.6 ThermocoupleThermocouple sensor with analog or digital dial gauge capableof measuring temperature from 0 to 60 0 C covered with stainlesssteel or mild steel casing with acid resistant treatment.

2.2.7 Mounting FlangeA pair of male/female flanges fabricated out of mild steelwith proper hole for mounting thermocouple sensor, samplingtube and pitot tube.

2.2.8anel Box SidesFabricated out of aluminium / mild steel / fiber glass sheetswith oven-baked stove-enamel finish. It should have suitablearrangements for housing stop-watch, manometer, rotameter,dry gas meter, etc.

2.2.9 Back PanelHinged door panel of mild steel to contain cold box with 6impingers.


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- 11 -2.2.10 Inclined-curn-Vertical Manometer

Fabricated out of solid acrylic sheets. Inlet and outlet providedat the ends for filling in gauge fluid. Spirit level attached forlevelling. Velocity range: 0 to 30 m/sec.

2.2.11 Rotameters0 to 100 fpm for particulate monitoring and 0 to 3 1pm forgaseous monitoring.

2.2.12 Stop-Watch0 to 60 minutes, one second readout with hold facility.

2.2.13 ImpingersFour number 100 ml and two number 300 ml capacity. Facilityshould be there for keeping ice at the bottom of impinger box.

2.2.14 Vacuum PumpRotary design, with a capacity of to 0 to 120 1pm gas flowwith single phase motor, 220 V. The pump will also have amoisture trap, air inlet valve and mounted inside a pump housingand should be portable.

2.2.15 Dry Gas Meter

The sampling train shall have a dry gas meter with the facilityfor measuring temperature and static pressure. The capacityof the meter should be adequate to record upto 100 1pm ofairflow and a minimum readout of 0.001 cubic meters.

2.2.16 Pump HousingMild steel case with oven-baked stove enamel finish and ON/OFFswitch with indicator lights.


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- 12 -2.2.17Tools

A kit containing the essential tools required for connectingvarious components shall be provided with the equipment.

2.2.18 Train LeakagesThe sampling train after having set up will be tested for leakageby plugging the inlet. The rotameter shall not give a readingbeyond 5 1pm when the flow has been set at 100 1pm. Also thedry gas meter should give a reading of less than 5 percentof the air flow.

2.3.0 Method of Testing.31election of Sampling SiteThe objective of sampling is to determine the amotjnt of pollu-tant being emitted from a stack. This limit will be as per theregulations of the Central and State Boards. The site shouldbe such that a laminar flow of air is present in the stack.The guidelines for selection are given under 2.4.0 of this chapter.32raversesThe number of traverses to be made will be as per 2.4.2. Allnew stacks should have a sampling port and sampling platform,the location of which will be decided by the relevant StateBoard.

2.3.3 Molecular Weight DeterminationThis is determined by drawing a known quality of gas into anOrsat Apparatus or a gas chromatograph. Also the moistureshould be found. Knowing the gas consituents, the molecularweight is founu as given in 3.3.0.


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- 13 -23.4Velocity Determination

The pitot tube is now connected as given in Figure 3.2. Thedynamic and a static pressure is found by using the manometer.The temperature inside the duct is also measured. The velocityof gas in the duct and the air quantity are found using theformula given in 3.4.0 and 3.4.1.

23.5Moisture DeterminationThe moisture content may be determined either by the condensormethod or by wet and dry bulb temperature and then referringto a suitable psychrometric chart. Latter should be limited tonon-acid gas streams with moisture content of less than 15percent and dew point less than 52 C. The condensor methodworks well for most gas streams and is also relatively easyto perform. These methods are given in 3.5.0 and 3.6.0.

2.3.6esultsAll results shall be normalized to 25 C and a pressure of 1.01 kPa(760 mm of mercury) on a dry basis (zero percent moisture).

24.0Selection of Sampling Site and Minimum Number of TraversePoints

Select the sampling site at any cross section of the stack orduct that is at least eight stack or duct diameters downstreamand two diameters upstream from any flow disturbance suchas bend, expansion, contraction, visible flame, or stack exit(see inset, Figure 2.3). For rectangular cross sections the largerdimension shall be used to represent the stack diameter.

2.4.1hen the above sampling site criteria can be met, determinethe minimum number of traverse points required, from Table 2.1.The. minimum required number of traverse points is a directfunction of stack or duct diameter.


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-14 -42hen a sampling site such as described in 2.4.0 is not accessible,choose a convenient sampling location and use Table 2.1 and

Figure2.3 to determine the minimum required number of traversepoints. First, measure the distance from the chosen samplinglocation to the nearest upstream and downstream disturbance.Then, from Figure 2.3 determine the corresponding sample pointmultiples for both distances and select the greater of these.Multiply it by the num5er obtained from Table 2.1. The resultof this calculation is the minimum number of traverse pointsrequired. This number may have to be increased such that forcircular stacks the number is a multiple of 4 and for rectangularstacks the number follows the criteria given in 2.4.4.

24.3Cross - Sectional Layout and Location of Traverse PointsFor circular stacks divide the cross section into equal partsby two right-angle diameters. Locate half the traverse pointssymmetrically along each diameter according to Figure 2.4and Table 2.2.or rectangular stacks divide the cros$ section into as manyequal rectangular areas as there are traverse points such thatthe ratio of the length to the width of the elements/area isbetween one and two. Locate the traverse points at the centroidof each area according to Figure 2 . 4 .

45nder no conditions shall a sampling point be selected within3 cm of the stack wall.Table21MINIMUM REQUIRED NUMBER OF TRAVERSEPOINTS FOR SAMPLING SITES WHICH MEETSPECIFIED CRITERIAInsid e diameter of stack or duct (m)

L^^ 5 0.30.3.D.060 . 6J. S 1.21.2 S I. D.2424


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toaC

ECCa1

H

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No. of duct diameters upstream of flow disturbance(distan ce-A )

1.0.5.0No. of duct diameters downstream of flow disturbance(distance-8 )

FIGURE 2.3 TRAVERS POINT MULTIPLES TO DETERMINE M INIMUMNUMBER OF TRAVERSE POINTS REQUIRED WHENA


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A

B

-EAST

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SOUTH

A -1O A -20 A -30 A -4O

g-1 8-2 B-3 B-40 0 0 0

C-1 C-2 C-3 C-40 0 0 0

FIGURE 2.4 LOCATION OF TRAVERSE POINTS ON CIRCULAR ANDRECTANGULAR CROSS SECTIONS DIVIDED INTO TWELVEEQUAL AREAS


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Table 2.2 LOCATION OF TRAVERSE POINTS ON DIAMETERS OFCROSS SECTIONS OF CIRCULAR STACKS

TRAVERSE PERCENT OF STACK DIAMETER FROM INSIDE WALLPOINTNUMBER TORAVERSE POINTON A Number of traverse points on aiameterDIAMETER 28 10 12 14 16 18 20 22 241 14.6.7.4 3.3 2 .5 2 .1 1.8 1.6 1.4 1.3 1.1 1.12 85.45.04.7 10.5 8.2 6.7 5.7 4.9 4.4 3.9 3.5 3.23 75.09.5 19.4 14.6 11.8 9.9 8.5 7.5 6.7 6.0 5.5

4 93.30 .5 32.3 22.6 17.7 14.6 12.5 10.9 9.7 8.7 7.95 85.3 67.7 34.2 25.0 2 0 .1 16.9 14.6 12 .9 11.6 10.56 95.6 80.6 65.8 35.5 26.9 22 . 0 18.8 16.5 14.6 13.27 89.5 77.4 64.5 36.6 28.3 23.6 20 .4 18.0 16.18 96.7 85.4 75.0 63.4 37.5 29.6 25.0 21.8 19.49 91.8 82 .3 73.1 62.5 38.2 30 .6 26.1 23.0

10 97.5 88.2 79.9 71.7 61.8 38.8 31.5 27.21 1 93.3 85.4 78.0 70.4 61.2 39.3 32.312 97.9 90.1 83.1 76.4 69.4 60.7 39.813 94.3 87.5 81.2 75.0 68.5 60.214 98.2 91.5 85.4 79.6 73.9 67.715 95.1 89.1 83.5 78.2 72.816 98.4 92.5 87.1 82.0 77.017 95.6 90.3 85.4 80.618 98.6 93,3 88.4 83.919 96.1 91.3 86.82 0 98.7 94.0 89.521 96.5 92.122 98.9 94.523 96.824 98.9


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- 18 -25.0Location of Sampling Port

To ensure laminar flow the sampling ports shall be locatedat atleast 8 times chimney diameter down stream and 2 timesup stream from any flow disturbance. For a rectangular crosssection the equivalent diameter (De) shall be calculated fromthe following equation to determine up stream, down streamdistances.2LWDe =L+WWhere L = Length in m, W = width in m.Sometimes it may so happen for existing chimneys that sufficientphysical chimney height is not available for desired samplinglocation in such cases additional traverse points shall be takenas given under 2.4.0.The sampling port should be preferably provided on the deliveryside of duct or chimney and not on the suction side.

25.1Number of Sampling PortThe pitot tubes commercially available in the country generallydo not exceed2meters in length. Any point on the horizontalcross-section of a stack (chimney) along any diameter can bemeasured for flow by the pitot tube, if the point is approachableby the pitot tube inserted through the sampling port (hole).Minimum two (mutually orthogonal) sampling ports are requiredin a circular chimney so that full stack cross-sectional areacan be covered for measurements, so long as the diameterof the stack is less than2 meters.The stack having a diameter between2 and4meters, the twomutually orthogonal sampling ports are to be increased to fourby having the other two sampling ports at diametrically oppositepositions to the first two sampling ports (Figure 2.5).


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2.5.2 Dimensions of Sampling Port

Port Type: Pitot tube, temperature and sampling probe areto be inserted together into the sampling, port for monitoringpurposes. Sampling port should be a standard flanged pipe of0.10 m inside diameter (ID) with 0.15- m bolt circle diameter.An easily removable blind flange should be provided to closeth_e port when not in use (Figure 2.5).Port Installation: Flanged pipe used as port should be installedwith the interior stack wall. Port should extend outward fromthe exterior stack wall not less than 50 mm and not more than200 mm only when additional length is required for gate -valveinstallation. Ports should be installed at a height between 0.90and 1.2 m above the floor of the working platforrri.Port Loading: The port installations should be capable of support-^ng the following loads:a. Vertical shear of 91 kgb. Horizontal shear of 23 kg andc. Radial tension of 23 kg (along stack diameter)

2.5.3 Work PlatformSize and extent of platform: If two ports are required at 90degrees the work platform should serve that half of the stackcircumference between the ports and extend at least 1.2 metresbeyond each port. If four ports are required at 90 degrees,the work platform should serve the entire circumference ofthe stack. The minimum platform width shall be always 1.2 metresregardless of diameter of stack and number of sampling ports.The detail dimension of platform are shown in Figure 2.6.


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- 20 -2.5.4 Platform Access

Safe and easy access to the work platfrom should be providedvia caged ladder, stairway, or other suitable means.Guardrails, Ladderweils and StairwellsA safe guardrail should be provided on the platform. Angularrather than round rail members should be used, if possible.No ladderwell, stairwell, or other such openings should be locatedwithin1 metre of any port. Ladderwells should be covered atthe platform. Any stairwell leading directly to the platformshould be equipped with a safety bar at the opening.

2.5.5 Platform Loading

The work platform should be able to support at least threemen (average 80kg each) and91 kg of test equipment (stackmonitoring kit, etc.). If the stack exists through a building roof,the roof may suffice as the work platform, provided the minimumtest site requirements are still met.

2.5.6 Clearance ZoneA three-dimensional, obstruction-free clearance zone shouldbe provided around each port. The zone should extend 0.6 mabove, below, to either side of the port. The zone should extendoutward from the exterior wall of the stack to a distance ofat least 3 metres The clearance zone is illustrated in Figure 2 .Power SupplyPower sources shall be as follows:a. Platform-one 220 volt, 15 amp, single phase AC circuit with

a grounded, two receptacle weatherproof outlet.b. Stack base-one220volt, 15amp, single phase AC circuit

with a grounded, two receptacle weatherproof outlet.


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- 21. -25.?Vehicle Access and Parking

Except for situations in which sampling operations must beconducted from a rooftop or similar structure, stack samplingis sometimes coordinated and controlled from a monitoringvan, which is parked near the base of the stack for the durationof the sampling period. Vehicle access and parking space mustbe provided, since various equipment transport lines will bestrung from the monitoring van to the stack platform and willremain in position during the operation.

2.5.8 Additional Requirements

In addition to above aspects the sampling platform, guard railsetc. should be regularly painted and checked for corrosion.There should be no leakages around the sampling port (speciallyneeded for stacks emitting corrosive chemicals).If anticorrosive lining is done inside the chimney, the sameshould be extended to the projected portion of the samplingport, monolithically. It has been observed that due to improperlining at the port, the chimney life is reduced considerably.The sampling port should be air tight and no moist air shouldbe allowed to enter the chimney.


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(2)A1 ,W HE

(1) Al A2WHEN D


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c g0ztnNC

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SA M P LINGORTS ^(OUTSIDE) PORT DIMENSIONEQUIREMENTSA. 2 PORTS, 90 W/ DIAMETER INSIDE) ^05M MIN^LESS THAN 3M+ PORT LENGTH 2M MAX. UNLESS GATE VALVE INSTA4 KORTS 90 APART/IAMETER 01 M ID(MIN)INDUSTRIAL FLANGE C,WHEN NO T IN USEOVER 3M PORT LENGTH INSTALL GATE VALVE IF STACK CONTDANGEROUS GASES OR GASES OVEFUNDER POSITIVE PRESSURE

AT LEAST TWO STACK DIAMETERS STRENGTH REQUIREMENTSBELOW STACK EXIT ^ 23 Kg SIDE LOADTENSION3 Kg RADIALOADGUARD

RAIL ^ ---91 Kg VERTICAL SHEAR LOAD105 Kg M MOMENT

- \ ^ AT LEAST ONE STACK DIAMETE- -..LUS 09M FROM STACK CIRCUMFAT LEAST EIGHT STACK DIAMETERS ^` ~ur1 ^BOVE LAST OBSTRUCTION T-Y CLE ARANCEWORK AREA CLEARANCE ^ZONE.9MWORKLATFORMA . AT LEAST IM WIDE (1.2M WIDE FORSTACKS WITH 3M OR GREATE R ID.)

AND CAPABLE OF SUPPORTING3 PEOPLE AND 91 Kg OF TEST POWER SOURCEEQIPMENT 220V 15A SINGLE PHAS E 50 HZ ACB. SAFE GUARDRAIL ON PLATFORM WITH LOCATED ON PLATFORMACCESS BY SAFE LADDER OR OTHERSUITABLE MEAN S IF LADDER IS USEDLADDER WELL MUST BE LOCATED ATLEAST 1M FROM PORTS

C.O OBSTRUCTIONS TO BE WITHIN 1 MHORIZONTAL RADIUS ON PLATFORMBENEATH PORTS

FIGURE 2.6 TYPICAL SAMPLING PROV ISION

r44W

ti.


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- 24 -CHAPTER -3

METHOD FOREASUREMENT OF EMISSION FROMSTATIONARY SOURCES

3.0.0his method is for sampling of particulate matter in a movinggas stream in a duct or a stack. The methods for determiningthe sulphur dioxide and total fluorides are given in Chapters4 and 5 .3.1.0he collector recommended for use under specified field condi-tions is shown and its use to obtain satisfactory results is described.These procedures utilize particulate filtering systenhs whichare located within the stack. If properly used, these systemsare satisfactory for determining the mass concentration ofparticulate matter in the gas stream at stack conditions. Theuse of collection systems located outside the stack for collectingsamples at other than in-stack conditions is an alternative.

3.2.0eterminationf the particulateoncentration consists ofsampling isokinetically a measured amount of gas from the flueand separating the particles from the gas and hence determiningthe particulate concentration. To obtain a representative par-ticulate sample, the sampling should be carried out isokinetically,that is, the kinetic energy of the gas stream in the stack shouldbe equal to - kinetic energy of the gas stream through thesampling nozzle.

3.2 .1ampling at otherthan isokinetic velocities induces errors fortwo reasons. First, sampling at greater or less than isokineticrates tends to cause respectively a larger or a smaller volumeto be. withdrawn from the flue than accounted for by the cross-sectional area of the probe, secondly, particles greater than3.5 micron in size have sufficient intertia so that particle motionmay deviate significantly from the gas flow streamline pattern.


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- 25 -

In that case, particles are selectively drawn into the probe ina size distribution different from that existing in the duct orflue. It has been observed that, if sampling velocity is greaterthan the isokinetic rate, the sampling will have a lower massconcentration of particulate material than the main streambecause of greater percentage of fine particles. However, ifthe sampling velocity is less than the isokinetic rate, the particu-late sample has a higher mass concentration than actuallypresent, with lower concentration of fine particles. The samplingconsists of several distinct steps as already described.

3.3.0he specific formula for each is given below.3.3.1Determination of Molecular Weight

The average molecular weight of the gas mixture is describedby the expression: n

= =Ix i M iwhere x is the mole fraction and M i the mole weight of eachconstituent in the mixture of n number of constituents.

3.3.2Dry and Wet Molecular WeightsFor the majority of sources, Equation I is used to calculatethe dry molecular weight of the sample. This equation maybe modified with additional terms if other gaseous constituentsthat will influence the molecular weight of the sample arepresent. Equation2is used to calculate the molecular weightof the stack gas on a wet basis.M d = 0.44 (%CO 2 ) + 0.32 (%0 2 ) + 0.28 (%N2 + %CO)M s M(1- Bo ) + 18 Bwo2


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- 26 -

0 .41.olecular weight of carbon dioxide divided by100, kg/kg-mole0. 32-olecular weight of oxygen divded by 100,

kg i' kg -mole0.28 molecular weight of nitrogen and carbon monoxidedivided by 100, kg / kg - mole

B proportion by volume of water vapour in stackga s

18olecular weight of water, kg / kg - moleN J G T EN41 is calculated using the difference method. In the

majority of cases the following equation may be used:%N 2 -100 (% CO- avg + ro 0 2 avg.-- % CO avy. )

FLEXIBLEPROBE-UBINGTO ANALYSER

-FILTER (GLASS WOOL)

SQUEEZE BULB

FIGURE 3.1GRAB SAMPLE TRAIN


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- 27 -whereM d=olecular weight of stack gas on dry basis, kg/kg-moleM s=olecular weight of stack gas on wet basis, kg/kg-mole%CO2 = Percent carbon dioxideyolume,ry basis%0 2 = Percent oxygenyolume, dry basis% N 2 = Percent nitrogenyolume, dry basis3.4.0Stack Gas VelocityU=KCA P)1/2 ( Ts_) 1 / 2sPs M s )whereU s = Stack gas velocity, m/sK p = Constant, 33.5 m/sg.mm Hg_/2Kg-mole KmmH 2 O C pS-type pitot tube coefficientT s - Absolute stack gas temperature, KAP = Stack gas velocity pressure, mm water columnP sAbsoluLe stack gas pressure, mm HgM s = Molecular weight of stack gas on wet basis, Kg/kg-mole

3.4.1tack Gas Volumetric Flow RateThe following equation is used to calculate the stack gas volu-metric flow rate, Qs (m 3 /hr)

PsQS)0 ( C ! 5) As l;-F3W OrefTsTsref


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-28-AsArea of the stack (duct), m 2B wo = Proportion by volume of water vapour in stack gasTref =2 98 KPref =760 mmIsAbsolute stack gas temperature, KP s= Absolute stack gas pressure3.5.0 Determination of Moisture in Gas Stream51ofiadensor Method - The condensor method, in principle, involves

extracting a sample of the stack gases through a filter forremoval of the particulate matter, then through a condensor,accumulating the condensate formed in process, and 'finallythrough a gas meter. The object of the test is to collect andmeasure the volume of all the condensate formed at the con-densing temperature from a measured amount of gas.

52pparatus - The apparatus necessary for determination of moisturecontent by the condensate method is given below.

Particulate Sampling Apparatus-onsisting of a probe of stain-lessteel oryrex glass, sufficientlyeated to prevent conden-sation and equipped withfilter to remove particulateatter.

3.5.3 Condensor equipped with temperature gauge. This may besubstituted with two condensor bottles in an we bucket, eachwith30 nil capacity or equivalent. The condensor / ondensorbottles are filled with chilled water. The equipment shall beassembled as shown in Figure 4.1 and tested for leaks.

3.5.4ry Gas Meter - to measure within 5 percent of the total samplevolume.


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- 29 -

3.5.5auges - two thermometers (range 0 - 1000 C), two calibratedvacuum gauges or U-tube mercury manometers (range0-500mrnmercury).

3.5.6as [lump - leak-free diaphragm type or equivalent, for suckinggas through sampling apparatus.3.5.7ittings - tubing (rubber, neoprene, etc.), rubber stoppers andflow control (needle-valve and shut-off ball valve).3.5.8rocedure - Except in unusual circumstances, the water vapour

is uniformly dispersed in the gas stream and therefore samplingfor moisture determination need not be isokinetic and is notsensitive to position in the duct. The sampling nozzle may bepositioned down-stream to minimize the buildup of pressuredrop across the thimble due to particulate catch. Safnple thegas at a rate of about 500 ml/sec. Run the test until enoughcondensate has been collected to enable an accurate measure-ment. Measure the temperature and pressure of _condensor closeto the meter, a5 an insignificant pressure loss ire the line betweenthem is expected. The meter pressure may be substituted forcondensate pressure. Measure the volume of gas sampled andbarometric pressure also in order to calculate the moisturecontent. Measure the volume of condensate collected in a gradu-ated measuring cylinder.

3.5.9alculationsCalculate the volurneof water vapour collected using the follow-ing equation:

(V C x 22.4)in60V v000 x I873Pbar -prn


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- 30 -whereV v= Equivalent vapour of condensate under sampling

conditions, m 3V = Volume of condensate in condensor, mlT n1 Absolute meter temperature, KP m Suction at meter, mm mercury columnPbarBarometric pressure, nim mercury columnCalculate the moisture contei tof the gases using the followingequation:

M=Vx100V+VvwhereMMoisture in the flue gases, percentVquivalent vapour volume of condensate undersampling conditionV ni Volume of gas sampled (m3 )

3.6.0Wet /Dry Bulb MethodThe equilibrium temperature attained by water which is vapour-izing a&abatically into a gas of constant composition and con-stant dry bulb or actual temperature, is termed as wet bulbtemperature. The amount of depression of the wet bulb temper-ature below the dry bulb temperature is a function of the degreeof saturation of the humidity of the gas. Therefore, the moisturecontent of the gas can be determined from the wet and drybulb temperatures.

3.(.ialculations - the moisture content may be determined frorrthe test data using a psychrometric chart. The percentage watervapour by volurne is found dir'ectly. Inputs are the dry bulttemperature and the wet bulb temperature.


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- 31 -

FIGURE 3.2 S - TYPE PILOT TUBE AND MANOMETER ASSEMBLY


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- 32 -.70rocedure.71election of Location of Sampling - Sample for particulate concen-

tration shall be done at the same traverse points where velocitymeasurements were carried out..72alculation of Proper Sampling Rate - The meter for measuringthe gas sample measures the gas at conditions of temperature,pressure and moisture content which are different than thosein the flue. Therefore, calculate the, sampling rate at the gasmeter for each sampling point before starting the test and

record on the log the required rate (Table 3.2). Calculate thesampling rate at the gas meter as follows:R=1An T mXbar Puxmmsbar- P mV+VwhereR m flow rate through meter, m 3 /sL s= Velocity of flue gas at sampling point, m/sAnArea of sampling nozzle, m 2T m == Absolute meter temperature, K1'Absolute stack gas temperature, KsP u= Suction in stack, mrn mercury columnP bar = Barometric pressure, mm mercury columnP = Suction at meter, mm mercury columnV m = Volume of gas sampled at meter conditions, m 3V = Equivalent vapour volume of condensate at meter con-ditions, m3


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- 33 -3.5.3elect the nozzle size, which will provide a meter samplingrate between 40 to 60 litres/min. Charts relating sampling rate

with stack and meter conditions may be prepared for the rangeof conditions expected.

3.7.4uration of Sampling-Deem the run to be of sufficient lengthif one of the following criteria have been obtained:a) A minimum of I m3 of dry gas has been withdrawn forsampling.b) The mass of particulate matter amounts to atleast 20 percentof the mass of the filtering medium in the sampler.3.7.5xperience and intelligent judgement should be applied in deter-mining the sampling time. Too short a time may give unreliableresults and too long a time may cause the resistance of thesampling train to exceed the pump's limits.3.80Preparation of the Sampling Train81fter proper nozzle and filtering medium have been selected

assemble the sample train as shown in Figure 3.3. Mark thesampling probe (including nozzle and filter holder) with thesame traverse points used for conducting the velocity traverse.

3.8.2lace a clean, preweighed thimble in the filter holder and tightensecurely.3.8.3tart the test after sampling rates have been calculated and

train assembled and checked for leakages. When the equipmentis ready in all respects, record the initial dry gas meter readingand push the sampling probe carefully into the duct to the pointnearest to the back wall. This will allow the probe to cool


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- 34 -in hot stack as it comes out, shortening the time required forcooling after the sample is taken. It is advisable to allow thenozzle and filter holder to preheat so that moisture presentin the gases does not condense in the filter during initial partof the sampling.

3.84When starting the test, the nozzle should be facing in the upstream direction, start operating the suction source, open thecontrol valve and start the stop watch. Note the time and recordit in- the log sheet. Adjust the flow rate with the help of therotameter and control valve until the desired flow rate forisokinetic conditions is obtained. As the test proceeds, dustbuild-up in the thimble will increase the amount of suctionrequired to maintain the proper meter rate, the valve shouldbe adjusted accordingly. This suction should not exceed 150 mmof mercury for paper thimbles. In case it exceeds this valuebefore the completion of sampling replace the same with anew thimble and restart sampling. During the test if the mercurysuction pressure at the meter drops suddenly it indicates thata leak has developed in the equipment or that thimble hascracked or burst. In this event, discard the test and repeat.Record the initial gas meter reading and pressure and temper-ature in the sampling train as well as condensor temperatureat half-minute interval during the test.

3.85When sampling at one point has been completed, move the samp-ling probe to the next point as quickly as possible. At the com-pletion of test, close the control valve, turn the direction of theprobe so that the sampling nozzle is facing down-stream andrecord the final gas volume and time. Remove the sampler care-fully from the flue and plug the nozzle to prevent the lossof sample.


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- 35 -

3.9.0Sample RecoveryAfter the sampler has cooled, brush down the dust on the insideof the nozzle carefully into the thimble using a small brushremove the thimble and place it in a dust-tight container fortransportation to the weighing room. In case the filter holderis kept outside during the sampling, the dust from the samplingprobe before the filter holder should be brushed down into thethimble.

3.9.1etermine the mass of dust collected in the thimble by differ-ence, that is, by weighing the thimble before and after therun. Dry the thimble in an oven for about 2 hours at 12 0 Cprior to sampling. After sampling, cool, dry and again weigh thethimble along with dust maintaining the same conditions asprior to sampling.

3.10.0 Calculations

3.10.1 Calculate the volume of gas sampled using the following equations:Volume of dry gas through the sampling train (25C, 760 mm Hg)

Pbar - P m73 + 25V stdm Y760+ 273mwhereT m = Temperature of gas at dry gas meter conditions, CV m = Volume of gas sampled at dry gas meter conditions,m 3(Pbar-Prn Actual pressure in sampling train, mm mercurycolumnPbarBarometric pressure, mm mercury columnp m= Static pressure in sampling train, mm mercurycolumnyCalibration factor of dry gas meter.


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- 36 -3.11.0 Dust Concentration - Calculate the dust concentration using

the following equations:MDust Concentration in mg/Nm 3 ,n

(25 C, 760 mmHg, dry basis)stdwhereM n= Mass of the dust in the thimble in mgV std = Volume of dry gas through the meter(25 C, 760 mmHg), Nm 3 .3.11.1 Emission Rate - Calculate the dust emission rate as follows:

S xDust Emission Rateskg/hr)06whereQFlue gas flow rate (25 C, 760 Hg mmHg), Nm 3 /hr.s3.12.0 All stack emission test results shall be given in dry basis asin 3.11.0 above, i.e. at zero percent moisture.


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- 37 -C .

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46/84

EhFu 1u a

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- 39 -

FIGURE 3.3 THIMBLE SAMPLING TRAIN

0 N D E


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- 40 -CHAPTER -4

4.0.0Determination of Sulphur Dioxide Emission from StationarySources (EPA Method).01rincipleA gas sample is extracted from the sampling point in the stack.The sulphuric acid mist (including sulphur trioxide) and thesulphur dioxide are separated. The sulphur dioxide fraction ismeasured by the barium-thorin titration method..02pplicabilityThis method is applicable for the determination of sulphur dioxideemissions from stationary sources. The minimum detectablelimit of the method has been determined to be 3.4 milligrams(mg) of S02 /m 3 . Although no upper limitas been establishedtests havehownhat concentrations as high as 80,000 mg/m 3o f .O 2cane collectedfficiently in two midgetmpingers,eachontaining 15illilitresfpercent hydrogen peroxideat a rate of.0 1pmor 20 minutes. Based on theoretical cal-cvlations,hepperoncentrationimit in a0-litreampleis about 93,300 mg/m 3 .Possible interferents are free ammonia, water soluble cationsand fluorides. The cations and fluorides are removed by glasswool filters and an isopropanol bubbler, and hence do not effectthe SO2 analysis.

4.1.0ApparatusThe sampling train is shown in Figure 4.1.


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- 42 -4.1.10 Volume Meter - Dry gas meter, sufficiently accurate to measure

the sample volume within 2 percent, calibrated at the selectedflow rate and conditions actually encountered during samplingand equipped with a manometer for measuring static pressureand a temperature gauge (dial thermometer, or equivalent)capable of measuring temperature to within 0.5 C.

4.1.11 Barometer - Mercury, aneroid, or other barometer capable ofmeasuring atmospheric pressure to within 2.5 mmHg (0.1 in Hg).In many cases, the barometric reading may be obtained froma nearby meteorological station.

4.20Reagents - Only AR grade reagents for sampling and analysisshould be used. Other specifications for sampling materialsas given below.

4.2.1ater - Deionized water4.2.2sopropanol, 89 percent - Mix 80 ml of isopropanol with 20 mlof deionized, distilled water. Check each lot of isopropanolfor peroxide impurities as follows:Shake10 ml of isopropanol with0 ml of freshly prepared10 percent potassium iodide solution. Prepare a blank by similarlytreating10 ml of distilled water. After 1minute, read theabsorbance at 352 nanometers on a spectrophotometer. If ab-sorbance exceeds 0.1, reject alcohol for use.4.2.3ydrogen Peroxide,3percent - Dilute 30 percent hydrogenperoxide 1:9 (v/v) with deinoized, distilled water (30 ml is neededper sample). Prepare fresh daily.

4.2.4otassium Iodide (KI) Solution; 10 percent - Dissolve 10.0 gram K Iin deionized distilled water and dilute to 100 ml,prepare whenneeded.


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- 43 -4.3.0pecifications for analytical materials as given below.4.3.1ater - Deionized water.4.3.2sopropanol; 100 percent.4 .3 .3hor in Indicator - 1-(O-arsonophenylazo)-2-naphthol-3,6-disul-phonic acid, disodium salt, or equivalent. Dissolve 0.20 gm in100 ml of deionized, distilled water.4.3.4arium Perchlorate Solution 0.0100 N - Dissolve 1.95 gm ofbarium perchlorate trihydrate Ba(C10 4 ) 2 . 3 H2O in 200 ml

distilled warser and dilute to I litre with isopropanol. Alter-natively, 1.22 gm of BaC12 .2H 2O may be used instead ofthe perchlorate.

4.3.5 Sulphuric Acid Standard; 0.0100 N - Standardised to 0.0002 Nagainst 0.0100 N NaOH which has been previously standardisedagainst potassium acid phthalate.

4.4.0 Procedure4.4.1 Sampling

Preparation of Collection Train - Measure 15 ml of 80 percentisopropanol into the midget bubbler and 15 ml of 3 percenthydrogen peroxide into each of the first two midget impingers.Leave the final midget impinger dry. Assemble the train asshown in Figure 4.1. Adjust probe heater to a temperaturesufficient to prevent water condensation. Place crushed iceand water around the impingers and bubbler.


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- 45 -4.4.5Sample Analysis

Transfer the contents of the storage container to a 100 mlvolume with deionized, distilled water. P ipette a 20 ml aliquotof this solution into a 250 ml-Erlenmeyer flask, add 80 mlof 100 percent isopropanol and two to four drops of thorinindicator, and titrate to a pink end point using 0.0100 N bariumperchlorate. Repeat and average the titration volumes. Runblank with each series of samples. Replicate titrations mustagree within 1 percent or 0.2 ml whichever is larger.

4.4.6alculationsCarry out calculations, retaining at least one extra decimalfigure, beyond that of the acquired data.

4.4.7omenclatureCConcentration of sulphur dioxide, dry basis convertedSD2 o standard conditions, mg/Nm3NNormality of barium perchlorate titrant milliequi-valents/mlPbarBarometric pressure at the exit orifice of the drygas meter, mm Hg'stdStandard absolute pressure, 760 mm HgT m = Average dry gas meter temperature, KTstdStandard temperature, 298 KV a= Volume of sample aliquot-titrated, mlV m = Dry gas volume as measured by the dry gas meter, m3V m(std) = Dry gas volume measured by the dry gas meter,corrected to standard conditions, Nm3


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-46-

V soln = Total volume of solution in which the SO2 sampleis contained, 100 miV t= Volume of barium perchlorate titrant used for the

sample, ml (average of replicate titration)V tb= Volume of barium perchlorate titrant used for the

b l a n k , m i .YEquivalent weight of SO24.4.8ry sample gas volume, corrected to standard conditions

T stdV m(std) - V m Ym Pbarx PstdKYVm Pbar

T mK 1 =.3858 K/mmHg

4.4.9ulphur dioxide concentrationK 2 (V - V tb)N (V s om n )VCS ^ 2 =V m(std)whereK 2=2.03 mg/meq.


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- 47 -W

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- 48 -CHAPTER -5

5.0.0etermination of Total Fluoride Emissions from StationarySources-pecific Ion Electrode MethodEPA Method)5.0.1pplicabilityThis method applies to the determination of fluoride (F) emis-sions from stationary sources as specified in the regulations.It does not measure fluorocarbons, such as freons.

5.0.2rincipleGaseous and particulate fluorides are withdrawn isokineticallyfrom the source and collected in water and on a filter. Thetotal F is then determined by the specific ion electrode method.5.0.3ange and SensitivityThe range of this method is 0.02 to 2.000pg F/ml; however,measurements of less than 0.1)ugF/ml require extra care.

5.0.4nterferencesGrease on exposed surfaces may cause low F results becauseof absorption.5.1.0pparatus5.1.1ampling Train and Sample Recovery - Same as method forS O 2 determination from stationary sources.


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- 49 -5.2.0nalysis21

istillation apparatus, Bunsen burner, electric muffle furnace,crucibles, beakers, volumetric flasks, Erlenmeyer flask or plasticbottles, constant temperature bath, and balance.

5.2.2luoride Ion Activity Sensing Electrode.5.2.3eference Electrode - Single junction, sleeve type.5.2.4lectrometer - A pH meter with millivolt-scale capable of0.1 my resolution or a specific ion meter made specially forspecific ion use.

5.2.5agnetic Stirrer and Fluorocarbon-Coated Stirring Bars.5.3.0eagentsAnalysis - Use the following AR grade chemicals (or equivalent)unless otherwise specified.5.3.1alcium Oxide (CaO) -- Certified grade containing G.005 percentF or less.5.3.2henolphthalein Indicator - Dissolve 0.1 gm of phenolphthaleinin a mixture of 50 ml of 90 percent ethanol and 50 ml


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- 50 -5.3.6odium Hydroxide 5 M- dissolve 20 gm of NaOH in 100 mlof deionized distilled water.5.3.7ulphuric Acid, 2.5 percent (V/V) - Mix 1 part of concentra ted

H 2 S O 4 with 3 parts of deionized distilled water.5.3.8otal Ionic Strength Adjustment Buffer (TISAB) - Place approxi-mately500 ml of deionized distilled water in a1 litre beaker.Add 57 ml of glacial acid, 58 gm of sodium chloride, and 4 gmof cyclohexylene -dinitro- tetraacetic acid. Stir to dissolve.Place the beaker in a water bath to cool it. Slowly add5 MNaOH to the solution, measuring the pH continuously

with a calibrated pH/reference electrode pair, until the pHis 5.3. Cool to room temperature. Pour into a 1 -litre volumetricflask, and dilute to volume with deionized distilled water.Commercially prepared TISAB may be substituted for the above.

5.3.9luoride Standard solution,0.1 M- ven dry some sodiumfluoride (NaF) for a minimum of2 hours ar 110 C, and storein a dessicator. Then add 4.2gm of NaF to a 1 -litre volumetricflaskaniadd enough deionized distilled water to dissolve.Dilute to volume with deionized distilled water.

5.4.0rocedureSampling, sample recovery, and sample preparation and distil-lation.Containero.Probe,ilterndmpingeratches,se agraduatedyclinder, measure toheearestl,ndecordthe volume of the water in the first of these impingers, includeanyondensaten therobe inhis determination.ransferthe impinger water from the graduated cylinder into this poly-ethyleneontainer. Add the filtero thisontainer,akingcare that dust on the outside of the probe of other exterior


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- 51 -surface does not get into the sample. Clean all sample exposedsurfaces (including the probe nozzle, probe fitting, probe liner,first three impingers, impinger connectors and filter holder)with deionized distilled water. Use less than 500 ml for theentire wash. Add the washings to the sampler container. Performthe deionized distilled water rinses as follows:Carefully remove the probe nozzle and rinse the inside surfacewith deionized water from a wash bottle. Brush with a n y Ionbristle brush and rinse until the rinse shows no visible particles,after which make a final rinse of the inside surface. Brushand r inse the inside parts of the Swagelok fitting with deionizeddistilled water in a similar way.Rinse the probe liner with deionized distilled water. Whilesquirting the water into the upper end of the probe, tilt androtate the probe so that all inside surface will be wetted withwater. Let the water drain from the lower end into the samplecontainer. A funnel (glass or polyethlene) may be used to aidin transferring the liquid washes to the container. Follow therinse with a probe brush. Hold the probe in an inclined position,and squirt deionized distilled water into the upper end as theprobe brush is being pushed with a twisting action throughthe probe. Hold the sample container underneath the lowerend of the probe and catch any water and particulate matterthat is brushed from the probe. Run the brush through theprobe three times or more. With a stainless steel or othermetal probe, run the brush through, in the above prescribedmanner at least six times, since metal probes have smallcrevices in which particulate matter can be entrapped. Rinsethe brush with deionized distilled water, and quantitativelycollect these washings in the sample container. After the brush-ing, make a final rinse of the probe as described above.


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- 52 -It is recommended that two people clean the probe to minimizesample losses. Between sampling runs, Keep brushes clean andprotected from contamination.Rinse the inside surface of each of the first three impingers(and connecting glassware) three separate times. Use a smallportion of deionized distilled water for each rinse, and brusheach sample--exposed surface with a nylon bristle brush, toensure recovery of fine particulate matter. Make a final rinseof each surface and of the brush.After ensuring that all joints have been wiped clean of thesilicone grease, brush and rinse with deionized distilled waterthe inside of the filter holder (front-half only, if filter is posi-tioned between the third and fourth impingers). Brush andrinse each surface three times or more if needed. Make afinal rinse of the brush and filter holder.After al1 water washings and particulate matter have beencollected in the sampler container, tighten the lid so thatwater will not leak out when it is shipped to the laboratory.Mark the height of the fluid level to determine whether leakageoccurs during transport. Label the container clearly to identifyits contents.Container No. 2 (Sample Blank) - Prepare a blank by placingan unused filter in a polyethylene container and adding a volumeof water equal to the total volume in Container No. 1. Proce - sthe blank in the same manner as for Container No. 1.

5.5.0Analysis

5.5.1Containers No. I and No.2 - Distill suitable aliquots from Con-tainer No. 1 and No. 2 (apparatus shown in Figure 5.2). Dilutethe distillate in the volumetric flask to exactly 250 ml with


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- 53 -deionized, distilled water and mix thoroughly. Pipette 25 mlaliquot from each of the distillate and separate beakers. Addan equal volume of TISAB and mix. The sample should be atthe same temperature as the calibration standards when measure-ments are made. If ambient laboratory temperature fluctuatesmore than 2C from the temperature at which the calibrationstandards were measured, condition samples and standardsin a constant temperature bath before measurement. Stir thesample with a magnetic stirrer during measurement to minimizeelectrode response time. if the sitrrer generates enough heatto change solution temperature, place a piece of temperatureinsulating material such as cork, between the stirrer and thebeaker. Hold dilute samples (below 10 -4 M fluoride ion content)in polyethylene beakers during measurement.Insert the fluoride and reference electrodes into the solution.When a steady millivolt reading is obtained, record it. Thismay take several minutes. Determine concentration from thecalibration curve. Between electrode measurements, rinse theelectrode with deionized distilled water.

5.6.0alibrationMaintain a laboratory log of all calibrations.

5.6.1ampling Train - Same as method for determination of SO?shown in Figure 5.1.5.6.2luoride Electrode - Prepare fluoride standardizing solutionsby serial dilution of the 0.1 M flouride standard solution. Pipette10 ml of 0.1 M fluoride standard solution into a 100 ml volu-metric flask and make up to the mark with deionized distilledwater for a 10-2 M standard solution. Use 10 ml of 10-2 Msolution to make a i0-3 M solution in the same manner. Repeatthe dilution procedure and make 10-4 M and 10-5 M solutions.


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-54-Pipette 50 ml of each standard into a separate beaker. Add50 ml of TISAB to each beaker. Place the electrode in themost dilute standard solution. When a steady millivolt readingis obtained, plot the value on the linear axis of semilog graphpaper versus concentration on the log axis. Plot the nominalvalue for concentration of the standard on the log axis e.g.when 50 ml of 10 -2 Mstandard is diluted with 50 ml of TISABthe concentration is still designated "10-2 M".Between measurements soak the fluoride sensing electrodein deionized distilled water for 30 seconds, and then removeand blot dry. Analyze the standards, going from dilute to con-centrated standards. A straight-line calibration curve willbe obtained, with nominal concentrations of 10 -4 , 10-3 , 10-2 and10 - 1 fluoride molarity on the log axis plotted versus electrodepotential (in mV) on the linear scale. Some electrodes maybe slightly nonlinear between 10 -5 Mand 10 -4 M. If this occurs,use additional standards between these two concentrations.Calibrate the fluoride electrode daily, and check it hourly.Prepare fresh fluoride standardizing solutions daily (10 -2 M orless). Store fluoride standardizing solutions in polyethyleneor polypropylene containers.Note: Certain specific ion meters have been designed specifical-ly for fluoride electrode use and give a direct readout offluoride ion concentration. These meters may be used in lieuof calibration curves for fluoride.

5.70CalculationsCarry out calculations, retaining atleast one extra decimalfigure beyond that of the acquired data. Round off figuresafter final calculation.


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- 55 -5.7.1omenclatureMF concentration from calibration curve, molarity.

V t= Total volume of F in sample, after final dilution, ml.A t= Aliquot of total sample added to still, mlV d= Volume of distillate as diluted, mlFTotal F in sample, mg5.7.2luoride in Sample - Calculate the amount of F in the samplingusing the following equation:

VF t = AV d ) (M)t5.7.3luoride Concentration in Stack Gas - Determine the fluorideconcentration in the stack gas, C S , using the following equation:F twhere Csm(std)

V m(std) = Volume of gas sample as measured by dry gas meter,corrected to standard conditions.


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TEMPERATURETACK WALLSENSOR PROBE-_ OPTIONAL FILTER'-ITOT TUBE:HOLDER LOCATION_T H E R M O M E T E Rf- FILTER HOLDER

PROBE"I -STACK WALL CHECK VALVEREVERSE T YAE ' --IPITOT TUBEPITOT MANOMETER

ICE BATHMPINGERSTHERMOMETERS VACUUM LINEBY-PASS VALVE

I '-ACUUMGAUGEAIR TIGHT PUMPEEDLE VALVEw DRY GAS METER

FIGURE5.1 FLUORIDE SAMPLING TRAIN

CONNECT12mm ID9 2440THERMOLA

w(rH T


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- 57 -CHAPTER-6

60.0Ambient Air Quality MonitoringThis section deals with the methods of ambient air qualitymonitoring. The industries that are required to do this aregiven in Chapter 1.

6.0.1ertificationA high volume sampler may be used for measuring suspendedparticulate matter with a provision for measuring pollutantgases. A low volume sampler may be used for measuring ambientQuantities of gaseous pollutants. Alternatively, properly calibrat-ed automatic continuous monitors may be used for this purpose.

6.0.2he high and low volume samplers as well as the automaticcontinuous monitors should be approved by the Central PollutionControl Board.6.0.3he group or laboratory performing the test should have to

be approved by the Central Board in those cases where theresults of the tests are being submitted to the Central Boardor the State Boards. Where a dispute occurs, this will be re-solved by the tests being conducted by the Central Board itselfor its approved laboratory.

61.0Specifications of High Volume Air Sampler11eneralHigh volume sampler complete in all respects including blower,filter holder free from leakages, cabinet, roof shelter, automaticvoltage stabilize, flow measurement device and arrangementof gaseous sampling with flow controller. Dimensions of highvolume sampler are given in Figure 6.1.


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- 58 -

6.1.2Blower Flow Rate1.4 to 1.8 m 3 /min free flow (without resistance)13oltage StabilizerAn automatic voltage stabilizer to keep the voltage between210 and230 V at 50 to 60 Hz shall be provided.14ilter Holder

A stainless steel (SS 304) filter holder assembly with rubbergasket to hold25 cmx 20 cm(10 inx 8 in) filter paper.Net size of filter paper for suction after putting the filterholder frame shall not be less than23 cmx 18 cm.15aseous SamplingThe gas inlet should be kept on the pipe after the cast alu-minium hopper but before the blower. There can be three inlets

for different gases or one inlet through a manifold. A calibratedrotameter (0 to 3 1pm) shall be provided for checking the flowrate.

16articulate SamplingThe inlet openings in the housing to the filter shall be suchthat particles collecting on the filter surface are less than100 microns. This will be done by keeping the angle of thegable roof at 4 5 0 to the horizontal.17ain HousingThe main housing on castors shall be rectangular (29 cm and36 cm) and made of unpainted sturdy aluminium.


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- 59 -6.1.8 Automatic Timer and Time Totalizer

The samples should have a timer for 4 to 24 hour of settingwith intermediate on-off. It should have in addition, a timetotalizer to indicate hours and minutes.

6.1.9alibrationThe blower should be calibrated against a standard orifice/meter or a U-tube manometer. The graph in case of the U-tubemanometer should be fixed on the sampler. The calibrationcertificate from the manufacturer of the rotameter shouldaccompany the sampler.

6.2.0 Method of SamplingThe sampling and analysis method for suspended particulatematter shall be as per Indian Standard Method for Measurementof Air Pollution; IS: 5182 (Part IV) 1973. The filter paper shouldbe type EPM -2 000 W hatm an, or equivalent .

6.2.2he measurement of sulphur dioxide shall be as per IndianStandard Method for Measurement of Air Pollution; IS: 5182(Part 11) 1969.6.2.3itrogen dioxides shall be analyzed using the Jacob and Hoch-heiser, modified method, given in Chapter 7.6.4.2he measurement of ambient total fluorides shall be as permethod given in APHA, given in Chapter 8.

6.3.0he results shall be reported in the format of Table 6.1.


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- 62 -CHAPTER -7

00etermination of Nitrogen Dioxide in Ambient Air(Jacob and Hochheiser, modified method)10rinciple and ApplicabilityNitrogen dioxide is colledted by bubbling air through a sodiumhydroxide-sodium arsenite solution to form a stable solutionof sodium nitrite. The nitrite ion produced during samplingis reacted with phosphoric acid, sulphanilamide, andN-1 (naph-

thyl) ethylenediamine dihydrochloride to form an azo dyeand then determined colourimetrically.The method is applicable to collection of4 to 24 hour samplesin the field and subsequent analysis in the laboratory.20ange an d S ensitivityThe rangef thenalysis is.04o.0 pgO 2 /ml. Beer's

law isbeyed throughhis rang_e0o.0bsorbance units).With 50 mi absorbing reagentnd aampling ratef200 cm 3 /min for 24 hours, the range of the method is 20 to250 pg /m (0.01 to 0.04 ppm) nitrogen dioxide.A concentration of 0.04 pg NO 2 /ml will produce an absorbanceof approximately 0.2with1 cm cells.

7.3.0nterferenceNitric oxide is a positive interferent. The presence of NO canincrease the NO2 response by 5 to15% of the NO 2 sampled.The interference of sulphur dioxide is eliminated by convertingit to sulphate ion with hydrogen peroxide before analysis.


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- 63 -

7.4.0recision Accuracy and StabilityThe relative standard deviations for sampling NO2 concentra-tions of 78, 105 and 328 pg/m3 are 3, 4 and 2%, respectively.Collected samples are stable for at least 6 weeks.

7.5.0pparatus51olumetric Flask - 50, 100, 200, 250,'500, 1000 ml.7.5.2raduated Cylinder - 1,000 ml.7.5.3ipettes - 1,2,5,10,15 ml volumetric, 2 ml graduated in 1/10 mlintervals.7.5.4est Tubes - Approximately 20 x 150 mm.7.5.5pectrophotometer - Capable of measuringbsorbance at540 mm.7.6.0eagents61odium Hydroxide - AR reagent grade.62odium Arsenite - AR reagent grade..7.6.3bsorbing Reagent - Dissolve 4.0 gm sodiumydroxide indistilled water, add 1.0 gm of sodium arsenite and dilute to

1,000 ml with distilled water.7.6.4ulphanilamide -Melting point of 165 to 1670C.


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- 64 -65-(1- Naphthy1)-Ethylenediamine Dihydrochloride (NEDA)Best grade available.66ydrogen Peroxide - AR reagent grade 30%.67odium Nitrite - Assay of 97% NaNO2 or greater.68hosphoric Acid - AR reagent grade, 85% minimum.69ulphanilamide Soln - Dissolve 20 gm sulphanilamide in 700 mldistilled water. Add with mixing, 50 ml concentrated phosphoric

acid and dilute to 1,000 ml. This solution is stable for onemonth, if refrigerated.

7.6.10 NEDA Solution - Dissolve 0.5 gm of NEDA in500 ml of distilledwater. This solution is stable for one month, if refrigeratedand protected from light.

7.6.11 Hydrogen Peroxide Solution - dilute 0.2 ml of30%hydrogenperoxide to 250 ml with distilled water. This solution maybe used for one month, if protected from light and refrigerated.

7.6.12 Standard Nitrite Solution - Dissolve sufficient desiccated sodiumnitrite and dilute with distilled water to 1,000 ml so that asolution containing 1,000 dug NO2/ml is obtained. The amountof Na NO2 to use is calculated as follows:G =1.500x100AwhereGAmount of NaNO 2 , gm1.500 = Gravimetric factor in converting NO 2 into NaNO2AAssay, percent.


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- 65 -7.7.0nalysisReplace any water lost by evaporation during sampling by

adding distilled water up to the calibration mark on the ab-sorption tube. Pipette in I ml hydrogen peroxide solution,10 ml sulphanilamide solution and 1.4 ml NEDA solution withthorough mixing after the addition of each reagent. Preparea blank in the same manner using 10 ml of unexposed absorbingreagent. After a 10 minute colour-development interval, measurethe absorbance at 540 nm against the blank. Read pg NO2/mlfrom the calibration curve. Samples with an absorbance greaterthan 1.0 must be reanalyzed after diluting an aliquot (lessthan 10 ml) of the collected sample with unexposed absorbingreagent.

7.8.0alculationCalculate volume of air sampled.F=2E2 x Tx 1fl6whereVVolume of air sampled, m 3E I= Measured flow rate at start of sampling, cc/minF 2= Measured flow rate at end of sampling, cc/minTtime of sampling, minutes10 -6 = Conversion of cm3 to m3 .Calculate the concentration of nitrogen dioxide as pg NO2 1m 3using:

3pg NO2 /ml) x 50Ng NO 2/m= V x 0.82


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-66-

where5 0Volume of absorbing reagent used in sampling, m lVvolume of air sampled, m 30.82 = Factor for collection efficiencyIf desired, concentration of nitrogen dioxide may be calculatedas ppm NO2 = (pg NO2 /m3 ) x 5.32 x 10-4.


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- 67 -CHAPTER-8

8.0.0etermination of Total Fluorides in Ambient Air(APHA Method)

8.1.0rincipleAtmospheric samples are taken using midget impingers contain-ing 10 ml of 0.1 M NaOH.Samples are diluted 1:1 with Total Ionic Strength ActivityBuffer (TISAB). The diluted samples are analyzed using thefluoride ion selective electrode.

8.2.0ange and SensitivityThe range and sensitivity have not been established. The re-commended range of the method is 0.009 to 95 mg/m3 air.8.3.0nterferenceHydroxide ion is the only significant electrode interference;however, addition of the TISAB eliminates this problem. Verylarge amounts of complexing metals such as aluminium mayresult in low readings even in the presence of TISAB.

8.4.0recision and AccuracyThe accuracy and precision of this method have not been deter-mined. No collaborative tests have been performed on thismethods.

85.0Advantages and Disadvantages of the MethodAdvantages over previous methods include simplicity, accuracy,speed, specificity and elimination of distillation, diffusion andashing of the samples.


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- 68 -No significant disadvantages are known at present.60

pparatus61ampling EquipmentThe sampling unit for the impinger collection method consistsof the following components.62Prefilter Unit - Consists of the filter media and cassettefilter holder.63Midget Impinger - Containing the absorbingolution orreagent.64pump suitable for delivering desired flow rates.The sampling pump is protected from splashover or watercondensation by an absorption tube loosely packed with a plugof glass wool and inserted between the exit arm of the impinger

and the pump.65rotameter to measure the air flow.66n Orion model 94-09 fluoride selective ionlectrode, orequivalent.67eference Electrode - Orion 90-01 single junction, or equivalentcalomel or silver / silver chloride electrode.68xpanded scale millivolt-pH meter, capable of measuring towithin 0.5 m V .8.6.9olyethylene beakers 50 ml capacity.


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- 69 -8.6.10 Laboratory Glassware8.6.11 Magnetic stirrer and stirring bars for 50 ml beakers.8.7.0eagents8.7.1urity - All chemicals must be ACS reagent grade, or equivalent.Polyethylene beakers and bottles should be used for holdingand storing all fluoride containing solutions.8.7.2ouble Distilled Water8.7.3lacial Acetic Acid8.7.4bsorbing solution, 0.1 M Sodium Hydroxide Solution - Dissolve4 gm sodium hydroxide pellets in 1 litre of distilled water.8.7.5odium Hydroxide, 5 M Solution - Dissolve 20 gm sodium hydro-xide pellets in sufficient distilled water to give 100 ml ofsolution.8.7.6odium Chloride8.7.7odium Citrate8.7.8otal Ionic Strength Activity Buffer (TISAB) - Place 500 mlof double distilled water in a I litre beaker. Add 57 ml ofglacial acetic acid, 58 gm of sodium chloride and 0.30 gm

of sodium citrate. Stir to dissolve. Place beaker in a waterbath (for cooling) and slowly add 5 M sodium hydroxide untilthe pH is between 5.0 and 5.5. Cool to room temperature andpour to a 1 litre volumetric flask and add double distilled waterto the mark.


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-71 -to make the joint between the prefilter and impinger shouldbe used. The air being sampled should not be passed throughany other tubing or other equipment before entering the im-pinger.

8.8.5urn on pump to begin - sample collection. Care should be takento measure the flow rate, time and / or volume as accuratelyas possible. The sample should be taken at a flow rate of2.5 1pm. A sample size of not more than 200 litres and noless than 10 litres should be collected. The minimum volumeof air sampled will allow the measurement at least 1/10 timesthe TLV, 0.2 mg/m 3 (760 mm Hg, 25 C).

8.8.6fter sampling, the impinger stem can be removed and cleaned.Tap the stem gently against the inside wall of the impingerbottle to recover as much of the sampling solution as possible.Wash the stem with a small amount (1 to\ 2 ml) of unused ab-sorbing solution and add the wash to the impinger. Seal theimpinger with a hard, non-reactive stopper (preferably Teflon).Do not seal with rubber. The stoppers on the impingers shouldbe tightly sealed to prevent leakage during shipping. If it ispreferred to ship the impingers with the stems in, the outletsof the stem should be sealed with parafilm or other non-rubbercovers, and the ground glass joints should be sealed (i.e. taped)to secure the top tightly.

8.8.7are should be taken to minimize spillage or loss by evapo-ration at all times. Refrigerate samples if analysis can notbe done within a day.

8.8.8henever possible, hand delivery of the samples is recom-mended.89"blank" impinger should be handled as the other samples(fill, seal and transport) except that no air is sampled throughthis impinger.


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- 72 -8.8.10 Where a prefilter has been used, the filter cassettes are capped

and placed in an appropriate cassette shipping container. Onefilter disc should be handled as the other samples (seal andtransport) excerpt that no air is sampled through, and this labledas a blank.90nalysis of Samples91ransfer the sample from thempinger to a 50 ml plasticbeaker, add 10ml TISAB and dilute to 25 ml with double distilledwater. Stir the solution.92he fluoride ion electrode and the reference electrode arelowered into the stirred solution and the resulting mV reading

recorded (to the nearest 0.5 millivolt) after it has, stabilized(drift less than 0.5 mV per min).

8.10.0 Calibration and StandardsPrepare a series of fluoride standard solutions by diluting 5 mlof each fluoride standard (8.7.10) and5 ml TISAB in a clearpolyethylene beaker to 25 ml with double distilled water. Insertthe fluoride ion electrode and the reference electrode intoeach of the stirred calibration solutions starting with the mostdilute solution and record the resulting mV reading to thenearest 0.5 mV. Plot the mV readings vs the fluoride ion concof the standard on semi-log paper. The fluoride ion conc inpg/ml is plotted on the log axis. The calibration points shouldbe repeated twice daily.

8.11.0 Calculations8.11.1he conc (dug/ml) of fluoride in the sample solution is obtainedfrom the calibration curve .


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- 73 -

8.11.2 Total pg F in the sample = sample conc (pg/ml) x samplesolution volume (ml).

8.11.3 The total dug F is divided by the volume in litres, of air sampledto obtain conc in pg F /litre or mg F - /m 3 .

mg F /m3 = Ng F /litrer(Section 8.11.4) mgF-./m3 _total VgFV S8.11.4 Convert the volume of air sampled to standard conditionsof 25 C and 760 mm Hg.

2 9 8V=VS 0 x T+273whereVVolume of air in litres at 25 C and 760 mm HgVVolume of air in litres as measuredp bar = Barometric pressure in rnm HgTTemperature of air in degree centigrade8.11.5 The conc can also be expressed in ppm, defined as p1 of com-ponent per litre of air. .45ppm F = N1 F /Vs2MWx pg F /VS = 1.29 plFIVswhere24.45 = Molar volume at 25 C.and. 760 mm HgMW19, weight of fluoride ion, (i.e., 19 ug F= 24.45ulat 25 C, 760 mm Hg)


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- 74 -8.11.6To calculate the conc of hydrogen fluoride as mg HF/m3 or

ppm HF, simply multiply the corresponding concentration ofF - (from 8.11.3 or 8.11.4) by 1.05


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Emission Regulations Part-Three

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Transcript of Emission Regulations Part-Three