“TECHNIQUES FOR MEASUREMENT OF ORGANIC POLLUTANTS LIKE BENZENE & BENZO(a)PYRENE

(& METALS) IN AMBIENT AIR”

S.K.TYAGI, SCIENTIST,

CENTRAL POLLUTION CONTROL BOARD(MINISTRY OF ENVIRONMENT & FORESTS)

Delhi-110 032

TRAINING PROGRAME (SHORT COURSE ) ON “APPROPRIATE INSTRUMENTS & TECHNIQUES FOR COMPLYING

WITH NEW AMBIENT AIR QUALITY STANDARDS”AT BBD INSTITUTE OF TECHNOLOGY ,GHAZIABAD

ORGANISED BY “ENVIROTECH CENTRE FOR R&D,NEW DELHI”

CENTRAL POLLUTION CONTROL BOARD(MINISTRY OF ENVIRONMENT & FORESTS)PARIVESH BHAVAN,EAST ARJUN NAGAR,

DELHI-110 032

Presntation CoversAbout Legislation

About CPCB

About Challenges

About Organic Pollutants

PAHs & BTX- Sampling & Analytical Techniques

About AAQ Standards

About Interventions & Strategies to control A.P.

Small Exercise

1. The Water (Prevention & Control of Pollution) Act, 1974

2. The Water (Prevention & Control of Pollution) Cess, Act, 1977 3. The Air (Prevention & Control of Pollution) Act, 1981

4. The Environment (Protection) Act, 19865. Environmental Impact Assessment Notification

6. The Hazardous Waste (Management and Handling) Rules 1989

7. The Bio - Medical Waste (Management and Handling) Rules 19888. The Municipal Solid Waste (Management and Handling) Rules 2000

9. The Noise Pollution (Regulation & Control) Rules, 2000

10. The Batteries (Management and Handling) Rules 2001

Major Environmental Major Environmental Acts/RulesActs/Rules

CPCB HEAD OFFICE, DELHICPCB HEAD OFFICE, DELHI

KANPUR KOLKATA SHILONG BHOPAL VADODARA BANGLORE

Uttar PradeshUttaranchalJammu &Kashmir, Himachal Pradesh,Punjab, Haryana UT Delhi

BiharBiharJharkhandJharkhandOrrisaOrrisaSikkimSikkimWest BengalWest BengalUT AndamanUT AndamanNicobarNicobar

AssamManipurMeghalayaMizoramNagalandTripura

MadhyaMadhyaPradeshPradeshRajasthanRajasthanChattisgarhChattisgarh

GujratMaharastraUT Daman,Diu and Dadra& NagarHaveli

Andhra PradeshAndhra PradeshGoaGoaKarnatakaKarnatakaKerlaKerlaTamilnaduTamilnaduUT LakshadweepUT LakshadweepUT UT PondicharyPondichary

ZONAL OFFICES OF CPCB

Offices of CPCB Offices of CPCB

17 Members Governing Board- Chairman, CPCB (Full Time)- 5 from Central Government- 3 from SPCB- 2 from local authorities- 3 from filed of agri./fishery/industry or trade- 2 from companies or corporation- Member Secretary, CPCB (Full Time)

Member SecretaryMember Secretary

ChairmanChairman

Planning Division

Planning Division

Pollution Assessment Monitoring &

Survey Division

Pollution Assessment Monitoring &

Survey Division

Infrastructure Division

Infrastructure Division

Pollution Control

Implementation

Pollution Control

Implementation

Zonal OfficeLucknow

Zonal OfficeLucknow Zonal Office

VadodaraZonal OfficeVadodara Zonal Office

BhopalZonal Office

Bhopal Zonal OfficeKolkata

Zonal OfficeKolkata Zonal Office

ShillongZonal Office

ShillongZonal OfficeBangalore

Zonal OfficeBangalore

AdministrationPersonnel

AdministrationPersonnel Administration

MaterialsAdministration

Materials AdministrationEstate

AdministrationEstate Administration

Publications, PRAdministrationPublications, PR Finance &

AccountsFinance &AccountsAdministration

RecruitmentAdministrationRecruitment

A.S. SectionA.S. Section Computer Section

Computer Section

TrainingTraining

ChemicalHaz. WasteEnv. PlanningBasicNoiseBio-medicalDG SetsNoise

Agro-based

Policy, SSILaw

R&D LaboratoryMonitoring

Assessment

PolicyPlanning

MSW

Coordina-tion

DraughtingSection

DraughtingSection

Existing Existing OrganogramOrganogram

Activities of IFD (Activities of IFD (LABsLABs.) .)

CPCB Laboratory, DelhiCPCB Laboratory, Delhi

WATERLABORATORY

AIRLABORATORY

SOPHISTICATEDINSTRUMENTATION LABORATORY

BIOLABORATORY

TREATABILITYLABORATORY

NATIONAL REFERRAL TRACE ORGANIC LABORATORY

- Laboratory management- Monitoring activities- Laboratory analysis- R & D Activities- Quality Assurance / Quality

Control system- Strengthening of laboratories- Scientific services to SPCBs,MoEF, etc.

- Training of Personnel

AIR LABORATORYIFD (LABs)

AIR TOXIC LABMETEOROLOGY

NAMP/Wet Anal

ONLINE AIR MONITORING

STACK MONITORING

PARTICULATE AND RAIN WATER CHARACTERIZATION

CALIBRATION AND QA/QC

Parameters monitored to support and infer air monitoring data

Organic / Hazardous air pollutants

Criteria air pollutants monitoring with manual sampling and physico-chemical analysis

Real time continuous ambient air monitoring network

Static injection facility for AQC of gaseous pollutants

QUALITY MANAGEMENT SYSTEM

In-depth analysis to know the composition

Source emission monitoring for compliance control efficiency and

or pollution potential estimationVEHICULAR EMISSION

MONITORING PUC Calibration

NABL related activities

NOISE MONITORING Ambient noise

Domestic8%

Vehicular72%

Industrial20%

Alveolar macrophages in sputuma, Rural control; b, Urban control; c & d, Exposed to vehicular emission

Epidemiological study by CNRI on children in Delhi to assess respiratory health status of 10,000 school children

National Ambient Air Quality Monitoring Programme (NAMP)

Started in 1984 - 7 Station ( Manual Station)

By 2000 - Increased to 295 Stations (Operated and Maintained by SPCB /CPCB / Universities, etc. and funded by CPCB)

By 2009 - Increased to 346 Stations Monitoring in Delhi

3 (old) +3 (new) Continuous AQMS

2 Mobile air Laboratories

6 Manual AQMS

1 Integrated Air Quality Monitoring Station being set up

About 300 continuous stations maintained by industries.

Parameters MonitoredCriteria Pollutants - SPM, RSPM (PM10), SO2, NOx,

CO, Pb, NH3 (additional parameters at few locations)

Other Parameters: - PM2.5, O3, BTX, PAHs

Monitoring Techniques

SO2 – Absorption in TCM and Spectrophotometric determination

SPM, RSPM (PM10), PM2.5 – High Volume / Low Volume Sampling followed by Gravimetric analysis

NOx – Absorption in NaOH, Na- Arsenite solution followed by Spectrophotometricdetermination

Pb + other metals – Particulate Lead AAS analysis after acid digestion

O3 – Both manual and automatic method; VOCs & PAHs -GCMS

CO, SO2, NOx, O3, BTX, -Automatic analyser

S. No.

Parameter Method Instrument

1. Determination of Suspendedparticulate matter (SPM) in the atmosphere

High Volume Method

High Volume Sampler(HVS)

2 Measurement of Respirable suspended particulate matter (PM10 in air

Cyclonic flow techniques

Respirable Dust Sampler (RDS)

3. Determination of Sulphur dioxide in air

Modified West and Gaeke Method

Spectrophotometer

4. Determination of Nitrogen dioxide in atmosphere

Sodium Arsenite Method

Spectrophotometer

5. Measurement of Carbon monoxide

In Air by U-V photometric O3Analysis

Automatic Analyser

6. Determination of Ozone in atmosphere

Buffered Potassium Iodide Method

Spectrophotometer

7. Determination of Hydrocarbon (HC), Benzene, Toluene and Xylene (BTX) & PAHs

G.C. Method Gas Chromatograph

8. Determination of Heavy Metal in atmosphere

AAS Method Atomic Absorption Spectrophotometer

Measurement Methods of Air Pollutants

• The complex organic compound have got into use in many diverse applicationsencompassing all types of human activities.

• While rural environments often have high levels of pesticides and other residues from sprays of weedicides and other chemicals used in modernfarming,

•urban environments have high doses of a host of organics coming from paints & varnishes, lacquers, solvents, foam blowingagents, sprays etc.

•Recent addition of Benzene in petrol, in place of a leadcompound, has made Benzene and itsderivatives a part of vehicular pollution.Already Benzene concentrations in high traffic areas and near petrol pumps have become a matter of concern.

•Unfortunately a majority ofthese compounds are highly toxic and many ofthem have been reported to the carcinogenic.

•Organic compounds are also reported to bepre-cursers for Ozone formation and play arole in secondary formation of oxidants.

•As such air pollution monitoring networks are now beginning intensive efforts for monitoring of specific organic compounds such as Benzene,Toluene & Xylene (BTX)and often a mixture of polynuclear aromatic hydrocarbons (PAHS) .

ORGANIC COMPOUNDS

33 URBAN AIR TOXICS IDENTIFIED BY US EPA  

acetaldehyde ethylene oxideacrolein formaldehydeacrylonitrile hexachlorobenzenearsenic compounds hydrazineBenzene lead compounds

beryllium compounds manganese compounds

1, 3-butadiene mercury compounds

cadmium compounds methylene chloride

carbon tetrachloride nickel compounds

chloroform polychlorinated biphenyls (PCBs)

chromium compounds Polycyclic Aromatic Hydrocarbon (PAH)

coke oven emissions quinolinedioxin 1, 1, 2, 2-tetrachloroethaneethylene dibromide perchloroethylenepropylene dichloride trichloroethylene1, 3-dichloropropene vinyl chlorideethylene dichloride --

METHOD FOR MEASUREMENT OF POLYNUCLEAR AROMATIC HYDROCARBONS (PAHS) IN AIR PARTICULATE MATTER

PRINCIPLEThis method is designed to collect particulate phase PAHs in ambient air and fugitive emissions and to determine individual PAH compounds. It is based on high volume ( ~ 1.2 m3 / min) sampling method capable of detecting sub ng/ m3 concentration of PAH with a total sample volume ~ 480 m3 / of air over a period of 8 hours with same filter. It Involves collection from air particulate on a fine particle (glass-fibre) filter using high volume sampler for total suspended particulate matter (TSPM) or respirable dust sampler for respirable suspended particulate matter (RSPM or PM10) and subsequent analysis by Capillary Gas Chromatograph (GC) using Flame Ionization Detector (FID). If sampling period is extended to 24 hours without changing the filter, it may enhance sample loss due to volatility or reactions of PAHs on collection media.

Major PAH CompoundsAcenaphthylene(C10H8) Benzo(b) f luoranthene (C20H12)Acenaphthene(C10H8) Benzo(k) fluoranthene (C20H12)Fluorene(C10H8) Coronene (C24H12) Naphthalene (C10H8) Benzo(e) pyrene (C20H12)

Phenanthrene (C14H10) Benzo(a) pyrene (C20H12)Anthracene (C14H10) Perylene (C20H12)Fluoranthene (C16H10) Benzo(ghi) perylene (C22H12)Pyrene (C16H10) Dibenzo(ah) anthracenes (C22H14)Chrysene (C18H12) Indeno(cd) pyrene (C22H12)Benzo(a) anthracene (C18H12)

SAMPLE PRESERVATIONSample should be wrapped in a aluminum-foil and should be stored in a refrigerator at 4oC in dark place to avoid photo-

oxidation of PAHs for a period upto two months. However, sample extracts may be strored in dried form for a longer period

SAMPLE PROCESSING

The filters samples are extracted with Toluene using ultrasonication & concentrated to 1ml volume .

GAS CHROMATOGRAPHIC ANALYSIS Dilute the extracted residue and make up to 0.5 ml or 1 ml. Inject 1 µl or 2

µl into GC-FID for analysis.

GAS CHROMATOGRAPHY CONDITIONS Gas chromatograph equipped with flame ionization detector (FID), a split

injector and capillary column (Phase cross linked 5% phenyl, methyl-silicone) : 25 meter length, 0.20 mm inner diameter (I.D.), 0.33 µm film

thickness with following GC conditions:

ANALYSIS

Rotary Vacuum Evaporator

Measurement Method of PAH (ISO, BIS, CPCB, Tyagi, 2004 Method) - Individual PAHS

The concentration in ng/ m3 of each analyte in the air sampled is given by:

C = Cs x Ve / Vs Where

Ve = final volume of extract, µl

CALCULATION

7.1 Calculate the concentration in (ng/µl ) of each identified analyte in the

sample extract ( Cs ) as follows:

Cs (ng/µl) = (As * Cis ) / ((Ais * RF ) Where

As = Area count of characteristic analyte sample/peak being measured.

Ais = Area count of characteristic internal standard/peak.Cis = Concentration of internal Standard.

METHODS FOR MEASUREMENT OF BENZENE ,

TOLUENE & XYLENE (BTX) IN AIR

Synspec May 2004 2 Component selection 25

Aromates• Benzene• Toluene• Ethylbenzene• M,P-Xylene• O-Xylene• Styrene

Common Monitoring Protocol Field sampling is critical as far as VOC is concerned 3

established sampling methods are available for field sampling

• Canister Method• Tenax Method• Charcoal Method

Other sampling methods that are followed have limitations are

• Tedlerbag method• PUF method

V a p o r P h a s e S a m p l i n g

• S o r b e n t t u b e

• C a n i s t e r

• O n - l i n e a i r s t r e a m

Results for Dichloroethane,

Benzene & Tolueneare within a

difference of 10%

When sorbent tube & Canister methods

are compared

METHOD ADVANTAGES DISADVANTAGES

Passive samplers

  Very low cost ·   Very simple·  No dependance on mains electricity·  Can be deployed in very large numbers· Useful for screening, mapping and baseline studies

    Useful for prelim survey only  In general only provide monthly and weekly averages      Slow data throughput       Samplers require laboratory analysis

Active Samplers Low cost

•Easy to operate•Reliable operation•Reliable performance•Historical dataset

Provide daily average•Labour intensive sample collection and analysis•Laboratory analysis required

Automatic Aanalysers

Proven•High performance•Hourly data•On-line information

Complex•Expensive•High skill (Repair & maintenance) requirement•High recurrent cost

THE TWO APPROACHES TO MEASUREMENT OF VOCS IN AIR:

a) Taking the sample:

adsorption on activated charcoal/Tenax-Chromosorb

b) Sample Processing:

solvent extraction(CS2)/ thermal desorption

c) Separation: gas chromatography with capillary columns

Identification & Quantification:

Flame ionisation detector (FID)/Mass spectrometry (MS)

d) PASSIVE / ACTIVE SAMPLING

Diffusion Tube for BTX Sampling

PASSIVE SAMPLING

Field Protection Shelterfor Diffusion Tubes

Adsorption on activated charcoal, solvent extraction

Procedure• Diffusion tube is exposed for two weeks in the

ambient air.• After exposure the charcoal of the exposed tube

is transferred in the sample vials and desorbed using carbon-disulfide(CS2 ).

• Desorption is done employing Ultra-sonic bath followed by centrifugation.

• Samples are analysed on Gas chromatograph.

Calculations

C = (M-Mblank) / DE x U t’

Where: C : concentration of the measured compound in g/m3

M : determined mass of the measured compound in ng M blank : weight (ng) of analyte organic vapour on blank tube DE : desorption efficiency ( 0.98 ) U : uptake rate in l/h at 25C(benzene 0.387 l/h, toluene 0.343 l/h) t’ : sampling duration in hours

Conc. (g/m3) = Conc. (g/m3) * 101.3 (273+T) At (STP) (at ambient condition) --------------------------------------------------

298 * Pa

Where: T: Temperature in Kelvin of the ambient air, Pa: Atmospheric pressure, kPa

ACTIVE SAMPLING

USING ACTIVATED CHARCOAL TUBES , DESOERBED BY CARBON-DI SULPHIDE

PRINCIPLE The charcoal tubes are available in different sizes and contain varying amount of activated charcoal. The ambient air is sucked through the tube using a low flow personal sampler in a way that results in an enrichment of the relevant substances in the activated charcoal.

Desorption of the adsorbed benzene is done using Carbon disulfide (CS2).

The substances desorbed in the CS2 are analyzed by capillary gas chromatography.

A flame ionization detector (FID) is used for analysis while quantification is performed using the internal/ external standard.

APPARATUS

1 LOW VOLUME PUMPIntrinsically safe, portable, battery powered pump with a low flow controller with operating range between 5 to 500 ml/min (+/- 0.2

ml/min).to suck the air sample , low flow pump* capable of accurate & adjustable flow with time programmable with selectable run time from

15minutes to 8hr, built in flow indicator and rechargeable battery should be preferred for sampling of BTX.

2 SAMPLING SORBENT (SAMPLE) TUBESThe most extensively used sorbent tubes are 1/4 inch or 6 mm O.D.

glass lined (or fused silica lined) stainless steel tub or stainless steel. Different suppliers provide different size tubes and packing lengths; however, 3.5 inch long tubes with a 6 cm of sorbent bed of 200 mg of activated charcoal (coconut shell) or other suitable adsorbent (Figure-

2.1) are generally used to collect the sample.

Envirotech had made an Organic Vapour Sampler (APM 850) several years ago. The APM 856 Organic Vapour Sampler has evolved from the experiences gained and the feedback received from the users of the APM850 and now provides a system which meets all important requirements for field measurements of gaseous organic pollutants in ambient air.

Organic Vapour Sampler Envirotech APM 856

SAPMLING ADSORPTION TUBES

A sample is collected by opening a tube at two ends, connecting it to a sample pump, and pulling air through the tube with the pump. Airborne chemicals are trapped onto the surface of the sorbent.

Two tubes are used in series to take care of breakthrough (if any) compatible to the thermal desorber . The sampling is carried out using low flow sampler. The sampling train is given in the figure –2.2

Keep the tube in a vertical position during sampling to prevent the possibility of channeling that can lead to under sampling

The arrow on the tube indicates air flow direction and should point to the tube holder and pump. If no arrow is present, the smallest section should be near the tube holder Sampling flow rate in the range of 20-30ml /min is required (+/- 0.2 ml/min) for ambient air.

SAMPLING PROCEDURE & SAMPLING RATE

Any suitable gas chromatograph with flame ionization detector (FID) with fused silica capillary columns having a length of 25 meter or more, an internal diameter of 320 µm or below and with a stationary phase film thickness less than 1.5 µm as follows or equivalent may be recommended.Capillary Column 624, Coating: cyanopropyl phenyl polysiloxane Length * ID: 30m* 0.25 mm , Film thickness (df) : 1.4m

CalibrationPrepare a mix stock standard solution of 50 g/l of benzene, toluene & xylene each gravimetrically. using a micro syringe in the eluting solvent i.e. CS2 . Prepare further diluted solutions of concentration range of 10, 1.0, 0.10 g/l with CS2 from stock standard in a clean vial. Make up to one ml solution. Introduce immediately 1L standard solution into the injector of GC directly and plot the curve between the concentration & response (peak area).

GAS CHROMATOGRAPHIC ANALYSIS

ATD

GC – ATD - MS

Electron IonisationElectron Ionisation : M + e- M+. + 2e-

CH4 + e- CH4+. + 2e-CH4+. CH3+ + H.

Primary ionsPrimary ions

Analytical Procedure

Samples collected through active sampling (sorbent tubes) are extracted or desorbed by conventional solvent (generally 1-2 ml of carbon disulfide) using ultrasonication for 15 minutes to remove analye from the sorbent material . Desorbed samples are analyzed using gas chromatograph (GC) fitted with capillary column and flame ionization detector (FID). A single tube may provide enough samples to permit several analyses.

y = 1E+06xR2 = 0. 9999

0

50000

100000

150000

200000

250000

300000

350000

400000

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4Amount (ugm)

area Linear (area)

y = 1E +06xR2 = 0.9999

0

50000

100000

150000

200000

250000

300000

350000

400000

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

Amount (ugm)

area

(uv.

s)

area Linear (area)

Calibration Graph of Benzene

Calibration Graph of Toluene

Amount of analyte compound found on tube can be converted into g/m3 by using the formula-

Volume of air (ml) = Sampling rate (ml/min) * Sampling time (Sucked through the adsorption tube)

Conc. (g/m3) = Amount of compound found (g) per l injection ample (at ambient condition) * Total volume of the sample extracted (ml) * 103

Vol. of sample extract injected into GC (l) * Vol. of Air sucked through the tube (m3)

CALCULATIONS

Blank value is to be subtracted from the amount of compound found in the sample.

Fig :1 BENZENE LEVELS IN AMBIENT AIR IN DELHI

110

248

382

116

169

428

0

50

100

150

200

250

300

350

400

450

August, 1998 Nov-98

CO

NC

. IN

ug/

m3

Residential Area Traffic intersection Petrol Pump

ON-LINE BENZENE ANALYZER

(THE SYNSPEC ALPHA 400 BENZENE ANALYSER)

THE NEW SYNSPEC ALPHA BENZENE IS A VERY SIMPLE BUT PRECISE FOR THE MEASUREMENT OF BENZENE IN AMBIENT AIR.

Alpha is a compact GC containing all the essential elements: preconcentration sampling unit, backflush valve, separation column in special small oven unit and detector. The detector is a PID.

BENZENE ANALYZER

MEASURING PRINCIPLE:

The gas sample is concentrated in a TRAP. The sample is then desorbed and injected over the valve into a column and benzene passes on to the detector. The system is optimized for ambient benzene concentrations.

Alpha is a compact GC containing all the essential elements: preconcentration sampling unit, backflush valve, separation column in special small oven unit and detector. The detector is a PID.

Chromatograph of MLU Analyser – 19Chromatograph of MLU Analyser – 19thth September 0330 hrs. September 0330 hrs.

0.00

2.00

4.00

6.00

8.00

10.00

12.00

28-03-01

29-03-01

30-03-01

31-03-01

Average 01-04-01 02-04-01 03-04-01 04-04-01 Average

DATES IN MARCH-APRIL 2001

CONC

ENTR

ATIO

N IN

V-P

PB

Benzene Toluene m,p-Xylene o-Xylene Ethyl-Benzene

TRENDS OF BTX IN MARCH-APRIL 2001 AT TRENDS OF BTX IN MARCH-APRIL 2001 AT I.T.O. (BSZ MARG),DELHII.T.O. (BSZ MARG),DELHI

Fig.-5:AVERAGE CONCENTRATION OF BENZENE AND TOLUENE DURING -2004

5.2 5.1 3.96.5 5.8 7.2 8.5 7.1

13.5

18.4

14.8

9.6 10.37.7

13.210 9.7

13

18.6

35.9

47.3

35.9

0.0

5.0

10.0

15.0

20.0

25.0

30.0

35.0

40.0

45.0

50.0

MONTH

CO

NC

ENTR

ATI

ON

(ug/

m3)

BENZENE TOLUENE

Maintenance and Calibration Tips for On-Line VOC Analyzer

Due to its design, the BTX Analyzer requires little maintenance.

However following regular maintenance must be carried out for continuous smooth operation of the Analyzer.

• Check or if needed replace the PTFE Sample Inlet dust Filter at an interval of every week/15-days.

• Check fluid , pressure & Flows parameters using instruments built-in diagnosis facility at an interval of every week/15-days

• Check the stability of retention times.If retention times of the measured compound is out side the retention time window which is usually +\- 0.5 seconds then make a reset.

Calibration:• Calibration must be carried out regularly to check

the quality of measurements made using the on-line BTX analyzer. This also make it possible to check whether or not programming of retention times and sensitivities is correct.

• Zero and a single point span check calibration checks can be performed on the analyzer for complete verification operation on the characteristics of the analyzer

• linearity, • detectable limits,• check of retention times etc

ppm = (mg/m3) x (24.45/MW)

Expressing Concentration in ppm

ppm= [(mg/m3)x(24.45/MW)x(760/P)x((T+273)/298)]

PM 10 & 2.5 CONTINUOUS MONITOR AT BHADUR SHAH ZAFAR MARG (ITO), NEW DELHI

SIDE VIEW CPCB CONTINUOUS MONITORING STATION AT DELHI COLLEGE OF ENGINEERING,BAWANA, DELHI

CALIBRATION AND AQC

Pioneer lab in India who developedthe ifrastructure and extended AQCfacilities to SPCBs, Industries etc.for gaseous pollutants

Primary Calibrations for all the online Parameters are being done here with tracable standard gases and Field based instruments are calibrated subsequently in regular intervals

Calibrations of all the manualInstruments are done with different calibrators time to time

ANNUAL TREND : TOTAL POLYCYCLIC AROMATIC HYDROCARBONS IN AMBIENT AIR IN DELHI (1993-2000)

0

10

20

30

40

50

60

70

80

Minimum Maximum Average Monsoon Winter Summer

Range ------>

Con

c. in

ng.

/ m

3

Year1993 Year1994 Year 1995 Year1996 Year1997 Year 1998 Year 1999 Year 2000

The ambient air quality objectives/standards are pre-requisite for developing programme for effective management of ambient air quality and to reduce the damaging effects of air pollution.

The objectives of air quality standards are:

• To indicate the levels of air quality necessary with an adequate margin of safety to protect the public health, vegetation and property;• To assist in establishing priorities for abatement and control of pollutant level;• To provide uniform yardstick for assessing air quality at national level; and• To indicate the need and extent of monitoring programme.

The Central Pollution Control Board had adopted first ambient air quality standards on November 11, 1982 as per section 16 (2) (h) of the Air (Prevention and Control of Pollution) Act, 1981.

The air quality standards have been revised by the Central Pollution Control Board on April 11, 1994. The latest revised National Ambient Air Quality Standards of CPCB notified as on November 16, 2009 are depicted as follows:

National Ambient Air Quality Standards

EXISTING NATIONAL AMBIENT AIR QUALITY STANDARDS (NAAQS)

Pollutant

Time WeightedAverage

Concentration in Ambient Air Method of Measurement

Industrial Area

Residential, Rural and

other Areas

Sensitive Area

Sulphur Dioxide (SO2)

Annual Average*

80 µg/ m3

60 µg/ m3 15 µg/ m3 1. Improved West and GaekeMethod2. Ultraviolet Fluorescence24 Hours

Average**120

µg/ m380 µg/ m3 30 µg/ m3

Oxides of Nitrogen as NO2

Annual Average*

80 µg/ m3

60 µg/ m3 15 µg/ m3 1. Jacob & Hochheiser modified (NaOH-NaAsO2) Method2. Gas Phase Chemiluminiscence24 Hours

Average**120

µg/ m380 µg/ m3 30 µg/ m3

Suspended ParticulateMatter (SPM)

Annual Average*

360 µg/ m3

140 µg/ m3 70 µg/ m3 High Volume Sampling (Average flow rate not less than 1.1m3/ minute)24 Hours

Average**500

µg/ m3200 µg/ m3 100 µg/ m3

RespirableParticulate Matter (Size less than 10µm) (RPM)

Annual Average*

120 µg/ m3

60 µg/ m3 50 µg/ m3

Respirable Particulate Matter Sampler24 Hours

Average**150

µg/ m3100 µg/ m3 75 µg/ m3

Lead (Pb) Annual Average*

1.0 µg/ m3

0.75 µg/ m3 0.50 µg/ m3 AAS Method after sampling using EPM 2000or equivalent filter paper24 Hour

Average**1.5

µg/ m31.0 µg/ m3 0.75 µg/ m3

Carbon Monoxide (CO)

8 Hours Average**

5.0 mg/ m3

2.0 mg/ m3 1.0 mg/ m3

Non dispersive Infrared Spectroscopy1 Hour

Average10.0mg/

m34.0 mg/ m3 2.0 mg/ m3

Ammonia (NH3) Annual Average*

0.1 mg/ m3 -

24 Hour Average**

0.4 mg/ m3

So far State Governments of the all the sixteen critically polluted cities as identified by the Hon’ble Supreme Court of India have submitted their action plan for controlling air Pollution from all the major sources including industrial, vehicular & domestic sources. The major actions those have been proposed for almost all the cities are:1. Industrial Pollution Shifting of Industries from non- confirming zones, Switching over to clean technologies, Using clean fuel, Installation of Pollution control Devices Development of green belt, etc.2. Vehicular Pollution Implementation of the emission norms as well as fuel quality in accordance with the road map proposed by the Auto Fuel Policy, Switching over to clean alternate fuels like CNG, LPG & Bio-fuels, Augmentation in Public Transport system ,Better traffic Management, Implementation of fiscal measures, etc3. Domestic Pollution Ban on open burning of garbage, biomass, Augmentation on supply of LPG as cooking fuel,

Action Plan for Controlling Air Pollution

Carbon Monoxide (CO) levels in Ambient Air

0

1

2

3

4

5

6

1997-98 1998-99 1999-2000 2000-01 2001-02 2002-03 2003-040

0.5

1

1.5

2

2.5

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4.5

Carbon Monoxide Vehicle Population

Year 1997-98 1998-99 1999-2000 2000-01 2001-02 2002-03 2003-04Carbon Monoxide 5.45 4.241 4.686 4.183 3.258 2.831 2.581Vehicle Population 3 3.2 3.4 3.5 3.6 3.8 4.1

Vehi

cle

Reg

istr

atio

n in

Mill

ions

Valu

es in

mg/

m3

IMPACTS OF INTERVENTIONS ON THE AIR POLLUTANTS IN DELHI

Dr. S.K.Tyagi

Methods of Sampling and Analysis of Metals in Ambient Air

(CADMIUM, CHROMIUM, IRON, LEAD, MANGANESE, NICKEL, COBALT, ALUMINUM, VANADIUM, AND ZINC)

PRINCIPLE This method is designed to collect particulate phase Metals in the ambient air and fugitive emissions and to determine individual metal . It is based on high volume ( ~ 1.2 m3 / min) sampling method capable of detecting ng/ m3 concentration of metal with a total sample volume ~ 480 m3 / of air over a period of 8 hours with same filter. It Involves collection from air particulate on a fine particle (glass-fibre) filter using high volume sampler for total suspended particulate matter (TSPM) or respirable dust sampler for respirable suspended particulate matter (RSPM or PM10) and subsequent analysis by Flame Atomic Absorption Spectroscopy (FAAS) after the digestion of samples with concentrated nitric acid & hydrochloric acid .

Atomic absorption spectrometer measures absorption of characteristic radiation by atoms of a particular element to be determined which are thermally atomized either by flame or by graphite furnace.

The element which is to be determined is dissolved in a suitable vehicle (normally an acid)

In case of furnace atomization auto sampler or micro syringe is used for transforming the sample solution into the furnace.

A hallow cathode lamp of the element to be determined is used as a source of radiation, which is absorbed by the atoms produced in flame or furnace of that element and absorption is directly proportional to the concentration of the analyte atoms.

PRINCIPLE

BURNER ADJUSTER

VAPOR VENT

DRAIN TUBING

EXHAUST

CHIMNEY

BENCH

SMALL NON-GLASSWASTE VESSEL

Cool and filter the solution in a 100 ml volumetric flask

Bring the solution up to the 100 ml mark using distilled water

Analyse the sample using the AAS with relevant Hollow Cathode

AAS Method for Metals

Digest Filter paper with HNO3:HCl (3:8ml) in 100ml at 80oC for 4 hour or so till the final volume is about 10 ml

Metals W. L. Detection Limit (ug/lit)

FAAS GFF

As 193.7 100 0.2

Ni 232 4 0.1

Pb 217 10 0.05

Q1. Calculate Volume of Air Sampled in m3 from following data?

Sampling Period 4 hour

Sampling Rate of LVS 200ml/min

Calculate Vol. of Air Sampled (m3) =

Q2. Calculate Volume of Air Sampled in m3 & Benzene Conc. In Ambient Air from following data

Slope (ug/ml) for 1ul inj4.35712452981368

E-06 Peak Area 5000

Flow Rate of LVS 80 ml/minTotal Sampling Time 4hrCalculate Tot Vol of Air(m3)Ambient Temp @45degree CCalculate Benzene Conc (ug/m3) @45degree C Ambient conditionCalculate Benzene Conc (ug/m3) @25degree C Ambient condition

Q1. Vol of Air Sampled (m3) = 0.048

Q2. Tot Vol of Air Sampled (m3) = 19.2

Bz Conc (ug/m3) @45degree C = 1.13

Bz Conc (ug/m3) @25degree C = 1.06

ANSWERS

PRESERVE PLANET EARTH

THROUGH YOUR DEEDS

The Photovac 2020 PRO uses photoionization, the technology of choice for detecting VOCs. The 2020 PRO is equipped standard with a 10.6 eV UV lamp, and has an optional 11.7 eV UV lamp for ionizing chlorinated compounds.

Operating concentration range is 0.1-2000 PPM or use the optional dilution probe to detect up to 20,000 PPM.

The Photovac photoionization detector is humidity-compensated so you can rely on the results in PPM range.

Portable Total VOC Sensor/Monitor

Voc Sampling Train

Voc Sampling Control Module

Heated TeflonSampling Tube