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Na Aqs Manual Volume i | Particulates | Titration
Guidelines for Manual Sampling & Analyses
Parivesh Bhawan, East Arjun Nagar Delhi- 110032 Website: http://www.cpcb.nic.in May, 2011
NAAQS Monitoring & Analysis Guidelines Volume-I
Contribution Overall Guidance & Supervision Sh. J. S. Kamyotra Dr. D. Saha Laboratory experiments & Drafting of Guidelines
Dr. D. Saha Dr. S. K. Tyagi Sh. A. K. Sen Dr. R. C. Srivastava Sh. A. Pathak Sh. M. Satheesh Sh. Ramesh Chand Sh. Fasiur Rehman Ms. Shaveta Kohli
Dr. Somendra Singh Sh. B. K. Jena
Editing, Charts & Computer Setting
Dr. D. Saha Sh. Fasiur Rehman Ms. Shaveta Kohli
Background Guidelines for Sampling and Measurement of notified Ambient Air Quality Parameters (NAAQS 2009) Under the provisions of the Air (Prevention & Control of Pollution) Act, 1981, the CPCB has notified fourth version of National Ambient Air Quality Standards (NAAQS) in 2009. This revised national standard aims to provide uniform air quality for all, irrespective of land use pattern, across the country. There are 12 identified health based parameters, which are to measure at the national level and with a view to have data comparison, need for uniform guidelines for monitoring, sampling, analyses, sample flow chart, data sheet based on standard method has been felt. The methods prescribed in the notification for respective parameters are the combination of physical method, wet-chemical method and continuous on-line method. Therefore, to meet the NAAQS requirement, a combination of both manual and continuous method is invariably required at each monitoring location, besides good laboratory set up and infrastructure. In addition to the above, an in house exercise for applicability of all prescribed / recommended analytical methods was also felt necessary. After review and demonstration in the Central Laboratory, Delhi, guidelines are being prepared and documented, as under: 1. Volume –I: Guidelines for manual sampling and analyses (along with sample flow chart and data sheets) 2. Volume-II: Guidelines for continuous sampling and real time analyses
Note: Guidelines are laboratory and infrastructure specific thus may not be applicable uniformly and need to develop based on infrastructure and expertise ii
ng/m3 Annual * Annual * Annual * 01 06 20 01 06 20 -Improved West and Gaeke Method -Ultraviolet Fluorescence -Jacob & Hochheiser modified (NaOH-NaAsO2) Method -Gas Phase Chemiluminescence -Gravimetric -TEOM -Beta attenuation -Gravimetric -TEOM -Beta attenuation -UV Photometric -Chemiluminescence -Chemical Method -AAS/ICP Method after sampling on EPM 2000 or equivalent filter paper -ED-XRF using Teflon filter -Non dispersive Infrared (NDIR) Spectroscopy -Chemiluminescence -Indophenol blue method -Gas Chromatography (GC) based continuous analyzer -Adsorption and desorption followed by GC analysis -Solvent extraction followed by HPLC/GC analysis -AAS/ICP Method after sampling on EPM 2000 or equivalent filter paper -AAS/ICP Method after sampling on EPM 2000 or equivalent filter paper * Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals. µg/m3 Nitrogen Dioxide (NO2).0 02 04 100 400 05 Methods of Measurement Sulphur Dioxide (SO2). they may exceed the limits but not on two consecutive days of monitoring.50 1. µg/m3 Particulate Matter (Size less than 2. NOTE: Whenever and wherever monitoring results on two consecutive days of monitoring exceed the limits specified above for the respective category.50 1. µg/m3 Benzene (C6H6). it shall be considered adequate reason to institute regular or continuous monitoring and further investigations. ng/m3 Arsenic (As). µg/m3 Ozone (O3) µg/m3 Lead (Pb) µg/m3 Carbon Monoxide(CO). 2% of the time.NAAQS Monitoring & Analysis Guidelines Volume-I NATIONAL AMBIENT AIR QUALITY STANDARDS (2009) Pollutants Time Weighted Average Concentration in Ambient Air Industrial. Sensitive Area Rural and (Notified by other Areas Central Government) 50 20 80 80 40 30 80 80 60 100 40 60 100 180 0.0 02 04 100 400 05 60 100 40 60 100 180 0. ng/m3 Nickel (Ni). mg/m3 Ammonia (NH3). ** 24 hourly or 8 hourly or 1 hourly monitored values. as applicable. µg/m3 Annual * 24 Hours ** Annual * 24 Hours ** Annual * 24 Hours ** Annual * 24 Hours ** 8 Hours * 1 Hour ** Annual * 24 Hours ** 8 Hours ** 1 Hour ** Annual * 24 Hours ** Annual * Benzo(a)Pyrene (BaP) Particulate phase only.5µm) or PM2. shall be complied with 98% of the time in a year. µg/m3 Particulate Matter (Size less than 10µm) or PM10. iii . Ecologically Residential.5.
NAAQS Monitoring & Analysis Guidelines Volume-I iv .
NAAQS Monitoring & Analysis Guidelines Volume-I v .
Guidelines for sampling and analysis protocol for ozone in ambient air 6.5 in ambient air Gravimetric Method 5. Guidelines for sampling and analysis protocol for ammonia in ambient air 7.No.NAAQS Monitoring & Analysis Guidelines Volume-I Contents S. Guidelines for sampling and Analysis of Benzo(a)pyrene & other PAHs in Ambient Air 8. Guidelines for sampling and analysis of Particulate Matter (PM10) in ambient air 4. Nickel and Arsenic in ambient air 9. Guidelines for sampling and analysis of Nitrogen dioxide in ambient air 3. Data sheets A-L 47-54 39-46 35-38 31-34 15-30 11-14 7-10 Page 1-6 vi . Guidelines for sampling and analysis of sulphur dioxide in ambient air 2. 1. Guidelines for sampling and analysis of Lead. Guidelines for determination of PM2.
2% of the time. Ecologically Sensitive Residential. at a particular site. the absorber solution may be stored for some time prior to analysis. as applicable. 3.NAAQS Monitoring & Analysis Guidelines Volume-I Guidelines for sampling and analysis of sulphur dioxide in ambient air (Improved West and Gaeke method) 1. Once formed. µg/m3 Annual * 24 Hours ** * Annual Arithmetic mean of minimum 104 measurements in a year. Principle of the method Modified West & Gaeke Method (IS 5182 Part 2 Method of Measurement of Air Pollution: Sulphur dioxide). Purpose The purpose of this protocol is to provide guidelines for monitoring and analysis of sulphur dioxide in ambient air. is formed. A dichlorosulphitomercurate complex. this complex is stable to strong oxidants such as ozone and oxides of nitrogen and therefore. Sulphur dioxide from air is absorbed in a solution of potassium tetrachloromercurate (TCM). Standard The national ambient air quality standards for sulphur dioxide is presented in the table Pollutant Time Weighted Average Concentration in Ambient Air Industrial. Rural Area (Notified by and other Areas Central Government) 50 20 80 80 Sulphur Dioxide (SO2). shall be complied with 98% of the time in a year. ** 24 hourly or 8 hourly or 1 hourly monitored values. taken twice a week 24 hourly at uniform intervals. they may exceed the limits but not on two consecutive days of monitoring. Instrument/Equipment The following items are necessary to perform the monitoring and analysis of nitrogen dioxide in ambient air: · Analytical balance: 1|Page Air Laboratory (May 2011) . The absorbance of the solution is measured by means of a suitable spectrophotometer 4. which resists oxidation by the oxygen in the air. The complex is made to react with para-rosaniline and formaldehyde to form the intensely coloured pararosaniline methylsulphonic acid. 2.
HCL and make up to volume with distilled water. The absorbing reagent is normally stable for six months. · Purified Pararosaniline Stock Solution (0. Add 15 ml conc.Place 12.Prepare approximately 0. If. Glass wares: low actinic glassware must be used for analysis Reagents / Chemicals All the chemicals should meet specifications of Analytical Reagent grade · Distilled water · Mercuric chloride · Potassium chloride / Sodium chloride · EDTA di sodium salt · Absorbing Reagent.6 g sulphamic acid in 100 ml distilled water.68 gm in water and bring to the mark in a 1 litre volumetric flask. · Starch Indicator Solution .Dissolve 0.7 g iodine in a 250 ml beaker. mercuric chloride. Prepare fresh daily. and transfer to a glass-stoppered bottle. flush off with water immediately. a precipitate forms. Prepare fresh daily. cool. · Formaldehyde (0. Absorber: all glass midget impinger Spectrophotometer: Capable of measuring absorbance at 560 nm equipped with 1 cm path length cells.0 g potassium chloride or sodium chloride 4.500 gm of specially purified pararosaniline (PRA) in 100 ml of distilled water and keep for 2 days (48 hours).6%) .2% Nominal) Dissolve 0.86 g.04 M Potassium Tetrachloro mercurate (TCM) Dissolve 10. · Sulphamic Acid (0.2%) . · Potassium iodate 2|Page Air Laboratory (May 2011) .0 but. and 6. 0. Continue boiling until the solution is clear.10 ml of stock PRA is taken in a 250 ml volumetric flask.01 N iodine solution by diluting 50 ml of stock solution to 500 ml with distilled water.Dilute 5 ml formaldehyde solution (36-38%) to 1 litre with distilled water. it has been shown that there is no appreciable difference in collection efficiency over the range of pH 5 to pH 3.2 to 1 l/min. then dilute to 1 litre with distilled water. · Pararosaniline Working Solution . add 40 g potassium iodide and 25 ml water. discard the reagent after recovering the mercury.066 g EDTA.4 gm soluble starch and 0.1 N) . 0. · Iodine Solution (0. Vacuum pump : Capable of maintaining an air pressure differential greater than 0. Caution : highly poisonous if spilled on skin.Triturate 0.NAAQS Monitoring & Analysis Guidelines Volume-I · · · · · 5. · Stock Iodine Solution (0. The pH of this reagent should be approximately 4. Stir until all is dissolved.01 N) .002 g mercuric iodide preservative with a little water and add the paste slowly to 200 ml boiling water.7 atmosphere at the desired flow rate Calibrated flow-measuring device to control the airflow from 0.
cooled distilled water making the solution up to a final volume of 1 litre. dissolve. transfer 50 ml of iodate solution by pipette. This solution contains the equivalent of 320-400 µg/ml of SO2.NAAQS Monitoring & Analysis Guidelines Volume-I · Stock Sodium Thiosulfate Solution (0. it is. titrate with stock thiosulfate solution to a pale yellow. and dilute to volume in a 500 ml volumetric flask.04 M TCM. Into a 500 ml Iodine flask. Analysis Replace any water lost by evaporation during sampling by adding distilled water up to the calibration mark on the absorber. distilled water.Measure 2 ml of the standard solution into a 100 ml volumetric flask by pipette and bring to mark with 0. Working Sulphite-TCM Solution . If not kept at 5oC. Allow the solution to stand one day before standardizing. Place 30 ml of absorbing solution in an impinger and sample for four hours at the flow rate of 1 L/min.5 g primary standard potassium iodate dried at 180 oC.Dissolve 0.01 N) . cooled. This solution is stable for 30 days if kept in the refrigerator at 5oC. prepare fresh daily. pipette out 10 ml of the collected sample into a 25 ml volumetric flask. Calculate the normality of the stock solution. accurately weigh to the nearest 0. 7. Add 2 g potassium iodide and 10 ml of N hydrochloric acid and stopper the flask. Sampling · · 5.6% Standard Impinger sulphamic acid and allow reacting for 10 minutes to destroy the nitrite resulting 3|Page Air Laboratory (May 2011) . add 0. · Sodium Thiosulphate Titrant (0. After sampling measure the volume of sample and transfer to a sample storage bottle. After 5 min. Mix thoroughly. important to use water of the highest purity to minimize this instability.30 g sodium metabisulphite (Na 2S2O5) or 0.1 g sodium carbonate and dissolve using boiled. 1.1 N) . Standardized Sulphite Solution for Preparation of Working SulphiteTCM Solution . Calculate the concentration of sulphur dioxide in the working solution in micrograms of sulphur dioxide per millilitre.40 g sodium sulphite (Na2SO3) in 500 ml of recently boiled.1 mg.Prepare a stock solution by placing 25 g sodium thiosulfate pentahydrate in a beaker. To standardize. Sulphite solution is unstable. Add 5 ml starch indicator solution and continue the titration until the blue colour disappears.Dilute 100 ml of the stock thiosulfate solution to 1 litre with freshly boiled and cooled distilled water. therefore. Add 1 ml 0.
2. By means of a burette containing standardized 0. 2. Add 2 ml of 0. measure. Prepare a blank in the same manner using 10 ml of unexposed absorbing reagent. Then add the remaining reagents as described in the procedure for analysis. After a 30 min colour development interval and before 60 minutes.5 ml. Use distilled water.1. as the optical reference 8. The reciprocal of slope gives the calibration factor (CF). Then add 5 ml starch solution and continue the titration until the blue colour disappears. Draw a line of best fit and determine the slope. 3. Stopper the flasks and allow to react for 5 minutes. measure and record the absorbance of samples and reagent blank at 560 nm. C = SO2 concentration in mg/ml V1 = Volume of thiosulfate for blank. Preparation of Standards Measure 0.0 ml. 8. Prepare the working sulphite-TCM solution at the same time iodine solution is added to the flasks. 1. Add sufficient TCM solution to each flask to bring the volume to approximately 10 ml.2% formaldehyde solution and 2 ml pararosaniline solution and make up to 25 ml with distilled water. not the reagent blank.01 N iodine solution into each of two 500 ml iodine flasks A and B.0 ml of working sulphite TCM solution in 25 ml volumetric flask.01 N thiosulfate. A reagent blank with 10 ml absorbing solution is also prepared.0 ml. ml 4|Page Air Laboratory (May 2011) . by pipette. titrate each flask in turn to a pale yellow.5 ml. To flask A (blank) add 25 ml distilled water and into flask B (sample) measure 25 ml sulphite solution by pipette. Calculation Concentration of sulphite solution: (V1-V2) x N x K ________________ V C = Where.0 ml. Read the absorbance of each standard and reagent blank 8. 2. 9. Standard Curve Plot a curve absorbance (Y axis) versus concentration (X axis).NAAQS Monitoring & Analysis Guidelines Volume-I from oxides of nitrogen.5 ml. 3. To back-titrate.5 ml and 4. 50 ml of the 0. 1. Calibration The actual concentration of the sulphite solution is determined by adding excess iodine and back titrating with standard sodium thiosulfate solution.
ml = Normality of thiosulfate = 32000 (Milliequivalent weight SO2/µg) = Volume of standard sulphite solution. The QC procedures for the air sampling and monitoring sections of this protocol include preventative maintenance of equipment. ml Vt = Volume of aliquot taken for analysis. µg/m3 As = Absorbance of sample Ab = Absorbance of reagent blank CF = Calibration factor Va = Volume of air sampled. m3 Vs = Volume of sample. Quality Control Quality Control (QC) is the techniques that are used to fulfill requirements for quality. C SO2 = Concentration of Nitrogen dioxide. 11. analysis of field blanks and lab blanks.NAAQS Monitoring & Analysis Guidelines Volume-I V2 N K V = Volume of thiosulfate for sample. ml 10. calibration of equipment. ml C (SO2 µg/m3 )= (As – Ab) x CF x Vs/ Va x Vt Where. Reference IS 5182 Part 2 Method of Measurement of Air Pollution: Sulphur Dioxide 5|Page Air Laboratory (May 2011) .
Flask ê Take 10/20 ml. Flask (blank) ê Add 1 ml Sulphamic acid. of unexposed sample in 25 ml.NAAQS Monitoring & Analysis Guidelines Volume-I FLOW CHART FOR MEASUREMENT OF SULPHUR DIOXIDE Place 30 ml of absorbing media in an impinger ê Connect it to the gas-sampling manifold of gas sampling device (RDS/HVS). ê Draw air at a sampling rate of 1 lpm for four hours ê Check the volume of sample at the end of sampling and record it ê Transfer the exposed samples in storage bottle and preserve ê Prepare calibration graph as recommended in method ê Take 10/20 ml. ê Keep it 30 minutes for reaction ê Set Zero of spectrophotometer with Distilled water ê Measure absorbance at 560 nm ê Calculate concentration using calibration graph ê Calculate concentration of Sulphur Dioxide in µg/m3 6|Page Air Laboratory (May 2011) . Keep it 10 minutes ê Add 2 ml formaldehyde ê Add 2 ml working PRA ê Make up to mark (25 ml. aliquot of sample in 25 ml. Vol. Vol.) with distilled water.
4. Ambient nitrogen dioxide (NO2) is collected by bubbling air through a solution of sodium hydroxide and sodium arsenite. Purpose The purpose of this protocol is to provide guidelines for monitoring of nitrogen dioxide in ambient.6 atmospheres across the flow control device.NAAQS Monitoring & Analysis Guidelines Volume-I Guidelines for sampling and analysis of Nitrogen dioxide in ambient air (Modified Jacob and Hochheiser Method) 1. they may exceed the limits but not on two consecutive days of monitoring. Residential. 2% of the time. ** 24 hourly or 8 hourly or 1 hourly monitored values. Principle of the method Modified Jacobs & Hochheiser Method (IS 5182 Part 6 Methods for Measurement of Air Pollution: Oxides of nitrogen). sulfanilamide. and N-(1-naphthyl)ethylenediamine di-hydrochloride (NEDA) and measuring the absorbance of the highly coloured azo-dye at 540 n m. Flow control device capable 7|Page Air Laboratory (May 2011) . µg/m3 Annual * 24 Hours ** * Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals. 3. 2. The concentration of nitrite ion (NO-2) produced during sampling is determined colorimetrically by reacting the nitrite ion with phosphoric acid. shall be complied with 98% of the time in a year. Instrument/Equipment The following items are necessary to perform the monitoring and analysis of nitrogen dioxide in ambient air: · Analytical balance: · Vacuum pump: Capable of maintaining a vacuum of at least 0. as applicable. Standard The national ambient air quality standard for nitrogen dioxide is presented in the table: Pollutant Time Weighted Average Concentration in Ambient Air Industrial. Rural and other Areas 40 80 Ecologically Sensitive Area (Notified by Central Government) 30 80 Nitrogen dioxide (NO2).
Glass wares: low actinic glassware must be used for analysis Reagents / Chemicals All the chemicals should meet specifications of ACS Analytical Reagent grade · Distilled water · Sodium hydroxide · Sodium Arsenite · Absorbing solution (Dissolve 4.Assay of 97% NaNO2 or greater Standard Impinger · Sodium Nitrite stock solution (1000 µg NO2/ml) · Sodium Nitrite solution (10 µg NO2/ml.0 g of sodium hydroxide in distilled water.000 ml with distilled water) · Sulphanilamide . This solution is stable for one month. refrigerated and protected from light · Sodium nitrite .2 to 1 l/min. with mixing. if.85% · Sulphanilamide Solution .2 to 1 L/min. of maintaining a constant flow of 200-1000 ml per minute through the sampling solution Calibrated flow measuring device: To control the airflow from 0. Add. and dilute to 1. This solution may be used for one month.2 ml of 30% hydrogen peroxide to 250 ml with distilled water. This solution is stable for one month.Dilute 0.Melting point 165 to 167 oC · N-(1-Naphthyl)-ethylenediamine Di-hydrochloride (NEDA) .0 g of sodium Arsenite.Dissolve 20 g of sulphanilamide in 700 ml of distilled water. prepare fresh daily) 6. 50 ml of 85% phosphoric acid and dilute to 1.000 ml. add 1. Sampling Place 30 ml of absorbing solution in an impinger and sample for four hour at the flow rate of 0. 8|Page Air Laboratory (May 2011) .30% · Phosphoric Acid .A 1% aqueous solution should have only one absorption peak at 320 nm over the range of 260-400 nm. NEDA showing more than one absorption peak over this range is impure and should not be used · Hydrogen Peroxide . After sampling measure the volume of sample and transfer to a sample storage bottle. if refrigerated and protected from light · Hydrogen Peroxide Solution .Dissolve 0. if refrigerated · NEDA Solution .) · Sodium Nitrite working solution (1 µg NO2/ml) (Dilute with absorbing reagent.5 g of NEDA in 500 ml of distilled water. Absorber: a midget impinger Spectrophotometer: Capable of measuring absorbance at 540 nm equipped with 1 cm path length cells.NAAQS Monitoring & Analysis Guidelines Volume-I · · · · 5.
Fill to 20 ml mark with absorbing solution. Draw a line of best fit and determine the slope. with thorough mixing after the addition of each reagent and make up to 50 ml with distilled water. ml 0.4 ml of NEDA solution. as the optical reference Samples with an absorbance greater than 1. measure and record the absorbance of samples and reagent blank at 540 nm. 6. A randomly selected 5-10% of the samples should be re-analyzed as apart of an internal quality assurance program. 5. 4. 10. A reagent blank with 10 ml absorbing solution is also prepared. 9. 15 and 20 ml of working standard solution in to 50 ml volumetric flask.1. 7.0 must be re-analyzed after diluting an aliquot of the collected samples with an equal quantity of unexposed absorbing reagent. 9. mix thoroughly. Add reagents to each volumetric flask as in the procedure for analysis. 12.82 = Sampling efficiency 9|Page Air Laboratory (May 2011) . 8. 3. m3 Vs = Volume of sample. Pipette in 1 ml of hydrogen peroxide solution. µg/m3 As = Absorbance of sample Ab = Absorbance of reagent blank CF = Calibration factor Va = Volume of air sampled.NAAQS Monitoring & Analysis Guidelines Volume-I 7.2. 10 ml of sulphanilamide solution. ml Vt = Volume of aliquot taken for analysis. Calculation C (NO2 µg/m3) = (As – Ab) x CF x Vs/ Va x Vt x 0. and 1.82 Where. Calibration Preparation of Standards Pipette 1. Prepare a blank in the same manner using 10 ml of unexposed absorbing reagent. not the reagent blank. After a 10 min colour development interval. The reciprocal of slope gives the calibration factor (CF). Analysis Replace any water lost by evaporation during sampling by adding distilled water up to the calibration mark on the absorber. 8. 8. 2. Use distilled water. Standard Curve: Plot a curve absorbance (Y axis) versus concentration (X axis). 8. Pipette out 10 ml of the collected sample into a 50 ml volumetric flask. C NO2 = Concentration of Nitrogen dioxide. Read the absorbance of each standard and reagent blank against distilled water reference.
Vol. ê Keep it 10 minutes for reaction ê Set Zero of spectrophotometer with Distilled water ê Measure absorbance at 540 nm ê Calculate concentration using calibration graph ê Calculate concentration of Nitrogen Dioxide in µg/m3 10 | P a g e Air Laboratory (May 2011) . The QC procedures for the air sampling and monitoring sections of this protocol include preventative maintenance of equipment. Flask (blank) ê Add 1 ml hydrogen peroxide. Reference IS 5182 Part 6 Methods for Measurement of Air Pollution: Oxides of Nitrogen FLOW CHART FOR MEASUREMENT OF NITROGEN DIOXIDE Place 30 ml of absorbing media in an impinger ê Connect it to the gas sampling manifold of gas sampling device (RDS/HVS). ê Add 10 ml sulphanilamide ê Add 1. Vol.) with distilled water. aliquot of sample in 50 ml. calibration of equipment. Flask ê Take 10 ml. of unexposed sample in 50 ml.4 ml NEDA ê Make up to mark (50 ml. analysis of field blanks and lab blanks.NAAQS Monitoring & Analysis Guidelines Volume-I 10. 11. Quality Control Quality Control (QC) is the techniques that are used to fulfil requirements for quality. ê Draw air at a sampling rate of 1 lpm for four hours ê Check the volume of sample at the end of sampling and record it ê Transfer the exposed samples in storage bottle and preserve ê Prepare calibration graph as recommended in method ê Take 10 ml.
PM10. 3. 4. Standard The national ambient air quality standards for Particulate Matter PM10 is presented in the table Pollutant Time Weighted Average Concentration in Ambient Air Industrial. shall be complied with 98% of the time in a year. The mass of these particles is determined by the difference in filter weights prior to and after sampling. µg/m3 Annual * 24 Hours ** * Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals. Instrument/Equipment The following items are necessary to perform the monitoring and analysis of Particulate Matter PM10 in ambient air: · Analytical balance: · Sampler : High Volume Sampler with size selective inlet for PM10 and automatic volumetric flow control · Calibrated flow-measuring device to control the airflow at 1132 l/min. they may exceed the limits but not on two consecutive days of monitoring. Particles with aerodynamic diameter less than the cut-point of the inlet are collected. The concentration of PM10 in the designated size range is calculated by dividing the weight gain of the filter by the volume of air sampled. as applicable. Principle of the method Air is drawn through a size-selective inlet and through a 20.4 cm (8 X 10 in) filter at a flow rate. 2.NAAQS Monitoring & Analysis Guidelines Volume-I Guidelines for sampling and analysis of Particulate Matter (PM10) in ambient air (Gravimetric Method) 1. Purpose The purpose of this protocol is to provide guidelines for monitoring and analysis of Particulate Matter PM10 in ambient air. · Top loading orifice kit 11 | P a g e Air Laboratory (May 2011) . 2% of the time. ** 24 hourly or 8 hourly or 1 hourly monitored values.3 X 25. Ecologically Sensitive Residential. Rural Area (Notified by and other Areas Central Government) 60 60 100 100 Particulate Matter. by the filter. which is typically 1132 L/min.
3 X 25. Condition the filter after sampling in conditioning room maintained within 20-30° C and 40-50% relative humidity or in an airtight desiccator for 24 hours. Condition the filter in conditioning room maintained within 20-30° C and 40-50% relative humidity or in an airtight desiccator for 24 hours.Tilt back the inlet and secure it according to manufacturer's instructions. record the flow meter reading.4 cm (8 X 10 in) size 6. Gently lower the inlet.NAAQS Monitoring & Analysis Guidelines Volume-I 5. During this period. Analysis Filter inspection: Inspect the filter for pin holes using a light table. Apply the filter identification number or a code to the filter if it is not a numbered. Reagents / Chemicals Filter Media – A Glass fibre filter of 20. Take initial weight of the filter paper (Wi) before sampling. The specified length of sampling is commonly 8 hours or 24 hours. Sampling Field Sampling .175 cm (1. Calibration Periodical calibration of the sampler is being done by Orifice Transfer Standard . PM10 Sampler (Impaction Inlet) PM10 Sampler (Cyclonic Inlet) 7. take out the filter media from the sampler.The PM10 sampler calibration orifice consists of a 3. several reading (hourly) of flow rate should be taken. Loose particles should be removed with a soft brush. Take final weight of the filter paper (Wf) 8. Loosen the faceplate wing nuts and remove the faceplate. After the required time of sampling. Remove the filter from its jacket and centre it on the support screen with the rough side of the filter facing upwards.25 in) diameter 12 | P a g e Air Laboratory (May 2011) . Replace the faceplate and tighten the wing nuts to secure the rubber gasket against the filter edge. record the designated flow rate on the data sheet. and put in a container or envelope. Record the reading of the elapsed time meter. For automatically flow-controlled units.
analysis of field blanks and lab blanks. 13 | P a g e Air Laboratory (May 2011) . Quality Control Quality Control (QC) is the techniques that are used to fulfill requirements for quality.62 cm (3 in) diameter by 20. m3 10. Top loading Orifice kit 9. calibration of equipment. C PM10 = Concentration of Nitrogen dioxide.NAAQS Monitoring & Analysis Guidelines Volume-I hole in the end cap of 7.3 cm (8 in) long hollow metal cylinder. µg/m3 Wf = Initial weight of filter in g Wi = Initial weight of filter in g 106 = Conversion of g to µg V = Volume of air sampled. This orifice is mounted tightly to the filter support in place of the inlet during calibration. Flow resistances that simulate filter resistances are introduced at the end of the calibrator opposite the orifice by a set of perforated circular disks. The relationship between pressure difference and flow rate is established via a calibration curve derived from measurements against a primary standard such as a Roots meter at standard temperature and pressure. The QC procedures for the air sampling and monitoring sections of this protocol include preventative maintenance of equipment. A flow rate of 1132 L/min through the orifice typically results in a pressure difference of several inches of water. Calculation C PM10 µg/m3 = (Wf – Wi) x 106 / V Calibration set up Where. A small tap on the side of the cylinder is provided to measure the pressure drop across the orifice.
Air Sampling and Analysis.1 Sampling of Ambient Air for Total Suspended Particulate Matter (SPM) and PM10 Using High Volume (HV) Sampler FLOW CHART FOR MEASUREMENT OF PM10 Check the filter for any physical damages ê Mark identification number on the filter ê Condition the filter in conditioning room / desiccator for 24 hours ê Record initial weight ê Place the filter on the sampler ê Run the sampler for eight hours ê Record the flow rate on hourly basis ê Remove the filter from the sampler ê Keep the exposed filter in a proper container ê Record the total time of sampling & average flow rate ê Again condition the filter in conditioning room / desiccator for 24 hours ê Record final weight ê Calculate the concentration of PM10 in µg/m3 14 | P a g e Air Laboratory (May 2011) .NAAQS Monitoring & Analysis Guidelines Volume-I 11. · · · Reference Method 501. Lewis publishers Inc. IS 5182 Part 23 Method of Measurement of Air Pollution: Respirable Suspended Particulate Matter (PM10) cyclonic flow technique Method IO-2. 3rd Edition.
Guidelines for determination of PM2.5 in ambient air (Gravimetric Method)
The purpose of this protocol is to provide guidelines for monitoring and analysis of Particulate Matter PM2.5 in ambient air. 2.0 Definition
PM2.5 refers to fine particles that are 2.5 micrometers (μm) or smaller in diameter. Ambient air is defined as any unconfined part of the Earth’s atmosphere, that the surrounding outdoor air in which humans and other organisms live and breathe. FRM – Federal Reference Method FEM – Federal Equivalent Method 3.0 Standard Time Weighted Average Concentration in Ambient Air Industrial, Ecologically Sensitive Residential, Rural Area (Notified by and other Areas Central Government) 40 40 60 60
Particulate Matter, PM2.5, µg/m3
Annual * 24 Hours **
* Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals. ** 24 hourly or 8 hourly or 1 hourly monitored values, as applicable, shall be complied with 98% of the time in a year. 2% of the time, they may exceed the limits but not on two consecutive days of monitoring. 4.0 Principle
An electrically powered air sampler draws ambient air at a constant volumetric flow rate (16.7 lpm) maintained by a mass flow / volumetric flow controller coupled to a microprocessor into specially designed inertial particle-size separator (i.e. cyclones or impactors) where the suspended particulate matter in the PM2.5 size ranges is separated for collection on a 47 mm polytetrafluoroethylene (PTFE) filter over a specified sampling period. Each filter is weighed before and after sample collection to determine the net gain due to the particulate matter. The mass concentration in the ambient air is computed as the total mass of collected particles in the PM2.5 size ranges divided by the actual volume of air sampled, and is expressed in μg/m3. The microprocessor reads averages and stores five-minute averages of ambient temperature, ambient pressure, filter temperature and volumetric flow rate. In
15 | P a g e Air Laboratory (May 2011)
addition, the microprocessor calculates the average temperatures and pressure, total volumetric flow for the entire sample run time and the coefficient of variation of the flow rate. 5.0 Interferences and Artefacts
The potential effect of body moisture or oils contacting the filters is minimized by using non-serrated forceps to handle the filters at all times. This measure also moderates interference due to static electricity. Teflon filters accumulate a surface electrical charge, which may affect filter weight. Static electricity is controlled by treating filters with a “Static Master” static charge neutralizer prior to weighing. Placement of filters on a “Static Master” unit is required for a minimum of 30 seconds before any filter can be weighed. Moisture content can affect filter weight. Filters must be equilibrated for a minimum of 24 hours in a controlled environment prior to pre- and postweighing. The balance room’s relative humidity must be maintained at a mean value range of 45 ± 5 % and its air temperature must be maintained at a mean value range of 25.0 ± ºC. Airborne particulate can adversely affect accurate mass measurement of the filter. Filters undergoing conditioning should not be placed within an airflow path created by air conditioning ductwork, computer printers, or frequently opened doorways. Cleaning laboratory bench-tops and weighing areas daily, installing “sticky” floor mats at doorway entrances to the balance room and wearing clean lab coats over regular clothing can further minimize dust contamination. 5.1 Precision and Accuracy
The performance segment of the PM2.5 FRM specifies strict guidelines for controls that must be observed, as well as the range of precision and accuracy of those controls. The flow rate through the instrument is specified as 16.67 lpm (1 m3/hr). This flow must be volumetrically controlled to a precision of 5% and an accuracy of 2%. The flow control must be upgraded at least every 30 seconds and recorded (logged) every five minutes. Barometric pressure, ambient temperature and filter temperature should be measured on the same schedule. Filter temperature, it must not exceed the ambient temperature by more than 5° C for more than 30 minutes. A fan blowing filtered ambient air through the enclosure provides the necessary cooling effect. It is necessary for the entire apparatus to provide accurate performance over a temperature range of –20 to 50° C. The supporting run-time (interval) data, which are stored in detailed 5minute intervals in the sampler’s microprocessor, as well as 24-hour integrated performance (filter) data, must be capable of being extracted at the completion of a 24-hour run. The FRM mandates the provision of an RS232 port for this purpose. Data may be extracted to a portable computer.
16 | P a g e Air Laboratory (May 2011)
Mass of the filter deposit, flow rate through the filter, and sampling time have typical precision of ± 0.2 mg, ± 5%, and ± 30 seconds, respectively. These uncertainties combine to yield a propagated precision of approximately ± 5 % at 10 µg/m3 and approximately ± 2% at 100 µg/m3. 6.0 Sitting Requirements
Samplers should be sited to meet the goals of the specific monitoring project. For routine sampling to determine compliance with the National Ambient Air Quality Standards (NAAQS), sampler sitting is described in CPCB guidelines shall apply The monitoring should be done at outside the zone of influence of sources located within the designated zone of representation for the monitoring site. Height of the inlet must be 3 – 10 m above the ground level. And at a suitable distance from any direct pollution source including traffic. Large nearby buildings and trees extending above the height of the monitor may present barriers or deposition surfaces for PM. Distance of the sampler to any air flow obstacle i.e. buildings, must be more than two times the height of the obstacle above the sampler. There should be unrestricted airflow in three of four quadrants. Certain trees may also be sources of PM in the form of detritus, pollen, or insect parts. These can be avoided by locating samplers by placing them > 20 m from nearby trees. If collocated sampling has to be performed the minimum distance between two Samplers should be 2 m. 7.0 · · Apparatus and Materials Sampling equipment designated as FRM (Federal Reference Method) or FEM (Federal Equivalent Method) Certified Flow Transfer Standard for Flow Calibration Following established EPA methods and procedures, all calibration transfer standards (i.e. temperature, pressure and flow) must be certified against traceable standards at least once per year. Calibration of these transfer standards will be conducted by the transfer standard manufacturer. Certified Standards for Pressure and Temperature (Optional) Electronic microbalance with a minimum resolution of 0.001 mg and a precision of ± 0.001 mg, supplied with a balance pan. The microbalance must be positioned on a vibration-damping balance support table. Calibration weights, utilized as Mass Reference Standards, should be non-corroding, range in weight from 100 mg to 200 mg, and be certified as traceable to NIST mass standards. The weights should be ASTM Class 1 category with a tolerance of 0.025 mg. Non-serrated forceps for handling filters.
17 | P a g e Air Laboratory (May 2011)
Light box. perform a sampler external leak check according to the manufacturer’s guidelines.2 mm effective diameter with a polypropylene support ring or filters as recommended by FRM / FEM sampler manufacturer. Filter equilibration racks. perform a sampler internal leak check according to the manufacturer’s guidelines 18 | P a g e Air Laboratory (May 2011) .NAAQS Monitoring & Analysis Guidelines Volume-I · · · · · · · · · · · · · · · · 8. 47 mm Filter: Teflon membrane. Radioactive (alpha particle) Polonium-210 (“Static Master”) antistatic strips for static charge neutralization however static charge gives lowmoderate interference in stability of reading of balance.1 External Leak Check: Upon initial installation of the sampler.2 Internal Leak Check: Upon initial installation of the sampler. Zip-lock plastic bags. and powder free vinyl gloves. following sampler repair or maintenance and at least monthly. Disposable laboratory wipes. Filter support cassettes and covers. nitrate-free. 6”x 9” . Plastic petri-slide filters containers (Filter Cassette). Filter equilibration cabinets.1 Non-metallic. NIST-certified ISO traceable Thermometer for calibration of temperature readings. Digital timer/stopwatch. NIST-certified or ISO traceable Hygrometer for calibration of relative humidity readings. phosphate-free. Antistatic. 46.1.0 8. following sampler repair or maintenance. non-serrated forceps for handling weights. sulphate-free. Impactor oil/grease Sampling and Analytical Procedure Calibration and performance check of Sampler 8. Relative Humidity / Temperature recorder. 8. and at least monthly.1.
8.6 Pressure Verification Check Single-point pressure verification must be performed at least once every month. 8. To perform the temperature calibrations of filter follow the manufacturer’s instructions.4 Ambient Temperature Calibration: The ambient temperature calibration is to be performed upon initial installation. and at any time thereafter when the sampler fails a verification check following manufacturer’s guidelines. 8.1.1. The Temperature check is performed following manufacturer’s guidelines 8. Pressure calibration shall be performed following manufacturer’s instructions.1.7 Pressure Calibration The pressure calibration is to be performed upon initial installation. and at any time thereafter when the sampler fails either a single-point or multi-point temperature verification check.3 Single-point Ambient Verification Check: Temperature and Filter Temperature A single-point temperature verification check of both the ambient temperature and filter temperature sensors must be performed at least once every month.1.8 Single-point Flow Verification Check A single-point flow verification check must be performed at least every month. and at any time thereafter when the sampler fails a single-point pressure verification check. 8. The pressure check is performed following manufacturer’s instructions.1.1. 8. The flow check is performed following manufacturer’s instructions. yearly after site installation.1. yearly after site installation. yearly after site installation after any major maintenance that might affect the temperature reading.9 Multi-Point Flow Calibration Procedure A multi-point flow calibration must be performed upon initial 19 | P a g e Air Laboratory (May 2011) .5 Filter Temperature Calibration The filter temperature calibration is to be performed upon initial installation.NAAQS Monitoring & Analysis Guidelines Volume-I 8.
and Cost and availability. Loading capacity. if any deformity is found. · Put the marked filters in petri dishes. The multi-point calibration is performed following manufacturer’s instructions. · Note down the batch/lot in log sheet. Particle or gas sampling efficiency.NAAQS Monitoring & Analysis Guidelines Volume-I installation and once per year thereafter. Reject. Chemical stability. which should be unique to represent a sample. 8. Artefact formation. In addition. Flow resistance. Blank values. 20 | P a g e Air Laboratory (May 2011) . Compatibility with analysis method. 8. During the selection of filters following points should be considered: · · · · · · · · · Mechanical stability. · Label all the filters following a general lab coding technique.1 Filter Inspection and Conditioning of Filter Papers Filter papers selected for different analytical objectives should be conditioned by following steps: · Inspect all the filter papers for holes or cracks.2. It is preferable to prepare the estimate for whole requirement and order the same in bulk with a request to supply the same batch/lot of filters to control analytical quality and blank values. the multi-point calibration must be performed whenever a single-point flow verification check indicates that the sampler flow deviates from the flow transfer standard by more than ± 4%. · Prepare a sample-tracking sheet for each filter paper or a batch of filter paper. 47 mm (diameter) Teflon (PTFE) filter paper with Polypropylene support ring manufactured by M/s Whatman or M/s Pall Life Sciences or equivalent having 2 µm pore sizes.2 Selection and Procurement of Filters The quality of filter papers to be used should technically meet the desired specifications. The filter papers should have very low background concentrations for ion and elements. · Use always proper (blunt) tweezers/forceps (made of non-reactive material) to handle the filter papers in lab and field as well.
2. found acceptable deviations in reweighing. followed by one week equilibration in the weighing environment. · Discoloration – Any obvious discoloration that might be evidence of contamination. This is done be an examination of the filter on a “ light table” . PM2. Before any filter is placed in a filter-handling container. it must be inspected for defects. A filter must be discarded if any defects are identified. Specific defects to look for are: · Pinhole – A small hole appearing as a distinct and obvious bright point of light when examined over a light table. 8. the filters are transferred from their sealed manufacturer’s packaging to a filter-handling container such as a plastic petri-slide. These filter equilibrium conditions are intended to minimize the liquid water associated with soluble compounds and to minimize the loss of volatile species. Gravimetric measurement is the net mass on a filter by weighing the filter before and after sampling with a balance in a temperature and relative humidity controlled environment as described in SOPs.4 Lot Blanks Check Randomly select three filters as lot blanks from each new lot received and place in individual containers. Weigh lot blanks every 24 hours on a designated balance. such as irregular surfaces or other results of poor workmanship. Lab personnel must wear vinyl gloves as secondary when filters are being prepared for conditioning and weighing. but still reduces extraneous airborne particles from settling on filters.2. · Other – A filter with any imperfection not described above. Equilibrate the exposed filters in a filter equilibration cabinet in the Balance Room that allows air circulation. · Chaff or flashing – Any extra material on the reinforcing ring or on the heat-seal area that would prevent an airtight seal during sampling. The filters are handled with non-serrated forceps. · Loose materials – Any extra loose materials or dirt particles on the filter.3 Filter Conditioning A one-month storage period in a controlled environment. 21 | P a g e Air Laboratory (May 2011) .5 reference methods require that filters be equilibrated for 24 hours at a constant (within ±5%) relative humidity 45 % and at a constant (within ±2ºC) temperature between 25ºC.2 Filter Inspection and Stability To equilibrate. To minimize particle volatilization and aerosol liquid water bias. · Separation of ring – Any separation or lack of seal between the filter and the filter support ring. 8.NAAQS Monitoring & Analysis Guidelines Volume-I 8.2.
The mass of the aerosol is determined by calculating the difference between the pre and post weights. Once the mass difference between weighing is less than 0. mass. which induces non-gravimetric forces. the filter is removed petri dishes and the post weight of the filter is measured after conditioning. It is established that residual charge on a filter could produce an electrostatic discharge between the filter on the pan and the metal casing of the electro balance. This information is designated as the minimum equilibration period required before filters from the same lot can be pre-weighed and used for routine sampling. The sensitivity and reliability of the electro-balance is about + 0. The area is cleaned with a high efficiency vacuum cleaner. these sensitive balances require isolation from vibration and air currents. polonium strip ionization units are used to reduce electrostatic effects in the weighing cavity and on individual filters. and trip blanks are equilibrated prior to pre. Though tolerances on re-weights of Teflonmembrane filters are typically ± 0. and dates of the lot blanks in the assigned quality control logbook.5 Laboratory Conditions for Weighing Gravimetric analysis of the filters needs to be performed with a microbalance. A segregated laboratory area is used to control human traffic and to stabilize the temperature and relative humidity of the weighing environment. If possible. Note the time taken from initial exposure of the filters to attainment of mass stability.2.001 mg or 1 µg. The pre weight of each filter is measured prior to being sent into the field for sampling.015 mg for all three lot blanks. Once exposed and returned to the sample handling room.or post-weighing.010 mg. Balances placed in laminar flow hoods with filtered air minimize contamination of filters from particles and gases in laboratory air. 8. Gravimetric analysis of filters currently uses the difference method to determine the mass of the collected aerosol. Electrostatic effects contribute another main interference in gravimetric analysis of filters.NAAQS Monitoring & Analysis Guidelines Volume-I Record the lot number. This charge can be removed from most filter media by exposing the filter to a low-level radioactive source (500 Pico curies of polonium210 ) prior to and during sample weighing. field blanks. and a tacky floor covering is installed at the entrance to the sample handling room to minimize dust artifact. filter number. 8.3 Electro Balance Controls and Calibration Gravimetric mass analysis is performed using single pan electronic balance. the filters have stabilized. the lot blanks become lab blanks which are set aside for long-term exposure in the same equilibration cabinet where routine samples. 22 | P a g e Air Laboratory (May 2011) . Once this minimum equilibration period is determined.
and close the door on the weighing chamber (if polonium strip is used). A calibration log database is maintained for each balance.3 Cleaning Regular cleaning should be performed as following: · Clean the metal and plastic forceps with ethanol and a Kimwipe™.3. Do not neglect to clean the ionizing unit in the electro balance. It is also recalibrated if the balance fails a "zero" test that is performed periodically. if necessary. if necessary) and Kimwipes™. This procedure reduces the possibility of contamination if a filter falls to the work surface.3.4 Thorough Calibration of Balance (Once in 6 Months) o Allow the balance to stabilize with no weights on the pan. · Replace the clean ionizing unit in the center back of the balance cavity. Significant events concerning the balance and any balance maintenance other than routine procedures are recorded in the log of the lab manager. The computer will automatically record the mass to the screen when the balance has stabilized.3. The floors are cleaned with a mild cleaning solution. 8. Following the Friday cleaning. after insuring that all filters have been protected against contamination. this is the "zero" mass. · Clean the work surface around the balance with ethanol and a Kimwipe™. the sample handling room should be thoroughly cleaned. all work surfaces are cleaned with reagent grade alcohol (or another reagent grade solvent. no analysis shall occur for at least twenty-four hours to reduce the potential for contamination of filters by compounds used in the cleaning process. temperature in the range of 25º C with variation less than ± 3º C. and relative humidity 45% ±5%. It should be 23 | P a g e Air Laboratory (May 2011) . over the twenty-four hour period prior to analysis of exposed filters. Every last working day. all surfaces are cleaned with a high efficiency vacuum. 8. · Clean the top surface and the strips of the anti static ionizing units by gently rubbing with a Kimwipe™ wetted with ethanol. To reduce fugitive dust levels. Finally.1 Cleaning and Maintenance of the Sample Handling Room The requirements for a sample handling room include a reduced dust environment. and.3.2 Calibration and Maintenance of balance The balance is cleaned and calibrated every day for ranges at the start of operation. 8.NAAQS Monitoring & Analysis Guidelines Volume-I 8.
Take readings. and replace it in its storage container.1 for lab manager procedures). using the nylon forceps.000 mg or suitable mass of graded Calibration weight. The electro balance is available to run controls or for routine determination of mass. Use a 200.000.2. Calibrate the balance. must be weighed and a regression line developed." Compare the zero value and the value determined for the 50.3. Take following steps for performing Linearity checks: o Use the nylon forceps to remove a weight from its container and place it on the weighing pan.NAAQS Monitoring & Analysis Guidelines Volume-I o o o o o o o o o o o within 0. The test weight is an old 50.2. If not.000. Momentarily ground yourself by touching the balance casing.000 mg or suitable mass graded Calibration weight. The results are used to verify the integrity of the electro balance and the standard masses used in daily calibrations. To run a linearity check on the balance (if the balance is suspected to be damaged). report to the laboratory manager so that he/she can take appropriate action (section 4.1 step 3).000 mg mass to the expected values posted on the balance. Set the zero on the balance by pressing the tare button on the balance. The computer will record a reading to the screen when the balance has stabilized. Momentarily ground yourself by touching the balance casing. Allow the balance to return to "zero. and 20 mg. Use the nylon forceps to remove the test weight from its container. and 20. On a random basis.000. section 4. but at least semiannually. If they exceed 02 micrograms.000 mg standards and report their masses to the supervisor. The four weights. 50.3. measure these 200. If variations greater than 10 micrograms are observed.000 gm calibration weight.010 mg of 0. Check the calibration of the balance using the test weight. Place the test weight in the center of the balance pan and allow the mass reading to stabilize and stop decreasing. utilize the series of four standard weights stored in the lab manager’s desk. repeat the procedure. 24 | P a g e Air Laboratory (May 2011) . Linearity checks (Once in a year otherwise after every repair/shifting of balance). Gently place it in the center and allow the mass reading to stabilize and stop decreasing.000. 100 mg. Use a 20. After calibration. the laboratory supervisor shall request a comparison of the normal calibration standards with a master set of reference standard masses maintained by the laboratory supervisor. 50 mg. This forces the "zero" mass to be exactly 0. 200 mg. Use nylon forceps to remove the certified calibration weight from its container. contact the lab manager (see step 3. Remove the calibration weight from the bail.
The liquid crystal display (LCD) should display “0.000 mg”. o Repeat steps (i) through (iii) for the other three weights. 8. Calculate the r2 value. If the standard deviation is greater than ±3 micrograms. and develop a regression line comparing the re-weight values to the original values.3. Press the “TARE” key when readout has stabilized to ensure zero-readout. temperature and relative humidity of the balance room. Place a 100 mg working reference standard calibration weight onto the microbalance pan with non-metallic forceps. 8.6 Daily Calibration of Balance Internal Calibration should be performed daily before any Pre. Derive the best line fit equation correlating the original weights to the reweights.7 Internal Calibration Open the draft shield door for at least one minute to allow the balanceweighing chamber to equilibrate to room temperature.3. 8.3. using the plastic forceps. Calculate the standard deviation and the r2 of the line fit. Press the key for ensuring the internal calibration. reweigh the last 20 archived control filters. the balance requires maintenance.5 Stability Check of Balance (Once in Month) To check the stability of the balance. and mass readout in the quality control logbook assigned to the microbalance. o Linearly regress the ‘y’ value versus the ‘x’ value. and replace it in its protective container. close the draft shield door.3. Remove the calibration weight and tare the microbalance as described above. 8. record the displayed weight as the ‘y’ value and the certified mass as the ‘x’ value. Plot the re-weights versus the original weights. and the r2 is not better than 0. Close the draft shield door. the balance should be carefully inspected and submitted for maintenance. Use following steps: · · · · · Reweigh the series of 20 old controls filters on the suspect balance. Record the date.995. o If the R2 is not better than 0.NAAQS Monitoring & Analysis Guidelines Volume-I o Wait until the balance has stabilized (approximately one minute).8 External Calibration Open the draft shield door. o Remove the weight from the pan. Then.995.or Postsampling weighing. then. Enter the calibration data 25 | P a g e Air Laboratory (May 2011) .
sample start and stop dates and times. close tightly.3. Transport the filters in a dry clean box (temperature control is optional) to the field. o Follow the same procedure for exposed filter o Place the weighed filter into a petri-slide. o Put Lab code on from Plastic petri-slide filter containers (Filter Cassette). External calibration must be performed for each day on which filters are pre-weighed and/or postweighed. · Check the system clock and make sure it is within 1 min of NIST time. o Put the values of all control measurement in Quality Control Charts against dates. 8. o Take out conditioned filter from Plastic petri-slide filter containers (Filter Cassette). 8. site name. filter ID number.5 Field sampling · On the Field Data Log. 26 | P a g e Air Laboratory (May 2011) .9 Weighing of Filters o Take out pre-conditioned filters by forceps one by one and weigh properly. · Perform all necessary pre-sampling procedures as described above. · Record all maintenance activities in the field log book. fill in the top portion of the form including: the date/time of visit.NAAQS Monitoring & Analysis Guidelines Volume-I into logbook records and assign to the calibration session in the quality control logbook assigned to the microbalance. Record the mass in data sheet and log books against respective filter numbers or code. include time. the site identification. 8. o Record and store it in laboratory coded filter cassette.4 Shipment of Pre-weighed filters Put the marked pre-weighed filters in Zip pouch. o Replace and close the filter container (Petri dishes). sampler identification. date. and any concerns that might affect the quality of the sample. Weigh one Control Filters (Archived one) with each batch of ten weighing. Keep separate controls for Pre (Blank filter) and Post (Exposed) sampling filters. if required. and store at 4ºC for at least one year after sampling. § Weigh the preconditioned filter. and field operator initials. · Perform QA/QC checks or maintenance. · Remove the filter to be installed from its protective filter cassette carrier. Always use gloved hands and blunt tweezers to handle filters. · Fix the filter following manufacturer’s instructions into place against the bottom of the WINS impactor.
27 | P a g e Air Laboratory (May 2011) . Do not disturb the sampler unless necessary. · Open the filter exchange mechanism by pulling straight back on the black handle. note the error in the field log book and make any repairs as needed. Average and Maximum Pressures – from the Pres fields i) If the sampler indicated there was an error.NAAQS Monitoring & Analysis Guidelines Volume-I · Strictly follow operator’s manual for setting up the sampling programme (24 hours) · The Filter Setup Screen shows the start date and time and the end date and time for the next sample. This allows the sampler to write the final information into storage for the current sample run and must be performed prior to filter exchange. If the sampler is in the WAIT mode or the SAMP (sampling) mode. Any fixes should be done prior to the next run date. · Using the information displayed on the Filter Data screen.6 Recovering the Sample and Data from a Completed Sample Run · From the Main Screen. right side of display). · Remove the filter carrier from the filter holder. Average and Maximum Filter Temperatures – from the FltT fields h) Minimum. 8. Average and Maximum Ambient Temperatures – from the AmbT fields g) Minimum. The filter holder will lower away from the WINS impactor. The sampler mode should now indicate STOP. · If the sampler is in the DONE mode or the ERR mode. field Average Flow Rate – from the Ave. Flow field Coefficient of Variation – from the %CV field Total Run Time – from the Tot field Maximum Temperature Difference – from the Temp Diff field Minimum. press STOP.7LPM) and Sample volume displays rightly on screen. note the current sampler-operating mode (top line. complete the Field Data Log with the following information from the completed sample run: a) b) c) d) e) f) Total Sample Volume – from the Vol. the sampler has not completed the previously scheduled sampling run. To change the sampling parameters follow the operator’s manual · Start Sampling run · Wait until the auto diagnosis for all relevant parameters finishes and the sampler automatically switch over to SAMPLING mode. access to the Filter Data screen following operator’s instruction. · Place the filter carrier in the filter cassette case. · From the Main Screen. Check flow (16.
5 = (Mf – Mi) mg x 103 µg Where.5 particulates (µg/m3) = total mass of fine particulate collected during sampling period (µg) = total volume of air sampled (m3) 28 | P a g e Air Laboratory (May 2011) .5 Where. V = total sample value (m3) Qavg = average flow rate over the entire duration of the sampling period (L/min) t = duration of sampling period (min) 103 = unit conversion factor for liters (L) into cubic meters (m3) 8.5 PM2.5 / V = mass concentration of PM2.7. The Format shall contain all information including calibration.0 Reporting Data reporting should be done in prescribed Format.1 The equation given below can be used to determine PM2.7 Calculation and Reporting of Mass Concentrations The equation to calculate the mass of fine particulate matter collected on a Teflon filter is as below: M2.5 V 9.NAAQS Monitoring & Analysis Guidelines Volume-I 8. The data sheet must be accompanied by Sample Tracking sheet. PM2.5 samplers are required to provide measurements of the total volume of ambient air passing through the sampler (V) in cubic meters at the actual temperatures and pressures measured during sampling. Use the following formula if V is not available directly from the sampler: V = Qavg x t x 10-3 m3 Where.5 mass concentration: PM2. M2. = M2.5 = total mass of fine particulate collected during sampling period (µg) Mf = final mass of the conditioned filter after sample collection (mg) Mi = initial mass of the conditioned filter before sample collection (mg) 103 = unit conversion factor for milligrams (mg) to micrograms (µg) · Field records of PM2.
5 Gravimetric Analysis . No.0 29 | P a g e Air Laboratory (May 2011) . 2007/Rules and Regulations PM2." 35(4):339-342 Federal Register/Vol.0 1.0 References 40 CFR Parts 53 and 58 Revised Requirements for Designation of Reference and Equivalent Methods for PM2. Page 2 of 24 RTI (Research Triangle Institute.NAAQS Monitoring & Analysis Guidelines Volume-I 10. August 14.Revision 7. Final Rule CARB SOP MLD 055 Aerosol Science & Technology: The PM 2. 2003. 112/Tuesday.0 4.0 5.5 and Ambient Air Quality Surveillance for Particulate Matter. 72. US) 2. June 12.5 Federal Reference Method (FRM).0 3.
5 in µg/m3 30 | P a g e Air Laboratory (May 2011) .5 Check the filter for any physical damages ê Mark identification number on the filter ê Condition the filter in conditioning room / desiccator for 24 hours ê Record initial weight ê Place the filter on the sampler ê Run the sampler for eight hours ê Record the flow rate on hourly basis ê Remove the filter from the sampler ê Keep the exposed filter in a proper container ê Record the total time of sampling & average flow rate ê Again condition the filter in conditioning room / desiccator for 24 hours ê Record final weight ê Calculate the concentration of PM2.NAAQS Monitoring & Analysis Guidelines Volume-I FLOW CHART FOR MEASUREMENT OF PM2.
2.NAAQS Monitoring & Analysis Guidelines Volume-I Guidelines for sampling and analysis protocol for ozone in ambient air (Chemical Method) 1. Air Sampling and Analysis. 3rd Edition (Determination of oxidizing substances in the atmosphere) Micro-amounts of ozone and the oxidants liberate iodine when absorbed in a 1% solution of potassium iodine buffered at pH 6. 2% of the time. ** 24 hourly or 8 hourly or 1 hourly monitored values. Instrument/Equipment The following items are necessary to perform the monitoring and analysis of ammonia in ambient air: · Analytical balance: · Vacuum pump: Any suction pump capable of drawing the required sample flow rate of 1 to 2 litre per minute 31 | P a g e Air Laboratory (May 2011) . Standard The national ambient air quality standards for ozone is presented in the table Pollutant Time Weighted Average Concentration in Ambient Air Industrial.2. The stoichiometry is approximated by the following reaction: O3 + 3 KI + H2O --> KI3 + 2 KOH + O2 4. they may exceed the limits but not on two consecutive days of monitoring. µg/m3 8 Hours * 1 Hour ** * Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals. The iodine is determined spectrophotometrically by measuring the absorption of tri-iodide ion at 352 nm. shall be complied with 98% of the time in a year. as applicable. 3. Rural Area (Notified by and other Areas Central Government) 100 100 180 180 Ozone (O3). Ecologically Sensitive Residential. Principle of the method Method 411.8 + 0. Purpose The purpose of this protocol is to provide guidelines for monitoring of ozone in ambient air.
05N) . Measure pH and adjust to 6. 12 H2O). 14.2 with NaOH or KH2PO4.2 g of disodium hydrogen phosphate (Na2HPO4) or 35. Place 10 ml of absorbing solution in a standard impinger and sample for one hour at the flow rate of 1 L/min.0 g of potassium iodide in sequence and dilute the mixture to 1 L with water.00 ml of the 0. Discard after use.025 M I2 (0. Standardize shortly before use. add water to bring the liquid volume to 10 ml. Measure the absorbance of the unexposed reagent and subtract the value from the absorbance of the sample. 32 | P a g e Air Laboratory (May 2011) .8 + 0. Analysis If.8 g of the dodecahydrate salt (Na2HPO2. against 0. Calibrated flow measuring device to control the air flow from 1 to 2 l/min. Protect from strong light.Pipette exactly 4.025 M Stock solution into a 100 m low actinic volumetric flask and dilute to the mark with absorbing solution.Dissolve 16 g of potassium iodide and 3.Dissolve 13. Keep at room temperature at least 1 day before use. Keep at room temperature for at least 1 day before use. Do not expose the absorbing reagent to direct sunlight. This solution can be stored for several months in a glass stoppered brown bottle at room temperature without deterioration.173 g of re-sublimed iodine successively and dilute the mixture to exactly 500 ml with water. It should not be exposed to direct sunlight.6 g of potassium dihydrogen phosphate (KH2PO4). M I2 Solution .NAAQS Monitoring & Analysis Guidelines Volume-I · · · · 5. 7. read the absorbance in a cuvette at 352 nm against a reference cuvette containing distilled water. After sampling measure the volume of sample and transfer to a sample storage bottle.1 m Phosphate Buffer) . appreciable evaporation of the absorbing solution occurs during sampling.025 M Na 2S2O3. and 10. Within 30 to 60 minutes after sample collection. · Stock Solution 0. Glass wares: low actinic glassware must be used for analysis Reagents / Chemicals All the chemicals should meet specifications of ACS Analytical Reagent grade · Distilled water · Absorbing Solution (1% KI in 0. Sampling · 6. The sodium thiosulfate is standardized against primary standard biiodate [KH(IO3)2] or potassium dichromate (K2Cr2O7). Absorber: All glass midget impinger Spectrophotometer: Capable of measuring absorbance at 352 nm.
0.1. 33 | P a g e Air Laboratory (May 2011) . analysis of field blanks and lab blanks.0. Discard this solution after use. Calibration Preparation of Standards Calibrating Iodine Solution .3 kPa and 25oC. Quality Control Quality Control (QC) is the techniques that are used to fulfil requirements for quality.0.962 = Conversion factor. 6. 9.0 and 10. 4. The reciprocal of slope gives the calibration factor (CF). Draw a line of best fit and determine the slope.11 ml of the 0. µl to µg 10. Calculation C (O3 µg/m3) = (As – Ab) x CF x 1.001 M I2 solution (or equivalent volume for other molarity) is diluted with absorbing solution just before use to 100 ml (final volume) to make the final concentration equivalent to 1 µl of O3/ml.0 ml volumetric flasks. Obtain a range of calibration points containing from 1 µl to 10 µl of ozone equivalent per 10.0 mL of the calibrating iodine solution to 10.NAAQS Monitoring & Analysis Guidelines Volume-I 8. The QC procedures for the air sampling and monitoring sections of this protocol include preventative maintenance of equipment. Prepare by individually adding 1.2.0.0 ml of solution. 2. Read the absorbance of each of the prepared calibration solutions at 352 nm against distilled water reference 8. This solution preparation accounts for the stoichiometry described in Section 3 at standard conditions of 101. 8. C NH3 = Concentration of Ammonia in µg/m3 As = Absorbance of sample Ab = Absorbance of reagent blank CF = Calibration factor Va = Volume of air sampled in m3 1. calibration of equipment.962/ Va Where.For calibration purposes exactly 5. 8. Bring each to the calibration mark with absorbing reagent. Standard Curve Plot a curve absorbance (Y axis) versus concentration (X axis).
Air Sampling and Analysis.NAAQS Monitoring & Analysis Guidelines Volume-I 11. ê Draw air at a sampling rate of 1 lpm for 60 minutes ê Do not expose the absorbing reagent to direct sunlight ê Add de ionized water to make up the evaporation loss during sampling and bring the volume to 10 ml. Reference Method 411. read the absorbance in a cuvette at 352 nm against a reference cuvette containing de ionized water ê Calculate concentration using calibration graph ê Calculate concentration of Ozone in µg/m3 34 | P a g e Air Laboratory (May 2011) . 3rd Edition (Determination of oxidizing substances in the atmosphere) FLOW CHART FOR MEASUREMENT OF OZONE (CHEMICAL METHOD) Place10 ml of absorbing media in an impinger ê Connect it to the gas sampling manifold of gas sampling device (RDS/HVS). ê Prepare calibration graph as recommended in method ê Within 30 to 60 minutes after sample collection.
** 24 hourly or 8 hourly or 1 hourly monitored values. µg/m3 Annual * 24 Hours ** * Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals. Instrument/Equipment The following items are necessary to perform the monitoring and analysis of ammonia in ambient air: · Analytical balance · Vacuum pump to maintain a flow rate up to 5 litre per minute · Calibrated flow measuring device to control the air flow from 1 to 2 litre/min. they may exceed the limits but not on two consecutive days of monitoring. 4. · Absorber: a midget impinger or a fritted bubbler · Spectrophotometer capable of measuring absorbance at 630 nm. Standard The national ambient air quality standard for ammonia is presented in the table: Pollutant Time Weighted Average Concentration in Ambient Air Industrial. Ecologically Residential. 3. 3 rd Edition) Ammonia in the atmosphere is collected by bubbling a measured volume of air through a dilute solution of sulphuric acid to form ammonium sulphate. 2. as applicable. shall be complied with 98% of the time in a year.NAAQS Monitoring & Analysis Guidelines Volume-I Guidelines for sampling and analysis protocol for ammonia in ambient air (Indophenol Blue Method) 1. 2% of the time. Principle of the method Indophenol method (Method 401. Rural Sensitive Area and other Areas (Notified by Central Government) 100 100 400 400 Ammonia (NH3). The reaction is accelerated by the addition of Sodium Nitroprusside as catalyst. The ammonium sulphate formed in the sample is analyzed colorimetrically by reaction with phenol and alkaline sodium hypochlorite to produce indophenol. Air Sampling and Analysis. · Glass ware: low actinic glass wares must be used for analysis 35 | P a g e Air Laboratory (May 2011) . Purpose The purpose of this protocol is to provide guidelines for monitoring of ammonia in ambient air.
8. 1.5. Measure the absorbance of the solution at 630 nm on a spectrophotometer using 1 cm cells. 36 | P a g e Air Laboratory (May 2011) . Maintain all the solutions and sample at 25 ° C. Add 2 ml buffer. After sampling measure the volume of sample and transfer to a sample storage bottle.0 ml of working standard solution in to 25 ml glass stoppered graduated cylinders. and fill to about 22 ml. Calibration Preparation of Standards Pipet 0. A reagent blank with 10 ml absorbing solution is also prepared.5.0. Fill to 10 ml mark with absorbing solution.1.NAAQS Monitoring & Analysis Guidelines Volume-I 5. 1. Dilute to 25 ml. Add reagents to each cylinder as in the procedure for analysis.5 ml of working hypochlorite solution and rapidly mix. mix and store in the dark for 30 minutes to develop colour. 8. Analysis Transfer contents of the sample bottle to a 25 ml glass stopper graduated cylinder. 2. mix. Prepare a reagent blank and field blank and measure the absorbance as done in the analysis of samples. Reagents / Chemicals All the chemicals should meet specifications of ACS Analytical Reagent grade · Distilled water · N Sulphuric Acid (Absorbing solution) · Sodium Nitroprusside · 6. Read the absorbance of each standard against reagent blank. Add 2.75 M sodium hydroxide · Sodium hypochlorite solution · Phenol solution 45% v/v · Sodium phosphate · Ammonium chloride or Ammonium Sulfate · Hydrochloric acid · Ammonia stock solution (1 mg NH3/ml) · Ammonia working solution (10 µg NH3/ml) (Prepare fresh daily) 6. Sampling Place 10 ml of absorbing solution in an impinger and sample for one hour at the flow rate of 1 to 2 L/min. Add 5 ml of working phenol solution. 7.
Draw a line of best fit and determine the slope. Standard Curve Plot a curve absorbance (Y axis) versus concentration (X axis). 11.NAAQS Monitoring & Analysis Guidelines Volume-I 8. Quality Control Quality Control (QC) is the techniques that are used to fulfill requirements for quality. Reference Indophenol method (Method 401. C NH3 = Concentration of Ammonia in µg/m3 As = Absorbance of sample Ab = Absorbance of reagent blank CF = Calibration factor Va = Volume of air sampled in m3 10.2. 3rd Edition). calibration of equipment. Lewis publishers Inc. 37 | P a g e Air Laboratory (May 2011) . Calculation C ( NH3 µg/m3 ) = (As – Ab) x CF / Va Where. Air Sampling and Analysis. 9. The QC procedures for the air sampling and monitoring sections of this protocol include preventative maintenance of equipment. The reciprocal of slope gives the calibration factor (CF). analysis of field blanks and lab blanks.
Transfer the contents from polyethylene bottles to 25 ml measuring flasks (Maintain all the solutions at 25°C) Add 2 ml of buffer (to maintain pH) Add 5 ml of working phenol solution. 1. Measure the absorbance of the solution at 630 nm using UV Spectrophotometer ê Pipette 0. transfer the solution in the impinger to polyethylene bottle and recap it tightly for transport to laboratory for analysis ê Prepare the absorbing media.1 M H2SO4).NAAQS Monitoring & Analysis Guidelines Volume-I FLOW CHART FOR MEASUREMENT OF AMMONIA Dilute 10ml of concentrated HCl (12M) to 100 ml with distilled water Wash the glassware with the water and finally rinse it thrice with distilled water ê Adjust the Flow rate at 1L/min of the rotameter and the manifolds of the attached APM 411/APM 460Dx ê Place 10 ml of absorbing media in each midget impinger for samples and field blanks Assemble (in order) prefilter &holder. flowmeter. Add the reagents as to each flask as in the procedure for analysis Read the absorbance of each standard against the reagent blank.0 and 1.5 ml of working standard solution (working ammonia solution) in 25 ml measuring flasks Fill to 10 ml mark with absorbing solution (0. impinger and pump Sample at the rate of 1L/min for 1hour duration ê Record the sampling time. fill to about 22 ml with distilled water and then add 2. mix. various reagents and working solutions as per the method described in protocol Standardize the sodium thiosulphate solution by titrating it against potassium iodate and Sodium hypochlorite by titrating it against standardized sodium thiosulphate solution ê Take 25 ml measuring flasks and rinse with distilled water.5 ml of working hypochlorite solution & mix rapidly Store in the dark for 30 mins to develop colour. average flow rate and final volume of the solution After the sample collection.5. ê Plot the calibration curve ê Calculate the concentration of NH3 in µg/m3 38 | P a g e Air Laboratory (May 2011) .
as applicable. In the vapour phase the concentration of B(a)P is significantly less than the particulate phase. The molecular formula of B(a)P is C20H12 having molecular weight 252 and structural formula is given in following figure: Structural Formula of Benzo (a) Pyrene (BaP) : 2. Standard The national ambient air quality standard for Benzo(a)pyrene is presented in table Concentration in Ambient Air (ng/m3) Industrial.NAAQS Monitoring & Analysis Guidelines Volume-I Guidelines for sampling and Analysis of Benzo(a)Pyrene & other PAHs in Ambient Air (Solvent Extraction & GC Analysis) 1. they may exceed the limits but not on two consecutive days of monitoring. shall be complied with 98% of the time in a year. ** 24 hourly or 8 hourly or 1 hourly monitored values. 2% of the time. Sensitive Area Rural & other Areas (Notified by Central Government) Benzo(a)pyrene Annual 01 01 * Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals. Therefore. Benzo (a) Pyrene (BaP) is one of the most important constituent of PAH compounds and also one of the most potent carcinogens. Ecologically Residential. more care to be taken for the measurement of Benzo (a) Pyrene in the particulate phase. 39 | P a g e Air Laboratory (May 2011) Pollutant Time weighted Average . Purpose The purpose of this protocol is to provide guidelines for monitoring of Benzo (a) Pyrene (BaP) in ambient air. This can be measured in both particulate phase and vapour phase.
ultra residue grade) solvents like Toluene. Equipment/Instruments PM10 high volume sampler.NAAQS Monitoring & Analysis Guidelines Volume-I 3. Amber colour Vials 3ml and 5ml capacity. other PAHs. 4. Triphenyl benzene (internal standard. Particulate laden Benzo(a)Pyrene samples are collected on glass fibre filter (EPM 2000 or equivalent) using PM10 sampler at a flow rate of more than 1m3/min per minute. 4. 3.17µm or more).3 Sampling Height Sampling height may be between 3-10 meters from the ground level for ambient air quality monitoring. Chromatographic column (200-250 mm*10mmwith Teflon stopcock). Ultra Sonicator (~40kHz frequency). 4. Beakers (250 ml).e. Cyclohexane (with minimum residue less than 0. Syringes (5 & 10 micro litre capacity). Chemical/Solvents All chemicals. sampling using PM10 high volume sampler with 8 hourly samples using EPM2000 glass fibre or equivalent filter. length 25 meter x 0.2m3/min) sampling method capable of detecting sub.ng/m3 concentration of PAH in 24 hours sample (i. Rotary Evaporator (Buchi type).) & other chemicals like Silica -Gel (6080 mesh size) should be of highest purity & of reputed make with traceability/purity and analysis certificate. collected in 3 shifts of 8 hour each with 480 m3 sampling volume of air). Variable volume micropipettes (0. total of 104 days monitoring in a year. 4. / Agilent Ultra 2 or equivalent. It is a high volume (1. 4. 4.1 Sampling Instrument/Filter Selection 24 hr.5 & 1.P. Principle of the Method It is based on BIS method IS 5182 (Part 12):2004 and USEPA method (TO-13).2 Sampling Frequency Sampling is done twice a week.005%) etc.4 Sample Filter Storage 40 | P a g e Air Laboratory (May 2011) . 0. calibration /reference standards of B(a)P .0 ml capacity). This method is designed to collect particulate phase PAHs in ambient air and fugitive emissions and to determine individual PAH compounds using capillary gas chromatograph equipped with flame ionization detector. Whatman Glass fibre (EPM-2000) or Equivalent Filter Paper.320mm. Gas Chromatograph with Flame Ionization Detector fitted with Capillary Column (H. at selected location(s).
NAAQS Monitoring & Analysis Guidelines Volume-I After sampling. Alternatively. 4. Add ~50 ml. Concentration: After filtration. Figure – 1: Sample Processing 41 | P a g e Air Laboratory (May 2011) . Extraction: Filter papers (half of all the filters papers collected in a day) are cut into strips using scissors and transfer to 250 ml beaker. of Toluene (GC/HPLC grade). sample can be extracted using soxhlet extraction apparatus for about 8 hr. Repeat the procedure twice (50ml x 2 times) for complete extraction. otherwise wrap the filters in Aluminium foil & kept it in refrigerator at 4°C in dark to avoid photo oxidation of PAHs. b. with Toluene and repeat it twice. c. filters are kept in the controlled laboratory conditions (20-25 ˚C) in an envelope marked with necessary identification information if processed immediately. the filtrate is concentrated using Rotary vacuum evaporator (Figure-2) to 2ml final volume. Filtration: Filter the extracted samples with Whatman filter paper no. Sample processing steps are shown in Figure – 1.5 Sample Processing a. These samples are extracted with toluene using ultra sonic bath for about 30 minutes.41 containing 2 gm of Anhydrous Sodium Sulphate (to remove moisture).
Alternatively Solid Phase Extraction (SPE) may be used for clean up the impurities of sample. e. Repeat the process for at least 3 times and collect it in the same beaker. Re-concentration with rotary vacuum evaporator: 42 | P a g e Air Laboratory (May 2011) . pass 2 ml of concentrated sample through silica gel column (pre conditioned. 60-80 mesh. After cleaning add 5ml cyclohexane and collect the elute in 25 ml beaker.NAAQS Monitoring & Analysis Guidelines Volume-I Filter Extraction with Ultrasonicator Figure – 2: Rotary Evaporator for Sample Concentration d. Clean-up with silica Gel: To clean up the impurities. and 200-250mm×10 mm with Teflon stopcock).
Extracted Sample Storage: Cover/Cap the sample vials /tubes and mark with necessary identification.50 ml/min Gases for FID Flame: H2 flow: 40 ml/min Zero grade air flow: 400 ml/min 5.NAAQS Monitoring & Analysis Guidelines Volume-I The Cleaned up extract/filtrate (approximately 17 ml) is further concentrated using rotary evaporator and it is evaporated to nearly dryness with Nitrogen. g. Final Sample volume: The dried sample is re-dissolved in 1ml of toluene and transfer into 4 or 5 ml amber vials final analysis. 0.71 minutes Carrier gas flow (N2): 0. Analysis/ Instrument Set-Up GC Conditions: Injector: 300°C FID Temp: 320°C Column: Ultra -2 (25m Length. Keep it in refrigerator at 4°C prior to the analysis as in Figure -3 Figure -3: Ready to Inject B(a)P Samples 5. f. 320µm diameter.1 Preparation of Standard Calibration Mixture 43 | P a g e Air Laboratory (May 2011) .17µ) or equivalent Oven: 120°C →2 min hold → 7°C/min → 300°C → 10 min hold Run Time: 37.
Germany make PAH mix 63) of concentration 1000mg/l (or 1000ng/µl) in Toluene. 10.e.3 Sample injection Take 2µl of sample from the amber vial using standard gas tight syringe and inject in the Capillary GC-FID instrument for analysis. 15. Ehrenstorfer. As a control Internal Standard of 10 ng/µl conc.2. 25 ng/µl) made in Toluene into GC-FID and plot the area of analyte viz. 10. 6. 15. A 10ng/µl concentration B(a)P or other PAH standards are to be injected in GC/FID instrument with every batch of samples. The instrument is calibrated as per its manual/software. 20.1 Internal Calibration Inject 1µl of each Working Standard (5. that is calibration factor (the ratio of response to the amount of mass injected). 25 ng/µl concentrations) are prepared from stock solution by diluting 200 to 40 times the stock B(a)P or other PAH solution of 1000mg/l (or 1000ng/µl) concentration with Toluene.B(a)P] against the corresponding concentration of the standard. 3-Tri Phenyl Benzene of concentration ~1000ng/µl is added in the working standard solution so that the final concentration of Internal standard is 10 ng/µl. 2. is added to each sample prior to the analysis in case of internal calibration is used.NAAQS Monitoring & Analysis Guidelines Volume-I Stock Standard Solution PAH mix standard solution of 16 Compounds including B(a)P (Dr. 5. 20. Internal Standard 1.2. 20. Record the resulting concentration of each PAH compound including B(a)P. 15. The instrument is calibrated as per its manual/software. 25 ng/µl) in triplicate and plot the area ratio of analyte PAH Compound [i. B(a)P] and the corresponding internal standard against the concentration for each compound and internal standard.2 Calibration of GC 5. 10.2.The retention time of various PAHs compounds are obtained under the above GC conditions.2 External Calibration Inject 1µl of each Working Standard (5. Calculations Calculate the concentration in ng/µl of each identified analyte or B(a)P in the sample extract (Cs) as follows: 44 | P a g e Air Laboratory (May 2011) .e. PAH Compound [i. 5. The quantification of that analyte will be based on peak area response of respective compounds with respect to working calibration standard. Working Standard Solution Working Standard Solutions ( 5. 5.
If substantial variation is found in observed concentration. Detection Limit The minimum detectable concentration in terms of B(a)P for a sampling period of 8hour (with about 480 m3 of air passed) will be 1ng /m3 assuming 1. High resolution capillary mass spectrometry or high pressure liquid chromatography can improve sensitivity down to 1ng/m3. in min. Internal Standard of 10 ng/µl conc.e 1µl) Vs : Volume of air sample in m3 7.NAAQS Monitoring & Analysis Guidelines Volume-I Calculate the air volume from the periodic flow reading taken during sampling using the following equation: V =Q x T Where. instrument should be recalibrated. References BIS Method IS 5182 (Part 12):2004 USEPA Method TO-13. 45 | P a g e Air Laboratory (May 2011) .125 % preferably.e 1000) Vi : Injection Volume (i. Cs : Concentration of Benzo (a) pyrene in ng / µl in the sample extract recorded by GC. Quality Control For recovery efficiency isotopically labelled B(a)P or other PAH surrogate standards are added to the samples prior to extraction & analysis. Q =Average flow rate of sampling m3/min T = sampling time. is added to each sample prior to the analysis in case of internal calibration is used.0 ml as the final volume of sample extract after clean-up and detectable concentration of 1ng/ µl of that sample extract. Ve : Final volume of extract in µl (i.e B(a)P: The concentration of PAH compound or Benzo(a)pyrene in ng /m3 in the air sampled is given by: C (ng /m3) = Cs * Ve / Vi *Vs Where. A 10 ng/µl concentration B(a)P or other PAH standards are to be injected in GC/FID instrument with every batch of samples or daily as a control. The recoveries should fall between 75. V = total sample volume at ambient conditions in m3 Concentration of analyte i. 8. 9.
5 ml Methanol ê HPLC/UV-Fluorescence Detector 46 | P a g e Air Laboratory (May 2011) .NAAQS Monitoring & Analysis Guidelines Volume-I FLOW CHART FOR MEASUREMENT OF BENZO(A)PYRENE EPM 2000 filter paper ê Ultrasonic extraction with Toluene (50 ml ´ 3 times) ê Filter & dry with Anhydrous Sodium Sulphate ê Concentration with Rotary Evaporator ê Clean up with Silica Gel Column Chromatography ê Elution with Cyclo-Hexane (5 ml ´ 3 times) ê Evaporate to nearly dryness under Nitrogen ê Re-dissolved in 0.5 to 1.0 ml Toluene ê Capillary GC-FID or GC-MS Re-dissolved in 2.
Annual * 06 06 3 ng/m * Annual Arithmetic mean of minimum 104 measurements in a year at a particular site taken twice a week 24 hourly at uniform intervals.NAAQS Monitoring & Analysis Guidelines Volume-I Guidelines for sampling and analysis of Lead. shall be complied with 98% of the time in a year. The method is based on active sampling using PM10 High Volume Sampler and then sample analysis is done by atomic absorption spectrophotometer. Ecologically Sensitive Residential. nickel and arsenic in ambient air. 4. Instrument/Equipment The following items are necessary to perform the protocol for monitoring of lead and nickel in ambient air: · PM10 sampler ( high volume design based) · Hot plate · Microwave Digestive System · Analytical balance 47 | P a g e Air Laboratory (May 2011) .0 20 20 Lead (Pb) . Rural Area (Notified by and other Areas Central Government) 0. nickel and arsenic is presented in the table Pollutant Time Weighted Average Concentration in Ambient Air Industrial. Standard The national ambient air quality standards for lead.50 0. they may exceed the limits but not on two consecutive days of monitoring. ng/m3 Annual * 24 Hours ** Annual * Arsenic(As).0 1. Nickel and Arsenic in ambient air (Atomic Absorption Spectrophotometer Method) 1. µg/m3 Nickel (Ni).50 1. as applicable. Principle of the method The Atomic Absorption Spectroscopy (AAS) technique makes use of absorption spectrometry to assess the concentration of an analyte in the sample. 2. ** 24 hourly or 8 hourly or 1 hourly monitored values. 2% of the time. 3. Purpose The purpose of this protocol is to provide guidelines for monitoring of lead.
20. Replace the face-plate and tighten the wing-nuts to secure the rubber gasket against the filter edge. Potassium iodide (GR/AR grade) Distilled / De-ionized Sampling Sampling procedure Tilt back the inlet and secure it according to manufacturer's instructions. record the designated flow rate on the data sheet. 48 | P a g e Air Laboratory (May 2011) . After the required time of sampling.NAAQS Monitoring & Analysis Guidelines Volume-I · · · · · Digestion chamber Polyethylene or polypropylene bottle Glasswares Top loading orifice kit FAAS (Flame Atomic Absorption Spectrophotometer) or GFAAS (Graphite Furnace Atomic Absorption Spectrophotometer) Reagents / Chemicals 5. 6. The maximum sample holding times is usually 180 days. Store these protective envelopes up to 30°C until analysis. · · · · · · · · 6.4 cm (8 X 10 in) Hydrochloric Acid (HCl) Concentrated (AR grade) Nitric Acid (HNO3) Concentrated (AR grade) Sulphuric Acid (H2SO4) Concentrated (AR grade) Metal Standard Solutions (Certified standard) Sodium borohydride (GR/AR grade). For automatically flow-controlled units. taking care to minimize contamination and loss of the sample. Loosen the face-plate wing-nuts and remove the face plate. Glass fibre filters should be transported or shipped in a shipping envelope. transport the filters to the laboratory. several reading (hourly) of flow rate should be taken. Remove the filter from its jacket and centre it on the support screen with the rough side of the filter facing upwards. Analyze the samples within 180 days. 6. During this period. The specified length of sampling is commonly 8 hours or 24 hours. Record the reading of the elapsed time meter.3 X 25. record the flow meter reading and take out the filter media from the sampler and put in a container or envelope. Gently lower the inlet.1 Filter Paper: EPM 2000 or equivalent.2 Sample storage After collecting samples.
the filtered sample is now ready for analysis. Place the filter in a beaker using vinyl gloves or plastic forceps.1. The filtered sample is now ready for analysis 49 | P a g e Air Laboratory (May 2011) . Using the plastic forceps. crush the filter strip down into the lower portion of the centrifuge tube to ensure acid volume will cover entire filter. Remove the beakers from the hot-plate and allow to cool.NAAQS Monitoring & Analysis Guidelines Volume-I 7. The final extraction solution concentration is 3 % HNO3/8% HCl.1 Analysis Extraction of Samples The collected sample on glass fibre filters may be extracted by either hot plate procedure or by microwave extraction (Method IO-3. Dilute to the mark with distilled water (Type I) water and shake.1). Do not allow sample to dry. Rinse the beaker walls and wash with distilled water. Cap the centrifuge tube tightly and mix the contents thoroughly for 2-3 minutes to complete extraction. The final extraction volume is 20ml based upon the above procedure. Transfer the extraction fluid in the beaker to a 100 mL volumetric flask or other graduated vessel. Place beaker on the hotplate. Place the vessel caps with the pressure release valves on the vessels hand-tight and tighten using the capping station to a constant torque of 12 ft-lb. Rinse the beaker and any remaining solid material with distilled water and add the rinses to the flask. Place the carousel containing the 12 vessels on to the turntable of the microwave unit. HNO3 and 8% conc. Place the vessels in the microwave carousel. HCl). 7. remove the labelled centrifuge tube containing samples. using the caping station uncap the microwave vessels. 7.2 Hot plate procedure Cut a 1" x 8" strip or half the filter from the 8" x 10" filter using a stainless steel pizza cutter. 41 and make up the final volume to 100 ml. Add approximately 10 mL reagent water to the remaining filter material in the beaker and allow to stand for at least 30 min.0 ml of the extraction solution to each of the centrifuge tubes (3% conc. Filter the extracted fluid with Whatman No. Allow the pressure to dissipate. Add 10. Add 10ml of deionized water to each centrifuge tube. and reflux gently while covered with a watch glass for 30 min. then remove the carousel containing the vessels and cool in tap water for 10 min. contained in a fume hood.1.1 Microwave extraction Cut 1 ”x 8” strip or half the filter from the 8”x10” filter sample and place on its edge in a labelled centrifuge tube using vinyl gloves or plastic forceps. Place the centrifuge tubes in a Teflon vessel containing 31 ml of deionized water. Irradiate the sample vessels at 486 W (power output) for 23 min. Cover the filter with the extraction solution (3% HNO3 & 8% HCl). Connect each sample vessel to the overflow vessel using the Teflon connecting tubes. 7.
2.NAAQS Monitoring & Analysis Guidelines Volume-I 7. the VGA should attach with Flame and the wavelength required for analysis is 193. 7.analyze the metals by Flame. 8. position the monochromator at the value recommended by the manufacturer. Tube life depends on sample matrix and atomization temperature.7nm. Flame Procedure Set the atomic absorption spectrophotometer for the standard condition as follows: choose the correct hollow cathode lamp. 50 | P a g e Air Laboratory (May 2011) .2. samples that can be analyzed by flame or furnace may be more conveniently run with flame since flame atomic absorption is faster. Atomic Absorption Spectrophotometer .2. Select at least three standards to cover linear range as recommended by method. adjust the burner for maximum absorption and stability and balance the meter. ignite the flame. if results are below detection limit then go for GTA.2. simpler and has fewer interference problems.1. This wavelength is observed by a monochromator and a detector that measure the amount of light absorbed by the element. Aspirate the standards into the flame or inject the standards into the furnace and record the absorbance. The method describes both flame atomic absorption (FAA) spectroscopy and graphite furnace atomic absorption (GFAA) spectroscopy. Calibration Prepare standard solutions from the stock solutions. Aspirate the blanks and samples.3. Prepare the calibration graph by plotting absorbance and concentration in μg/ml. A conservative estimate of tube life is about 50 firings. align the instrument. regulate the flow of fuel and oxidant. hence the number of atoms in the ground state in the flame or furnace. Instrument / Equipment A light beam containing the corresponding wavelength of the energy required to raise the atoms of the analyte from the ground state to the excited state is directed through the flame or furnace. select the proper monochromator slit width. Read the metal value in μg/L from the calibration curve or directly from the read-out of the instrument.2 Analysis of samples 7. the wavelength required for analysis is 217nm and 232nm respectively. Dilute samples that exceed the calibration range. Where as in case of Arsenic (As). set the light source current. Furnace Procedure As a general rule. For Lead (Pb) and Nickel (Ni). Arsenic is analyzed by Flame – VGA. Run a series of standards of the metal of interest and construct a calibration curve. A hollow cathode lamp for the element being determined provides a source of that metal’s particular absorption wavelength. 7.
Detection limit and working range for each metal should be followed of the working instrument. Calculate the mean and the standard deviation. 9. m3 average sampling rate.2. 51 | P a g e Air Laboratory (May 2011) . m3/min.100/mean value. Standard Curve Standard curve is prepared by using standard solutions of known concentration. 10. Calculate the standard deviation (S) and coefficient of variation (CV) where CV = S.2 Accuracy Analyze the pretreated Certified Reference Material (CRM) or internal reference material. Preparation of Standards For each metal that is to be determined. perform quality control checks and independent audits of the measurement process. standards of known concentration must be acquired commercially certified standards. 10.1. check the whole procedure. time in minutes. 8. instruments and measurement procedures that can be traced to an appropriate standard of reference.NAAQS Monitoring & Analysis Guidelines Volume-I 8.1 Calculations Sample Air Volume Sample air volume can be calculated by using the following equation: V = (Q) (t) Where. If not.1 Precision Analyze the pretreated sub-samples. V = Q = t = volume of air. The precision of the method is normally better than + 5% at the 95% confidence level. If the CV is greater than 10%. 9. 9. Quality Control To produce good quality data. Shewart’s analytical quality control chart should be maintained for good quality data. check the whole procedure for possible errors and/or contamination. the method has the required accuracy. If the value given for the CRM is within the interval of mean + standard deviation. document their data and use materials.
2 Standard Method. FLOW CHART FOR SAMPLE PROCESSING OF LEAD. µg metal/m3. ê Divide the filter paper in two equal parts ê Half portion of filter paper for the measurement of lead. · · · · · · · concentration. nickel and arsenic ê Extract the sample by either hot plate procedure or by microwave extraction ê Analysis of extracted sample using recommended method 52 | P a g e Air Laboratory (May 2011) .1 Sampling of Ambient Air for Total Suspended Particulate Matter (SPM) and PM10 Using High Volume (HV) Sampler Method 501.1 EPA compendium method IO 3. Air Sampling and Analysis. 1998.2 Metal Concentration C = (Ms – Mb) x Vs x Fa/V x Ft Where. 20th Edition.NAAQS Monitoring & Analysis Guidelines Volume-I 10. Lewis publishers Inc. IS 5182 Part 23 Method of Measurement of Air Pollution :Respirable Suspended Particulate Matter (PM10) cyclonic flow technique EPA compendium method IO 3 EPA compendium method IO 3.American Public Health Association (APHA). 3 rd Edition. metal concentration µg/mL blank concentration µg/mL total volume of extraction in mL total area of exposed filter in cm2 Volume of air sampled in m3 Area of filter taken for digestion in cm2 References Method IO-2. NICKEL AND ARSENIC IN AMBIENT AIR Collect the particulate matter on glass fibre filter (EPM 2000 or equivalent) using PM10 sampler (High Volume Sampling). C = Ms = Mb = Vs = Fa = V = Ft = 11.
2) Switch on Atomic Absorption Spectrophotometer ê Place the furnace.IO-3.IO-3. adjust and align the instrument as per requirement of GTA.NAAQS Monitoring & Analysis Guidelines Volume-I FLOW CHART FOR MEASUREMENT OF LEAD AND NICKEL BY FLAMEATOMIC ABSORPTION SPECTROPHOTOMETER: Method I (Method IO-3 . Open the Nitrogen gas ê Clean the Graphite Tube with a firing ê Click the START Button ê Calibration with metal standards as recommended in method ê Prepare calibration graph ê Analyze the digested samples ê Calculate the concentration using calibration graph ê Note: Always follow the instructions of the Instrument/ Operational manual given by the supplier 53 | P a g e Air Laboratory (May 2011) .2) Switch on Atomic Absorption Spectrophotometer ê Select and set the Hollow Cathode Lamp of desired metal and programming the instrument accordingly ê Adjust and align the instrument as per requirement ê Switch on Compressor for Air and Open the required gas cylinders (Air Acetylene for Flame analysis). Ignite the Flame Calibration with metal standards as recommended in method ê Prepare calibration graph ê Analyze the digested samples ê Calculate the concentration using calibration graph FLOW CHART FOR MEASUREMENT OF LEAD. ê Select and set the Hollow Cathode Lamp of desired metal and programming the instrument accordingly for standards and samples ê Switch on Chiller and keep the Temperature at 200 C. NICKEL AND ARSENIC BY GRAPHITE TUBE-ATOMIC ABSORPTION SPECTROPHOTOMETER: Method II (Method IO-3.
American Public Health Association (APHA).ATOMIC ABSORPTION SPECTROPHOTOMETER USING VAPOUR GENERATION ASSEMBLY (VGA): Method III (Standard Method.NAAQS Monitoring & Analysis Guidelines Volume-I FLOW CHART FOR MEASUREMENT OF ARSENIC BY FLAME. 1998. 20th Edition.) Switch on Atomic Absorption Spectrophotometer ê Select and set the Hollow Cathode Lamp of Arsenic and programming the instrument accordingly ê Adjust and align the instrument as per requirement –VGA ê Switch on Compressor for Air and Open the required gas cylinders (Air Acetylene for Flame analysis and Nitrogen for Hydride Generator) ê Ignite the Flame ê Check the flow rate of Hydride Generator ê Calibration with Arsenic standards as recommended in method ê Prepare calibration graph ê Analyze the digested samples ê Calculate the concentration using calibration graph Note: Always follow the instructions of the Instrument / Operational manual given by the supplier 54 | P a g e Air Laboratory (May 2011) .
© Central Pollution Control Board. United States Environment Protection Agency and Inter Society Committee) based on field and laboratory experiences. Efforts have been made to make it user friendly and easily understandable.NAAQS Monitoring & Analysis Guidelines Volume-I DISCLAIMER The guidelines for the measurement of Ambient Air Pollutants (NAAQS 2009) are based on the reference methods (Viz. however comments and suggestions towards its improvement are solicited. 2011 55 | P a g e Air Laboratory (May 2011) . Indian Standards.
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