Air Quality Monitoring Techniques Methods (Options)

Abhijit Pathak, Scientist apathak.cpcb@nic.in 43102348, 9971566700

Over all understanding on air quality perspectives include Monitoring and Assessment, Prediction & Forecasting, Mitigation (short term or long term planning), National and International commitments etc.

Environmental definitions (Ambient, Fugitive / Process) Atmospheric dynamics (Physics & Chemistry) Thorough in monitoring methodology Expression of air quality data (Units) Understanding on health impact Logical Reasoning aptitude Fair to strong mathematical and statistical knowledge Fair geographical and geological ideas Ability to understand economics

The Atmosphere
Atmospheric pressure (millibars)

200

400

600

800

78% N2, 21% O2

Altitude (kilometers)

120

Temperature Pressure Thermosphere Mesopause Heating via ozone Mesosphere

1,000 75
65

110
100 90 80 70 60

55

45

Stratopause 50 40 30 20 10 0 Stratosphere

35

25

Tropopause
Ozone layer Heating from the earth Troposphere 15

5 Pressure = 1,000 millibars at ground level

(Sea Level)

80

40 0 40 80 Temperature (C)

120

Altitude (miles)

Effects of Atmospheric Aerosols (PM)

Back Scattering (Cooling)

Kolb, Nature, 2002

Impacts: Air quality, Acid Rain, Climate, Hydrological Cycle, Agriculture, and Health

Prefix Yotta Zetta Exa Peta Tera Giga Mega Kilo hecto deca

Symbol Y Z E P T G M K, k h da g, m, L 10 10 10 10 10 10 10 10

Factor
24 21 18 15 12 9 6 3

Examples of usage 0.2 YW, 1.23Y [W] 3.33 Zs, 3.33Z [s] 1.23 Ekg, 1.23E [kg] 7.5 Ps, 7.5P [s] 0.5 Tm, 0.5T [m] 1.2 G, 1.2G [] 7 MW, 7M [W] 33 km, 33K [m] Deprecated by SI Deprecated by SI

Origin Greek 'octo' (eight, 1000 ) French 'sept' (seven, 1000 ) Greek 'six' (1000 ) Greek 'five' (1000 ) Greek 'teras' = monster Greek 'gigas' = giant Greek 'megas' = large Greek 'kilioi' = thousand Greek 'hekaton' = hundred Greek 'deka' = ten
5 6 7 8

100 10 1 0.1 0.01 10 10 10 10 10 10 10 10

-3 -6 -9 -12 -15 -18

deci centi milli micro nano pico femto atto zepto yocto

d c m, k , u n p f a z y

Deprecated by SI Deprecated by SI 22 mm , 1.2m [m] 2.7 uJ , 2.7 [J] 2.2 nF, 2.2n [F] 1.5 pA, 1.5p [A] 4.8 fs, 4.8f [s] 1.2 ag, 1.2a [g] 0.2 zm, 1.2z [m] 1 ys, 1y [s]

Latin 'decima pars' = one tenth Latin 'centesima pars' = one hundredth Latin 'millesima pars' = one thousandth Greek 'mikros' = small Latin 'nanus' = dwarf Spanish 'pico' = minimal measure Danish and Norvegian 'femten' = fifteen (10 ) Danish and Norvegian 'atten' = eighteen (10 18 ) French 'sept' (seven, 1000 ) Greek 'octo' (eight, 1000 )
-8 -7 -15

-21 -24

The conversion in air is little complicated This is for homogeneous mixture, therefore reporting in ppm or ppb in air is restricted to gaseous parameters

As the volume of gasses changes widely with Pressure and Temperature the use of reference Temperature and Pressure is mandatory. Normally 25C (298 K) and 760mm Hg pressure is considered as reference
Concept of Gas Laws are important Universal Gas Law (P1 V1)/ T1 = (P2 V2) / T2 Avogadro's Law 1 mole of gas occupies 22.4 litre at NTP

1 mole (Molecular weight) of gas occupies 22.4 litre at 0 C (273 K) and 1 atmos. (760mm of Hg) Pressure (P1 V1) / T1 = (P2 V2) / T2 Or, (P2 V2) / T2 = (P1 V1) / T1 Or, V2 = (P1 V1) *T2 / T1 * P2 Here, P1 = 760 mm of Hg, V1 = 22.4 L T1 = 273 K and P2 = 760 mm of Hg, V2 = Unknown) and T2 = 298 K Or, V2 = 760 * 22.4 *298 / 273 * 760 Or, V2 = 22.4 * 1.0915751 Or, V2 = 24.45128 L Now, 24.45128 L of a gas weighs 1 molar mass (x gm) in STP = x / 24.45128 g/L = x * 1000/ 24.45128 mg /L = ppm So, the Factor is = (1000/ 24.45128) (x) = 40.8976 (x) = 40.9 * (x) If mg is converted to g and Litre converted to m3, The equation remains same So, ppm of any gas = (x) ppm * 40.9 * Molecular weight = g / m3

SURVEY & MONITORING

SURVEY The method of collecting qualitative or quantitative or both information of a subject in a population at any time
MONITORING Systematic activities performed to obtain information for observing any changes in the state of a system which may occur over a time period

Objectives

Time frame

Site Selection

Frequency
Sampling Plan

Parameters

Grab Sample Single Sample Collected at a particular time and place that represents the composition (Qualitative and Quantitative) at the said time and place Composite Sample A representative sample created by the homogenization of multiple samples taken to indicate the average concentration within the same general area. Time weighted Flow weighted Combined spatial samples

Sample is the representative subset of a population Types of Sample

SAMPLE

Sampling ?
A process consisting of the withdrawal or isolation of a fractional part of a whole. In air or gas analysis, the separation of a portion of an ambient atmosphere with or without the simultaneous isolation of selected components.

Atmospheric Monitoring
Surface Stations Satellites Aircraft Balloons Ships UAVs: Assimilation Models

NATIONAL AMBIENT AIR QUALITY STANDARDS

Pollutant Time Weighted Average 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 * Annual * Annual * Annual * Concentration in Ambient Air

Industrial, Residential, Rural and other Areas

50 80 40 80 60 100 40 60 100 180 0.50 1.0 02 04 100 400 05 01 06 20

Ecologically Sensitive Area (Notified by Central Government)

20 80 30 80 60 100 40 60 100 180 0.50 1.0 02 04 100 400 05 01 06 20

Sulphur Dioxide (SO2), g/m3 Nitrogen dioxide (NO2), g/m3 Particulate Matter (Size less than 10m) or PM 10, g/m3 Particulate Matter (Size less than 2.5m) or PM 2.5, g/m3 Ozone (O3) , g/m3 Lead (Pb) , g/m3 Carbon Monoxide (CO), mg/m3 Ammonia (NH3), g/m3 Benzene (C6H6), g/m3 Benzo(a)Pyrene (BaP) Particulate phase only, ng/m 3 Arsenic (As), ng/m3 Nickel (Ni), ng/m3

* 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.

MONITORING METHODS
MANUAL (WET CHEMICAL - GASEOUS) MANUAL (PHYSICAL PARTICULATE) CONTINUOUS MONITORING (INSTRUMENTAL)

MANUAL ANALYTICAL METHODS FOR AIR POLLUTANTS

AIR POLLUTANT ABSORBING / COLLECTION MEDIA SODIUM TETRACHLOROME RCURATE (0.04M) SODIUM ARSENITE +NaOH (1:4) DILUTE H2SO4 PRINCIPLE METHODOLOG Y WEST & GAEKE METHOD : JACOB HOCHHEISER METHOD INDOPHENOL BLUE METHOD RANGE

SO2 (SULFUR DIOXIDE)

COLORIMETRIC (560nm)

4 -1050g/m3

NO2 (NITROGEN DIOXIDE) NH3 (AMMONIA) O3 (OZONE)

COLORIMETRIC (540nm) COLORIMETRIC (630 nm)

6 750 g/m3

1g / sample

PARTICULTES (SPM, PM10, PM2.5) METALS (Pb, Ni. As) PAH (BaP)

FILTER PAPER

GRAVIMETRIC

EPA, BIS

SPM / PM10 (HIGH VOL) 5 1000 g/m3 PM2.5 (LOW VOL) 2 200 g/m3 EPA IO 5

FILTER PAPER Digestion FILTER PAPER EXTRACTION

ATOMIC ABSORPTION / PLASMA SPECTROSCOPY GAS CHROMATOGRAPHY

EPA, BIS

1ng / m3

REAL TIME ANALTYCAL METHODS FOR AIR POLLUTANTS

AIR POLLUTANTS SO2 (SULFUR DIOXIDE) PRINCIPLE / METHOD PULSED FLUORESCENCE MEASUREMENT RANGE 1 -1000 ppb 2 1000 ppb

NO2 (NITROGEN DIOXIDE) CHEMILUMINISCENCE

O3 (OZONE)
CO (CARBON MONO OXIDE) SPM PM10 PM2.5

UV PHOTOMETRY
NON - DISPERSIVE IR

1 -1000 ppb
0.1 100 ppm

BETA ATTENUATION TEOM

1 - 1000 g/m3

Frequency and Duration of Monitoring

Manual Monitoring: Duration - 24 Hours Frequency - Twice a Week Frequency of subsample depends upon the monitoring objectives and method selected Automatic Monitoring: Round the Clock
(Real Time data)

Criteria for Siting of Station

Height of the inlet must be 3 10 m above the ground level. The sampler must be more than 20 m from trees. 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 Free from direct impact of pollution source Safety & Security, Power supply and accessibility

Method for Measurement of Sulphur dioxide

(West and George Gaeke Method)

Principle: SO2 is collected by bubbling ambient air in a solution of TCM (0.04M) Di-sulphitomercurate complex formed is treated with HCHO and acid bleached PRA to give a violet colour of para-rosaniline methyl sulphonic acid. The intensity of the colour is measured on spectrophotometer at 560 nm

Interference
NO2 in the range of 2 ppm induce fading of colour and is removed by adding Sulphamic acid. Ozone is eliminated is eliminated by aging the sample Trace elements like Mn, Cr (III), and V are eliminated by adding EDTA in absorbing solution

Method for Measurement of Nitrogen dioxide (Jacob and Hochheisers method)

Principle: NO2 is collected by scrubbing a known volume of air in a solution of sodium hydroxide sodium arsenite. The absorbed NO2 is determined as the Azo Dye by diazotising it with sulphanilamide in the presence of phosphoric acid and coupling it with NEDA. Intensity of the coloured complex is measured on a spectrophotometer at 540 nm after 20 mins.

Interference
Sulphur dioxide is a major interferrent Interference of SO2 is removed by adding hydrogen peroxide

Absorbing solution
Nitrogen dioxide is absorbed in alkaline solution of 0.1N sodium hydroxide containing sodium arsenite (4:1 ratio) Absorption efficiency 82%

OZONE IN AMBIENT AIR

Principle of the method Micro-amounts of ozone and the oxidants liberate iodine when absorbed in a 1% solution of potassium iodide buffered at pH 6.8 + 0.2. The iodine is determined spectrophotometrically by measuring the absorption of tri-iodide ion at 352 nm. The stoichiometry is approximated by the following reaction: O3 + 3 KI + H2O --> KI3 + 2 KOH + O2

AMMONIA IN AMBIENT AIR

Principle
Indophenol method Ammonia in the atmosphere is collected by bubbling a measured volume of air through a dilute solution of sulphuric acid to form ammonium sulphate. The ammonium sulphate formed in the sample is analyzed colorimetrically by reaction with phenol and alkaline sodium hypochlorite to produce indophenol. The reaction is accelerated by the addition of Sodium Nitroprusside as catalyst.

Components of Particulate Monitoring

Sampling
Selection of Sampler

Analysis
Filter Selection & Inspection Pre-conditioning of Filter

Calibration of Sampler

Calibration of microbalance Pre-weighing of Filter Post-conditioning of Filter

Loading of pre-weighed Filter

Field Sampling

Calibration of microbalance Post - weighing of Filter

Filter and Flow data retrieval

Calculation and reporting

SPM High Volume Sampling

Designed Flow Rate 67.8 m3 /hour or 1.13 m3 / minute

Respirable Dust Sampler (RDS) ?

High Volume PM10 Sampler with impaction principle

High Volume PM2.5 Sampler with impaction principle

Low volume PM2.5 sampler (FRM Partisol 2000)

PM10 inlet

Coarse PM Channel

PM2.5 Channel

Dicot Sampler

Sampling
Volume / m3

Analysis Quantity / g

Concentration

g / m3

WET CHEMICAL
low costs simple equipment normal laboratories performances sufficient accepted as basic reference methods internal calibration possible automatic integration of sampling period any chemically reactive component detectable

Sampling Concentration Analysis

Need of Automatic Monitoring System

Continuous Information Flow Warning at critical period Accuracy and precision information Minimise Human Error

of

Continuous Instruments
Advantages low response times less than 1 min high selectivity high temporal resolution in non-stop coverage good stability under normal conditions intermittent calibrations and zero checks automatically or manually triggered

Continuous Instruments
Disadvantages high costs in investment and maintenance calibration methods, systems and units required; science of their own; Ring Tests absolutely necessary dedicated & trained personnel required for service, calibration checks, data acquisition etc. integration requires computerization ambient conditions, e.g. dust, shocks, condensation may cause serious problems

Continuous Measurement of Carbon Monoxide

PRINCIPLE
Non Dispersive Infra-Red (NDIR) photometry provides a method of utilising the integrated absorption of infra-red energy over most of the spectrum for a given compound to provide a quantitative determination of the concentration of Carbon Monoxide (CO) in ambient air. The spectrometer measures the absorption by CO at 4.7 m using two parallel infrared beams through a sample cell, a reference cell and a selective detector. The detector signal is led to an amplifier control section and the analyser output measured on a meter and recording system.

CARBON MONOXIDE

Continuous Measurement of Sulphur Dioxide

Principle: The UV fluorescence method is based on the fluorescence emission of light by SO2 molecules previously excited by UV radiation. The first reaction step is : SO2 + h1 (UV) SO2* Then in the second step, the excited SO2* molecule returns to the original ground state, emitting an energy H1 according to the reaction : SO2* SO2 + h1 (UV) The intensity of the fluorescent radiation is proportional to the number of SO2 molecules in the detection volume and is therefore proportional to the concentration of SO2.

SULPHUR DIOXIDE ANALYSER

OXIDES OF NITROGEN

Continuous Measurement of Oxides of Nitrogen

Principle: The measurement method is based upon the rapid chemiluminescent reaction of nitric oxide (NO) with excess ozone (O3). The reaction is made to take place in a light free chamber. NO + O3 NO*2 + O2 A portion of the resultant nitrogen dioxide is produced in a highly excited energy state (NO*2) and subsequently decays to the ground level state emitting light in a broad frequency band with a peak at about 1200 nm : NO*2 NO2 + photons (hv) The intensity of the light emitted is linearly proportional to the nitric oxide concentration and is measured by a photomultiplier tube.

Continuous Measurement of Ozone

Principle: The method is based on the photometric assay of ozone (O3) concentrations in a dynamic flow system. The concentration of O3 is determined in an absorption cell from the measurement of the amount of light absorbed at a wavelength of 254 nm. The method is based on the absorption coefficient of O3 at 254 nm, the optical path length through the sample, and the transmittance, temperature and pressure of the sample. The quantities above are related by the Beer-Lambert absorption law. Transmittance = = e -cl o Where: = absorption coefficient of O3 at 254 nm = 310 atm-1 c m-1 at 0o C and 101.3 kPa e = O3 concentration in units of atmosphere l = optical path of absorption cell length in cm I = intensity of light passing through cell with an ozone sample Io = intensity of light passing through cell with zero air

DUST ANALYSER (PM10 & PM2.5)

MEASUREMENT PRINCIPLE BETA RAY ATTENUATION

Beta-Ray Attenuation
The Dust monitor automatically measures and records airborne particulate concentration levels (in milligrams or micrograms per cubic meter) using the principle of beta ray attenuation. Each hour, a small 14C (Carbon-14 or Krypton 85) element emits a constant source of high-energy electrons (known as beta rays) through a spot of clean filter tape. These beta rays are detected and counted by a sensitive scintillation detector to determine a zero reading. The Monitor automatically advances this spot of tape to the sample nozzle, where a vacuum pump then pulls a measured and controlled amount of dust-laden air through the filter tape, loading it with ambient dust. At the end of the hour this dirty spot is placed back between the beta source and the detector thereby causing an attenuation of the beta ray signal which is used to determine the mass of the particulate matter on the filter tape and the volumetric concentration of particulate matter in ambient air.

-radiator

Filter Tape

Detector

Air Flow Display Amplifier

Utilizes TEOM technology to provide direct mass measurements U.S. and internationally approved particulate monitor Configurable to measure PM-10, PM2.5, PM-1 or TSP concentrations Easily accommodates all sighting requirements