Air Pollution

1. Air Pollution Module-2

2. Module-2 • Ambient air pollution monitoring: techniques and instrumentation; monitoring stations • Stack monitoring: techniques and instrumentation. • Experimental analysis: gaseous and particulates; standards and limits.

3. Lecture-1 Ambient Air Pollution Monitoring

4. Introduction • Most frequently occurring pollutants in an urban environment are particulate matters (suspended particulate matter i.e. SPM and respirable suspended particulate matter i.e. RSPM), carbon monoxide (CO), hydrocarbons (HC), sulfur dioxide (SO2), nitrogen dioxide (NO2), ozone (O3) and photochemical oxidants.

5. Monitoring of Air pollutants Source monitoring instruments Stack sampler (APM 620): Parameters monitored are a. Pollutants b. Velocity (Isokinetic) c. Temperature d. Pressure Source Ambient As per WHO ambient monitoring protocol SOx Essential NOx SPM HC CO Additional O3 Point SOX NOX CO PM Line CO NOx HC RPM

6. The recommended criteria for siting the monitoring stations • The site is dependent upon the use/purpose of the results of the monitoring programs. • The monitoring should be carried out with a purpose of compliance of air quality standards. • Monitoring must be able to evaluate impacts of new/existing air pollution sources. • Monitoring must be able to evaluate impacts of hazards due to accidental release of chemicals. • Monitoring data may be used for research purpose.

7. Type of ambient monitoring stations

8. Frequency of data collection • Gaseous pollutants: continuous monitoring • Particulates: once every three days

9. Number of stations • Minimum number is three. • The location is dependent upon the wind rose diagram that gives predominant wind directions and speed. • One station must be at upstream of predominant wind direction and other two must at downstream pre dominant wind direction. • More than three stations can also be established depending upon the area of coverage.

10. Components of ambient air sampling systems • Four main components are: • Inlet manifold • Air mover • collection medium • flow measurement device Inlet manifold transports sampled pollutants from ambient air to collection medium or analytical device in an unaltered condition. The manifold should not be very long. Air mover provides force to create vacuum or lower pressure at the end of sampling systems. They are pumps. The collection mediums are liquid or solid sorbent or dissolving gases or filters or chamber for air analysis (automatic instruments). The flow device like rotameters measure the volume of air sampled.

11. Characteristics for ambient air sampling systems • Five important characteristics are: • collection efficiency • sample stability • recovery • minimal interference • understanding the mechanism of collection The first three must be 100% efficient. For e.g. for SO2, the sorbent should be such that at ambient temperature it may remove the SO2 from ambient atmosphere 100%. Sample must be stabled during the time between sampling and analysis. Recovery i.e. the analysis of particular pollutant must be 100% correct.

12. Basic considerations for sampling • Sample must be representative in terms of time, location, and conditions to be studied. • Sample must be large enough for accurate analysis. • The sampling rate must be such as to provide maximum efficiency of collection. • Duration of sampling must accurately reflect the fluctuations in pollution levels i.e. whether 1-hourly, 4-hourly, 6-hourly, 8-hourly, 24-hourly sampling. • Continuous sampling is preferred. • Pollutants must not be altered or modified during collection.

13. Errors in sampling by HVS • Particulates may be lost in sampling manifold – so not too long or too twisted manifold must be used. • If ’isokinetic’ conditioned are not maintained, biased results may be obtained for particulate matters.

14. Advantages of HVS • High flow rate at low pressure drop • High particulate storage capacity • No moisture regain • high collection efficiency • Low coast • Not appreciable increase in air flow resistance • Filter is 99% efficient and can collect the particles as fine as 0.3 μm • Absorption principle is 99% efficient in collecting the gases

15. Lecture-2Stack Monitoring: techniques & instrumentation

16. Stack Sampling • The sample collected must be representative in terms of time and location. • The sample volume should be large enough to permit accurate analysis. • The sampling rate must be such as to provide maximum efficiency of collection. • The contaminants must not be modified or altered in the process of collection.

17. Diagrammatic view of stack sampling

18. Impingers are glass bubble tubes designed for the collection of airborne particles into a liquid medium (Figure 1). When using an air sampler, a known volume of air bubbles is pumped through the glass tube that contains a liquid specified in the method. The liquid is then analyzed to determine airborne concentrations. Figure 1: Glass Impinger

19. Selection of sampling location • The sampling point should be as far as possible from any disturbing influence, such as elbows, bends, transition pieces, baffles. • The sampling point, wherever possible should be at a distance of 5-10 diameters down-stream from any obstruction and 3-5 diameters up-stream from similar disturbance.

20. Size of sampling point • The size of the sampling point may be made in the range of 7-10 cm, in diameter.

21. Traverse points • For the sample become representative, it should be collected at various points across the stack. • The number of traverse points may be selected with reference to Table 1. Table 1: Traverse Points

22. In circular stacks, traverse points are located at the center of equal annular areas across two perpendicular diameters as shown in Figure 2 Figure 2 In case of rectangular stacks, the area may be divided in to 12 to 25 equal areas and the centers for each area are fixed. (Figure 3) Figure 3

23. Isokinetic conditions • Isokinetic conditions exist when the velocity in the stack ‘Vs’ equals the velocity at the top of the probe nozzle ‘Vn’ at the sample point (Figure 4). Figure 4

24. Lecture-3 Experimental analysis: Gaseous & particulates; standards & limits

25. Principles of Sampling and Analysis • The components of an air pollution monitoring system include the • collection or sampling of pollutants both from the ambient air and from specific sources, • the analysis or measurement of the pollutant concentrations, and • the reporting and use of the information collected. • Emissions data collected from point sources are used to determine compliance with air pollution regulations, determine the effectiveness of air pollution control technology, evaluate production efficiencies, and support scientific research.

26. Conti…. • The EPA has established ambient air monitoring methods for the criteria pollutants, as well as for toxic organic (TO) compounds and inorganic (IO) compounds. • The methods specify precise procedures that must be followed for any monitoring activity related to the compliance provisions of the Clean Air Act. • These procedures regulate sampling, analysis, calibration of instruments, and calculation of emissions. • The concentration is expressed in terms of mass per unit volume, usually micrograms per cubic meter (µg/m3).

27. Particulate Monitoring • Particulate monitoring is usually accomplished with manual measurements and subsequent laboratory analysis. • A particulate matter measurement uses gravimetric principles. Gravimetric analysis refers to the quantitative chemical analysis of weighing a sample, usually of a separated and dried precipitate. • In this method, a filter-based high-volume sampler (a vacuum- type device that draws air through a filter or absorbing substrate) retains atmospheric pollutants for further laboratory weighing and chemical analysis. Particles are trapped or collected on filters, and the filters are weighed to determine the volume of the pollutant. The weight of the filter with collected pollutants minus the weight of a clean filter gives the amount of particulate matter in a given volume of air. • Chemical analysis can be done by atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS), inductively couple plasma (ICP) spectroscopy, and X-ray fluorescence (XRF) spectroscopy.

28. Atomic Absorption Spectrometry (AAS) • AAS is a sensitive means for the quantitative determination of more than 60 metals or metalloid elements. • Principle: This technique operates by measuring energy changes in the atomic state of the analyte. For example, AAS is used to measure lead in particulate monitoring. Figure: Atomic absorption spectrometry

29. Conti…. • Particles are collected by gravimetric methods in a Teflon (PTFE) filter, lead is acid-extracted from the filter. • The aqueous sample is vaporized and dissociates into its elements in the gaseous state. The element being measured, in this case lead, is aspirated into a flame or injected into a graphite furnace and atomized. • A hollow cathode or electrode less discharge lamp for the element being determined provides a source of that metal's particular absorption wavelength. • The atoms in the unionized or "ground" state absorb energy, become excited, and advance to a higher energy level. • A detector measures the amount of light absorbed by the element, hence the number of atoms in the ground state in the flame or furnace. • The data output from the spectrometer can be recorded on a strip chart recorder or processed by computer. • Determination of metal concentrations is performed from prepared calibration curves or read directly from the instrument.

30. Gaseous pollutant monitoring • Gaseous pollutant monitoring can be accomplished using various measurement principles. • Some of the most common techniques to analyze gaseous pollutants include • Spectrophotometry, • Chemiluminescence, • Gas chromatography-flame ionization detector (GC-FID), • Gas chromatography-mass spectrometry (GC-MS), and • Fourier transform infrared spectroscopy (FTIR).

31. Conti… • With all sampling and analysis procedures, the end result is quantitative data. • The validity of the data depends on the accuracy and precision of the methods used in generating the data. • The primary quality control measure is calibration. • Calibration checks the accuracy of a measurement by establishing the relationship between the output of a measurement process and a known input.

33. Spectrophotometry • A spectrophotometer measures the amount of light that a sample absorbs. • The instrument operates by passing a beam of light through a sample and measuring the intensity of light reaching a detector. • Spectrophotometry commonly used to measure sulfur dioxide (SO2) concentrations. • The amount of light absorbed indicates the amount of sulfur dioxide present in the sample. Figure: Schematic of a UV-VIS spectrophotometer

34. Chemiluminescence • An ambient air sample is mixed with excess ozone in a special sample cell. A portion of the NO present is converted to an activated NO2 which returns to a lower energy state and in the process emits light. This phenomenon is called chemiluminescence. Figure: Chemical reaction to determine oxides of nitrogen by chemiluminescence

35. Conti…. • Chemiluminescence methods for determining components of gases originated with the need for highly sensitive means for determining atmospheric pollutants such as ozone, oxides of nitrogen, and sulfur compounds. • The intensity of this light can be measured with a photomultiplier tube and is proportional to the amount of NO in the sample. A second reaction measures the total oxides of nitrogen in the air sample and in turn, the concentration of NO2 can be calculated.

36. Gas Chromatography (GC) • Gas chromatography (GC) coupled with a flame ionization detector (FID) is employed for qualitative identification and quantitative determination of volatile organic compounds (VOCs) in air pollution monitoring. • The GC, consists of a column, oven and detector. In the gas chromatograph, a sample goes to the column, separates into individual compounds and proceeds through the hydrogen flame ionization detector. Figure: Schematic gas chromatography

37. Conti…. • The flame in a flame ionization detector is produced by the combustion of hydrogen and air. • When a sample is introduced, hydrocarbons are combusted and ionized, releasing electrons. • A collector with a polarizing voltage located near the flame attracts the free electrons, producing a current that is proportional to the amount of hydrocarbons in the sample. • The signal from the flame ionization detector is then amplified and output to a display or external device. • Gas chromatography-mass spectrometry (GC-MS) instruments have also been used for identification of volatile organic compounds. Mass spectrometers use the difference in mass-to-charge ratio (m/z) of ionized atoms or molecules to separate them from each other. Mass spectrometry is useful for quantification of atoms or molecules and also for determining chemical and structural information about molecules.

38. Fourier Transform Infrared Spectroscopy • FTIR can detect and measure both criteria pollutants and toxic pollutants in ambient air • FTIR can directly measure more than 120 gaseous pollutants in the ambient air, such as carbon monoxide, sulfur dioxide, and ozone. • The technology is based on the fact that every gas has its own "fingerprint," or absorption spectrum. Figure: FTIR can directly measure both criteria pollutants and toxic pollutants in the ambient air. • The FTIR sensor monitors the entire infrared spectrum and reads the different fingerprints of the gases present in the ambient air.

39. Conti…. • Carbon monoxide is monitored continuously by analyzers that operate on the infrared absorption principle. • Ambient air is drawn into a sample chamber and a beam of infrared light is passed through it. • CO absorbs infrared radiation, and any decrease in the intensity of the beam is due to the presence of CO molecules. • This decrease is directly related to the concentration of CO in the air. • A special detector measures the difference in the radiation between this beam and a duplicate beam passing through a reference chamber with no CO present. • This difference in intensity is electronically translated into a reading of the CO present in the ambient air, measured in parts per million.

40. Ambient Air Quality standards & Limits

41. National Ambient Air Qu ality Standards POLLUTANTS AVERAGE TIME CONCENTRATION 3 Sulphur dioxide (SO2) Annual average 60 µg/m 3 24 hour 80 µg/m Oxides of Nitrogen 3 A.A 60 µg /m (NO2) 3 24H 80 µg /m Suspended Particulate 3 A.A 140 µg/m Matter ( SPM) 3 24H 200 µg/m 3 Lead A.A 0.75 µg/m 3 24H 1.0 µg/m 3 Carbon Monoxide A.A 2.0 µg/m 3 24H 4.0 µg/m Respirable Particulate 3 A.A 60 µg/m Matter (RPM) 3 24H 100 µg/m Central Pollution Control Board 2006

42. NAAQS by USEPA 2006 (1) Not to be exceeded more than once per year. (2) Due to a lack of evidence linking health problems to long-term exposure to coarse particle pollution, the agency revoked the annual PM10 standard in 2006 (effective December 17, 2006). (3) Not to be exceeded more than once per year on average over 3 years. (4) To attain this standard, the 3-year average of the weighted annual mean PM2.5 concentrations from single or multiple community-oriented monitors must not exceed 15.0 µg/m3. (5) To attain this standard, the 3-year average of the 98th percentile of 24-hour concentrations at each population-oriented monitor within an area must not exceed 35 µg/m3 (effective December 17, 2006). (6) To attain this standard, the 3-year average of the fourth-highest daily maximum 8-hour average ozone concentrations measured at each monitor within an area over each year must not exceed 0.08 ppm. (7) (a) The standard is attained when the expected number of days per calendar year with maximum hourly average concentrations above 0.12 ppm is < 1, as determined by appendix H. (b) As of June 15, 2005 EPA revoked the 1-hour ozone standard in all areas except the fourteen 8-hour ozone nonattainment Early Action Compact (EAC) Areas.

43. WHO Air Quality Guidelines Value Source: WHO, 2005. WHO air quality guidelines global update 2005, WHOLIS number E87950.

44. References • USEPA, 2007. Online literature from www.epa.gov • WHO, 2005. WHO air quality guidelines global update 2005, WHOLIS number E87950. • CPCB 2006, Central Pollution Control Board. http://www.cpcb.nic.in/standard2.htm