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Ambient Monitoring and Source Apportionment Workshop on Air Quality Index and Emission Inventory Development for Delhi

This workshop focuses on the chemical and physical processes relevant to ambient ozone and particulate matter, with a special emphasis on source attribution and emission inventory evaluation. The workshop aims to provide recommendations for improving air quality in Delhi.

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Ambient Monitoring and Source Apportionment Workshop on Air Quality Index and Emission Inventory Development for Delhi

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  1. Ambient Monitoring and Source ApportionmentWorkshop on Air Quality Index andEmission Inventory Development for DelhiCenter for Science and EnvironmentDelhi, India June 6-8, 2000 Eric M. Fujita Desert Research Institute University and Community College System of Nevada Reno, Nevada

  2. Overview • Chemical and Physical Processes Relevant to Ambient Ozone and Particulate Matter • Chemical Mass Balance (CMB) fundamentals • Volatile organic compound • Ambient Data • Source Profiles • Source Attribution • Particulate Matter • Ambient Data • Source Profiles • Source Attribution • Emission Inventory Evaluation • Summary and Recommendations

  3. WORLWIDE PARTICLE LEVELS

  4. Volume Size Distribution Modes - Transformation and Growth Mechanisms Adapted from Wilson and Suh (1997)

  5. Extinction Efficiencies as Function of Particle Size for White and Black Smoke Other assumptions in the calculation are a particle mass density of 1250 kg/m^3 and a wavelength of 550 nm, corresponding to the peak of both solar radiation and eye sensitivity.

  6. Sources of Nuclei Mode Particles Heavy Metals • Metallic impurities in coal or oil • metals in oil or fuel additives in gasoline or diesel fuel. Elemental carbon or soot • Condensation of C2 molecules generated during the combustion. Sulfates • H2 SO4 or its neutralization product(NH4)2SO4 or NH4HSO4 Organic Carbon • Nucleation of highly oxidized organic compounds produced in the atmosphere.

  7. Mechanisms for Formation of Secondary Organic PM • Condensation of end-products of photochemical reactions • Adsorption of organic gases on existing solid particles • Dissolution of soluble gases which undergo reactions in particles Precursors and Aerosol Formation Potential • Whole gasoline: 7-10% yield from mono-substituted aromatic and 3-4% from multi-substituted aromatics with existing carbon levels of 13 to 100 g/m3 (Odum et al). • Biogenic emissions: ~5% yield for open-chain, 5 to 25% for monounsaturated cyclic monoterpenes, ~40% for cyclic monoterpenes with two double bonds, and 100% for sesquiterpene with initial hydrocarbon of 100 ppb (Hoffmann et al).

  8. Particle Size Distribution at Tunnel Inlet * Source: Preliminary results from HEI Project 98-3 courtesy of Dr.Fred Rogers, Desert Research Institute.

  9. Particle Size Distribution in Background AirTuscarora Tunnel * Source: Preliminary results from HEI Project 98-3 courtesy of Dr. Fred Rogers, Desert Research Institute.

  10. Particle Size Distribution at Tunnel Outlet * Source: Preliminary results from HEI Project 98-3 courtesy of Dr. Fred Rogers, Desert Research Institute.

  11. Carbon Source Profiles Gasoline-fueled vehicles Diesel-fueled vehicles

  12. Organic Carbon Distributions in Source and Ambient Samples

  13. Ozone Formation Chemistry O HCHO, RCHO 3 n h NO 2 CO, VOC PAN RO 2 HO H O 2 2 HO 2 ROOH from HNO HO 3 2 from RO 2 NO NO 2 n h O 3 Low ROG/NOx NO2 + h = O + NO O + O2 + M = O3 + M O3 + NO = NO2 + O2 High ROG/NOx

  14. Desert Research Institute, 11/16/99

  15. Trends in Federal 1-Hr Exceedances 80s 90s

  16. NO2* = NOx-NO

  17. Chemical Mass BalanceReceptor Model Fundamentals

  18. Chemical Mass Balance • Equation: • Input: • Ambient concentrations (Cj)and uncertainties (sCj),source composition (Fij),and uncertainties (sFij). • Output: • Source contributions (Sj)and uncertainties (sSj). • Measurements: • Size-classified mass, elements, ions, and carbon concentrations on both ambient and source samples.

  19. Source Contribution Estimates SOURCE CONTRIBUTION ESTIMATES - SITE: WELBY DATE: 01/17/97 CMB8(97350) SAMPLE DURATION 6 START HOUR 06 SIZE: F R SQUARE .92 PERCENT MASS 92.9 CHI SQUARE .61 DF 71 B and L: No SRC ELIM: No WEIGHTS: CHISQR 1.000 R SQR 1.000 PCMASS 1.000 FRCEST 1.000 SOURCE EST CODE NAME SCE(UG/M3) STD ERR TSTAT ---------------------------------------------------- YES N001 NVNSP 3.32177 2.04933 1.62090 Cold Start Gas YES N007 NVNSP2 .92356 .41105 2.24682 Normal Gas YES N010 NVSM 6.60239 3.71219 1.77857 High Emitter Gas YES N013 NWHD 7.21937 1.83529 3.93364 Diesel YES N050 NMc 1.87745 2.01630 .93114 Meat Cooking YES N055 NWFSc .81366 .47104 1.72739 Softwood Burning YES N067 NWSHc2 2.44912 1.30503 1.87668 Hardwood Burning YES N074 NRDC 5.53905 1.55074 3.57188 Dust YES N082 AMSUL 6.82026 .82871 8.22998 Ammonium Sulfate YES N084 AMNIT 13.69944 1.33690 10.24715 Ammonium Nitrate YES N124 PCHCLC1 .04272 1.19172 .03585 Coal Power Station ---------------------------------------------------- MEASURED CONCENTRATION FOR SIZE: F 53.1+- 2.7

  20. Ambient Concentrations SPECIES CONCENTRATIONS - SITE: WELBY DATE: 01/17/97 CMB 8.0 SAMPLE DURATION 6 START HOUR 06 SIZE: F R SQUARE .92 PERCENT MASS 92.9 CHI SQUARE .61 DF 71 SPECIES-------I---MEAS------------------CALC-------------RATIO C/M----RATIO R/U MSGC MSGU 53.08030+- 2.70112 49.30879+- 2.75460 .93+- .07 -1.0 CLIC CLIU .45540+- .05500 .16968+- .14611 .37+- .32 -1.8 N3IC N3IU * 10.48780+- .69455 10.67327+- 1.06226 1.02+- .12 .1 S4IC S4IU * 5.03660+- .39970 5.09780+- .50206 1.01+- .13 .1 N4CC N4CU * 5.04460+- .26760 4.96042+- .37563 .98+- .09 -.2 KPAC KPAU * .06260+- .00540 .02144+- .10408 .34+- 1.66 -.4 TCTC TCTU 21.55080+- 1.38265 21.47490+- .56656 1.00+- .07 -.1 OCTC OCTU * 13.42380+- 1.14530 13.44489+- .85198 1.00+- .11 .0 ECTC ECTU * 8.12700+- .77460 8.03003+- .93283 .99+- .15 -.1 NAXC NAXU * .07980+- .04150 .10208+- .09784 1.28+- 1.39 .2 MGXC MGXU * .01450< .04340 .04659< .06822 3.21< 10.71 .4 ALXC ALXU * .13630+- .01320 .31693+- .18586 2.33+- 1.38 1.0 SIXC SIXU * .52050+- .02830 1.01873+- .45401 1.96+- .88 1.1 PHXC PHXU * .00000< .01640 .00782< .06720 .00< .00 .1 SUXC SUXU 2.05200+- .10310 1.74534+- .16945 .85+- .09 -1.5 CLXC CLXU * .34080+- .02290 .18274+- .13900 .54+- .41 -1.1 KPXC KPXU * .12110+- .00820 .14971+- .06074 1.24+- .51 .5 CAXC CAXU * .21120+- .01240 .16502+- .09707 .78+- .46 -.5

  21. MPIN Matrix TRANSPOSE OF SENSITIVITY MATRIX FOR SITE: WELBY DATE: 01/17/97 DURATION: 6 , START HOUR: 06, SIZE: F SPECIES NVNSP NVNSP2 NVSM NWHD NMc NWFSc NWSHc2 NRDC AMSUL AMNIT PCHCLC N3IU .00 .00 .01 .00 .00 .00 .00 -.03 -.26 1.00 .04 S4IU .00 .00 .01 .00 .00 .00 .00 -.02 1.00 -.33 .03 N4CU .00 .00 -.01 .00 .00 .00 .00 .04 .33 .63 -.05 OCTU -.26 -.40 .97 .01 .03 -.01 .01 -.01 .00 .00 .00 ECTU .06 -.08 -.04 1.00 -.18 -.02 .01 -.03 -.01 .00 .00 NAXU .00 .02 -.03 .02 .00 .00 -.01 .43 .02 -.01 -.15 MGXU -.02 .04 .00 .03 -.01 .00 .00 .25 .01 .00 -.09 ALXU .00 .01 -.02 -.01 .00 .01 -.01 .46 -.03 .01 .13 SIXU .00 .01 -.02 .01 -.02 .01 -.02 .87 .01 -.01 -.13 KPXU .02 .04 -.14 -.01 .04 -.03 .07 1.00 .04 -.01 -.28 PHENAN .40 .27 -.32 -.16 .12 -.07 .06 -.01 .00 .00 .00 FLUORE 1.00 -1.00 -.22 -.36 .03 -.03 -.04 .00 .00 .00 -.01 A_MFLU .42 -.31 .12 -.18 -.11 .01 -.07 -.01 .00 .00 .00 M_1FLU .33 -.19 .05 -.13 -.08 -.01 -.02 -.01 .00 .00 .00 B_MFLU .17 -.12 .10 -.07 -.08 .00 -.02 -.01 .00 .00 .00 C_MFLU -.27 .87 .17 .06 -.08 .00 .01 -.02 .00 .00 .00 A_MPHT -.10 .72 -.01 .02 .00 .00 -.01 -.01 .00 .00 .00 RETENE -.01 -.01 .02 -.01 .00 .17 -.06 .00 .00 .00 .00 GNONLA .18 .43 -1.00 .01 1.00 .00 -.04 -.05 .00 .00 .02 F4GUCL .31 -.38 -.11 -.12 .04 .42 -.07 .00 .00 .00 .00 M4SYRG -.03 .20 -.47 .05 -.05 -.78 1.00 -.08 -.01 .00 .03 E4SYRG -.02 .09 -.21 .02 -.03 -.32 .46 -.04 -.01 .00 .01 ISOEUG -.06 .00 -.01 -.04 -.01 1.00 -.11 .00 .00 .00 .00

  22. Volatile Organic Compound (VOC) Ambient Data, Source Profilesand Source Apportionment

  23. Examples of atmospheric organic species (Seinfeld and Pandis, 1998)

  24. 55 Photochemical Assessment Monitoring Stations (PAMS) compounds

  25. Hydrocarbon Sampling and Speciation • C2 – C10 (canister) • C11 – C20 (Tenax) • Semivolatile PAH (filter/PUF/XAD) • Carbonyl (DNPH-coated C18 cartridge) • Oxygenated compounds (e.g., alcohol, ethers, esters) (Carbotrap canister)

  26. LD/HD Speciated Emissions

  27. LD/HD Fuel-Specific Emissions Data courtesy of J. Sagebiel

  28. Dallas Austin San Antonio Houston 1998 Central Texas On-Road Hydrocarbon StudyVOC Ambient and Source Measurement Sites Audubon North Austin San Marcos Central Austin South Austin * Sampling on Sunday, Monday, Wednesday, Friday, and Saturday. On-road samples - congested freeway and morning downtown traffic On-road samples - free-flow freeway and afternoon surface streets Industrial source areas McKinney Falls State Park

  29. Wind-Directional Dependence of Source Contributions by Time of the Day at Clinton site (wt%).

  30. Hourly Source Contributions, O3, and Meteorological Data - Galleria

  31. Particulate Matter Ambient Data, Source Profilesand Source Apportionment

  32. Commonly Applied Chemical Analysis Methods

  33. Commonly Applied Chemical Analysis Methods (continued)

  34. NFRAQS Winter 1996-97 NFRAQS Field StudyIntermittent Aerosol Sampling and Analysis

  35. Important Emissions Characteristics • Emissions Rate:Amount emitted per unit. • Particle Size:Determines deposition properties and which particles can enter the human lung. • Chemical Composition:Fractional abundance of different chemical elements and compounds in emissions. Used to apportion ambient concentrations to sources and to evaluate health effects. • Temporal Variation:Emissions change on daily, weekly, seasonal, and annual cycles. The timing of emissions affects their transport, dilution, and human exposure to outdoor air pollution.

  36. Current Measurement Methods • In-Stack Sampling: Hot or diluted, best for ducted sources. • Dynamometer Testing of Vehicles: Can obtain full chemical speciation, but number of vehicles tested is limited and conditions are contrived. • Upwind/Downwind Sampling: Used for fugitive dust and roadway sources. Makes simple, and not always valid, assumptions about dispersion and dilution. • Laboratory Dust Suspension: Good for chemical characterization, but does not measure emission rate.

  37. Chemicals from Different Particles in Emissions Sources

  38. Chemicals from Different Particles in Emissions Sources (continued)

  39. Size Distributions of Several Particulate Source Emissions

  40. NFRAQS NFRAQS Source Composition ProfilesSource Categories and Associated Marker Species

  41. Gas- and Particle-Phase Distribution of PAHsClark and Washoe County Remote Sensing Study (CWCRRS) Data courtesy of J. Sagebiel

  42. Hopanes and Steranes:

  43. Lactones and Sterols:

  44. NFRAQS Meat Cooking Marker SpeciesWeight Fraction of Lactones and Sterols DRI - 10/97

  45. Application of Ambient Measurements in the Evaluation of Emission Inventory Estimates

  46. On-Road Motor Vehicle Emissions by EMFAC VersionsSouth Coast Air Basin, 1990 Inventory Year

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