1. Preparation of Fine Particulate Emissions Inventories Lesson 1 Introduction to Fine Particles (PM 2.5 )

2. Preparation of Fine Particulate Emissions Inventories 2 What will We Discuss in Lesson 1?  After this lesson, participants will be able to describe: –the general composition of fine particulate matter in the atmosphere –how fine particulate matter are formed – typical composition of ambient air in 2 western areas –sources that contribute to the formation of fine particulate matter, nationally and in this area

3. Preparation of Fine Particulate Emissions Inventories 3 Why is This Information Important?  This information –puts the local inventory efforts in perspective, –shows how source types fit into the overall accounting of PM 2.5 –provides a foundation for setting inventory priorities in your area

4. Preparation of Fine Particulate Emissions Inventories 4 PM 2.5 In Ambient Air - A Complex Mixture

5. Preparation of Fine Particulate Emissions Inventories 5 PM 2.5 Composition  Definitions –Crustal ~ Metallic oxides in earth’s crust –Fugitive Dust ~ Crustal matter emitted into the air directly, not thru a stack or vent. –Sulfate ~ H 2 SO 4 (condensed), (NH 4 )HSO 4 (NH 4 )2SO 4 –Nitrate ~ NH 4 NO 3 –Organic Carbon ~ OC –Organic Matter ~ OC + the associated O & H –Elemental Carbon ~ EC –Primary ~ Directly emitted –Secondary ~ Formed in air from precursor gases (generally considered to be all PM 2.5 )

6. Preparation of Fine Particulate Emissions Inventories 6 Why is Ambient Composition Important?  Identifying important source types on days with high PM 2.5 concentration  Help prioritize inventory efforts –Carbonaceous vs. Crustal –Sulfate vs. Nitrate –Role of Ammonia  Help in benchmarking the validity of the EI

7. Preparation of Fine Particulate Emissions Inventories 7 PM 2.5 Composition (cont’d)  Other characteristics: Sulfate, Carbon & NO 3 –Sulfate forms slowly, over long distances –Sulfate patterns relatively “flat” over large regions. –Regionally disbursed sources –Carbon has both regional & urban components –High Nitrate concentrations are usually  more localized  tend to form in urban areas, or  where abundance of animal or fertilizer NH 3

8. Preparation of Fine Particulate Emissions Inventories 8 PM 2.5 Composition Varies Across U.S. Northwest Midwest Southeast Sulfate Nitrate EC OC Crustal

9. Preparation of Fine Particulate Emissions Inventories 9 Urban (EPA STN) Annual Averages Sep 2001-Aug 2002

10. Preparation of Fine Particulate Emissions Inventories 10 Mid-Atlantic Area Air Quality in More Detail Maryland Baltimore County Kentucky Pennsylvania Allegheny Co Northampton County Lancaster County Delaware County Philadelphia County

11. Composition of PM 2.5 in Baltimore Co, MD BALTIMORE 240053001

12. Composition of PM 2.5 in Allegheny Co, PA PITTSBURGH 420030008

13. Composition of PM2.5 in Northampton Co, PA BETHLEHAM 420950025

14. Composition of PM 2.5 in Lancaster Co, PA LANCASTER 420710007

15. Composition of PM 2.5 in Delaware Co, PA PHILADELPHIA 420450002

16. Composition of PM 2.5 in Philadelphia Co, PA PHILADELPHIA 421010004

17. Preparation of Fine Particulate Emissions Inventories 17  Components of PM are higher in the urban area than in the surrounding area  Urban Excess is that part of the urban AQ that is higher than in surrounding areas  Simplistically, urban excess is assumed mostly associated with urban sources Composition AND Urban Excess ENFI 2007

18. Preparation of Fine Particulate Emissions Inventories 18 Urban Excess Concept in Mid-Atlantic http://www.cambridge.org/us/catalogue/catalogue.asp?isbn=0521842875 Excess of OC and Nitrate PM 2.5 (esp in Winter) in Urban Areas of Mid Atlantic

19. Preparation of Fine Particulate Emissions Inventories 19 Rural Monitors used for Comparison ( + ) Draft Analysis SulfateEst. AmmoniumNitrateEC+OCCrustal 0 2 4 6 8 10 ug/m3 Atlanta, GA / Ring of Rural Locations Bottom: Regional Contribution Top: Urban Excess “Urban Excess” in Atlanta, GA

20. Preparation of Fine Particulate Emissions Inventories 20 What are the Key Source Types Emitting PM 2.5 and it’s Precursors (Nationally)?

21. Preparation of Fine Particulate Emissions Inventories 21 Overview of PM 2.5 Sources in NE U.S. PM 2.5 (OC, EC, Ammonium Nitrate and Sulfate, Crustal) Open Fires (primary OC, EC, VOC, NO x & NH 3 ) Open burning, land clearing debris, prescribed fires Motor Vehicles (NO x, VOC, NH 3, OC, EC) Non road emissions (NO x, VOC, NH 3, OC, EC) aircraft, lawn, construction, and agricultural equipment. Residential Wood Combustion (OC, EC, VOC) Boilers (OC, EC, VOC, NOx, SO 2, some crustal) Fugitive Dust (mostly crustal, some OC, EC) More ~ Anti-skid sanding, Construction Lesser ~ Agriculture, unpaved roads, windblown dust

22. Preparation of Fine Particulate Emissions Inventories 22 Overview of PM 2.5 Sources in NE U.S. PM 2.5 (Crustal, OC, EC, Ammonium Nitrate) Misc VOC Sources (precursor to secondary OC) household and industrial products, such as paints and varnishes, cleaners, disinfectants, and degreasers. Fuel combustion and the handling and distribution of fuel Dairies and other livestock waste Open Burning and Prescribed fires Misc Ammonia Sources (precursor to ammonium nitrate) Livestock wastes from dairies and agricultural operations

23. Preparation of Fine Particulate Emissions Inventories 23 Mid-Atlantic Area 2005 PM 2.5 Emissions (TPY) STATEPM2.5VOC*NOxSO2NH3 Delaware8,53734,80754,83285,17414,045 Dist. of Columbia1,44510,70614,5883,914450 Maryland57,400224,255273,777381,31331,814 New Jersey31,135295,479294,775101,43315,221 N Carolina129,390605,757522,620650,560173,581 Pennsylvania147,592560,136677,4991,181,24994,066 Virginia98,964405,053436,358345,66958,246 W Virginia64,310137,768291,372536,39214,216 Totals538,7742,273,9622,565,8213,285,703401,640 Note: Anthropogenic VOC (Biogenic VOC > Anthropogenic VOC in Mid Atlantic, SE US)

24. Preparation of Fine Particulate Emissions Inventories 24 Mid-Atlantic Area 2005 PM 2.5 Emissions (TPY) STATE Paved RoadsConstruction Agricultural Tilling Unpaved Roads Delaware1683522620 Dist. of Columbia2838300 Maryland9233,7992,60863 New Jersey80711838428 N Carolina5,4973,86710,2872,340 Pennsylvania5,4187,7327,5558,316 Virginia2,9653,1152,7135,842 W Virginia1,0672,4513494,201 Total16,87321,81623,81321,191

25. Preparation of Fine Particulate Emissions Inventories 25 Mid-Atlantic Area 2005 PM 2.5 Emissions (TPY) STATE Agricultural Burning* Residential Waste - Open Burning Land Clearing Debris - Open Burning Residential Wood Combustion Delaware042741,228 Dist. of Columbia00084 Maryland06117,4818,194 New Jersey2043209,361 N Carolina6,7889,6197,86810,473 Pennsylvania02,4897,01610,283 Virginia05,7275,0079,880 W Virginia03,6423,0173,025 Total6,99222,16230,46352,528 Note: Extent of Ag Biomass Waste Burning is not fully understood

26. Preparation of Fine Particulate Emissions Inventories 26 Let’s Talk More About Crustal and Carbon

27. Preparation of Fine Particulate Emissions Inventories 27 Crustal Material – Sources & Composition  Fugitive Dust ~ Main source of Crustal –Unpaved roads –Anti-skid materials on paved roads –Agricultural tilling, dairies –Wind-blown dust –Construction  Fly ash  Composition of Fugitive Dust ~ a mixture of: –“earth oxides” (e.g., oxides of Ca, Al, Si, Fe & Ti) –carbonaceous material (EC, OCM)

28. Preparation of Fine Particulate Emissions Inventories 28 Speciation of Crustal  “Speciation” ~ process of estimating the components of the sample, e.g., crustal by using the chemical characteristics of the sample: Crustal% = C1  Al% + C2  Ca% + C3  Si% +C4  Fe% + C5  Ti% where Al%, Ca%, Si%, Fe% & Ti% are these species % of the sample’s mass  Speciation can be done on both ambient measurements AND emissions  More about emissions speciation later

29. Preparation of Fine Particulate Emissions Inventories 29 Carbonaceous Material – “Matter”  Ratio of OC to EC changes with source –Mobile Sources Gas: 5 - 15 –Mobile Sources Diesel: 0.4 –Open Fires: 10 - 12 –Residential Wood Burning: 7 - 8 –Fugitive Dust: 15 - 25 Hannaford 2009

30. Preparation of Fine Particulate Emissions Inventories 30 Organic Carbon “Matter” (OCM) Emissions  “Matter” is the O and H that are part of the OC molecule –The OC measurement must be “augmented” to account for the “matter”  Augmentation of Primary (Fresh) Emissions – augmentation done using a multiplier – – OCM = C * OC – C(E) = 1.2 to 1.8 (depending on source type) – C(E) applied in Emissions processor *C(E) values documented in Reff 2009  Augmenting Aged Aerosol -- C(E) = 1.8 - 2.4 (depends on aging, other factors)

31. Preparation of Fine Particulate Emissions Inventories 31 Organic Carbon “Matter” (OCM) Emissions  Aerosol Aging and Secondary Formation: –2 aging / formation processes:  1 st – particles oxidize as they “age”  2 nd – additional “secondary” particles form –AQ Models age the aerosols and account for the formation of secondary organic carbon –In ambient aerosols, the C(A) can be as high as 2.4  ambient OC includes secondary formation (which has a high matter content) and  aerosol aging by oxidation, which adds O and H “matter”

32. Preparation of Fine Particulate Emissions Inventories 32 Extra Information for Use in Understanding Precursor Importance in Particle Formation More about Precursor Interrelationships NH4NO3 (NH4)2SO4

33. Preparation of Fine Particulate Emissions Inventories 33 Let’s Review and Summarize  A Complex Mixture –Speciated Ambient Data –Composition –Primary vs. Secondary  Key Sources –Composition by source type –Directly emitted vs. precursors

34. Preparation of Fine Particulate Emissions Inventories 34 Review: PM 2.5 In Ambient Air - A Complex Mixture NH4NO3

35. Preparation of Fine Particulate Emissions Inventories 35 Review of Important PM 2.5 Source Categories

36. Preparation of Fine Particulate Emissions Inventories 36 Questions? Typical Haze in the Blue Ridge Mountains TPace 2009