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

Transcription

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

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 2

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 3

4 PM 2.5 In Ambient Air - A Complex Mixture 4

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 ) 5

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 6

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 7

8 PM 2.5 Composition Varies Across U.S. Northwest Midwest Southeast Sulfate Nitrate EC OC Crustal 8

9 Urban (EPA STN) Annual Averages Sep 2001-Aug

10 Mid-Atlantic Area Air Quality in More Detail Maryland Baltimore County Kentucky Pennsylvania Allegheny Co Northampton County Lancaster County Delaware County Philadelphia County 10

11 Composition of PM 2.5 in Baltimore Co, MD BALTIMORE

12 Composition of PM 2.5 in Allegheny Co, PA PITTSBURGH

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

14 Composition of PM 2.5 in Lancaster Co, PA LANCASTER

15 Composition of PM 2.5 in Delaware Co, PA PHILADELPHIA

16 Composition of PM 2.5 in Philadelphia Co, PA PHILADELPHIA

17 Composition AND Urban Excess 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 ENFI

18 Urban Excess Concept in Mid-Atlantic Excess of OC and Nitrate PM 2.5 (esp in Winter) in Urban Areas of Mid Atlantic 18

19 Urban Excess in Atlanta, GA Atlanta, GA / Ring of Rural Locations 10 8 Bottom: Regional Contribution Top: Urban Excess ( + ) Draft Analysis Rural Monitors used for Comparison ug/m Sulfate Est. Ammonium Nitrate EC+OC Crustal 19

20 What are the Key Source Types Emitting PM 2.5 and it s Precursors (Nationally)? 2005 Nat l Emissions (1000 short tons) Source Category PM2.5 NH3 NOx SO2 VOC FUEL COMB. ELEC. UTIL ,856 10, FUEL COMB. INDUSTRIAL ,042 1, FUEL COMB. OTHER ,375 CHEMICAL & ALLIED PRODUCT MFG METALS PROCESSING PETROLEUM & RELATED INDUSTRIES OTHER INDUSTRIAL PROCESSES SOLVENT UTILIZATION ,278 STORAGE & TRANSPORT ,484 WASTE DISPOSAL & RECYCLING HIGHWAY VEHICLES , ,078 OFF-HIGHWAY , ,858 MISCELLANEOUS 3,256 3, ,970 TOTAL 5,536 4,143 18,711 14,714 19,976 20

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 21

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 22

23 Mid-Atlantic Area 2005 PM 2.5 Emissions (TPY) STATE PM2.5 VOC* NOx SO2 NH3 Delaware 8,537 34,807 54,832 85,174 14,045 Dist. of Columbia 1,445 10,706 14,588 3, Maryland 57, , , ,313 31,814 New Jersey 31, , , ,433 15,221 N Carolina 129, , , , ,581 Pennsylvania 147, , ,499 1,181,249 94,066 Virginia 98, , , ,669 58,246 W Virginia 64, , , ,392 14,216 Totals 538,774 2,273,962 2,565,821 3,285, ,640 Note: Anthropogenic VOC (Biogenic VOC > Anthropogenic VOC in Mid Atlantic, SE US) 23

24 Mid-Atlantic Area 2005 PM 2.5 Emissions (TPY) STATE Paved Roads Construction Agricultural Tilling Unpaved Roads Delaware Dist. of Columbia Maryland 923 3,799 2, New Jersey N Carolina 5,497 3,867 10,287 2,340 Pennsylvania 5,418 7,732 7,555 8,316 Virginia 2,965 3,115 2,713 5,842 W Virginia 1,067 2, ,201 Total 16,873 21,816 23,813 21,191 24

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 Delaware ,228 Dist. of Columbia Maryland ,481 8,194 New Jersey ,361 N Carolina 6,788 9,619 7,868 10,473 Pennsylvania 0 2,489 7,016 10,283 Virginia 0 5,727 5,007 9,880 W Virginia 0 3,642 3,017 3,025 Total 6,992 22,162 30,463 52,528 Note: Extent of Ag Biomass Waste Burning is not fully understood 25

26 Let s Talk More About Crustal and Carbon 26

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) 27

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 28

29 Carbonaceous Material Matter Ratio of OC to EC changes with source Mobile Sources Gas: 5-15 Mobile Sources Diesel: 0.4 Open Fires: Residential Wood Burning: 7-8 Fugitive Dust: Hannaford

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) = (depends on aging, other factors) 30

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 31

32 Extra Information for Use in Understanding Precursor Importance in Particle Formation More about Precursor Interrelationships (NH4)2SO4 NH4NO3 32

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 33

34 Review: PM 2.5 In Ambient Air - A Complex Mixture NH4NO3 34

35 Review of Important PM 2.5 Source Categories DIRECT EMISSIONS PRECURSOR EMISSIONS Combustion a, b Open Burning (all types) Non-Road & On-Road Mobile Residential Wood Burning Wildfires Power Gen Boilers (Oil, Gas, Coal) Boilers (Wood) Crustal / Metals b Fugitive Dust Mineral Prod Ind Ferrous Metals SO 2 c Power Gen (Coal) Boilers (Coal) Power Gen (Oil) Boilers (Oil) Industrial Processes NO x On-Road Mobile (Gas, Diesel) Power Gen (Coal) Non-Road Mobile (Diesel) Boilers (Gas, Coal) Residential (Gas, Oil) Industrial Processes NH 3 On-Road Mobile Animal Husbandry Fertilizer Application Wastewater Treatment Boilers VOCd Biogenics Solvent use On-Road (Gas) Storage and Transport Residential Wood Petrochemical Industry Waste Disposal a b c d Includes primary organic particles, elemental carbon and condensible organic particles; also some flyash Impact of carbonaceous emissions on ambient PM 5 to 10 times more than crustal emissions impact Includes SO2, and SO3 and H2SO4 condensible inorganics Contributes to formation of secondary organic aerosols NOTE: Categories in BOLD are most important nationally. Their relative importance varies among and between urban and rural areas. 35

36 Questions? Typical Haze in the Blue Ridge Mountains TPace