preparation of fine particulate emissions inventories

Preparation of Fine Particulate Emissions

Inventories Lesson 1

Introduction to Fine Particles (PM 2.5 )

2Preparation of Fine Particulate Emissions Inventories

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


Why is This Information Important?

This information

– puts the local inventory efforts in perspective,

– shows how source types fit into the overall accounting of PM2.5

– provides a foundation for setting inventory priorities in your area


PM2.5 In Ambient Air - A Complex Mixture


PM2.5 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 ~ H2SO4 (condensed), (NH4)HSO4 (NH4)2SO4

– Nitrate ~ NH4NO3

– 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 PM2.5)


Why is Ambient Composition Important?

Identifying important source types on days with high PM2.5 concentration

Help prioritize inventory efforts– Carbonaceous vs. Crustal

– Sulfate vs. Nitrate

– Role of Ammonia

Help in benchmarking the validity of the EI


PM2.5 Composition (cont’d)

Other characteristics: Sulfate, Carbon & NO3

– 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 NH3


PM2.5 Composition Varies Across U.S.

NorthwestMidwest

Southeast

Sulfate Nitrate EC OC Crustal


Urban (EPA STN) Annual AveragesSep 2001-Aug 2002


Mid-Atlantic Area Air Quality in More Detail

• Maryland

• Baltimore County

• Kentucky

• Pennsylvania

• Allegheny Co

• Northampton County

• Lancaster County

• Delaware County

• Philadelphia County

Composition of PM2.5 in Baltimore Co, MD

BALTIMORE240053001

Composition of PM2.5 in Allegheny Co, PA

PITTSBURGH420030008

Composition of PM2.5 in Northampton Co, PA

BETHLEHAM420950025

Composition of PM2.5 in Lancaster Co, PA

LANCASTER420710007

Composition of PM2.5 in Delaware Co, PA

PHILADELPHIA420450002

Composition of PM2.5 in Philadelphia Co, PA

PHILADELPHIA421010004


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


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


Rural Monitors used for

Comparison( + ) Draft Analysis

Sulfate Est. Ammonium Nitrate EC+OC Crustal0

2

4

6

8

10

ug/m

3

Atlanta, GA / Ring of Rural Locations

Bottom: Regional ContributionTop: Urban Excess

“Urban Excess” in Atlanta, GA


What are the Key Source Types Emitting PM2.5 and it’s Precursors (Nationally)?

19,97614,71418,7114,1435,536TOTAL

3,9701352113,5393,256MISCELLANEOUS

2,8585164,4033292OFF-HIGHWAY

4,0781456,407307127HIGHWAY VEHICLES

3952611126268WASTE DISPOSAL & RECYCLING

1,484519123STORAGE & TRANSPORT

4,2780707SOLVENT UTILIZATION

442327429177354OTHER INDUSTRIAL PROCESSES

601257354318PETROLEUM & RELATED INDUSTRIES

4621369354METALS PROCESSING

249259702330CHEMICAL & ALLIED PRODUCT MFG

1,37557873317421FUEL COMB. OTHER

1521,7842,04217178FUEL COMB. INDUSTRIAL

4810,4693,85627508FUEL COMB. ELEC. UTIL.

VOCSO2NOxNH3PM2.5Source Category

2005 Nat’l Emissions (1000 short tons)


Overview of PM2.5 Sources in NE U.S.

• PM2.5 (OC, EC, Ammonium Nitrate and Sulfate, Crustal)

• Open Fires (primary OC, EC, VOC, NOx & NH3)

• Open burning, land clearing debris, prescribed fires

• Motor Vehicles (NOx, VOC, NH3, OC, EC)

• Non road emissions (NOx, VOC, NH3, OC, EC)

• aircraft, lawn, construction, and agricultural equipment.

• Residential Wood Combustion (OC, EC, VOC)

• Boilers (OC, EC, VOC, NOx, SO2, some crustal)

• Fugitive Dust (mostly crustal, some OC, EC)

• More ~ Anti-skid sanding, Construction

• Lesser ~ Agriculture, unpaved roads, windblown dust


Overview of PM2.5 Sources in NE U.S.

• PM2.5 (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


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 3,914 450

Maryland 57,400 224,255 273,777 381,313 31,814

New Jersey 31,135 295,479 294,775 101,433 15,221

N Carolina 129,390 605,757 522,620 650,560 173,581

Pennsylvania 147,592 560,136 677,499 1,181,249 94,066

Virginia 98,964 405,053 436,358 345,669 58,246

W Virginia 64,310 137,768 291,372 536,392 14,216

Totals 538,774 2,273,962 2,565,821 3,285,703 401,640

Note: Anthropogenic VOC (Biogenic VOC > Anthropogenic VOC in Mid Atlantic, SE US)



STATEPaved Roads Construction

Agricultural Tilling

Unpaved Roads

Delaware 168 352 262 0

Dist. of Columbia 28 383 0 0

Maryland 923 3,799 2,608 63

New Jersey 807 118 38 428

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 2,451 349 4,201

Total 16,873 21,816 23,813 21,191



STATEAgricultural

Burning*

Residential Waste - Open

Burning

Land Clearing Debris -

Open Burning

Residential Wood

Combustion

Delaware 0 42 74 1,228

Dist. of Columbia 0 0 0 84

Maryland 0 611 7,481 8,194

New Jersey 204 32 0 9,361

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


Let’s Talk More About Crustal and Carbon


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)


Speciation of Crustal

“Speciation” ~ process of estimating the components of the sample, e.g., crustal by using the chemical characteristics of the sample:

Crustal% = C1Al% + C2Ca% + C3Si% +C4Fe% + C5Ti%

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


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


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)


Organic Carbon “Matter” (OCM) Emissions

Aerosol Aging and Secondary Formation: – 2 aging / formation processes:

1st – particles oxidize as they “age”

2nd – 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”


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


Review: PM2.5 In Ambient Air - A Complex Mixture

NH4NO3


Review of Important PM2.5 SourceCategories

Combustion a, b

Open Burning (all types)Non-Road & On-Road MobileResidential Wood BurningWildfiresPower Gen Boilers (Oil, Gas, Coal)Boilers (Wood)

Crustal / Metals b

Fugitive DustMineral Prod IndFerrous Metals

SO2 c

Power Gen (Coal)Boilers (Coal)Power Gen (Oil)Boilers (Oil)Industrial Processes

NOx

On-Road Mobile (Gas, Diesel)Power Gen (Coal)Non-Road Mobile (Diesel)Boilers (Gas, Coal)Residential (Gas, Oil)Industrial Processes

NH3

On-Road MobileAnimal HusbandryFertilizer ApplicationWastewater TreatmentBoilers

VOC d

BiogenicsSolvent useOn-Road (Gas)Storage and TransportResidential WoodPetrochemical IndustryWaste Disposal

DIRECT EMISSIONS

a Includes primary organic particles, elemental carbon and condensible organic particles; also some flyashb Impact of carbonaceous emissions on ambient PM 5 to 10 times more than crustal emissions impactc Includes SO2, and SO3 and H2SO4 condensible inorganicsd Contributes to formation of secondary organic aerosols

PRECURSOR EMISSIONS

NOTE: Categories in BOLDare most important nationally. Their relative importance varies among and between urban and rural areas.


Questions?

Typical Haze in the Blue Ridge Mountains

TPace 2009

preparation of fine particulate emissions inventories

Documents

fine particles pm

high pm2

composition contd

ambient composition

overall accounting of

ocorganic matter

crustal matter

important source types