Character of Baltimore PM as derived from detailed ... · • Atmospheric Chemistry • Source/Receptor Reconciliation ... Alkanoic Acids (C24,C26,C28,C30,C32) ... Major Organic Compounds

2006 National Air Monitoring Conference – Nov.6-9 in Las Vegas – PM Supersite Baltimore – Wolfgang F. Rogge, Ph.D, P.E., FIU, Miami, FL

Character of Baltimore PMas derived from detailed Characterization

ofMolecular Organic Source Markers

in 3-hr Samples

Wolfgang F. Rogge, Ph.D., P.E.

[email protected]

Department of Civil & Environmental Engineering

College of Engineering and Computing

Florida International University, Miami, FL


Problem:

No knowledge available about the diurnal concentration patterns and dynamics of organic compounds associated with PM2.5

Time resolved data needed for:

Approach:

• Design and test sequential multi-channel PM2.5 sampler

• 3-Hourly sampling with Filter/PUF in Baltimore during a Summer 2002 and Winter 2002/2003

• Analyze Filter and PUF for organic constituents using GC/MS

• Health Effects Studies

• Atmospheric Chemistry

• Source/Receptor Reconciliation

• Regional Scale Atmospheric Transport Modeling

2006 National Air Monitoring Conference – Nov.6-9 in Las Vegas – PM Supersite Baltimore – Wolfgang F. Rogge, Ph.D, P.E., FIU, Miami, FLMass Flowmeter

Primary Pump

Pressure Gauges

Leak Test Pump

Trailer Roof

Marple

PM2.5 Inlet

Impactor

P

U

F

P

U

F

P

U

F

P

U

F

P

U

F

Filter Holder: Ø 125 mm

2” Electric Actuated Ball Valve

PUF Holder: Ø 103 mm, L=25cm

2 meter

Ceiling

Sequential Control Module

Electronic Timer

Leak Test Air Outlet

2” Electric Actuated Ball Valve

System for 3-Hourly PM2.5 Sampling

Air Condition


Major Organic Source Marker

Cigarette SmokeIso-, Anteiso-Alkanes

(>C26)

Burning of Vegetative Detritus, Soil Dust, Vegetarian CookingLeaf Surface Waxes

Odd-Carbon n-Alkanes (>C25)

Even-Carbon n-Alkanoic Acids (>C23)

Heavy Oil BurningVehicular Emissionn-Alkanes (< C25)

Alkylcyclohexanes, PAHs

Hopanes & Steranes

Phytosterol:

ß-Sitosterol, Stigmasterol, Campesterol

Saccharides

Palmitic & Stearic Acids

Palmitoleic & Oleic Acids

Source Indicators

Wildfires, Forest Fires

Fugitive Dust from Cultivated Land

Saccharides: Mycose, Sucrose, α-, β-Glucose

Hard Wood LigninSyringyl Derivatives

Soft Wood BurningResin Acids

Biomass Burning (Cellulose)Levoglucosan

Meat CookingCholesterol

Plastic Waste BurningEven-Carbon n-Alkanes

Associated SourcesMajor Source TypeSource Markers


Monoterpens: e.g. α-& β-Pinene

O3

OH·

NO3·

Secondary Organic Aerosol:

e.g.:•Nopinone• Norpinic Acid• Norpinonic Acid• Pinonic Acid• Pinic Acid

Primary Organic Aerosol:

Biogenic Aerosol Sources

e.g.: • Waxy Substances

e.g.: • Biopolymer Breakdown• Resin Acids• PAHs• Waxy Substances• Phytosterols• Sugars

e.g.: • Waxy Substances• Sugars (Mycose)• Phytosterols• Triterpenoids


Particulate (PM2.5) Leaves Surface Abrasion Products

Carbon Number

0

1 0 0 0

2 0 0 0

3 0 0 0

4 0 0 0

5 0 0 0

6 0 0 0

7 0 0 0

8 0 0 0

9 0 0 0

1 0 0 0 0

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Green Leaves

Dead Leaves

0

5 0 0

1 0 0 0

1 5 0 0

2 0 0 0

2 5 0 0

3 0 0 0

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Green Leaves

Dead Leaves

n-Alkanes

n-Alkanoic Acids

1 µm

Particle

Leaf SurfaceSources: Waxes on Leaf Surfaces, Burning of Vegetative Detritus, Soil Dust, Vegetarian Cooking

2006 Nationa

l Air M

onitoring Confe

rence

–Nov.6

-9 in L

as V

egas –

PM Supe

rsite Baltim

ore –

Wolfga

ng F. R

ogge, Ph

.D, P.E

., FIU, M

iami, F

L

0 1 2 3 4 5 6 7192021222425262728293031323334353637383940414243444546474849505152535455565758596061626364656667686970717273747576777879808182838485868788899091929394959697126127128129130131132133134135136137138139140141142143144145146147148149150151152153154155156157158159160161162163164165166167168169170171172173174175176177178179180181182183184185186187188189

Wind Speed (m/sec)

Wind Speed

Leaf S

urface W

axes

0

10

20

30

40

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Tuesday 23th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

July 2002 A

ugust 2002

ng/m3

Alkanes (C

27,C29,C31,C33)

Alkanoic Acids (C

24,C26,C28,C30,C32)


0

50

100

150

200

250

300

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

ng/m3

0

50

100

150

200

250

300

Waxy n-Alkanes (C27-C35)

Total n-Alkanes (C19-C35)

July 2002 August 2002

0

5

10

15

20

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35

n-Alkane Carbon Number

ng/m3

0

10

20

30

40

50

60

70

80

90

100

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35


ng/m3

Mainly Vehicular Exhaust

Waxy Leaf Surface Abrasions

Ambient Concentrations of n-Alkanes for Summer 2002 – Short Time Compositional Changes of Organic Compounds in PM2.5

Plastic Burning


< 1%Inorganics (Ash)

Extraneous

SubstancesFats, waxes, starches, terpenes,

tannins, phenolics, pectins, sugars,

sapins, mucilages, glycosides, essential oils, sterols, others

GumsResins

4 – 10%

Minor

20 – 30%30 – 40%Lignins

25 – 35%Hemicelluloses

40 – 50%Cellulose

Polymers

Major

Deciduous Trees

(angiosperms)

“Hard Wood”

Conifers

(gymnosperms)

“Softwood”Wood Constituents

< 1%Inorganics (Ash)

Extraneous

SubstancesFats, waxes, starches, terpenes,

tannins, phenolics, pectins, sugars,

sapins, mucilages, glycosides, essential oils, sterols, others

GumsResins

4 – 10%

Minor

20 – 30%30 – 40%Lignins

25 – 35%Hemicelluloses

40 – 50%Cellulose

Polymers

Major

Deciduous Trees

(angiosperms)

“Hard Wood”

Conifers

(gymnosperms)

“Softwood”Wood Constituents

Organic Markers in Wood Smoke

•Marker for Cellulose Burning: Levoglucosan

•Markers for Lignins from Hardwood Burning: Syringyl Derivatives (Syringaldehyde, Acetosyringone, Syringic acid)

Cellulose is the abundant organic polymer on earth, found in any wood, vegetative detritus, biomass, etc.

Second most abundant organic polymer on earth: Hardwoods have about 50% guaiacyl and 50% syringyl unitsSoftwoods have 90% - 100% guaiacyl units

• Markers for Softwood Burning: Resin Acids [dehydroabietic acid (major), 7-oxo-dehydroabietic acid, pimaric acid, abietic acid, etc.]


0

1

2

3

4

5

6

7

8

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

Resin Acids, Phenols (ng/m3)

0

5

10

15

20

25

Levoglucosan (ng/m3)

Phenols = (Syringaldehyde, Acetosyringone, Syringic Acid)

Resin Acids = (Pimaric Acid, Sanadracopimaric Acid, Dehydroabietic Acid, 7-Oxo-Dehydroabietic Acid)

Levoglucosan


0

5

10

15

20

25

30

35

40

45

50

Thursday 7th

Friday 8th

Saturday 9th

Sunday 10th

Thursday

Friday 15th

Saturday 16th

Tuesday 19th

Wednesday

Thursday 21st

Friday 22nd

Sunday 24th

Monday 25th

Tuesday 26th

Friday 27th

Friday 21st

Saturday

Sunday 23rd

Monday 24th

Resin Acids, Phenols (ng/m3)

0

50

100

150

200

250

300

350

400

450

500

Levoglucosan (ng/m3)

Phenols = (Syringaldehyde, Acetosyringone, Syringic Acid)

Resin Acids = (Pimaric Acid, Sanadracopimaric Acid, Dehydroabietic Acid,

7-Oxo-Dehydroabietic Acid)Levoglucosan

November 2002 February 2003


6.6 ± 3.2Average

3.9SoftwoodSchauer et al., 2001

3.1Fire Place

West US

Hardwood

2.8SoftwoodFine et al., 2004b

8.1Wood Stove

Hardwood

8.1SoftwoodFine et al., 2004a

5.5Fire Place

West-Midwest US

Hardwood

23.5SoftwoodFine et al., 2002

7.4Fire Place

South US

Hardwood

13.1SoftwoodFine et al., 2001

7.8Fire Place

Northeast US

Hardwood

ReferenceOC/LevoglucosanCombustorFuel Type

Estimating Ambient OC Contributions from Wood Burning

AmbientWoodsmoke

Ambient

LevoglucosanOC% Ambient OC from Wood Burning =

Levoglucosan OC

Levoglucosan% Ambient OC from Wood Burning = 6.6±3.2

OC


Estimating Ambient OC Contributions from Wood Burning

0

5

10

15

20

25

30

35

40

Thursday 7th

Friday 8th

Saturday 9th

Sunday 10th

Thursday 14th

Friday 15th

Saturday 16th

Tuesday 19th

Wednesday 20th

Thursday 21st

Friday 22nd

Sunday 24th

Monday 25th

Tuesday 26th

Friday 27th

Friday 21st

Saturday 22nd

Sunday 23rd

Monday 24th

%

% OC from Wood Burning

November 2002 February 2003


Schematics for the formation routes of secondary biogenic reaction products following the ozonolysis of α-pinene and β-pinene.

(from Kamens)

Baltimore Supersite:

Secondary Biogenic Atmospheric Reaction Products: Nopinone, Pinonic Acid, Norpinonic Acid


0

2

4

6

8

10

12

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Tuesday 23th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

Nopinone (ng/m3)

Nopinone


0

10

20

30

40

50

60

70

80

90

-

10

20

30

40

50

60

70

80

90

Ozone in ppb

Nopinone: Secondary Biogenic Reaction Products - Summer 2002


Nopinone: Secondary Biogenic Reaction Products - Summer 2002

0

2

4

6

8

10

12

14

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

Nopinone (ng/m3)

0

10

20

30

40

50

60

70

80

90

100

%

Nopinone

% Rel. Humidity



Major Organic Compounds associated with PM2.5 Cooking Emissions

Number of Experiments in ( )

From: Rogge et al., Emission Factors for Residential Cooking

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

Hamburgers (4) Sausages (4) Pizza (6) Fish (6&8) French Fries (2) Stir-Fried

Vegetables (8)

Emission Factors (ug/kg of Food)

9-Hexadecenoic Acid (Palmitoleic Acid)

9-Octadecenoic Acid (Oleic Acid)

9,12-Octadecenoic Acid (Linoleic Acid)

Cholesterol


Diurnal Cooking Activities over 48 Hours

0

2

4

6

8

10

12

14

0 2 4 6 8

10

12

14

16

18

20

22

24

26

28

30

32

34

36

38

40

42

44

46

48

0

5

10

15

20

25

30

35

0 2 4 6 8

10

12

14

16

18

20

22

24

26

28

30

32

34

36

38

40

42

44

46

48

Local Cooking Source

Distant Cooking Source (travel time 8 hrs) + Local Cooking Source


0

2

4

6

8

10

12

14

16

18

20

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

Alkenoic Acids (ng/m3)

0

5

10

15

20

25

Cholesterol (ng/m3)

9-Hexadecenoic Acid (Palmitoleic Acid)

9-Octadecenoic Acid (Oleic Acid)

Cholesterol


Ambient Concentrations of Palmitoleic Acid, Oleic Acid, and Cholesterol Summer 2002

Any Daily Patterns ?

2006 Nationa

l Air M

onitoring Confe

rence

–Nov.6

-9 in L

as V

egas –

PM Supe

rsite Baltim

ore –

Wolfga

ng F. R

ogge, Ph

.D, P.E

., FIU, M

iami, F

L

0

90

180

270

360

192021222425262728293031323334353637383940414243444546474849505152535455565758596061626364656667686970717273747576777879808182838485868788899091929394959697126127128129130131132133134135136137138139140141142143144145146147148149150151152153154155156157158159160161162163164165166167168169170171172173174175176177178179180181182183184185186187188189

Wind Direction (deg) Ambient C

oncentra

tions of Palmitole

ic Acid

, Oleic A

cid, a

nd Chole

sterol

vs. Wind

Dire

ction -Sum

mer 2

002

0 2 4 6 8

10

12

14

16

18

20

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

Alkenoic Acids (ng/m3)

0 5 10

15

20

25

Cholesterol (ng/m3)

9-Hexadecenoic Acid (P

almito

leic Acid)

9-Octadecenoic Acid (O

leic Acid)

Cholesterol

July 2002

August 2002

?

?

2006 Nationa

l Air M

onitoring Confe

rence

–Nov.6

-9 in L

as V

egas –

PM Supe

rsite Baltim

ore –

Wolfga

ng F. R

ogge, Ph

.D, P.E

., FIU, M

iami, F

L

0

10

20

30

40

50

60

70

80

90

100

17α(H)-22,29,30-trisnorhopane

17α(H),21b(H)-29-norhopane

17α(H),21β(H)-hopane

22-S,17α(H),21β(H)-30-homohopane

22-R,17α(H),21β(H)-30-homohopane

22-S,17α(H),21β(H)-30-bishomohopane

22-R,17α(H),21β(H)-30-bishomohopane

20R-5α(H),14β(H),17β(H)-Cholestane

20S-5α(H),14β(H),17β(H)-Cholestane

20R-5α(H),14α(H),17α(H)-Cholestane

20R-5α(H),14β(H),17β(H)-Ergostane

20S-5α(H),14β(H),17β(H)-Ergostane

20R-5α(H),14β(H),17β(H)-Sitostane

20S-5α(H),14β(H),17β(H)-Sitostane

Tunnel Emission Factors in µg/Kg of Fuel

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Ambient concentrations in ng/m3

Tunne

lvs. A

mbient

Orga

nic Marke

rs for Vehicle

Exhaust: H

opanes &

Steranes

Squirre

l Hill T

unnel, P

ittsburgh

2006 Nationa

l Air M

onitoring Confe

rence

–Nov.6

-9 in L

as V

egas –

PM Supe

rsite Baltim

ore –

Wolfga

ng F. R

ogge, Ph

.D, P.E

., FIU, M

iami, F

L

0

10

20

30

40

50

60

70

80

90

100

17α(H)-22,29,30-trisnorhopane

17α(H),21b(H)-29-norhopane

17α(H),21β(H)-hopane

22-S,17α(H),21β(H)-30-homohopane

22-R,17α(H),21β(H)-30-homohopane

22-S,17α(H),21β(H)-30-bishomohopane

22-R,17α(H),21β(H)-30-bishomohopane

20R-5α(H),14β(H),17β(H)-Cholestane

20S-5α(H),14β(H),17β(H)-Cholestane

20R-5α(H),14α(H),17α(H)-Cholestane

20R-5α(H),14β(H),17β(H)-Ergostane

20S-5α(H),14β(H),17β(H)-Ergostane

20R-5α(H),14β(H),17β(H)-Sitostane

20S-5α(H),14β(H),17β(H)-Sitostane

Tunnel Emission Factors in µg/Kg of Fuel

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Ambient concentrations in ng/m3

Tunne

lvs. A

mbient

Orga

nic Marke

rs for Vehicle

Exhaust: H

opanes &

Steranes

How do a

mbient conce

ntration pa

tterns for th

e

Hopa

nes com

pare to:

1. A

lkylcy

clohexanes ?

2. n-

Alka

nes (C

19-C25) ?

3. PA

Hs ?

2006 Nationa

l Air M

onitoring Confe

rence

–Nov.6

-9 in L

as V

egas –

PM Supe

rsite Baltim

ore –

Wolfga

ng F. R

ogge, Ph

.D, P.E

., FIU, M

iami, F

L

0 5

10

15

20

25

30

35

40

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

Alkylcyclohexanes (C19-C25) (ng/m3)

0 1 2 3 4 5 6

Hopanes (ng/m3)

Alkylcyclohexanes (C

19-C25)

Hopanes

July 2

002

August 2002

0

10

20

30

40

50

Thursday 7th

Friday 8th

Saturday 9th

Sunday 10th

Thursday 14th

Friday 15th

Saturday 16th

Tuesday 19th

Wednesday 20th

Thursday 21st

Friday 22nd

Sunday 24th

Monday 25th

Tuesday 26th

Friday 27th

Friday 21st

Saturday 22nd

Sunday 23rd

Monday 24th

Akylcyclohexanes (ng/m3)

0 5 10

15

20

25

30

35

Hopanes (ng/m3)


19-C25)

Hopanes

November 2

002

February 2

003

11.89

2006 Nationa

l Air M

onitoring Confe

rence

–Nov.6

-9 in L

as V

egas –

PM Supe

rsite Baltim

ore –

Wolfga

ng F. R

ogge, Ph

.D, P.E

., FIU, M

iami, F

L

0

20

40

60

80

100

120

140

160

180

200

Wednesday 17th

Thursday 18th

Friday 19th

Saturday 20th

Sunday 21th

Monday 22th

Wednesday 24th

Thursday 25th

Sunday 4th

Monday 5th

Tuesday 6th

Wednesday 7th

Thursday 8th

Friday 9th

Saturday 10th

Sunday 11th

Monday 12th

Alkanes (C19-C25) (ng/m3)

0 2 4 6 8 10

12

14

16

18

Alkylcyclohexanes (ng/m3)


19-C25)

Alkanes (C

19-C25)July 2

002

August 2002

0

50

100

150

200

250

300

350

400

450

Thursday 7th

Friday 8th

Saturday 9th

Sunday 10th

Thursday 14th

Friday 15th

Saturday 16th

Tuesday 19th

Wednesday 20th

Thursday 21st

Friday 22nd

Sunday 24th

Monday 25th

Tuesday 26th

Friday 27th

Friday 21st

Saturday 22nd

Sunday 23rd

Monday 24th

Alkanes (C19-C25) (ng/m3)

0 5 10

15

20

25

30

35

40

45

Alkylcyclohexanes (ng/m3)


19-C25)

Alkanes (C

19-C25)

November 2

002

February 2

003

0

10

20

30

40

50

60

70

80

90

100

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35


ng/m3

2006 Nationa

l Air M

onitoring Confe

rence

–Nov.6

-9 in L

as V

egas –

PM Supe

rsite Baltim

ore –

Wolfga

ng F. R

ogge, Ph

.D, P.E

., FIU, M

iami, F

L

0

50

100

150

200

250

300

Thursday 7th

Friday 8th

Saturday 9th

Sunday 10th

Thursday 14th

Friday 15th

Saturday 16th

Tuesday 19th

Wednesday 20th

Thursday 21st

Friday 22nd

Sunday 24th

Monday 25th

Tuesday 26th

Friday 27th

Friday 21st

Saturday 22nd

Sunday 23rd

Monday 24th

Total PAHs (ng/m3)

0 5 10

15

20

25

30

35

Hopanes (ng/m3)

Total P

AHs (P

henanthrene to Coronene)

Hopanes

November 2

002

February 2

003


Conclusions:

• For the very first time, insight into the daily patterns of atmospheric organic compounds associated with PM2.5 with an 3 hourly time-resolution

• For Summer 2002: 18 days of data available

• For Winter 2002-03: 17 days of data available

• For 111 individual organic compounds, about 62,000 data points have been generated

• Although, only a very short view into the data set has been presented, already several interesting aspects about the atmospheric dynamic of fine particle bound organic compounds have been demonstrated:

• Compositional changes of organic matter associated with PM2.5 occurs with a time scale of less than 3 hours

• With very few exceptions, no diurnal concentration patterns have been found for individual organic compounds, indicating that PM2.5 at the sampling site is impacted by sources close and far

• Wood smoke markers are also detectable in summer time

• Wood smoke from softwood burning and hardwood burning can be distinguished well using resin acids and phenolic derivatives from the syringyl type “building blocks” in lignins

• Vehicular marker concentrations (hopanes) compare very well to n-alkanes (C19-C25) and alkylcyclohexanes and is responsible for most of the PAH emissions

Documents

Character of Baltimore PM as derived from detailed ... · • Atmospheric Chemistry • Source/Receptor Reconciliation ... Alkanoic Acids (C24,C26,C28,C30,C32) ... Major Organic Compounds