Assessment of Exposures to Mobile Source Air Toxics Eric M. Fujita Barbara Zielinska Division of...

Assessment of Exposures to Mobile Source Air Toxics

Eric M. FujitaBarbara Zielinska

Division of Atmospheric SciencesDesert Research Institute

Reno, NV

Air Toxics Workshop IIHouston, Texas

June 12-13, 2007

Desert Research Institute June 12, 2007

Estimating Exposures to MSAT Ambient concentrations at fixed sites versus vehicle dominated

microenvironments.

Time spent in various microenvironments by population groups.

Ambient versus personal breathing zone concentrations.

Variations in pollutant concentrations and composition in mobile source dominated locations. Spatial variations due to proximity.

Temporal variations (diurnal, daily, day-of-week, and seasonal).

Traffic mix (diesel vs. gasoline, gross polluters vs. normal emitters, vehicle operating mode).

Atmospheric transformation (chemical and physical).

Assessing Exposures to MSATs


Acknowledgments• Comparative Toxicity Study

– Sponsor: DOE’s Office of FreedomCAR and Vehicle Technologies

• Weekend Ozone Study– Sponsor: DOE’s Office of FreedomCAR and Vehicle Technologies; Coordinating Research Council

– Additional Support: South Coast Air Quality Management District

• Gasoline/Diesel PM Split Study– Sponsor: DOE’s Office of FreedomCAR and Vehicle Technologies

– Additional Support: U.S. Environmental Protection Agency. California Bureau of Automotive Repair, South Coast Air Quality Management District, Ralph’s Supermarket Distribution Center

• Kansas City Vehicle Characterization Study– Sponsor: U.S. Environmental Protection Agency Office of Transportation and Air Quality

– Additional Support: DOE’s Office of FreedomCAR and Vehicle Technologies, Coordinating Research Council, U.S. Federal Highway Administration.

• Section 211(B) Tier 2 High End Exposures – Sponsor: American Petroleum Institute

– Additional Input: U.S. Environmental Protection Agency

• Assessing Exposure to Air Toxics in Microenvironments Dominated by Mobile Sources – Sponsor: Health Effects Institute

– Additional Support: South Coast Air Quality Management District.

• Atmospheric Transformations of Diesel Exhaust – Sponsor: Health Effects Institute

References


Fujita, E.M., D.E. Campbell, B. Zielinska, J.C. Sagebiel, J.L. Bowen, W. Goliff, W.R. Stockwell, and D.R. Lawson (2003). Diurnal and Weekday Variations in Source Contributions of Ozone Precursors in California’s South Coast Air Basin. J. Air & Waste Manage. Assoc. 53: 844-863.

Zielinska, B., W.S. Goliff, M. McDaniel, T. Cahill, D. Kittleson and W. Watts (2003). Chemical Analyses of Collected Diesel Particulate Matter Samples in the CRC E-43 Project. Prepared for the National Renewable Energy Laboratory, Golden, CO.

Zielinska, B. J. Sagebiel, J.D. McDonald, K. Whitney and D.R. Lawson (2004). Emission Rates and Comparative Chemical Composition from Selected In-Use Diesel and Gasoline-Fueled Vehicles. J. Air & Waste Manage. Assoc. 54:1138-1150.

Fujita, E.M. and D.E. Campbell (2006). Spatial and Temporal Variations in Exposure to Air Toxics in the South Coast Air Basin. Final report submitted by Desert Research Institute to the National Renewable Energy Laboratory, Golden, CO, August 31, 2006.

Fujita, E.M., D.E. Campbell, B. Zielinska, W.P. Arnott and J.C. Chow (2007). Exposure to Air Toxics in Mobile Source Dominated Microenvironments. Draft report submitted by Desert Research Institute to the Health Effects Institute, Boston, MA, February 6, 2007.

Fujita, E.M., B. Zielinska, D.E. Campbell, W.P. Arnott, J. Sagebiel, L. Reinhart, J.C. Chow, N. P.A. Gabele, W. Crews, R. Snow, N. Clark, S. Wayne and D.R. Lawson (2007). Variations in speciated emissions from spark-ignition and compression ignition motor vehicles in the California's South Coast Air Basin. J. Air & Waste Manage. Assoc. 57:705-720.

Fujita, E. M., D. E. Campbell, W. P. Arnott, B. Zielinska (2007). Evaluations Of Source Apportionment Methods for Determining Contributions Of Gasoline and Diesel Exhaust to Ambient Carbonaceous Aerosols. J. Air & Waste Manage. Assoc. 57:721-740.

Zielinska, B., J. Sagebiel, S. Samy, JC. Seagrave, J. McDonald, P. Wiesen and K. Wirtz (2007) Atmospheric Transformation of Diesel Emissions, Poster presented at 2006 HEI Annual Conference, Chicago, Il, April 15-17, 2006.

Average Hourly Light-Duty and Heavy-Duty Traffic Volumes Weigh-in-Motion Sites in Interior of South Coast Air Basin


DOE NREL Weekend Ozone StudyCourtesy of Sonoma Technology, Inc., 2002

Heavy-Duty

Light-Duty

Photoacoustic Black Carbon (1-minute averages)


Gasoline/Diesel PM Split Study

Sunday

Weekday

Weekday Variations in CO and Black Carbon at Azusa9/30/00 to 10/8/00 - Weekend Ozone Study


0

1

2

3

4

50:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

00:

006:

0012

:00

18:0

0

Sat, 9/30 Sun, 10/1 Mon, 10/2 Tue, 10/3 Wed, 10/4 Thu, 10/5 Fri, 10/6 Sat, 10/7 Sun, 10/8

bla

ck c

arb

on

(u

g/m

3)

0

0.5

1

1.5

2

2.5

3

CO

(p

pm

)

Black Carbon (ug/m3)

CO (ppm)

Weekend Ozone Study


0

100

200

300

400

500

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00

0:0

06

:00

12

:00

18

:00


NM

HC

(p

pb

C)

0.0

0.4

0.8

1.2

1.6

2.0

CO

(p

pm

)

NMHC

CO (ppm)0

1

2

3

4

5

0:0

0

6:0

01

2:0

01

8:0

00

:00

6:0

01

2:0

0

18

:00

0:0

06

:00

12

:00

18

:00

0:0

0

6:0

01

2:0

01

8:0

00

:00

6:0

01

2:0

0

18

:00

0:0

06

:00

12

:00

18

:00

0:0

0

6:0

01

2:0

01

8:0

00

:00

6:0

01

2:0

0

18

:00

0:0

06

:00

12

:00

18

:00


bla

ck

ca

rbo

n (

ug

/m3

)

0

20

40

60

80

100

NO

x (

pp

b)

BC (ug/m3)

NOx (ppb)

Weekday Variations in BC & NOx versus CO & NMHC at Azusa9/30/00 to 10/8/00 - Weekend Ozone Study

BC and NOx

CO and NMHC

Weekend Ozone Study

CMB Source Contribution Estimates for Total Carbonat Azusa, Los Angeles and Other Sites


Total Carbon (IMPROVE)

0.0

0.2

0.4

0.6

0.8

1.0

Fra

ctio

nal

SC

E

Diesel Gasoline Residual

Total Carbon (STN)

0.0

0.2

0.4

0.6

0.8

1.0

Azu

sa

Su

n

Azu

sa

Mo

n

Azu

sa

Tu

e

Azu

sa

We

d

Azu

sa

Th

u

Azu

sa

Fri

Azu

sa

Sa

t

LA

NM

S

un

LA

NM

M

on

LA

NM

T

ue

LA

NM

W

ed

LA

NM

T

hu

LA

NM

F

ri

LA

NM

S

at

Sa

n D

ima

s M

on

Ve

nic

e S

at

Ro

se B

ow

l Sa

t

I-4

05

Su

n

Fra

ctio

nal

SC

E

Gasoline/Diesel PM Split Study

Mainly diesel at Azusa and LA, but mixed at other sites

Large residual fraction.


CMB Source Contribution Estimates for Benzene & Toluene

Benzene

0.0

1.0

2.0

3.0

4.0

5.0

1999 2000 1999 2000 1999 2000 1999 2000

Azusa Los Angeles N.Main

Pico Rivera Upland

pp

b

Gasoline Exhaust Gasoline Vapor Gasoline Liquid

Diesel Exhaust Coatings Consumer Products

Toluene

0.0

4.0

8.0

12.0

16.0

1999 2000 1999 2000 1999 2000 1999 2000

Azusa Los Angeles N.Main

Pico Rivera Upland

pp

b

Weekend Ozone Study

DustTrak PM mass (ug/m3) for Phase 2 of the LA92 CycleSummer Study

Stratum 5 (pre-81)Stratum 6 (1981-90)

Stratum 7 (1991-95)Stratum 8 (1996+)

Kansas City Vehicle Emissions Characterization Study


Ascending PM2.5 Emission Rates within Model Year GroupsKansas City Vehicle Emissions Characterization Study

0

50

100

150

200

250

300

350

400

Emissions in Ascending Order wihin Model Year Groups

PM

Em

issi

on

Rat

es,

mg

/mil

e

Ascending Age

High emitters contributed a disproportionate share of the PM emissions (17% in Round 1 and 24% in Round 2 contribute 75% of the total).

Source: EPA OTAQ


Kansas City Vehicle Characterization Study- Summer Volatile, Semi-Volatile and Particulate PAHs

Emissions of Total PAHs (mg/mile)

0

40

80

120

160

S1

-1S

1-2

S2

-1S

2-2

S2

-3S

2-4

S3

-1S

3-2

S4

-1S

4-2

S5

-1S

5-2

S5

-3S

5-4

S5

-5S

6-1

S6

-2S

6-3

S6

-4S

7-1

S7

-2S

7-3

S7

-4S

8-1

S8

-2S

8-3

Trucks Cars

Em

iss

ion

s (

mg

/mile

)

26 other PAHs indeno[123-cd]pyrenebenzo(ghi)perylene coronene63 Volatile and SV PAHs 1-methylnaphthalene2-methylnaphthalene napthalene

Total PAHs (% of Total)

0%

25%

50%

75%

100%

S1-

1S

1-2

S2-

1S

2-2

S2-

3S

2-4

S3-

1S

3-2

S4-

1S

4-2

S5-

1S

5-2

S5-

3S

5-4

S5-

5S

6-1

S6-

2S

6-3

S6-

4S

7-1

S7-

2S

7-3

S7-

4S

8-1

S8-

2S

8-3

Trucks Cars

Pe

rce

nt

26 other PAHs indeno[123-cd]pyrenebenzo(ghi)perylene coronene63 Volatile and SV PAHs 1-methylnaphthalene2-methylnaphthalene napthalene


Kansas City Vehicle Characterization Study

Comparative Emissions and Toxicity of Gasoline and Diesel Vehicles


0

5000

10000

15000

20000

25000

30000

35000

40000

F P F P F P F P F P F P F P F P

ug

/mile

naphth menaph dmenaph mebiph tmenaph acnapy acnape fluore phenan meflu fl9one

xanone mephen anrquone dmephen anthra fluora pyrene mepy/fl bzcphen baanth chrysn

bbjkfl bepyrn bapyrn incdpy bghipe dbanth corone

-----G------

-----BG----

------WG-----

-----D----------HD----

---G30 --- ---D-30 ---

----NG---

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

G BG WG D HD G30 D30 NG

Filter Only

0

200

400

600

800

1000

1200

1400

1600

G BG D HD G30 D30 NG

Gasoline VehiclesG: Average Gasoline at 72° FBG: Black Smoker at 72° FWG: White Smoker at 72° FG30: G at 30° FNG: New Technology

Diesel Vehicles D: Average Diesel at 72° FHD: High PM Emitter at 72° FD30: D at 30° F

F = FilterP = PUF/XAD

In Vivo Toxicity Per Unit Mass

• Gs ~ Ds in nature and potency• High G & D > Normal G & D

Seagrave et al., Toxicol. Sci.,70, 212-226, 2002

Chamber Reaction of Toluene with Diesel ExhaustOpen Path FTIR Data


HEI Study – Atmospheric Transformations of Diesel Exhaust

Diesel Exhaust + Toluene, Light

0

10

20

30

40

50

60

70

7:48

8:08

8:28

8:48

9:08

9:28

9:48

10:0

8

10:2

8

10:4

8

11:0

8

11:2

8

11:4

8

12:0

8

12:2

8

12:4

9

13:0

9

13:2

9

13:4

9

14:1

0

14:3

0

14:5

1

15:1

1

15:3

2

15:5

2

16:1

3

16:3

4

16:5

4

Time (GMT)

pp

b (

HC

HO

, H

CO

OH

, G

lyo

xal,

P

AN

, H

NO

3)

0

100

200

300

400

500

600

700

pp

b (

NO

x, O

3, T

olu

ene)

HCHO HCOOH Glyoxal PAN HNO3 Nox O3 Toluene

Toluene

NOx

Ozone

PAN-like

Glyoxal

HNO3

HCOH

HCOOH

May 19, 2005

Time Evolution of Diesel Exhaust Particle Size Distributions with Photochemical Reactions of Toluene


Particle Size distribution Chamber B

0

10000

20000

30000

40000

50000

60000

70000

80000

0 50 100 150 200 250 300

Dp (nm)

dN

/dL

og

Dp

(#

/cm

3 )

8:10:23

10:40:20

13:40:16

5/19/2005

• Addition of ~500 ppb of toluene (NOx ~100 ppb) resulted in a substantial secondary aerosol formation.

• Initial DPM concentration: 9 µg/m3

• peak PM concentration: 57 µg/m3

HEI Study – Atmospheric Transformations of Diesel Exhaust

Particle Number Concentration Distribution at the Tuscarora Tunnel, 5/21/99


TunnelInlet

Tunneloutlet

RegionalBackground

* Source: HEI Project 98-3 courtesy of Dr. Fred Rogers, Desert Research Institute.

Concentration Distributions on nano-MOUDI Stagesof Organic Compounds in Diesel Exhaust (Light Cruise)


Source: Zielinska et al. 2003, Project Report for CRC-E43.

Semi-volatile PAH

0

10

20

30

40

50

60

0.0

10

0.0

18

0.0

32

0.0

56

0.1

00

0.1

80

0.3

20

0.5

60

1.0

00

1.8

00

3.2

00

5.6

20

10

.00

0

ng

/m3

dmph fluora

pyrene mfl/mpy

bzcphen baanth

chrysn

Particle PAH

0.0

0.5

1.0

1.5

2.0

0.0

10

0.0

18

0.0

32

0.0

56

0.1

00

0.1

80

0.3

20

0.5

60

1.0

00

1.8

00

3.2

00

5.6

20

10

.00

0

nano-MOUDI stages (um)

ng

/m3

bbjkfl bepyrn

bapyrn incdpy

bghipe dbanth

corone

Hopanes & Steranes

0

100

200

300

400

500

0.0

10

0.0

18

0.0

32

0.0

56

0.1

00

0.1

80

0.3

20

0.5

60

1.0

00

1.8

00

3.2

00

5.6

20

10

.00

0

nano-MOUDI stages (um)

ng

/m3

Steranes

Hopanes

Total Alkanes

0

10000

20000

30000

40000

500000

.01

0

0.0

18

0.0

32

0.0

56

0.1

00

0.1

80

0.3

20

ng

/m3


Health Effects Institute Project RFA03-1

Black Carbon (1-minute) by Photoacoustic

Sampling Location

ug

/m3

BC - 1 minute averages, September

110 Fwy 405 Fwy 60 Fwy Truck Rt. Dmnd Bar LongBeach Lynwood-15

0

15

30

45

60

75

90

105

120

135

150

MaximumMinimum75%25%MedianOutliersExtremes

Sampling Location

ug

/m3

PM2.5 - 1 minute averages, September


0

40

80

120

160

200

240

280

320

360

400


Sampling Location

pp

bV

BTEX - 1 minute surrogate & 24hr canisters, September

110 Fwy 405 Fwy 60 Fwy Truck Rt. Dmnd Bar LongBeach Lynwood0

4

8

12

16

20

24

28

32

36


Sampling Location

pp

bV

1,3 butdiene - 1 minute surrogate & 24hr canisters, September


0.4

0.8

1.2

1.6

2

2.4

2.8

3.2

3.6

4


Figure 3. Box and whisker plots of one-minute black carbon and PM 2.5 (DustTrak) concentrations. DustTrak exceeds gravimetric mass measurements by a factor of 2 to 2.5. Correlations of time-averaged PID and canisters measurements were used to reconstruct one-minute BTEX and 1,3-butadiene mixing ratios.

Ranges in On- and Near-Road Exposure

Sampling Location

ug

/m3

BC - 1 minute averages, September


0

15

30

45

60

75

90

105

120

135

150


Sampling Location

ug

/m3

PM2.5 - 1 minute averages, September


0

40

80

120

160

200

240

280

320

360

400


Sampling Location

pp

bV

BTEX - 1 minute surrogate & 24hr canisters, September


4

8

12

16

20

24

28

32

36


Sampling Location

pp

bV

1,3 butdiene - 1 minute surrogate & 24hr canisters, September


0.4

0.8

1.2

1.6

2

2.4

2.8

3.2

3.6

4


Figure 3. Box and whisker plots of one-minute black carbon and PM 2.5 (DustTrak) concentrations. DustTrak exceeds gravimetric mass measurements by a factor of 2 to 2.5. Correlations of time-averaged PID and canisters measurements were used to reconstruct one-minute BTEX and 1,3-butadiene mixing ratios.

Ranges in On- and Near-Road Exposure405

110

60

710605

91

Long Beach

Diamond Bar

Lynwood

Comparisons of On-Road Versus Fixed StationSummer Morning CO



Comparisons of On-Road Versus Fixed StationSummer Morning NOx



Distributions of BTEX Exposures in Atlanta MEs


Sum BTEX

2.4

132

9.2

14.2

1.4

65

10.1

9.8

1.3

583

18.0

40.0

3.1

304

17.5

25.8

0.6

25

3.7

7.3

2.2

2454

13.3

97.6

0.8

58

5.1

5.8

2.6

80

7.0

9.4

2.1

98

14.1

24.3

60.1

465

152.4

172.1

5.8

40

11.7

13.3

2.9

533

11.9

29.7

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME8_9 ME10 ME11 ME12 ME13

0

20

40

60

80

100

120

Sum BTEX

2.4

132

9.2

14.2

1.4

65

10.1

9.8

1.3

583

18.0

40.0

3.1

304

17.5

25.8

0.6

25

3.7

7.3

2.2

2454

13.3

97.6

0.8

58

5.1

5.8

2.6

80

7.0

9.4

2.1

98

14.1

24.3

60.1

465

152.4

172.1

5.8

40

11.7

13.3

2.9

533

11.9

29.7


0

20

40

60

80

100

120

Sum BTEX

2.4

132

9.2

14.2

1.4

65

10.1

9.8

1.3

583

18.0

40.0

3.1

304

17.5

25.8

0.6

25

3.7

7.3

2.2

2454

13.3

97.6

0.8

58

5.1

5.8

2.6

80

7.0

9.4

2.1

98

14.1

24.3

60.1

465

152.4

172.1

5.8

40

11.7

13.3

2.9

533

11.9

29.7


0

20

40

60

80

100

120

1. In-Cabin Congested Freeway 5. In-Cabin Toll Plaza 10. Outdoor Surface Parking2. In-Cabin Urban Canyon 7. Outdoor Refueling 11. Outdoor Underground Garage3. In-Cabin Refueling 8. Sidewalk 12. Outdoor Toll Plaza4. In-Cabin Underground Garage 9. Sidewalk/Bus Stop 13. Following High Emitters

1st Qtr

Max

Min

3rd Qtr

Med

Ave

API Section 211(B) Tier 2 Exposure Study

132 65 583 304 25 2454 58 80 46598 40 533

Mean ME to Air Monitoring Station Ratiosof MSAT for Corresponding Hours - Houston


Houston- Summer

1

10

100

1000

10000

1 2 3 4 5 6 7 8 9 10 11 12

Microenvironment

ME

/Sta

tio

n R

ati

o

Benzene

Toluene

m&p-Xylenes

Houston - Winter

1

10

100

1000

10000

1 2 3 4 5 6 7 8 9 10 11 12

Microenvironment

ME

/Sta

tio

n R

ati

o

Log Scale

1. In-vehicle congested freeway 5. In-vehicle toll plaza 9. Outdoor bus stop

2. In-vehicle urban canyon 6. In-vehicle road tunnel 10. Outdoor surface parking

3. In-vehicle refueling 7. Outdoor refueling 11. Outdoor underground garage

4. In-vehicle underground garage 8. Outdoor sidewalk 12. Outdoor toll plaza

API Section 211(B) Tier 2 Exposure Study

• Ambient levels of volatile organic MSATs in the SoCAB were mainly associated with gasoline vehicles.

– On-road CO, NMHC, and volatile MSATs were 2-5 times higher than fixed monitoring sites (1-hour averages).

• Diesel vehicles were the dominant mobile source of EC and TC at two fixed monitoring sites (Azusa and Los Angeles).

– However source contributions of gasoline and diesel vehicles varied with location and time.

– On-road NO and BC were about an order of magnitude higher than at fixed monitoring sites (1-hour averages).

• Short-term on-road exposures (few minute or less) can be substantially higher (10 to 100 times higher) and depend on proximity of high gasoline emitters and diesel trucks.

• Over half of the organic carbon during summer in the SoCAB could not be apportioned to directly-emitted PM emissions from motor vehicles.

– Gasoline vehicles are predominant source of anthropogenic SOA precursors (volatile and semi-volatile aromatic hydrocarbons.

• Concentrations of ultrafine particles (<0.1 m) are greatest in fresh emissions and rapidly grow to accumulation size particles (0.1 to 1.0 m).

• High emitters contributed a disproportionate share of the PM emissions (about 20% of the vehicles contributed 75% of the total).

Summary and Conclusions


Assessment of Exposures to Mobile Source Air Toxics Eric M. Fujita Barbara Zielinska Division of...

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