Air Toxics in Allegheny County: Sources, Airborne Concentrations, and Human Exposure

AIR TOXICS IN ALLEGHENY COUNTY: SOURCES, AIRBORNE CONCENTRATIONS, AND HUMAN EXPOSURE

CMU: Jennifer Logue, Kara Huff-Hartz, Andrew Lambe, Allen Robinson, Neil Donahue, Mitch Small, Cliff Davidson ACHD: Roger Westman, Darrel Stern, Jason Maranche Pitt: Bernie Goldstein

1 Description of the Problem

Q Purpose: Characterize air toxics concentrations, sources, and risks in Allegheny County Q Rationale: Large uncertainties still exist regarding sources, exposure, and health risks mostly due to a lack of data Q Context: Time resolution and consistency of these measurements allow for more in-depth analysis than has previously been possible

2 Project Objectives

Q AmbientAmbient measurementsmeasurements

T BaselineBaseline (ACHD)

T IntensivesIntensives (CMU)

Q EstimateEstimate healthhealth risksrisks (CMU, Pitt) Q DetermineDetermine sourcesource contributionscontributions (CMU) Q EvaluateEvaluate relativerelative risksrisks (CMU)

T LocalLocal vs.vs. regionalregional sourcessources

T PittsburghPittsburgh vs.vs. otherother citiescities

3 Monitoring Sites

Mobile Dominated Avalon Site Industrial Sites

Stowe Downtown Regional Background South Site Fayette

4 Design and Implementation of Project

Q Two types of measurements T Baseline Q 4-sites Q 24hr average concentrations Q Measured 1:6 for a year Q Canisters (TO-15 standard) Q Cartridges (TO-11a standard) T Intensives Q 3-sites Q Hourly measurements for 1 to 2 months Q Gas and particle phase measurements

5 Automated Field Instrument Gas Chromatograph Mass Spectrometer/ Flame Ionization Detector (GCMS/FID)

Q 1 hour resolution

Q 70+ compounds

Q Low detection limit(<.2μg/m3)

(Millet JGR, 2005) 6 Compounds Measured Toluene Chrysene Chloromethane 2-Butanone (MEK) Benzo[ a]anthracene Quinoline Methyl alcohol Fluorene Benzo[k]fluoranthene Styrene Tetrachloroethene 1,1,2-Trichloroethane Benzene Acenaphthene Chlorobenzene 4-Methyl-2-pentanone (MIBK) Anthracene cyclohexane Naphthalene o-Xylene 1-Propanol Ethylbenzene Chloroform Chloroethane Carbon disulfide p-Xylene Acrylonitrile Methyl-t-butyl either(mtbe) Vinyl chloride 1,2-Dichloroethane 1,2,4-Trimethylbenzene Heptane 1,1-Dichloroethane Isopropylbenzene Ethyl acetate 1,1,1-Trichloroethane Ethylene oxide Trichloroethene Benzo[ b]fluoranthene Phenanthrene 1,1,2,2-Tetrachloroethane Bromochloromethane Methylene chloride Vinyl acetate Pyridine Methyl methacrylate 1,4-Dioxane n-Propylbenzene Bromomethane Acrolein (Propenal) 1,2-Dichlorobenzene Fluoranthene Acenaphthylene Bromoform Pyrene Benzyl chloride m-Xylene 1,4-Dichlorobenzene

*Simultaneous measurements of local meteorology and criteria pollutants 7 Measurement Inter-comparison

TolueneToluene BenzeneBenzene 12 6 Slope=Slope=1.394 1.4 10 5 Slope=Slope= 1.6 1.6 8 4

6 3

4 2 Canister Canister (microg/m3) (microg/m3) 2 1 Canister Measurements 0 Canister Measurements 0 024681012 0123456 Hourly Measurments (microg/m3) Hourly Measurments (microg/m3) Averaged Hourly Averaged Hourly

8 Air toxic concentrations relative to South Fayette

6 Pittsburgh Avalon Stowe 5 4:1 4 3 2:1 2 1 0

e e e e n ne ne ne e e en tate e e en ene ylen yl z e z z Ratio with Regional Background Regional with Ratio h X nz nz Styrene t - e en e enzene en o-Xylenep lb lb lb b Benzene oe ob y yl r hy h lo lor t thy th t m & h Ethyl Ac 1,3-ButadiE ch ic ime Me ime ra d r - r t - -T -T ,3 4 5 Te 1 , , 1,4-Dichloroben ,2 ,3 1 1 1-Ethyl-4 9 Seasonal Variations

10 High Temporal Resolution

24hr Average Hourly Concentration

11 Wind from Wind from Neville Island Downtown 14

12 benzene 10 toluene styrene g/m3) 8 μ 6

4 Conc. ( 2

0 1 3 9 10111718192122 October 2006 1.0

0.8 Styrene 1.0 Plume Events 0.6 0.8 Toluene 0.4 0.5

Benzene 0.2 0.3

0.0 0.0 12 Benzene by Day of the Week in Avalon Benzene

12 Benzene 10 g/m3) μ 8

4 Concentration (micrograms/m3) 2 Hourly Concentration (

Sat Sun Mon Tues Wed Thurs Fri

13 Average Diurnal Patterns at Avalon 2.8 4

2.6 benzene 3.5 toluene 2.4

2.2 3

2 2.5 1.8 (microg/m3) (microg/m3) Concentration 1.6 Concentration 2

1.4 1.5 1.2 g/m3) g/m3) μ μ 1 1

0 0 0 0 0 0.25 0 0 0 0 0 0 0 0 : : 1.8 :0 :0 :0 :00 :00 2:00 4:00 6 8 4: 6: 2:00 2:00 4 6:00 8:00 0 2 10:00 12:00 1 1 18:00 20:00 2 1 1 14:00 16 18 20:00 22:00 Military cyclohexaneTime Military Time 0.2 1.6

0.15 1.4

0.1

(microg/m3) 1.2 (microg/m3) Concentration Concentration Concentrations ( Concentrations ( Concentrations 0.05 1 styrene

0 0.8 0 0 0 0 0 0 0 0 0 0 0 0 :00 0 0 :0 :0 :0 : : : 6am6:00 8:00 122:00pm 16:00 6pm18:00 20:00 22:00 : 6am 8 0 12pm2 4 6pm20:00 22:00 2:00 4:0 10:00 1 14:00 2:00 4 6 1 1 1 16 18 14 Time ofMilitary day Time Time ofMilitary day Time Estimating Lifetime Cancer Risk

Linear No-Threshold Model:

Lifetime Individual Cancer Risk: LIR = LADD*SF

SF=Slope Factor

C95th, percentile * fa * IR Lifetime Averaged Daily Dose: LADD = BW

15 Air Toxics Cancer Risks Dichloropropane,1,2-

Bromodichloromethane Stowe Methylene Chloride Risk=10-6 Downtown Hexachlorobutadiene Avalon Background Dichloroethane,1,2-

Dichlorobenzene,1,4-

Tetrachloroethene

Chloroform

Butadiene, 1,3-

Trichloroethene

Carbon Tetrachloride

Benzene

0.E+000E00 5.E-06 5E-6 1.E-05 1E-5 2.E-05 1.5E-05 2.E-05 2E-5 Lifetime Cancer Risk 16 Non-Cancer Health Risks Concentration HQ = RfC

HQ=Hazard Quotient RfC = Reference Concentration

Q Chronic th T Annual 95 percentile canister data Q Intermediate and Acute

T Maximum hourly concentration at Avalon: 14 days to 1 year

17 Non-Cancer Risks

XYLENE, o- Stowe CARBON Downtown TETRACHLORIDE Avalon BROMOMETHANE Background CHLOROMETHANE

TOLUENE

XYLENE, m-

BENZENE

ACETONE

HEXACHlOROBUTADIENE

BUTADIENE, 1,3-

HAZARD INDEX

0.00 0.20 0.40 0.60 0.80 1.00 Hazard Qoutient 18 Comparison of Aggregate Air Toxics Risks

HAP Risk (Flag Plaza)

HAP Risk (Avalon)

Metals Risk (Background)

HAP Risk (Stowe)

HAP Risk (South Fayette)

PAHs Risk (Background)

0.0E+00 5.0E-05 1.0E-04 1.5E-04 2.0E-04 Lifetime Cancer Risk

19 How does Allegheny County compare to other cities? 3.5 40

35 3 Avalon Stowe 30 2.5 Downtown g/m3)

μ Background 25 2 20 Values Values 1.5 15

1 10 Concentration (

5 0.5

0 0 1 2 1,3 Butadiene1 CCl2 4 Chlorform3 TCE4 Chloroethene5 Benzene Toluene Column Number Colu

20 Downtown Exposure: Trichloroethene

50 1.E-03 Annual Averaged 40 8.E-04

30 6.E-04 g/m3) μ 20 4.E-04 (95% (95%

Concentration Concentration 10 2.E-04 (95th percentile) (95th

0 0.E+00 Cancer Risk Lifetime 1.0 1996 1998 2000 2002 2004 2006 2008 Year 0.8

0.6 Time Series 2006

g/m3) 0.4 μ

0.2

0.0 1/5/0 2/5/0 3/ 4/ 5/5/0 6/5/0 7/5/0 8/5/0 9/5/0 10/ 11/ 1 Concentration ( Concentration 5/0 5/0 2/5 5/0 5/0 /0 6 6 6 6 6 6 6 6 6 6 6 6 21 Source Apportionment

PMF solves: X = GF

scores loadings

Q Main issue: Associating sources and factors

T Event profiles

T Source profiles

22 Mobile Gasoline Factor

1 00 Styrene 330 330 3030 0.9

0.8 300300 6060 0.7

M/P 40 0.6 30 M/P Xylene 10 20 270270 9090 Xylene 0.5

0.4 Toluene 240 120120 Toluene 0.3 240

0.2 210210 150150 0.1 Benzene 180180 0 Factor Contribution vs. Pittsburgh PMF Source Wind Direction Factor Profile

23 Water Treatment Factor

0 0 30 330330 30

300300 60 60

50 30 40 10 20 Tetrachloro 270270 90 90 ethylene

240240 120120 ACSA Toluene 210210 150150 180180

1 Factor Contribution vs. PMF ACSA Factor Emission Wind Direction Profile

24 1,2,4_trimethylbenzene

Linking Risk too-xylene Sources

acetone Cancer Risk Exposure Styrene 1,1,1_trichloroethane

Toluene Avalon Site methylene chloride

MEK

Benzene toluene

styrene

benzene Neville Factor 0% 20% 40% 60% 80%

25 NATA Evaluation by Pollutant

2.0 2:1 8 1:1 g/m3) 2:1 g/m3) μ Styrene μ Toluene 1.5 6

1.0 1:1 CCl4 4 1:2

0.5 1:2 2

1-3 Butadiene Benzene Measured Concentration ( Concentration Measured 0.0 ( Concentration Measured 0 00.5102468 Modeled Conc.(μg/m3) Modeled Conc.(μg/m3)

26 NATA Evaluation by Site

3 25

2.5 20

2 15

1.5 10 1

Measured Modeled / 5 0.5

0 0 1,3-Butadiene Benzene Chloroform Toluene Styrene TCE

2.5

1. 5

1 Avalon Stowe Downtown Background 0.5

1, 3 - But adien e Benzene Chlor of or m Toluen e

27 NATA Evaluation: Source Apportionment Benzene

100%

Background 75%

50% Mobile

25% Point

0% DowntownDowntown Avalon Avalon BackgroundBackground Stowe Stow e Avalon Avalon (NATA) (NATA) (NATA) (NATA) (PMF) (PMF) (NATA)

28 Application of Results

Q Quantifying risk

Q Source Apportionment

Q Policy and funding decisions

Q NATA evaluation

29 Lessons Learned

Q Meeting all of our goals.

Q Design of the project was sufficient to meet goals and additional scientifically interesting work is being done using the results.

Q In retrospect

30 Future Work

Q Intensives

T Downtown

T South Fayette Q Expand and improve PMF analysis Q Synergistic risk models Q NATA evaluation

31 Acknowledgments

QFunding

TClean Air Fund

TEPA

32 Questions