Air Toxics in Allegheny County Sources Airborne Concentrations

Air Toxics in Allegheny County: Sources, Airborne Concentrations, and Human Exposure Jennifer Logue, Andrew Lambe, Kara Huff. Hartz, Allen Robinson, Neil Donahue, Mitch Small, Cliff Davidson, Darrel Stern, Jason Maranche 1

Project Objectives n n What are the concentrations and health risks of air toxics in Allegheny County? How do the concentrations and risks in Allegheny County compare to other U. S. Cities? What are priority air toxics for Allegheny County? What are the sources of these priority toxics? 2

Baseline Monitoring (2/06 -1/08) Heavily Industrialized Downtown Flag Plaza Regional background n n n 32 organic air toxics 1 in 6 day sampling Methods TO-11 A & TO-15 (background) 3

Air toxics considered in analysis Baseline: 38 HAPs Intensives: 38 HAPs Archive: Acetaldehyde Ethyl benzene Acetaldehyde Formaldehyde Antimony (PM 10, PM 2. 5) Acrolein Formaldehyde Benzene Hexachlorobutadiene Arsenic (PM 10, PM 2. 5) Benzene Hexachlorobutadiene Benzyl chloride Hexane Beryllium (PM 10, PM 2. 5) Benzyl chloride Hexane Bromoform Methyl isobutyl ketone Cadmium (PM 10, PM 2. 5) Bromoform Methyl isobutyl ketone Bromomethane Methylene chloride Chromium (PM 10, PM 2. 5) Bromomethane Methylene chloride Butadiene, 1, 3 - MTBE Cobalt (PM 10, PM 2. 5) Butadiene, 1, 3 - MTBE Carbon disulfide Styrene Lead (PM 10, PM 2. 5) Carbon disulfide Propionaldehyde Carbon tetrachloride Tetrachloroethane, 1, 1, 2, 2 - Manganese (PM 10, PM 2. 5) Carbon tetrachloride Styrene Chlorobenzene Tetrachloroethene Nickel (PM 10, PM 2. 5) Chloroethane Toluene Chlorobenzene Tetrachloroethane, 1, 1, 2, 2 - Chloroform Trichlorobenzene, 1, 2, 4 - Chloroethane Tetrachloroethene Chloromethane Trichloroethane, 1, 1, 1 - Chloroform Toluene Dibromoethane, 1, 2 - Trichloroethane, 1, 1, 2 - Chloromethane Trichlorobenzene, 1, 2, 4 - Dichlorobenzene, 1, 4 - Trichloroethene Dibromoethane, 1, 2 - Trichloroethane, 1, 1, 1 - Dichloroethane, 1, 1 - Vinyl chloride Dichlorobenzene, 1, 4 - Trichloroethane, 1, 1, 2 - Dichloromethane, 1, 1 - Dichloroethane, 1, 2 - Xylene, m/p Trichloroethene Dichloroethene, 1, 1 - Xylene, o- Dichloroethane, 1, 2 - Vinyl chloride Dichloropropane, 1, 2 - Diesel particulate matter Dichloroethene, 1, 1 - Xylene, m/p Ethyl benzene POM Dichloropropane, 1, 2 Dibenz(A-H)Anthracene (PM 10, PM 2. 5) Selenium (PM 10, PM 2. 5) POM 4

Identifying Priority Toxics n n n Large Local Sources High Concentrations Relative to National Data High Risk 5

Comparisons with National Concentration Data *Sonoma Tech. provided national data 6

Air Toxics with Elevated Concentrations 7

Spatial variation and local sources 25 12 4: 1 2: 1 1: 1 8

Cancer Risk n 3 toxics above 10 -5 q q q n Formaldehyde Benzene Trichloroethene 12 toxics above 10 -6 9

Additive Cancer LIR at Baseline Sites Trichloroethene Flag Plaza Avalon Formaldehyde Benzene Stowe South Fayette 0. 0 0. 2 0. 4 0. 6 0. 8 1. 0 1. 2 Cancer LIR (x 10 -4) 10

Comparison of LIR in Select U. S. Cities 0 0. 5 1. 0 Cancer LIR (x 10 -4) 1. 5 11

Non-Cancer Risks n Chronic q n Acrolein No Acute 12

Other Air Toxics n Downtown: q n Avalon q n Diesel Particulate Matter metals Archived CMU Supersite Data (regional background) q q q Diesel Particulate Matter Metals Polycyclic aromatic hydrocarbons 13

Diesel particulate matter n Complex pollutant q q q n n 40 -80% BC or EC Organics Sulfate No way to directly measure Estimate using source apportionment model q q BC/EC Hopanes & steranes n-alkanes aromatics 14

Diesel Particulate Concentrations and Risks Cancer LIR (x 10 -3)* 0 1 3 2 2. 0 1. 5 1. 0 Archived Data 0. 5 Probability BC or EC ( g m-3) 2. 5 Downtown 0. 2 0. 0 0 2 4 6 8 10 DPM ( g m-3) D ow G nto re w en n H sb az u el rg w La oo w d Sc ren he cev nl ey ille Fl Par or k en ce 0 Schenely Park 0. 4 *Based on CA Office of Environmental Health Hazard Assessment URE for DPM 15

Risk of metals in different cities * * 1 2 3 * * 4 5 6 7 Cancer LIR (x 10 -5) 16

Risks for Different Classes of Air Toxics 17

Air Toxics of Interest High Greatest Health Risks : diesel PM benzene formaldehyde Medium Health Risks : carbon tetrachloride tetrachloroethene trichloroethene 1, 4 -dichlorobenzene 1, 3 -butadiene acetaldehyde acrolein metals Potential Concerns : chloroform styrene toluene MIBK propionaldehyde ethylbenzene methylene chloride xylenes 18

Intensive Monitoring Downtown Heavily Industrialized Diamond Building Carnegie Mellon 19

Automated Field Instrument Gas Chromatograph Mass Spectrometer/ Flame Ionization Detector (GCMS/FID) n 1 hour resolution n 70+ compounds n Low detection limit(<. 2 mg/m 3) (Millet JGR, 2005) 20

Neville Island Downtown High Time Resolved Measurements 21

Concentration (mg/m 3) High time resolved measurements Hour of the day 22

Source Apportionment 0 Coke Factor 270 90 180 23

Benzene 24

Formaldehyde n n n Sources: q Secondary Formation q Mobile sources q Point Sources: 9 TPY Predominately Secondary Avalon is statistically significantly higher than other sites q 27% [0% 57%] increase from SF 25

Tetrachloroethene n n Avalon: ACSA Downtown: Dry Cleaning Downtown Avalon Background Avalon ACSA 26

Risk Apportionment 27

Industry Risk Apportionment 28

Risk Apportionment 29

Conclusions n Priority air toxics q Substantial risk from regional air toxics n n q Formaldehyde Carbon tetrachloride Local risk drivers n n n DPM Benzene Chlorinated compounds 30

Acknowledgments n Funding Clean Air Fund q EPA q 31

1, 4 -dichlorobenzene Downtown Background 32

Trichloroethene: Unknown Source 33

Acrolein n Sources q q n Mobile sources Point Sources: 9 TPY HQ>1 at all sites n Predominately Diesel emissions 34

Regional Sources n Propionaldehyde is high throughout the county q n Highest in Fall Formaldehyde, Carbon Tetrachloride, and Chloromethane are on par with nation 35

Small Local Sources n Benzene in Avalon q q n Neville Industry Mobile sources Toluene both sites q q Industry Mobile sources 36

Large Regional Sources n n Chlorinated Compounds downtown Hydrogen sulfide and styrene at Avalon 37

Air Toxics Health Risks Cancer Air Toxics Respiratory Problems Birth Defects Neurological issues Developmental Problems Other health issues n Two types of risk q q n Cancer: chronic Non-Cancer: Acute, intermediate or chronic Risks are modeled using a linear no-threshold model 38

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Regional Pollutants: Formaldehyde Carbon Tetrachloride 41

Local plumes contribute to elevated exposure Toluene 42

Determining Sources: Increased Resolutions of Hourly measurements 43

Increases Measurement Resolution 44

Neville Island Downtown Plume events drive local exposure 45

Benzene n n n Mobile Sources Industrial Sources High Relative to the National Data 46

Water Treatment Factor 0 330 30 60 300 270 Tetrachloro ethylene 90 240 Toluene PMF Factor 120 210 ACSA Emission Profile 150 ACSA 180 Factor Contribution vs. Wind Direction 47

Inlet for GCMS/FID Automated Valve Assembly Compound traps Gas Chromatograph Mass Spectrometer Flame Ionization Detector 48

Neville Island Plume Events 40 Compounds were measured hourly Downtown Styrene Toluene Benzene 49

Positive Matrix Factorization (PMF) Measured Data compound time PMF solves: Main issue: Identifying factor q q Event profiles Inventory profiles source fs 11 fs 12 fs 21 fs 22 fs 31 fs 32 compound source n loadings time scores c 11 c 12 c 13 c 21 c 22 c 23 c 31 c 32 c 33 a 11 a 12 a 13 a 21 a 22 a 23 50

Measurement Intercomparison: Slopes varied from. 3 to 2 51

Quantitative Source Apportionment Receptor Modeling: Goal: To determine emissions rates/source contributions 52