# Presentation: 876524

## 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

## Project Objectives

- 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?

## Baseline Monitoring (2/06-1/08)

**32 organic air toxics**
**1 in 6 day sampling**
**Methods TO-11A & TO-15 **

**Flag Plaza**

**(background)**

**Regional background**

**Heavily Industrialized**

**Downtown**

**Notes:**
Mention that Allegheny County is in Penn, add a map of PA
(1in 6 sampling)

## Air toxics considered in analysis

| Acetaldehyde | Ethyl benzene |
| --- | --- |
| Acrolein | Formaldehyde |
| Benzene | Hexachlorobutadiene |
| Benzyl chloride | Hexane |
| Bromoform | Methyl isobutyl ketone |
| Bromomethane | Methylene chloride |
| Butadiene, 1,3- | MTBE |
| Carbon disulfide | Propionaldehyde |
| Carbon tetrachloride | Styrene |
| Chlorobenzene | Tetrachloroethane, 1,1,2,2- |
| Chloroethane | Tetrachloroethene |
| Chloroform | Toluene |
| Chloromethane | Trichlorobenzene, 1,2,4- |
| Dibromoethane, 1,2- | Trichloroethane, 1,1,1- |
| Dichlorobenzene, 1,4- | Trichloroethane,1,1,2- |
| Dichloromethane, 1,1- | Trichloroethene |
| Dichloroethane,1,2- | Vinyl chloride |
| Dichloroethene, 1,1- | Xylene, m/p |
| Dichloropropane, 1,2- | Xylene, o- |

| Acetaldehyde | Formaldehyde |
| --- | --- |
| Benzene | Hexachlorobutadiene |
| Benzyl chloride | Hexane |
| Bromoform | Methyl isobutyl ketone |
| Bromomethane | Methylene chloride |
| Butadiene, 1,3- | MTBE |
| Carbon disulfide | Styrene |
| Carbon tetrachloride | Tetrachloroethane, 1,1,2,2- |
| Chlorobenzene | Tetrachloroethene |
| Chloroethane | Toluene |
| Chloroform | Trichlorobenzene, 1,2,4- |
| Chloromethane | Trichloroethane, 1,1,1- |
| Dibromoethane, 1,2- | Trichloroethane,1,1,2- |
| Dichlorobenzene, 1,4- | Trichloroethene |
| Dichloroethane, 1,1- | Vinyl chloride |
| Dichloroethane,1,2- | Xylene, m/p |
| Dichloroethene, 1,1- | Xylene, o- |
| Dichloropropane, 1,2- | Diesel particulate matter |
| Ethyl benzene | POM |

**Baseline: 38 HAPs**

**Intensives: 38 HAPs**

| Antimony (PM10,PM2.5) |
| --- |
| Arsenic (PM10,PM2.5) |
| Beryllium (PM10,PM2.5) |
| Cadmium (PM10,PM2.5) |
| Chromium (PM10,PM2.5) |
| Cobalt (PM10,PM2.5) |
| Lead (PM10,PM2.5) |
| Manganese (PM10,PM2.5) |
| Nickel (PM10,PM2.5) |
| Dibenz(A-H)Anthracene (PM10,PM2.5) |
| Selenium (PM10,PM2.5) |
| POM

 |

**Archive:**

## Identifying Priority Toxics

**Large Local Sources**
**High Concentrations Relative to National Data**
**High Risk**

## Comparisons with National Concentration Data

- *Sonoma Tech. provided national data

## Air Toxics with Elevated Concentrations 

## Spatial variation and local sources

**Notes:**
Describe the plot first and before explaining meaning

Color code the sites with with the bars, rename sites downtown and background 

## Cancer Risk

- 3 toxics above 10-5
- Formaldehyde
- Benzene
- Trichloroethene
- 12 toxics above 10-6

## Additive Cancer LIR at Baseline Sites

**Flag Plaza**

**Avalon**

**Stowe**

**South Fayette**

**  ****0.0            0.2            0.4           0.6            0.8            1.0            1.2    **

**Cancer LIR (x 10****-4****)**

**Formaldehyde**

**Benzene**

**Trichloroethene**

## Comparison of LIR in Select U.S. Cities

## Non-Cancer Risks

- Chronic
- Acrolein
- No Acute

## Other Air Toxics

- Downtown:
- Diesel Particulate Matter
- Avalon
- metals
- Archived CMU Supersite Data (regional background)
- Diesel Particulate Matter
- Metals
- Polycyclic aromatic hydrocarbons

## Diesel particulate matter

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

## Diesel Particulate Concentrations and Risks

- Downtown

- Greensburg

- Hazelwood

- Lawrenceville

- Schenley Park

- Florence

**BC or EC (********g m****-3****)**

**0**

**2.0**

**1.5**

**1.0**

**0.5**

**2.5**

**Archived Data**

- *Based on CA Office of Environmental Health Hazard Assessment URE for DPM

## Risk of metals in different cities

**Risk of metals in different cities**

**1**

**2**

**4**

**3**

**5**

**6**

**   ****7**

**Cancer LIR (x 10****-5****)**

*****

*****

*****

*****

*****

*****

## Risks for Different Classes of Air Toxics

## Air Toxics of Interest

_**High Greatest Health Risks**_ : 								diesel PM							benzene							formaldehyde

_**Medium Health Risks**_ : 							carbon tetrachloride	1,3-butadiene 				tetrachloroethene 	acetaldehyde				trichloroethene		acrolein		           			1,4-dichlorobenzene 	metals

_**Potential Concerns**_ : 							chloroform 	propionaldehyde 				styrene 		ethylbenzene 					toluene 		methylene chloride 				MIBK 		xylenes

**Notes:**
Update

## Intensive Monitoring

**Carnegie Mellon**

**Heavily Industrialized**

**Downtown**

**Diamond Building**

**Notes:**
Mention that Allegheny County is in Penn, add a map of PA
(1in 6 sampling)

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

- (Millet JGR, 2005)

- 1 hour resolution
- 70+ compounds
- Low detection limit(<.2g/m3)

## High Time ResolvedMeasurements

**Neville Island****	****   ****	****	****Downtown**

- High Time ResolvedMeasurements

**Notes:**
Better verbal transition 

## High time resolved measurements

- Concentration (g/m3)

- Hour of the day

- Concentration (g/m3)

## Source Apportionment

**180**

**90**

**270  **

**270  **

**90**

**0**

**Coke Factor**

**Notes:**
More about apportionment risk_> sources , wind directional temporal patterns, PMF factor to source profiles, example of benzene elements 

## Benzene	

- Benzene

## Formaldehyde

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

## Tetrachloroethene

- Avalon: ACSA
- Downtown: Dry Cleaning

- Downtown
-  Avalon
-   Background

**ACSA**

**Avalon**

## Risk Apportionment

**Notes:**
Secondary breakdown

## Industry Risk Apportionment

## Risk Apportionment

## Conclusions

- Priority air toxics
- Substantial risk from regional air toxics
- Formaldehyde
- Carbon tetrachloride
- Local risk drivers
- DPM
- Benzene
- Chlorinated compounds

## Acknowledgments

- Funding
- Clean Air Fund
- EPA

## 1,4-dichlorobenzene

- Downtown

- Downtown

- Background

## Trichloroethene:Unknown Source

## Acrolein

- Sources
- Mobile sources
- Point Sources: 9 TPY
- HQ>1 at all sites

- Predominately Diesel emissions

## Regional Sources

- Propionaldehyde is high throughout the county
- Highest in Fall
- Formaldehyde, Carbon Tetrachloride, and Chloromethane are on par with nation

**Notes:**
Break it up into a few different plots

## Small Local Sources

- Benzene in Avalon
- Neville Industry
- Mobile sources
- Toluene both sites
- Industry
- Mobile sources

## Large Regional Sources

- Chlorinated Compounds downtown
- Hydrogen sulfide and styrene at Avalon

## Air Toxics Health Risks

**Cancer**
**Respiratory Problems**
**Birth Defects**
**Neurological issues**
**Developmental Problems**
**Other health issues**

**Air Toxics**

- Two types of risk
- Cancer: chronic
- Non-Cancer: Acute, intermediate or chronic
- Risks are modeled using a linear no-threshold model

**Notes:**
Put in what they stand for 

Table to graph

Change to a graph 

**Notes:**
Add acrolien

## Slide 40

## Regional Pollutants: Formaldehyde Carbon Tetrachloride

## Local plumes contribute to elevated exposure

**Toluene**

**Notes:**
Explain what drives the air toxic concentrations in the area, explain , time seiries of wind direction versus time-

Slide after that shows what the same situation would look for 24 hour average

## Determining Sources: Increased Resolutions of Hourly measurements

**Notes:**
Add windrose to show wind direction

## Increases Measurement Resolution

**Notes:**
Explain what drives the air toxic concentrations in the area, explain , time seiries of wind direction versus time-

Slide after that shows what the same situation would look for 24 hour average

## Plume events drive local exposure

**Neville Island****	****   ****	****	****Downtown**

## Benzene

- Mobile Sources
- Industrial Sources
- High Relative to the National Data

## Water Treatment Factor

- PMF         Factor

- Factor Contribution vs.
- Wind Direction

- 0

- 30

- 60

- 90

- 120

- 150

- 180

- 210

- 240

- 270

- 330

- 300

**ACSA**

- ACSA Emission Profile

**Tetrachloroethylene**

**Toluene**

**Notes:**
Need to repace this

## Inlet for GCMS/FID

- Compound
- traps

- Automated Valve Assembly

- Gas Chromatograph Mass Spectrometer Flame Ionization Detector

**Notes:**
Descibe how the instrument runs, detection limits, etc. 

Point out more the routine calibration

## Plume Events

**40 Compounds were measured hourly**

**Neville Island****	****   ****	****	****Downtown**

- Styrene
- Toluene
- Benzene

**Notes:**
Better verbal transition 

## Positive Matrix Factorization (PMF)

- Main issue: Identifying factor
- Event profiles
- Inventory profiles

- PMF solves:

- scores     loadings

- fs11  fs12 fs21  fs22 fs31  fs32

- a11  a12  a13 a21  a22  a23

- c11  c12  c13 c21  c22  c23 c31  c32  c33

- _Measured Data_

- time

- compound

- time

- compound

- source

- source

## Measurement Intercomparison: Slopes varied from .3 to 2

## Quantitative Source Apportionment

- _Receptor Modeling_:

- _Goal:_ To determine emissions rates/source contributions

**Notes:**
Define the terms on the slide, add in what I, j, add time
You need to walk them through the equation.

Mention that there are several methods, mention the limitations 

Test the fij assumption 
 why do we need to constrain the model.  

Mention example , used for source types but we are trying to identify specific source contributions from the same source class, no distinct chemical tracer/profiles