# APPENDIX D –
Emissions Inventory Evaluation by Sonoma Technology, Inc.

# A Top-Down Emissions Inventory Evaluation for the Upper Midwest

Final Report
Prepared for National Renewable Energy Laboratory Golden, CO

May 2011

### Cover graphic illustrates the locations of monitoring sites included in the top-down emissions inventory evaluation. See Section 1 for more information. 

# A Top-Down Emissions Inventory Evaluation for the Upper Midwest

Final Report NREL Contract # AFA-9-99135-0 STI-909028-3808-FR

Prepared by

Stephen B. Reid

Erin K. Pollard Yuan Du John C. Stilley Sonoma Technology, Inc. 1455 N. McDowell Blvd., Suite D Petaluma, CA 94954-6503 Ph 707.665.9900 | F 707.665.9800 sonomatech.com

Prepared for

National Renewable Energy Laboratory 1617 Cole Boulevard Golden, CO 80401-3393

May 31, 2011

### Upper Midwest Emissions Inventory Evaluation Acknowledgments



# Acknowledgments

Funding for this project was provided by th e U.S. Department of Energy Office of Vehicle Technologies under the direction of Dr. James Eberhardt, Chief Scientist. The authors acknowledge the assistance of Mark Janssen an d Mike Koerber of the Lake Michigan Air Directors Consortium (LADCO), w ho provided access to the emissions inventory data that was used for the analyses described in this repor t. We also acknowledge Doug Lawson of the National Renewable Energy Laboratory (NREL) , who managed the project for NREL and provided technical guidance and su pport throughout the project.

### Upper Midwest Emissions Inventory Evaluation Table of Contents



## iii 

# Table of Contents

Section Page

List of Figures................................................................................................................................. v List of Tables ................................................................................................................. ..............viii Glossary ......................................................................................................................................... ix

1. Introduction ................................................................................................................ ........ 1-1 1.1 Background............................................................................................................... 1- 1 1.2 Overview of Technical Approach............................................................................. 1-2 1.2.1 Site Selection and Data Processing .............................................................. 1-2 1.2.2 Comparison of Ambient- and Emissions Inventory-Derived Criteria Pollutant Ratios ............................................................................................ 1-4 1.2.3 Comparison of Ambient- and Emissions Inventory-Derived Hydrocarbon Compositions.......................................................................... 1-6 1.3 Uncertainty Issues..................................................................................................... 1-6 1.3.1 Emissions Inventory Uncertainties............................................................... 1-6 1.3.2 Ambient Measurement Uncertainties........................................................... 1-7 1.3.3 Uncertainties Associated with the Comparisons .......................................... 1-7 1.4 Summary of Results.................................................................................................. 1-8

2. Data Acquisition and Processing........................................................................................ 2-1 2.1 Ambient Monitoring Data......................................................................................... 2-1 2.1.1 Ambient Data Acquisition............................................................................ 2-1 2.1.2 Ambient Data Validation.............................................................................. 2-2 2.1.3 Ambient Site Characterization ..................................................................... 2-5 2.1.4 Ambient Concentration Data...................................................................... 2-11 2.1.5 Ambient Data Screening ............................................................................ 2-24 2.2 Emissions Inventory Data....................................................................................... 2-24 2.2.1 Emissions Data Acquisition and Processing .............................................. 2-24 2.2.2 Emissions Data Characterizations by Site.................................................. 2-27

3. Pollutant Ratio Comparison Results .................................................................................. 3-1 3.1 TNMOC/NO x 

# Ratio Comparisons............................................................................ 3-1 3.1.1 Ratio Comparison Results for Chicago-Jardine ........................................... 3-2 3.1.2 Ratio Comparison Results for Chicago-Northbrook .................................... 3-3 3.1.3 Ratio Comparison Results for Gary ............................................................. 3-5 3.1.4 Ratio Comparison Results for Detroit-East 7 Mile ...................................... 3-5 3.1.5 Ratio Comparison Results for Milwaukee ................................................... 3-6 3.2 CO/NO x 

# Ratio Comparisons..................................................................................... 3-8 3.2.1 Ratio Comparison Results for Chicago-Mannheim ..................................... 3-9 3.2.2 Ratio Comparison Results for Chicago-Franklin ....................................... 3-11 3.2.3 Ratio Comparison Results for Chicago-Northbrook .................................. 3-13 3.2.4 Ratio Comparison Results for Detroit-Linwood ........................................ 3-14 3.2.5 Ratio Comparison Results for Milwaukee ................................................. 3-15

### Upper Midwest Emissions Inventory Evaluation Table of Contents



## iv 

# Section Page

4. Hydrocarbon Composition Comparison Results................................................................ 4-1 4.1 Relative Hydrocarbon Com position Comparisons ................................................... 4-1 4.2 Hydrocarbon Reactiv ity Comparisons...................................................................... 4-4

5. Findings and Recommendations ........................................................................................ 5-1

6. References .................................................................................................................. ........ 6-1

Appendix A: Chemical Species Cross-Reference List .............................................................. A-1 Appendix B: Monitoring Site Photographs.................................................................................B-1 Appendix C: Diurnal Concentration Plots for 2008 and 2009....................................................C-1 Appendix D: Additional Comparisons of Pollutant Ratios........................................................ D-1 Appendix E: Additional Comparisons of Hydrocarbon Compositions ......................................E-1

### Upper Midwest Emissions Inventory Evaluation List of Figures



## v 

# List of Figures

Figure Page

1-1. Locations of monitoring sites include d in the top-down emissions inventory evaluation..................................................................................................................... .... 1-3

1-2. Example of a full extent grid analysis zone, showing the spatial configuration of grid cells for which ambient- and emissi ons inventory-derived ratio comparisons were calculated................................................................................................................ . 1-5

2-1. Time series of propane and ethane concentrations (ppbC) at Gary, IN........................... 2-3

2-2. Time series of CO concentrations (p pb) for Linwood site in Detroit, MI ....................... 2-4

2-3. Yearly variations in summer wee kday TNMOC concentrations (ppbC) at the Northbrook site in Chicago, IL. ....................................................................................... 2-5

2-4. Image of the area around the Jardine and Franklin sites in Chicago ............................... 2-6

2-5. Image of the area around the Northbrook site in Chicago............................................... 2-7

2-6. Image of the area around the Mannheim site in Chicago ................................................ 2-8

2-7. Image of the area around the Gary site ............................................................................ 2-9

2-8. Image of the area around the East 7 Mile and Linwood sites in Detroit ....................... 2-10

2-9. Image of the area around the Milwaukee site ................................................................ 2-11

2-10. Interpretation of notched box whisker plots produced by SYSTAT ............................. 2-15

2-11. Hourly TNMOC and NO x 

# concentrations for the Chicago-Jardine site for summer weekdays, Saturdays and Sundays, 2004–2006............................................................. 2-16

2-12. Hourly TNMOC and NO x 

# concentrations for the Chicago-Northbrook site for summer weekdays, Saturdays, and Sundays, 2004–2006.............................................. 2-17

2-13. Hourly TNMOC and NO x 

# concentrations for the Gary site for summer weekdays, Saturdays and Sundays, 2004–2006 .............................................................................. 2-18

2-14. Hourly TNMOC and NO x 

# concentrations for the Detr oit-East 7 Mile site for summer weekdays, Saturdays, and Sundays, 2004–2006.............................................. 2-19

2-15. Hourly TNMOC, NO x 

# , and CO concentrations for the Milwaukee site for summer weekdays, Saturdays, and Sundays 2004–2006............................................................. 2-20

### Upper Midwest Emissions Inventory Evaluation List of Figures



## vi 

# Figure Page

2-16. Hourly CO and NO x 

# concentrations for the Chicago-Mannheim site for summer weekdays, Saturdays, and Sundays, 2004–2006............................................................ 2-21

2-17. Hourly CO and NO x 

# concentrations for the Chicago-Franklin site for summer weekdays, Saturdays, and S undays (right), 2004–2006 ................................................ 2-22

2-18. Hourly CO and NO x 

# concentrations for the Detroit-Linwood site for summer weekdays, Saturdays, and Sundays, 2004–2006............................................................ 2-23

2-19. Emissions grid domains for the LADCO 2005 Base M inventories.............................. 2-25

2-20. January weekday emissions by source sect or for the grid analysis zone around each monitoring site for hours 0600 to 0900 ......................................................................... 2-30

2-21. July weekday emissions by source sector for the grid analysis zone around each monitoring site for hours 0600 to 0900 ......................................................................... 2-31

2-22. January and July weekday on-road mobile source emissions for the grid analysis zone around each monitoring site for hour 0600-0900.................................................. 2-32

2-23. Spatial distributions of NO x 

# emissions from on-road mobile sources in Cook County for LADCO’s 2005 and 2008 inventories......................................................... 2-33

2-24. Day of week emissions profiles for on-road mobile sources......................................... 2-33

3-1. TNMOC/NO x 

# ratios by wind quadrant and day of week for the Jardine site, 2004-2006 ...................................................................................................................... .. 3-3

3-2. TNMOC/NO x 

# ratios by wind quadrant and day of week for the Northbrook site, 2004–2006...................................................................................................................... .. 3-3

3-3. TNMOC/NO x 

# ratios by wind quadrant and day of week for the Northbrook site, 2008........................................................................................................................... ....... 3-4

3-4. TNMOC/NO x 

# ratios by wind quadrant and day of week for the Gary site, 2004-2006 ...................................................................................................................... .. 3-5

3-5. TNMOC/NO x 

# ratios by wind quadrant and day of week for the East 7 Mile site, 2004–2006...................................................................................................................... .. 3-6

3-6. TNMOC/NO x 

# ratios by wind quadrant and day of week for the Milwaukee site, 2004–2006...................................................................................................................... .. 3-7

3-7. TNMOC/NO x 

# ratios by wind quadrant and day of week for the Milwaukee site, 2008........................................................................................................................... ....... 3-7

### Upper Midwest Emissions Inventory Evaluation List of Figures



## vii 

# Figure Page

3-8. CO/NO x 

# ratios by season, wind quadrant, and day of week for the ChicagoMannheim site, 2004–2006............................................................................................ 3-10

3-9. CO/NO x 

# ratios by season, wind quadrant, and day of week for the ChicagoMannheim site, 2008...................................................................................................... 3-11

3-10. CO/NO x 

# ratios by season and by day of w eek for the Chicago-Franklin site, 2004-2006. ..................................................................................................................... 3-12

3-11. CO/NO x 

# ratios by season and by day of week for the Chicago-Franklin site, 2008...... 3-12

3-12. CO/NO x 

# ratios by season, wind quadrant, and day of week for the ChicagoNorthbrook site, 2008. ................................................................................................... 3-14

3-13. CO/NO x 

# ratios by season and by day of week for the Detroit-Linwood site, 2004-2006. ..................................................................................................................... 3-15

3-14. CO/NO x 

# ratios by season, wind quadrant, and day of week for the Milwaukee site, 2004–2006...................................................................................................................... 3-16

4-1. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Chicago-Jardine site....................................................................... 4-2

4-2. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Chicago-Northbrook site................................................................ 4-2

4-3. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Gary site. ........................................................................................ 4-3

4-4. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Detroit- East 7 Mile site.................................................................. 4-3

4-5. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Milwaukee site. .............................................................................. 4-4

### Upper Midwest Emissions Inventory Evaluation List of Tables



## viii 

# List of Tables

Table Page

1-1. Monitoring sites included in the top- down emissions inventory evaluation ................... 1-3

1-2. Dimensions of the full grid analysis z one around each monitoring site of interest......... 1-5

2-1. Hourly data available at individual monitoring sites ....................................................... 2-2

2-2. Mean summer TNMOC and NO x 

# concentrations.......................................................... 2-12

2-3. Mean summer (June–August) CO and NO x 

# concentrations. ......................................... 2-13

2-4. Mean winter (December–February) CO and NO x 

# concentrations................................. 2-14

2-5. LADCO emissions inventory files for January 14, 2005............................................... 2-25

2-6. Summary of summer (July) VOC and NO x 

# emissions for hours 0600 to 0900 for the grid analysis zone around each monitoring site analyzed........................................ 2-28

2-7. Summary of summer (July) CO and NO x 

# emissions for hours 0600 to 0900 for the grid analysis zone around each monitoring site analyzed.............................................. 2-29

2-8. Summary of winter (January) CO a nd NOx emissions for hours 0600 to 0900 for the grid analysis zone around each monitoring site analyzed........................................ 2-29

3-1. TNMOC/NO x 

# ratios by site for the hours 0600 to 0900 (emission ratios for full grid extent around each site; ambient ratios for 2005 based on 2004–2006 data). ................. 3-2

3-2. CO/NO x 

# ratios by site (emission ratios for fu ll grid extent around each site; ambient ratios for 2005 based on 2004–2006 data)....................................................................... 3-9

4-1. Reactivity values by site, day of week, month, and season. ............................................ 4-5

4-2. Reactivity values by wind quadrant (all summer months included)................................ 4-6

### Upper Midwest Emissions Inventory Evaluation Glossary



## ix 

# Glossary

Term Definition

AQS Air Quality System – the U.S. Enviro nmental Protection Agency’s repository of ambient air quality data CAMx Comprehensive Air Quality Model with extensions
CO Carbon monoxide CONCEPT Consolidated Community Emissions Processing Tool
DRI Desert Research Institute EGU Electrical generating units EPA Environmental Protection Agency HC Hydrocarbon LADCO Lake Michigan Air Directors Consortium MIR Maximum incremental reactivity
NO Nitric oxide
NO x 

# Oxides of nitrogen NREL National Renewable Energy Laboratory PAMS Photochemical Assessment Monitoring Stations PAMSHC Hydrocarbon species measured at Photochemical Assessment Monitoring Stations
PAR Paraffin carbon bond
PMF Positive matrix factorization ppb Parts per billion ppbC Parts per billion carbon TNMOC Total nonmethane organic compounds VOC Volatile organic compounds VOCDat Volatile Organic Compound Data Validation and Analysis Software

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-1 

# 1. Introduction

The Health Impacts Program of the Nationa l Renewable Energy Laboratory (NREL) is responsible for quantifying the e ffects of new vehicle technologi es and fuels on air quality and human health and, as such, is interested in the quality of on-road mobile source emissions inventories. Under funding from the U.S. Depa rtment of Energy Office of Vehicle Technologies through NREL, Sonoma Technology, Inc. (STI) performed a top-down evaluation of the 2005 and 2008 emissions inventories that the Lake Mi chigan Air Directors Consortium (LADCO) is using to conduct regional air qual ity modeling in the Upper Midwes t, with a special focus on the on-road mobile source component of the inventories.

Several techniques can be used to evaluate the accuracy and representativeness of any emissions inventory that is intended for use in air quality modeling: “common sense” review of the data; bottom-up evaluations that start with emissions activity data to estimate corresponding emissions; and top-down evaluations that compar e emissions estimates to ambient air quality data or use ambient data to estimate emissions profiles. As a top- down emissions inventory evaluation, the work described in this report was focused on compari ng the LADCO emissions inventories to ambient monitoring data collected at four urban ar eas in the region of interest: Chicago, Illinois; Milwaukee, Wi sconsin; Gary, Indiana; and Detr oit, Michigan. The goals of the project were to identify areas of agreemen t and differences between the ambient data and emissions inventories, to identify areas of the emissions inventories that may need improvement, and to demonstrate the usefulness of top-down emissions inventory evaluation techniques.

The basic approaches used to perform the top-down evaluation followed methods developed by Fujita et al. (1992) and outlined in a 2005 Desert Research Institute (DRI) report (Desert Research Institute, 2005) and elsewhere (Chinkin and Re id, 2006; Roberts et al., 2004). The approaches include comparisons of pollutant ratios (e.g., total non-methane organic carbon [TNMOC]/oxides of nitrogen [NO x 

# ] and carbon monoxide [CO]/NO x 

# ) that are derived from ambient data (ambient-derived) with those de rived from the emissions inventory (emissions inventory-derived), as well as comparisons of am bient- and emissions i nventory-derived relative hydrocarbon compositions. Results of these comparis ons were used to address the reliability and completeness of, and to make recommendations for improving, the LADCO emissions inventories.


# 1.1 Background

The objective of this project is to evaluate the hourly emissions inventory for different urban areas in the Upper Midwest, using ambi ent data collected from 2004 through 2006 and 2008 through 2010. This work focuses on assessing recent (2005 and 2008) emissions estimates and how well they represent real -world pollutant concentrations in the areas of interest. 1 

# Ambient-derived and emissions inventory-de rived primary pollutant ratios (TNMOC/NO x 

# and CO/NO x 

# ) and relative hydrocarbon compositions were spatially and temporally compared for ambient site locations in Chicago, Milwaukee, Ga ry, and Detroit. In addition, analyses were

1 

## The initial focus of the project was comparing 2004

– 2006 ambient data with 2005 emissions estimates; however, analyses of 2008 ambient and emissions data were included once 2008 emissions inventories became available.

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-2 

# performed on 2009-2010 ambient data to evalua te ambient measurement trends during the current economic downturn.

Comparison of ambient- and emissions inve ntory-derived primary pollutant ratios has proven to be a useful tool for assessing and then improving emissions estimates. However, these types of comparisons are confounded by the fact th at ambient concentrati ons are influenced not only by fresh pollutants emitted in the vicinity of a monitor, but also by aged pollutants transported from sources farther away and chemi cal reactions that may have occurred after the pollutants were emitted. The influence of these effects on comparisons can be minimized (but not eliminated) by selecting ambient data collect ed at times when emission rates are high and chemical reaction rates are low. Morning sampli ng periods offer the best potential to minimize the effects of pollutant transport and other influences in the ambient/emissions inventory comparisons. During early morning hours, because of low mixing heights, emissions from elevated sources may be injected above the mixe d layer and may not affect surface-level ambient concentrations. Pollutant ratios were calculated with and without elevated sources to evaluate the potential effects of this phenomenon.


# 1.2 Overview of Technical Approach

STI used techniques outlined by DRI (Desert Research Institute, 2005) to perform this top-down emissions inventory ev aluation. These techniques have been previously applied by STI to emissions inventories for several other geographic areas, including central California (Chinkin and Reid, 2006), Southern California (F ujita et al., 1992; Chinkin et al., 2005), and Houston, Texas (Roberts et al., 2004). The tec hnical approach for this top-down emissions inventory reconciliation was di vided into three elements:

1. Site selection and data processing;

2. Comparison of emissions i nventory and ambient criter ia pollutant ratios; and

3. Comparison of emissions inventory and ambient relative hydrocarbon compositions.

The approach used to carry out each work el ement is described in the following sections.

1.2.1 Site Selection and Data Processing

To support a top-down emissions inventory evaluation for the cities of Chicago, Milwaukee, Gary, and Detroit, STI acquired availa ble air quality and meteorological data from the U.S. Environmental Protection Agency’s (EPA) Air Quality System (AQS) for eight monitoring sites, as shown in Table 1-1 and Figure 1-1 . To effectively evaluate on-road mobile source emissions estimates, an effort was made to focus on monitoring sites that are likely to be impacted by fresh mobile source emissions. Ho wever, some of the sites included in these analyses were in the vicinity of other emissi ons sources, including non-road mobile sources (e.g., the Jardine and Mannheim sites in Chicago) and industrial sources (e.g., the Gary site), as described in Section 2.2. Hourly data for the years 2004–2006 and 2008–2010 2 

# were acquired

2 

## It should be noted that 2008

– 2010 data were not available for several sites that reported 2004

– 2006 data, as documented in Section 2.1.1.

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-3 

# from AQS for summer (June-August) and winter (December-February) months, and data were validated following established protocols.

Table 1-1. Monitoring sites included in the top-down emissions inventory evaluation.



# Site Name AQS Code Site Type a 

# Latitude Longitude Chicago, IL – Jardine 17-031-0072 PAMS II 41.8958 -87.6077 Chicago, IL – Northbrook 17-031-4201 PAMS 42.1400 -87.7992 Chicago, IL – Franklin 17-031-0063 SLAMS/Other 41.8770 -87.6343 Chicago, IL – Mannheim 17-031-3103 SLAMS/Other 41.9652 -87.8763 Gary, IN 18-089-0022 PAMS II 41.6067 -87.3047 Detroit, MI – E7Mile 26-163-0019 SLAMS/Other 42.4308 -83.0001 Detroit, MI – Linwood 26-163-0016 SLAMS/Other 42.3578 -83.0960 Milwaukee, WI 55-079-0026 PAMS II 43.0611 -87.9125

a 

## PAMS = Photochemical Assessment Monitoring Stations; SLAMS = State/Local Air Monitoring Stations.

Figure 1-1. Locations of monitoring sites included in the top-down emissions inventory evaluation.

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-4 

# STI also acquired 2005 Base M and 2008 Base B/C emissions inventory data files and supporting files (e.g., speciation profile libraries ) for area, point, non-ro ad mobile, on-road mobile, and biogenic sources fr om LADCO. In general, LADCO provided hourly, gridded criteria pollutant (e.g., volatile organic compounds [VOC], NO x 

# , and CO) emissions data representing an average weekday, Saturd ay, and Sunday for each month of 2005 and 2008. 3 

# Emission file formats varied by source sector 4 

# , so to prepare the emissions data for use in subsequent analyses, STI convert ed all data files to a common comma-separated-values (CSV) format and extracted data records for the grid cells included in the grid analysis zones around each monitoring site of interest (see Section 1.2.2 for a description of how grid analysis zones were defined for each site). In addition, ST I speciated anthropogenic VOC emissions using speciation profiles and cross-re ference files provided by LADC O, then matched individual chemical species in the speciated inventories to those species measured in the ambient data (i.e., PAMS hydrocarbons). The compounds reported in the emissions inventory that were not measurable in the ambient samples were excluded from the analysis. Finally, STI converted the speciated inventories from mass to molar units to place the emissions and ambient data on a common basis.

1.2.2 Comparison of Ambient- and Emi ssions Inventory-Derived Criteria Pollutant Ratios

For the selected sites, TNMOC/NO x 

# and CO/NO x 

# ratios from the ambient and emissions inventory data were computed by day-of-week (weekday 5 

# , Saturday, and Sunday), month (June, July, and August), and summer season (June-August). Because CO data were available for winter and summer months, CO/NO x 

# ratios were also calculated for individual winter months (December, January, and February) and th e winter season (December-February). Ambient-derived ratios were compared with em issions inventory-derive d ratios by spatially matching ambient data to corresponding groups of 4-km x 4-km grid cells surrounding each ambient monitoring site. These groups of grid cells were identified for each site based on predominant wind speeds during th e early morning hours (0600–0900).

Because meteorological factors can affect differences between ambient- and emissions inventory-derived ratios, several different ratio comparisons were considered, each representing a different spatial configuration of wind quadrants and grid cells around each site. The extent of each quadrant-grid cell configuration, or analys is zone, was based on the maximum distance an air parcel could travel during the 3-hour sampling period, given average wind speeds during that period. Figure 1-2 illustrates an example of a full extent grid analysis zone 6 

# centered on an ambient monitoring site and shows the wind quadr ant definitions, whose extents vary according

3 

## For on-road mobile sources, emissions were provided for January and July only. For biogenic sources, emissions were provided for each day of 2005. Additional details on the processing of emissions data for these source categories are provided in Section 2.2.1.
4 

## For 2005, biogenic emissions were provided as CAMx-ready binary files, on-road emissions were provided as PostgreSQL files, and the remaining source sectors were provided as SAS files. All 2008 data were provided as SAS files.
5 

## For pollutant ratio comparisons and all remaining analyses, ambient data from Tuesday

– Thursday were considered “weekday.” Emissions inventory data were not provided for individual weekdays.
6 

## The full extent grid analysis zone surrounding each site is based on the quadrant analysis zone with the highest average wind speed.

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-5 

# to the observed wind speeds at each site. The center point of th e grid represents the ambient monitoring site, the hollow grid represents the entire grid an alysis zone, and the colored regions represent the wind quadrant analys is zones. The individual wi nd quadrant analysis zones are larger for quadrants where wind speeds are great er and smaller for quadrants where wind speeds are light. For the Gary site and th ree of the Chicago area sites, the grid analysis zone consists of a 9 x 9 grid cell region 7 

# with the monitoring site in the cent er cell. For the Northbrook site in Chicago and the sites in Detr oit and Milwaukee—where average morning wind speeds were lower—the grid analysis zone consists of a 7 x 7 grid cell region ar ound each monitoring site (see Table 1-2 ).

Wind Quadrant 1 (1-90°) Wind Quadrant 2 (91-180°) Wind Quadrant 3 (181-270°) Wind Quadrant 4 (271-360°)



## Figure 1-2. Example of a full extent grid analysis zone, showing the spatial configuration of grid cells for which ambient- and emissions inventory-derived ratio comparisons were calculated. The monitoring site is represented by a small triangle.

Table 1-2. Dimensions of the full grid analysis zone around each monitoring site of interest.



# Site Name Dimensions of Grid Analysis Zone Area of Grid Analysis Zone (km 2 

# )

Chicago, IL – Jardine 9 x 9 cells 1,296 Chicago, IL – Northbrook 7 x 7 cells 784 Chicago, IL – Franklin 9 x 9 cells 1,296 Chicago, IL – Mannheim 9 x 9 cells 1,296 Gary, IN 9 x 9 cells 1,296 Detroit, MI – E7Mile 7 x 7 cells 784 Detroit, MI – Linwood 7 x 7 cells 784 Milwaukee, WI 7 x 7 cells 784



# To make consistent comparisons of total hyd rocarbons between the ambient data and the emissions inventory, the emissions inventory data were converted from mass to molar units. In

7 

## Note that each individual grid cell measures 4 km x 4 km, so the total area of a 9 x 9 grid cell region is 1,296 km 2



## , as shown in Table 1-2.

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-6 

# addition, the individual chemical species reporte d in the emissions inventory were matched to those in the ambient data, and only TNMOC species that are id entified by the PAMS program (i.e., PAMSHC, or the sum of PAMS-identified hydrocarbons) were included in the analyses. Appendix A contains the detailed chemical species cro ss-reference list that was used to match emissions inventory species to the ambient species.

1.2.3 Comparison of Ambient- and Emi ssions Inventory-Derived Hydrocarbon Compositions

In addition to ratio comparisons, the chemi cal composition of hydrocarbons reported in the emissions inventory was compared to the chemical composition of the ambient air at individual monitoring sites. These “fingerprint” analyses were used to determine how accurately the speciation of the emissions inventory comp ares to the data measured at the ambient monitoring sites. Fingerprint analyses were performed for each site by day of week (weekday, Saturday, and Sunday), month (June, July, August), and wind quadrant.

As a further review of the sp eciation of the emissions inve ntory, STI also computed and compared the relative reactivity of the organic species in the emissions inventory and ambient data. The reactivity of each species was estimated using published maximum incremental reactivity (MIR) values that represent the oz one formation potential of various organic compounds (Carter, 2003). Weight ed reactivity values for the em issions inventory and ambient data will be calculated as follows:

R = 

# 

 n

i 1 

# (MIR) i 

# w i



# where: R = weighted reactivity (MIR) i 

# = maximum incremental reactivity for species i

w i 

# = weight fraction of species i in th e emissions inventory or ambient data

Reactivity comparisons were performed by day of week (weekday, Saturday, and Sunday), month (June, July, August), and wind quadrant for each monitoring site.


# 1.3 Uncertainty Issues

Understanding the uncertainties associated with comparisons of ambi ent- and emissions inventory-derived pollutant ratio s is essential to assess the su itability of top-down evaluation analyses. Three general categories of uncertainty issues are associated with top-down emissions reconciliation analyses: (1) accuracy of the emissions inve ntory, (2) accuracy of the ambient concentration measurements, and (3 ) suitability of comparisons.

1.3.1 Emissions Inventory Uncertainties

To compare ambient pollutant ratios to emi ssions inventory ratios, it is important to accurately characterize, to the extent possible, the magnitude, spatial distribution, chemical composition, and diurnal pattern of emissions. Un certainties and inaccura cies associated with emissions inventory data gene rally stem from (1) emissions estimation techniques and

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-7 

# (2) emissions processing techniques. Inaccuracies and uncertainties associated with emissions estimation techniques include misc lassification or exclus ion of major emissi ons sources, the use of incorrect emissions activity data, the use of in correct emission factors, and the use of incorrect chemical speciation profiles. For on-road m obile sources, which are key emissions sources impacting the monitoring sites addressed in the project—particularly during the morning periods evaluated—emissions estimates have historic ally been prepared using EPA’s MOBILE6.2 model. The MOBILE6.2 model, which was used in the development of LADCO’s 2005 Base M inventory, calculates gram per mile emission rates for on-road mobile sources operating under various conditions, and though model outputs have been compared to data from tunnel studies and other “real-world” data (P ollack et al., 2004), EPA does not provide estimates of its uncertainty. Recently, EPA has replaced MOBI LE6.2 with the MOVES model, which is based on updated emissions test results (U.S. Envi ronmental Protection Agency, 2010). LADCO’s 2008 emissions inventory was developed using MOVES.

To perform a top-down emissions inventory evaluation, emissions estimates must be spatially and temporally resolved for the regi on surrounding the ambient monitoring sites. To accomplish this task, hourly gridded emissions estimates of VOC, NO x 

# , and CO were acquired from LADCO. The methods used to disaggreg ate annual average county wide total emissions estimates into gridded, hourly data can introduce inaccuracies into the emissions inventory data. For example, spatial surrogate data that are not representative of the locations of emissions sources can result in misrepresentation of th e geographic location of emissions sources. Similarly, temporal profiles that are not repr esentative of the monthl y, weekly, and diurnal distribution of emissions source ac tivity can result in misrepresentation of the diurnal activity patterns for sources within the vicinity (grid cells) of the ambient monitor.

To perform a top-down emissions inventory ev aluation, emissions estimates must also be chemically resolved, with VOC emissions disaggre gated into individual chemical species. STI used speciation profiles and cros s-reference files provided by LADCO to perform this step. Emissions inventory uncertainties can be introd uced during the speciation process through the incorrect assignments of specia tion profiles to emissions sources and/or by speciation profiles that do not represent the chemical source composition.

1.3.2 Ambient Measurement Uncertainties

Uncertainties associated with ambient measurements include instrument detection limits, precision of measurements, and sampling and hand ling losses. Prior to conducting an emissions inventory evaluation, the ambient data measuremen t methods should be assessed to ensure that the collection methods yield adequa te data for this type of analysis. Furthermore, the ambient data sets intended for use must be quality-assured to eliminate invalid samples. For this study, ambient data were subjected to a data validati on process that followed established protocols.

1.3.3 Uncertainties Associated with the Comparisons

Uncertainties associated with the comparison of ambient and emissions inventory data arise from the spatial and temporal matchi ng of ambient and emi ssions inventory data, meteorological factors, and atmospheric reac tions. To minimize differences between ambient- and emissions inventory- derived ratios due to mismatches in time and space, it is best

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-8 

# to use emissions estimates as close to the vintage of the ambient data as pr actical. For this study, emissions estimates representative of the winter and summer of 2005 were compared to ambient data for the winters and summers of 2004, 2005, and 2006, and emissions estimates representative of the winter a nd summer of 2008 were compared to ambient data for the winter and summer of 2008. 8



# A major premise of the top-down evaluation is that only monitoring sites and sampling periods that are dominated by fresh emissions should be considered in the analysis. It is possible that temporal uncertainties may be caused by ea rly morning ambient ratio s that include carryover emissions in which PAMSHC and/or NO x 

# have been preferentially removed by chemical conversion overnight. Spatial unc ertainties due to different in fluences of surface and aloft emissions may arise. For example, PAMSHC, CO, and NO x 

# emissions from nearby elevated sources may be injected aloft and, as a resu lt, may not mix into the surface air sample.

Meteorological factors such as wind speed, direction, and mixing depth determine the spatial distribution of emissions and thus dete rmine which emissions are sampled. Atmospheric reactions modify the species distribution and mass of midday and afternoon ambient samples. Thus, comparisons from midday and afternoon periods are likely to be less reliable than morning comparisons.


# 1.4 Summary of Results

The on-road mobile source component of LADCO’s 2005 emissions inventory was developed using EPA’s MOBILE6.2 model and link-level activity data. The top-down evaluation for the 2005 emissions inve ntory indicates that, in genera l, on-road mobile sources are represented accurately in the emissions data. This conclusion is based on the fact that agreement between ambient- and emissions-inventory-deriv ed pollutant ratios was closest (±20%) for wintertime CO/NO x 

# ratios, and on-road mobile sources accounted for 57% to 80% of wintertime CO and NO x 

# emissions at all sites for which ratios we re calculated. For sites in the Chicago area, agreement between ambient- and emissions inventory-derived pollutant ratios was as close as could be expected, given the limitations of the analysis techniques. However, comparisons with ambient data indicate that the emissions inventory for Sundays may not be representative of actual activity patterns on that day of the wee k, perhaps due to decreases in on-road mobile source emissions from Saturdays to Sundays, as we ll as inaccurate temporal characterizations of other source categories. In addition, sources of VOC emissi ons appear to be missing or underrepresented in the emissions inventory near sites that ar e influenced by industrial and residential emissions, such as the Gary site and the East 7 Mile site in Detroit.

The on-road mobile source component of LADCO’s 2008 emissions inventory was developed using EPA’s M OVES model with default input data , and county-level outputs from MOVES were spatially allocated using spatial surrogate data. 9 

# For the 2008 inventory, agreement between ambient- and emissions-invent ory derived pollutant ratios was generally

8 

## Ambient data from 2009-2010 were also evaluated as part of this project but were not compared directly with emissions data.
9 

## LADCO plans to update the 2008 inventory with state- specific MOVES inputs and link-level activity data. The 2008 inventory used in this analysis was the most current version as of April 29, 2011.

### Upper Midwest Emissions Inventory Evaluation Introduction



## 1-9 

# poorer than was observed for the 2005 inventory. The greater discrepancy between ambient- and emissions inventory-derived pollutant ratios prim arily results from large decreases in on-road NO x 

# emissions from 2005 to 2008 that outpaced reductions in ambient NO x 

# concentrations. However, the Saturday-to-Sunday differences in pollutant ratio comparisons observed for the 2005 inventory were not observed for the 2008 in ventory, as there was no variation between Saturday and Sunday on-road mobile source emi ssions in the 2008 inventory (as was the case for 2005).

For both 2005 and 2008, the speciation of the VOC emissions inventory at all sites does not compare well with the hydrocarbon compositi on of the ambient data , resulting in a VOC emissions inventory that is more reactive (i.e., prone to contribute to ozone formation) at all sites than the corresponding ambient data. As a result , ozone modeling efforts for the region may be influenced by “compensating errors,” as the underestimated magnitude of VOC emissions is offset by the overestimated r eactivity of those em issions. Key findings that support these conclusions include:

 For 2005, the agreement between overall ambient- and emissions inventory-derived CO/NO x 

# ratios is good (±30%) across all sites, particularly for winter months, and onroad mobile sources dominate the wintertime CO and NO x 

# inventories for all sites.

 For 2008, the agreement between overall ambient- and emissions inventory-derived CO/NO x 

# ratios is poorer (±60%) across all sites, and on-road mobile s ources continue to dominate the CO and NO x 

# inventories for all sites.

 For both 2005 and 2008, the agreement betw een overall ambient- and emissions inventory-derived TNMOC/NO x 

# ratios is good (±20%) for Chicago’s Jardine (2005 only) and Northbrook sites.

 For 2005, the agreement between overall ambient- and emissions inventory-derived TNMOC/NO x 

# ratios is poorest at the De troit East 7 Mile site and the Gary site, which are likely to be affected by industrial and residential emissions sources.

 For 2005, the agreement between ambient- and emissions i nventory-derived TNMOC/NO x 

# and CO/NO x 

# ratios is generally better on we ekdays and Saturdays than on Sundays. For 2008, the agreement between am bient- and emissions inventory-derived pollutant ratios is generally similar across all days.

 Comparison with the ambient data shows that the speciation of th e emissions inventory tends to overestimate the contribution of some species (e.g., acetylene, ethylene, toluene, and isoprene) and underestimate the contribu tion of other species (e.g., ethane, propane, and C6-C11 alkanes).

 Across all sites, the overall weighted reactivit y of the species pres ent in the emissions inventory for the summer season is 16% to 80% higher than the weight ed reactivity of the species present in the ambient data.

A detailed description of the analysis techniqu es and results that served as the basis for these conclusions and recommendations is pr ovided in the sections that follow.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-1 

# 2. Data Acquisition and Processing

Preparing ambient concentrati on, meteorological, and emissions inventory data for use in a top-down emissions inventory ev aluation involves several steps. This section presents a detailed discussion of the data preparation and processing performed for this emissions evaluation.


# 2.1 Ambient Monitoring Data

2.1.1 Ambient Data Acquisition

To support this top-down emissions evaluation, air quality and meteorological data for the years 2004

– 2006 and 2008

– 2010 were acquired from AQS for eight monitoring sites in the Upper Midwest. To effectively evaluate on-road mobile source emissions estimates, an effort was made to focus on monitoring sites that are likely to be impacted by fresh mobile source emissions. However, some of the sites included in these analyses were in the vicinity of other emissions sources, including non-road mobile sources (e.g., the Jardine and Mannheim sites in Chicago) and industrial sour ces (e.g., the Gary site), as described in Section 2.2.

Hourly data for summer (June

– August) and winter (December

– February) months were acquired from AQS for speciated hydrocarbons (HC), TNMOC, carbonyl compounds, CO, NO x 

# , wind speed, and wind direction. For the 2004

– 2006 period, hourly HC data are available for summer months at only five site s in the region. Available winter HC data are limited to 24-hour measurements of a small number of species (e.g., benzene and toluene) collected every six days, making these data insufficiently time-resolved for further analyses. 10 

# For CO and NO x 

# , hourly data are available for summer and winter months for all cities except Gary, for which wintertime CO data are unavailable (see Table 2-1 ).

Hourly HC data for 2008 and 2009 are availa ble for summer months at the ChicagoNorthbrook site, and for 2008 only at the Milwaukee site. Hourly CO and NO x 

# data are available for 2008, 2009, and the first quarter of 2010 at three sites in the Chicago area (see Table 2-1).

10 

## Comparisons between ambient data and emissions data are generally limited to morning hours, when ambient concentrations are most likely to be influenced by fresh pollutants (i.e., emission rates are high and chemical reaction rates are low).

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-2 Table 2-1. Hourly data available at individual monitoring sites (S=summer; W=winter).



# Site Name HC NO x 

# CO Wind Data
2004-2006 Data Availability Chicago-Jardine S S/W S/W Chicago-Northbrook S S/W S/W Chicago-Mannheim S/W S/W S/W Chicago-Franklin S/W S/W Gary S S/W S/W
Detroit-Linwood S/W S/W
Detroit-E7Mile S S/W S/W
Milwaukee S S/W S/W S/W
2008 Data Availability Chicago-Jardine a 

## S S/W Chicago-Northbrook b 

## S S/W S/W S/W Chicago- Mannheim S/W S/W S/W Chicago-Franklin S/W S/W Gary a 

## S/W S/W
Milwaukee S S/W S/W

2009 c 

## Data Availability Chicago-Jardine a 

## S S/W Chicago-Northbrook S S/W S/W S/W Chicago-Mannheim S/W S/W S/W Chicago-Franklin S/W S/W
Detroit-E7Mile S/W S/W Gary, IN a 

## S/W S/W
Milwaukee S/W S/W

a 

### Though 2008



# – 2009 TNMOC data for the Jardine and Gary site s were not found in AQS, these data may be available from state agencies. However, the data were not available for use in these analyses. b 

### The only winter data available for Northbrook are from December 2008 (no January/February data available).

c 

### Data available for January and February of 2010 were included in 2009 winter analyses. At the time analyses were conducted, NO x

### and CO data were available for the first quarter of 2010 at the Northbrook, Mannheim, and Franklin sites in Chicago.



# 2.1.2 Ambient Data Validation

Data validation was performed to identify a re presentative data set for each monitoring site of interest. Ambient data from 2004

– 2006 and 2008

– 2010 were brought into a Microsoft Access database, sorted, and imported into the Volatile Organic Compound Data Validation and Analysis Software (VOCDat) for validation. VOCD at allows visual inspection of the data and application of screening criteria. To ensure qua lity data for analysis, established protocols for

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-3 

# validation of the VOC data were followed. Data validation methods incl uded inspection of time series (e.g., TNMOC with total alkanes, alkenes, aromatics, carbonyl compounds, NO x 

# and ozone), scatter plots (e.g., ben zene/acetylene, benzene/toluene, ethane/propane, TNMOC/groups of species) and fingerprint plots (i.e., plots showing the concen tration of each species in a sample). Data quality issues identified during the validation process included:

 Data outliers

– Data outliers were defined as a si ngle sample spike in concentration observed in a species or group of species. These high values were excluded from analysis because, even if the measuremen ts were truly representative of ambient conditions during that hour, the values are not representative of the typical influence of emissions sources around the monitoring site and would skew the overall average. An example of a single sample high value from th e Gary, Indiana, PAMS site is shown in Figure 2-1 . This propane measurement may have been real but was more than 10 times higher than typical measurements at this site ; this value was not included in subsequent analyses.

 Low concentration values

– Abnormally low concentration values were also addressed by the data validation. For example, ethane and propane typically co rrelate well with one another, but there were samples at the Chica go-Jardine site in which ethane values were low relative to propane. Therefore, measurem ents were flagged as suspect when ethane values were less than 1 ppbC while propane va lues were greater than 2 ppbC. Typically, ethane concentrations drop below 2 ppbC only when there are problems with the analytical system. This problem occurred onl y at the Jardine site for the time period of interest.

Figure 2-1. Time series of propane and ethane concentrations (ppbC) at Gary, IN. 

# Ethane

Propane

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-4 

#  Shifts in species patterns

– In some cases, shifts in m easurements for a given species were unlike measurements during the previous and following weeks. For example, the CO baseline at Detroit Linwood site typica lly falls in the range between 100 ppb to 300 ppb. However, CO concentrations droppe d to zero from July 22 to July 26, 2006 (see Figure 2-2 ). Data from this anomalous period were excluded from subsequent analyses. In addition, TNMOC measuremen ts at the Northbrook site in Chicago increased sharply from 2005 to 2009. However, these increases were largely associated with the unidentified portion of TNMOC (see Figure 2-3 ), which may indicate changes in instrument sensitivity post-2005. Th e higher TNMOC measurements for 2008 and 2009 were included in our analyses but should be viewed with caution. 11



# Data quality issues identified during the validation process resulted in data being flagged as suspect and excluded from subsequent an alyses. For the 2004–2006 time period, only about 10% of the data were flagged as suspect for summ er months, and only about 8% of the data were flagged as suspect for winter months. For th e 2008–2010 time period, only a bout 4% of the data were flagged as suspect for summer months, a nd only about 1% of the data were flagged as suspect for winter months.

Figure 2-2. Time series of CO concentrations (ppb) for Linwood site in Detroit, MI.

11 

## It should also be noted that a significant amount of repair work occurred at the Northbrook site during 2008 and 2009. though this work did not directly involve the TNMOC instrument (auto-GC).

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-5 0 10 20 30 40 50 60 70

2004 2005 2006 2008 2009TNMOC (ppbC) 

### Unidentified
Identified



## Figure 2-3. Yearly variations in summer weekday TNMOC concentrations (ppbC) at the Northbrook site in Chicago, IL.



# 2.1.3 Ambient Site Characterization

To help characterize the land use pattern s and emissions sources surrounding each ambient monitoring site and to verify that all s ites were likely to be significantly impacted by mobile source emissions, digital images of the 5 km x 5 km area around each site were generated using Google Earth. In additi on, photographs taken around severa l of the monitoring sites are provided in Appendix B , as well as digital images of a larger area (28 km x 28 km) 12 

# around each site. A description of the area ar ound each monitoring site appears below.

12 

## The grid analysis zones around individual monitoring sites were all at least 7 x 7 grid cells, or 28 km x 28 km.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-6 

# Chicago – Jardine and Franklin



# The Chicago-Jardine site is located at the Ja rdine Water Filtration Plant on the shore of Lake Michigan. The site is east of downt own Chicago and about 0.7 km from Highway 41, making it subject to significant emissions from pleasure craft and commercial marine vessels, especially during summertime. The Chicago-Fra nklin site is in downtown Chicago about 3 km southwest of the Jardine site and about 0.2 km north of the Eisenhower Expressway (see Figure 2-4 ), making it an ideal site for capturing the effects of fresh downtown mobile emissions.

Figure 2-4. Image of the area around the Jardine and Franklin sites in Chicago.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-7 

# Chicago – Northbrook



# The Chicago-Northbrook site is located at the Northbrook Water Plant in a northern suburb of Chicago. The site is about 0.7 km s outh of the Tri-State Tollway and about 0.7 km west of a major highway (see Figure 2-5 ).

Figure 2-5. Image of the area around the Northbrook site in Chicago.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-8 

# Chicago – Mannheim



# The Chicago-Mannheim site is about 22 km nort hwest of downtown Chicago adjacent to O’Hare International Airport (see Figure 2-6 ) and subject to significan t aircraft and airportrelated emissions. The site is 0.2 km nor th of a toll booth on the Tri-State Tollway.

Figure 2-6. Image of the area around the Mannheim site in Chicago.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-9 

# Gary



# The Gary site is just south of the Mittal Steel Works and about 1.5 km northeast of downtown Gary. The site is about 0.6 km north of the interchange that connects two interstate highways (see Figure 2-7 ).

Figure 2-7. Image of the area around the Gary site.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-10 

# Detroit – East 7 Mile and Linwood



# The East 7 Mile and Linwood site s are both located in residen tial areas. The East 7 Mile site is about 11 km northeast of downtown Detroit, 4 km north of Interstate 94, and 4 km southeast of the Daimler Chrysler Warren Plant. The Linwood site is about 3 km northwest of downtown Detroit and is adjacent to several arterial roads, in cluding the Rosa Parks Memorial Highway (see Figure 2-8 ).

Figure 2-8. Image of the area around the East 7 Mile and Linwood sites in Detroit.



# Milwaukee



# The Milwaukee site is located in a largely urban and re sidential area about 2.5 km north of downtown Milwaukee and 3 km west of Lake Michigan. The site is about 0.5 km east of

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-11 

# Highway 43 and about 3 km northeast of the Mar quette Interchange that connects Interstates 94 and 43 near downtown Milwaukee (see Figure 2-9 ).

Figure 2-9. Image of the area around the Milwaukee site.



# 2.1.4 Ambient Concentration Data

For sites with summer TNMOC measurements , morning (0600–0900) concentrations of TNMOC and NO x 

# were summarized by day of w eek for data from 2004–2006 and 2008–2009 (see Table 2-2 ). For 2005, mean morning TNMOC concentr ations were highest at the Gary site and the East 7 Mile site in Detroit, which is lik ely due to a greater density of industrial emissions sources around those sites. TNMOC concentrat ions were 13% to 34% lower on weekend days relative to weekdays, with the Chicago-Jardine and Milwaukee sites having the largest weekend decreases in TNMOC concentra tions. At all sites except th e Milwaukee site, Sunday TNMOC concentrations were about the same as or highe r than Saturday TNMOC concentrations in 2005.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-12 

# Although mean morning NO x 

# concentrations did not vary among sites as widely as mean TNMOC concentrations did, NO x 

# concentrations were also lo wer on weekend days, decreasing by 11% to 53% on Saturdays and Sundays relative to weekdays. At all s ites except the Jardine site, Sunday NO x 

# concentrations were lower than Saturday NO x 

# concentrations by 16% to 40%. At the Gary site, Saturday NO x 

# concentrations were more simila r to weekday concentrations than to Sunday concentrations.

For 2008, ambient TNMOC measurements were only available at the Northbrook and Milwaukee sites. At Northbrook, TNMOC concentra tions were slightly higher in 2008 than in 2004

– 2006, while weekday NO x 

# concentrations were 13% lower in 2008 than in 2004–2006. 13 

# At the Milwaukee site, weekda y TNMOC concentrations were 24% higher in 2008 than in 2004-2006, while weekday NO x 

# concentrations decreased by 16% in 2008 (see Table 2-2).

For 2009, ambient TNMOC measurements were only available at the Northbrook site, where 2009 TNMOC concentrations were signifi cantly higher than in previous years (see Table 2-2). However, it should be noted that there were potential instrument issues at Northbrook, as described in Section 2.1.2 above.

Table 2-2. Mean summer TNMOC and NO x 

## concentrations.



# TNMOC (ppbC) NO x 

# (ppb) Site Weekday Saturday Sunday Weekday Saturday Sunday
2004-2006 Data Chicago-Jardine 43.9 30.1 37.5 30.3 14.3 16.7 Chicago-Northbrook 45.6 36.9 39.7 23.5 16.2 11.8
Milwaukee 74.8 59.8 49.7 21.9 13.1 11.0 Gary 142.4 122.0 119.2 26.2 23.2 13.8
Detroit-E7 Mile 157.8 131.6 132.3 22.2 14.4 10.4

2008 Data Chicago-Northbrook 47.3 37.8 43.9 20.5 10.2 10.1
Milwaukee 92.5 81.8 69.9 18.3 11.3 6.8

2009 Data Chicago-Northbrook 67.3 61.9 74.6 14.2 8.9 6.7



# For sites with summer and winter CO measurements, morning (0600–0900) concentrations of CO and NO x 

# were summarized by day of w eek for data from 2004–2006 and 2008–2009 (see Tables 2-3 and 2-4 ). In general, mean morning CO and NO x 

# concentrations were higher in winter than in summer, which is likely due to both meteorological conditions (e.g., lower mixing heights in winter) and increased CO emissions from light-duty vehicles in

13 

## Weekend NO x 

## concentrations for 2008 at Northbrook showed a sharper decrease on Satu rdays than on Sundays relative to data from 2004–2006, but note that the use of data from only one summer limits the sample size for individual days of the week.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-13 

# winter. 14 

# CO and NO x 

# concentrations for both summer and wi nter were highest at the Franklin and Mannheim sites in Chicago. Across all years, CO concentrations were 5% to 45% lower on weekend days relative to weekdays , with the Chicago-Franklin si te having the largest weekend decrease in CO concentrations. NO x 

# concentrations were 15% to 77% lower on weekend days relative to weekdays, with the Ch icago-Franklin site again havi ng the largest weekend decrease in concentrations.

Ambient data from the Chicago-Mannheim s ite showed that summer and winter CO concentrations decreased by about 40% in 2008 compared to 2004–2006. Measurements of NO x 

# concentrations in 2008 showed a decrease of abou t 13% in the winter an d little change in the summer compared to 2004–2006. At the Chicago-Fra nklin site, winter CO concentrations in 2008 decreased by about 20% compared to 2004–2006 (see Table 2-4).

For 2009, CO concentrations at the Mannheim s ite increased relative to 2008, particularly for summer months, while NO x 

# concentrations continued to decrea se. At the Franklin site, both CO and NO x 

# concentrations decreased between 2008 and 2009. At the Northbrook site, CO and NO x 

# concentrations generally increased between 2008 and 2009 for winter months and decreased for summer months. It should also be noted that 2009 wintertime NO x 

# concentrations decreased by 45% on Saturdays at the Franklin and Mannh eim sites relative to 2008, while weekday and Sunday concentrations decreased by less than 20 %. This sharper decrease on Saturdays may be due to reduced heavy-duty truck traffic on Saturdays as a result of the recent economic downturn. However, at the Northbrook site, weekend NO x 

# concentrations rose sharply between 2008 and 2009, while weekday NO x 

# concentrations were virtually unchanged.

Table 2-3. Mean summer (June–August) CO and NO x 

## concentrations.



# CO (ppb) NO x 

# (ppb) Site 

# Weekday Saturday Sunday Weekday Saturday Sunday

2004-2006 Data Chicago-Franklin 643 371 417 85.9 37.7 25.0 Chicago-Mannheim 541 440 384 76.4 44.5 27.1
Milwaukee 306 266 263 21.9 13.1 11.0
Detroit-Linwood 414 304 318 34.9 21.8 16.3
2008 Data Chicago-Franklin 641 439 389 88.2 40.3 20.1 Chicago-Mannheim 331 255 212 73.1 44.4 30.0 Chicago-Northbrook 227 196 198 21.0 10.5 9.2
2009 Data Chicago-Franklin 471 335 313 57.9 31.8 20.4 Chicago-Mannheim 388 304 283 55.6 26.8 19.5 Chicago-Northbrook 210 184 178 14.2 8.9 6.7

14 

## Note that the Franklin site was an exception to this pattern in 2008, when summer weekday CO concentrations were 11% higher than corresponding winter concentrations.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-14 Table 2-4. Mean winter (December–February) CO and NO x 

## concentrations.



# CO (ppb) NO x 

# (ppb) Site Weekday Saturday Sunday Weekday Saturday Sunday

2004-2006 Data Chicago-Franklin 742 520 411 119.1 61.3 38.9 Chicago-Mannheim 745 560 487 132.6 75.1 55.4
Milwaukee 448 425 338 49.5 41.6 21.6
Detroit-Linwood 510 476 429 57.1 48.3 39.8

2008 Data Chicago-Franklin 579 433 350 111.8 66.0 40.8 Chicago-Mannheim 436 310 283 115.6 68.0 47.8 Chicago-Northbrook a 

## 282 199 199 42.8 11.9 16.4

2009 b 

## Data Chicago-Franklin 524 422 360 90.7 36.3 39.4 Chicago-Mannheim 463 304 331 93.5 36.2 41.7 Chicago-Northbrook 335 256 269 41.9 18.9 28.7

a 

### Wintertime concentrations listed for the Northbrook site represent the month of December 2008 only. b 

### Wintertime concentrations listed for 2009 include available data from January and February 2010.



# Diurnal patterns of TNMOC, NO x 

# , and CO concentrations were explored using notched box whisker plots ( Figure 2-10 ). Across all years, weekday TNMOC, NO x 

# , and CO concentrations generally showed a morning p eak, consistent with traffic activity, and an afternoon decrease, which could be a function of both decreased tr affic activity and increased atmospheric mixing. Diurnal plots of pollu tant concentrations for 2004–2006 are shown in Figures 2-11 through 2-18 , and diurnal plots for addi tional years are provided in Appendix C

. On weekend days, a small increase in concentr ations is generally observed for both TNMOC and NO x 

# just after noon, consistent with delayed traffic activity on w eekends compared to weekdays (also seen by Chinkin et al., 2002). At Jardine (Figure 2-11), the diurnal profile for TNMOC on weekend days is much flatter than on weekdays (i .e., concentrations vary less from hour to hour). However, at Northbrook, the weekend and w eekday diurnal profiles for TNMOC are very similar (Figure 2-12). For CO, diurnal variati ons are somewhat dampened by the resolution of the data. In addition, the instrume nt used at the Gary site appear s to have a detection limit of 250 ppb, so there are no data below that value.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-15 25 th 

### percentile 75 th 

### percentile



# 0 100 200 300Measure 

# Outliers

Notch around median Median 95 % C.I.

95 % C.I. Whisker

25 th 

### percentile 75 th 

### percentile



# 0 100 200 300Measure 

# Outliers

Notch around median Median 95 % C.I.

95 % C.I. Whisker

Figure 2-10. Interpretation of notched box whis ker plots produced by SYSTAT. Boxes show the 25 th 

## to 75 th 

## percentiles (interquartile range, or IQR); whiskers extend to 1.5IQR; and concentrations beyond the whiskers are designated by asterisks. Concentrations beyond 3IQR are designated with open circles. The median and 95% confidence intervals (C.I.) are shown by a notch.

## 2-1601234567891011121314151617181920212223Hour050100150200

T N M O C ( p p b C )01234567891011121314151617181920212223Hour050100150200

T N M O C ( p p b C )01234567891011121314151617181920212223Hour050100150200

T N M O C ( p p b C )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )Figure 2-11.Hourly TNMOC and NOxconcentrations for the Chicago-Jardine site for summer weekdays (left), Saturdays(center), and Sundays (right), 2004–2006.

## 2-1701234567891011121314151617181920212223Hour0100200300

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300

T N M O C ( p p b C )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )Figure 2-12.Hourly TNMOC and NOxconcentrations for the Chicago-Northbrook site for summer weekdays (left), Saturdays(center), and Sundays (right), 2004–2006.

## 2-1801234567891011121314151617181920212223Hour0100200300400500

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300400500

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300400500

T N M O C ( p p b C )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )Figure 2-13.Hourly TNMOC and NOxconcentrations for the Gary site for summer weekdays (left), Saturdays (center), andSundays (right), 2004–2006.

## 2-1901234567891011121314151617181920212223Hour0100200300400500

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300400500

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300400500

T N M O C ( p p b C )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )Figure 2-14.Hourly TNMOC and NOxconcentrations for the Detroit-East 7 Milesite for summer weekdays (left), Saturdays(center), and Sundays (right), 2004–2006.

## 2-2001234567891011121314151617181920212223Hour0100200300

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300

T N M O C ( p p b C )01234567891011121314151617181920212223Hour0100200300

T N M O C ( p p b C )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour02004006008001000

C O ( p p b )01234567891011121314151617181920212223Hour02004006008001000

C O ( p p b )01234567891011121314151617181920212223Hour02004006008001000

C O ( p p b )Figure 2-15.Hourly TNMOC, NOx, and CO concentrations for the Milwaukee site for summer weekdays (left), Saturdays (center),and Sundays (right), 2004–2006.

## 2-2101234567891011121314151617181920212223Hour050010001500

C O ( p p b )01234567891011121314151617181920212223Hour050010001500

C O ( p p b )01234567891011121314151617181920212223Hour050010001500

C O ( p p b )01234567891011121314151617181920212223Hour050100150200

N O x ( p p b )01234567891011121314151617181920212223Hour050100150200

N O x ( p p b )01234567891011121314151617181920212223Hour050100150200

N O x ( p p b )Figure 2-16.Hourly CO and NOxconcentrations for the Chicago-Mannheim site for summer weekdays (left), Saturdays (center),and Sundays (right), 2004–2006.

## 2-2201234567891011121314151617181920212223Hour02004006008001000

C O ( p p b )01234567891011121314151617181920212223Hour02004006008001000

C O ( p p b )01234567891011121314151617181920212223Hour02004006008001000

C O ( p p b )01234567891011121314151617181920212223Hour050100150200

N O x ( p p b )01234567891011121314151617181920212223Hour050100150200

N O x ( p p b )01234567891011121314151617181920212223Hour050100150200

N O x ( p p b )Figure 2-17.Hourly CO and NOxconcentrations for the Chicago-Franklin site for summer weekdays (left), Saturdays (center),and Sundays (right), 2004–2006.

## 2-2301234567891011121314151617181920212223Hour050010001500

C O ( p p b )01234567891011121314151617181920212223Hour050010001500

C O ( p p b )01234567891011121314151617181920212223Hour050010001500

C O ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )01234567891011121314151617181920212223Hour020406080100

N O x ( p p b )Figure 2-18.Hourly CO and NOxconcentrations for the Detroit-Linwood site forsummer weekdays (left), Saturdays (center), andSundays (right), 2004–2006.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-24 

# 2.1.5 Ambient Data Screening

As described in Section 1.3.3, a major premise of the top-down evaluation is that only monitoring sites and sampling peri ods that are dominated by fresh emissions are considered in the analysis. Therefore, ambient measurements that do not exceed background thresholds were not included in the data sets used to calculate pollutant ratios. For th is analysis, we used concentration thresholds of VOC > 50 ppbC, NO x 

# > 10 ppb, and CO > 0.150 ppm (Chinkin and Reid, 2006; LADCO, 1998).


# 2.2 Emissions Inventory Data

2.2.1 Emissions Data Acquisition and Processing

LADCO provided 2005 Base M emi ssions inventory data file s and supporting files (e.g., speciation profile libraries) fo r area, point, non-road mobile, on-road mobile and biogenic sources. LADCO’s anthropogenic emission files c ontain criteria pollutant emissions that have been spatially resolved to a 4-km grid resolution and temporally resolved to an hourly basis. For all anthropogenic source sector s other than on-road mobile sources, emissions data were provided for a representative weekday, Saturd ay, and Sunday in each month of 2005. For on-road sources, gridded criteria pollutant em issions were provided for a January weekday, Saturday, and Sunday, and air quality model-re ady emission inputs were provided for January and July weekdays, Saturdays, and Sundays. For biogenic sources, hourly emissions data for isoprene and other air quality m odel-ready biogenic species we re provided at a 12-km grid resolution for each day of 2005. Emissions grid domains and file formats varied by source sector (see Figure 2-19 and Table 2-5 ), with file formats includi ng SAS, PostgreSQL, and CAMx binary.

For 2008, LADCO provided Base B (on-road an d non-road mobile sources) and Base C (area and point sources) anthropogenic 15 

# inventories at the same sp atial (4-km) and temporal (hourly) resolution as the 2005 emissions inventorie s. All 2008 emissions were provided in SAS format for the innermost grid domain shown in Figure 2-19, and files for a representative weekday, Saturday, and Sunday in each month were again made available. For on-road mobile sources, 2008 emissions were generated by runni ng the MOVES model with county-level default data for the region, then gridding the county-le vel emissions using sp atial surrogate data. 16 

# By contrast, the 2005 on-road invent ory was developed at the link level using MOBILE6.2 emission factors within the Consolidated Commun ity Emissions Processing Tool (CONCEPT). 17 

# As a result, some differences between the 2005 and 2008 on-road inventories result from this change in models, rather than from changes in vehicle fleets and activities alone.

15 

## Biogenic emissions for 2008 were not available, so emissions from this source sector were held constant from 2005.
16 

## For light-duty vehicles, LADCO used a hybrid surrogate that combined vehicle mile s traveled (weighted 75%) with population data (weighted 25%). For trucks, LADCO used miles traveled on rural secondary roads as the spatial surrogate.
17 

## For subsequent versions of the 2008 on-road invent ory, LADCO will replace MOVES default data with local information on vehicle characteristics and activities a nd will generate link-level emissions using CONCEPT.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-25 Figure 2-19. Emissions grid domains for the LADCO 2005 Base M inventories.

Table 2-5. LADCO emissions inventory files for January 14, 2005.



# File Name Description
areaemis.sas7bdat.050114.other_baseM_v3_4km SAS file for area source emissions

areaemis.sas7bdat.050114.mar_baseM_4km SAS file for marine, aircraft, and rail emissions

areaemis.sas7bdat.050114.nonroad_baseM_v3_4km SAS file for non-road mobile source emissions other than marine, aircraft, and rail

ptemis.sas7bdat.050114.egu_baseM_4km SAS file for electrical generating units (EGUs) ptemis.sas7bdat.050114.pt_nonutil_baseM_4km SAS file for non-EGU point sources

ocin_[network]_01142005_01.mv_emissions_raw.sql PostgreSQL file for on-road mobile source emissions (files provided for transportation networks covering Chicago, Milwaukee, Gary, and Detroit) camx_mv.[network]_01142005_01.base.out.200514.bin CAMx-ready on-road emissions file biog.20050114.upmw.12.megan.ld.bin CAMx-ready biogenic emissions file

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-26 

# To prepare the emissions data for use in subs equent analyses, we converted all data files to a common CSV format. We then extracted data records for the grid cells included in the grid analysis zones around each of the eight monitoring sites of interest. These grid analysis zones were identified for each site on the basis of predominant wind speeds during the early morning hours (0600–0900), as described in Section 1.2.2. For the Gary si te and three of the Chicago area sites, the grid analysis zone consists of a 9 x 9 grid cell ar ea with the monitoring site in the center cell. For the Northbrook site in Chicago and the sites in Detroi t and Milwaukee—where average morning wind speeds were lower—the grid analysis zone consists of a 7 x 7 grid cell area around each site.

Additional pre-processing was required for 2005 on-road mobile and biogenic sources because it was necessary to use emissions data th at had been prepared for the Comprehensive Air Quality Model with extensions (CAMx). For 20 05, gridded, hourly criteria pollutant emissions for on-road mobile sources were available only fo r January, so gridded hourly emissions for July were developed on the basis of CAMx-ready emissions. 18 

# The CAMx-ready files for January and July contain gridded, hourly emissions, but the emissions for orga nic species are grouped together by carbon bond mechanisms rather than reported by indi vidual hydrocarbon species (as required for comparisons with ambient data). As a result, scaling factors were derived from the January and July CAMx emissions data that coul d be used to convert January criteria pollutant emissions data to July emissions data. Specifi cally, CAMx-ready species CO, nitric oxide (NO), and paraffin carbon bond (PAR 19 

# ), were extracted for the grid analysis zone around each monitoring site; the rati o of January and July morning hour (0600–0900) emissions for each site was used to scale January criteria pollutant emissions that had been extracted from PostgreSQL files. For other months of interest, on-road emissions data were prepared by performing a linear interpolation on January and July emissions, in keeping with the method LADCO has used to develop emissions estimates for on-road sources for months other than January and July.

For biogenic sources, CAMx-ready emission input s were provided at a 12-km resolution for each day of 2005. Emissions data from these f iles were averaged across months of interest (December–February and June–August), and isoprene 20 

# emissions for each monitoring site’s grid analysis were then extracted from each monthly average file. Because biogenic emissions data were reported at a 12-km resolution, gridded emi ssions were disaggregated to a 4-km resolution by evenly distributing the emissions for each 12-km grid cell across the ni ne 4-km grid cells contained within the larger 12-km cell.

Once pre-processing of the emissions da ta was complete, STI speciated (i.e., disaggregated into individual hydrocarbon species) anthropogenic VOC emissions using the speciation profiles and cross-refe rence files provided by LADCO. At LADCO’s direction, the same speciation data was applied to both the 2005 and 2008 inventories, and this process resulted in a speciated inventory with hundreds of chem ical species. However, the ambient data collection and analysis method is capable of quantifying only hydrocarbons containing between approximately 2 and 12 carbon atoms (i.e., PAMS hydrocarbons). To ensure that the same

18 

## This step was unnecessary for the 2008 inventories, as gridded, hourly on-road emissions data was available for all months.
19 

## PAR is the dominant organic species in the on-road emissions inventories and was used as a surrogate for VOC emissions.
20 

## Isoprene is the dominant biogenic species and is the only biogenic species measured at PAMS sites.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-27 

# chemical compounds are being compared in th e ratio comparisons, the individual chemical species reported in the emissions inventory were matched to those measured in the ambient data. The compounds reported in the emissions inventor y that were not measurable in the ambient samples were excluded from the analysis. To co mpare the emissions inventory data to ambient data, the emissions inventor y data were converted from mass to molar units.

2.2.2 Emissions Data Char acterizations by Site

To gain an understanding of the source mi x around each monitoring site, we summarized the 2005 and 2008 emissions data for each site’s grid analysis zone. Tables 2-6 through 2-8 summarize morning (0600-0900) emi ssions for sites where TNMOC/NO x 

# and CO/NO x 

# ratios were evaluated, while Figures 2-20 and 2-21 break down morning emissions by source sector and year for all sites. These tables and figures show that, in general, CO and NO x 

# emissions decreased more sharply from 2005 to 2008 than VOC emissions. This difference was largely driven by the on-road mobile so urce sector, as 2008 CO and NO x 

# emissions from the MOVES model were 28% to 78% lower for winter m onths than corresponding 2005 estimates generated with MOBILE6.2, while 2008 on-road VOC emissions were comparable to (and, in some cases, higher) than corresponding 2005 emissions for both summer and winter months (see Figure 2-22 ). It should be noted that the sharp decreases in on-road NO x 

# emissions around the monitoring sites was driven, in part, by differences in the spatial distributions of emissions for 2005 and 2008. For example, Figure 2-23 shows the spatial dist ribution of on-road NO x 

# emissions for 2005 and 2008 for Cook County, and emissions have clearly been shifted from the lakefront area to the northwestern part of the county. 21 

# However, the total on-road NO x 

# emissions for Cook County decreased by 32% from 2005 to 2008 (for January weekdays), so the significant NO x 

# emissions reductions around the Chicago-area monitoring sites was not solely due to spatial differences in the 2005 and 2008 inventories.

The 2008 inventories also show less of an em issions decrease from Saturdays to Sunday than the 2005 inventories, which is again driv en by differences in the on-road mobile source sector. The 2008 MOVES-based in ventories treat Saturdays and Sundays the same and also show less of a decrease from weekdays to weekend days than th e 2005 inventories (see Figure 2-24 ). However, it should be noted that this f eature of the 2008 on-road emissions data results from using MOVES default day-of-week profiles.

Emissions summaries by source sector for each monitoring site of interest (see Figures 2-20 and 2-21) show that on-road mob ile source emissions account for 61% to 80% of the January CO emissions in both 2005 and 2008. For 2005, on-road mobile sources account for 50% to 73% of the January and July NO x 

# emissions around each monitoring site except for the Gary site, where the point source CO and NO x 

# inventories were more do minant than at the other sites. However, for 2008, on-road mobile sour ces account for only 29% to 54% of the January and July NO x 

# emissions around the non-Gary sites due to sharp reductions in on-road NO x 

# emissions between the 2005 and 2008 inventories. For VOC, area sources account for 35% to

21 

## These differences in the spatial distribution of on-road NO x 

## emissions result from the use of link-level vehicle activity data for the 2005 inventory vs. the gridding of county-level 2008 emissions using spatial surrogate data (e.g., rural secondary roads for truck activity).

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-28 

# 57% of the January and July emissions around each site in both 2005 and 2008, 22 

# while on-road mobile sources account for only 15% to 39% of th e January and July emissions around each site.

For the sites where TNMOC/NO x 

# ratios were evaluated, VOC emissions were highest around the Chicago-Jardine site and lowest ar ound the Gary and Milwaukee sites for both 2005 and 2008 (see Table 2-6). Conversely, 2005 ambient TNMOC concentrations were highest at the Gary and Detroit-East 7 Mile si tes, and lowest at the Jardine site. In addition, VOC emissions around the East 7 Mile site were 18% lower th an VOC emissions around the Jardine site (see Table 2-6). These discrepancies suggest that VOC emissions are underestimated at the Gary and East 7 Mile sites in the 2005 inventories.

For 2008, weekday VOC emissions decreased by 26% at the Milwaukee site relative to 2005, while 2008 ambient TNMOC concentrations in creased by 24% relative to 2004. At the Chicago-Northbrook site, both VOC emissions and ambient TNMO C concentrations showed little change from 2005 to 2008 (Milwaukee and No rthbrook were the only two sites for which 2008 ambient TNMOC measurements were available).

For sites where CO/NO x 

# ratios were evaluated, 2005 a nd 2008 emissions were highest at the Franklin and Mannheim sites in Chicago and lo west at the Milwaukee site (see Tables 2-7 and 2-8). Across all sites and years, emissions decreased more sharply relative to weekdays on Sundays than on Saturdays, though this effect wa s much more pronounced in the 2005 data than the 2008 data because Saturday and Sunday emissions were identical in the 2008 MOVES-based on-road inventory (as discussed above).

Table 2-6. Summary of summer (July) VOC and NO x 

## emissions for hours 0600 to 0900 for the grid analysis zone around each monitoring site analyzed.



# VOC (tons/day) NO x 

# (tons/day) Site Weekday Saturday Sunday Weekday Saturday Sunday

2005 Data Chicago-Jardine 43.7 41.3 34.3 43.0 37.1 32.2ChicagoNorthbrook 19.0 19.9 15.9 16.6 15.1 12.7

Milwaukee 18.3 12.2 9.7 19.5 9.9 6.0 Gary 13.1 15.9 12.0 22.3 21.8 19.3
Detroit-E7 Mile 35.9 25.2 18.2 29.0 13.0 9.4
2008 Data Chicago-Jardine 40.2 40.5 40.3 28.0 24.5 23.9ChicagoNorthbrook 19.6 19.8 19.7 12.3 10.5 10.2

Milwaukee 13.6 13.2 13.2 11.6 9.9 9.4 Gary 11.6 13.8 13.8 17.3 17.3 16.0
Detroit-E7 Mile 26.1 22.8 22.7 15.7 12.8 12.5

22 

## Key area sources of VOC include architect ural coatings and consumer products.

## 2-29Table 2-7.Summary of summer (July) CO and NOxemissions for hours 0600 to 0900 for the grid analysis zone around eachmonitoring site analyzed.CO (tons/day)NOx(tons/day)SiteWeekdaySaturdaySundayWeekdaySaturdaySunday2005 DataChicago-Franklin237.1279.4193.746.440.635.5Chicago-Mannheim324.1386.5254.556.349.341.6Milwaukee91.075.146.419.59.96.0Detroit-Linwood169.5147.4102.235.718.314.12008 DataChicago-Franklin178.3162.1159.928.125.124.5Chicago-Mannheim225.0197.0194.428.123.823.2Milwaukee73.565.064.311.69.99.4Detroit-Linwood130.8113.6112.419.616.515.8Table 2-8.Summary of winter (January) CO and NOx emissions forhours 0600 to 0900 for the grid analysis zone around eachmonitoring site analyzed.CO (tons/day)NOx(tons/day)SiteWeekdaySaturdaySundayWeekdaySaturdaySunday2005 DataChicago-Franklin255.9178.5139.948.239.434.2Chicago-Mannheim332.5235.1181.159.747.739.8Milwaukee152.340.842.023.47.96.8Detroit-Linwood241.6130.999.143.820.418.42008 DataChicago-Franklin181.9144.9143.430.526.926.5Chicago-Mannheim206.7164.0162.229.425.324.8Milwaukee77.663.062.512.310.710.3Detroit-Linwood123.5101.1100.321.118.317.7

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-30 Jardine

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad Northbrook

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad

Franklin

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad Mannheim

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad

Gary

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad E7Mile

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad

Milwaukee

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad Linwood

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad



## Figure 2-20. January weekday emissions by source sector for the grid analysis zone around each monitoring site for hours 0600 to 0900.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-31 Jardine

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad Northbrook

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad

Franklin

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad Mannheim

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad

Gary

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad E7Mile

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad

Milwaukee

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad Linwood

0 10 20 30 40 50 60

2005 2008 2005 2008 2005 2008

CO/10 NOx VOCEmissions (tons) Biogenic
Point
Area
Nonroad
Onroad



## Figure 2-21. July weekday emissions by source sector for the grid analysis zone around each monitoring site for hours 0600 to 0900.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-32 ROG - January

0 2 4 6 8 10 12 14

J a rdin

e

N

ort

hb

ro ok Franklin Ma n nhe

im G ary

East 7 Mil e

L inw

o od MilwaukeeEmissions (tons) 2005
2008 ROG - July

0 2 4 6 8 10 12 14

Jardine Nort h brook

F ra nklin Ma nnh

eim Gary

E ast

7 Mil e
Li nw

ood Milwau ke

eEmissions (tons) 2005
2008

NOx - January

0 5 10 15 20 25 30 35 40 45 50

J a rdine Northb ro ok Fr a nklin

M ann

heim Gary

E ast 7 M ile

L inwoo d Milwa uk

eeEmissions (tons) 2005
2008 NOx - July

0 5 10 15 20 25 30 35 40 45 50

Jar

din

e No rthb

roo

k Fr an

klin Man n heim G ary

Ea

s t 7 Mi le Linwood
Mi lw

aukeeEmissions (tons) 2005

2008

CO - January

0 50 100 150 200 250 300

Jardine No rthb

rook Fran k lin Man nhe

im Gary
Ea

st

7 Mile Linw ood

M ilwauk e eEmissions (tons) 2005
2008 CO - July

0 50 100 150 200 250 300

Jardine No rth

broo

k Franklin Ma nnh

eim Gar y

E ast

7 M

ile Lin w ood Milw a ukeeEmissions (tons) 2005

2008



## Figure 2-22. January (left) and July (right) weekday on-road mobile source emissions for the grid analysis zone around each monitoring site for hours 0600 to 0900.

### Upper Midwest Emissions Inventory Evaluation Data Acquisition and Processing



## 2-33 Figure 2-23. Spatial distributions of NO x 

## emissions from on-road mobile sources in Cook County for LADCO’s 2005 (left) and 2008 (right) inventories.

0% 2% 4% 6% 8% 10% 12% 14% 16% 18% 20%

Mon Tues Wed Thu Fri Sat SunPercentage of weekly emissions



### 2005 - Chicago
2005 - Detroit
2005 - Milwaukee 2005 - Gary
2008 - All Cities



## Figure 2-24. Day-of-week emissions profile s for on-road mobile sources.

.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-1 

# 3. Pollutant Ratio Comparison Results

To evaluate the relative amounts of TNMOC (PAMSHC), NO x 

# , and CO in the urban areas of interest, ambient- and em issions inventory-derived TNMOC/NO x 

# and CO/NO x 

# ratios were compared. Comparisons were made for the full extent grid analysis zone surrounding each monitoring site and for each indi vidual wind quadrant within the analysis zone. Ambient data average and median ratios were calculated, and ratios were calculated for the emissions inventory with and without elevated sources. 23



# 3.1 TNMOC/NO x 

# Ratio Comparisons

TNMOC/NO x 

# ratios for the summer months were calculated by day of week (weekday, Saturday, and Sunday), month (June, July, and August), summer season (June through August), and wind quadrant. For 2005, comparisons between ambient- and emissions-inventory-derived TNMOC/NO x 

# ratios were made for five sites: Ch icago-Jardine, Chicago-Northbrook, Gary, Detroit-East 7 Mile, and Milwaukee. For 2008, comparisons were made for the two sites for which ambient TNMOC measuremen ts were available: Chicago-Northbrook and Milwaukee.

Table 3-1 shows calculated ratios for the full grid extent around each monitoring site (previously shown in Table 1-2) for all summer days. For both 2005 and 2008, these data show good agreement 24 

# (±20%) between ambient- and emissions inventory-derived ratios at the Chicago sites. However, at the remaining site s, ambient-derived rati os were higher than emissions inventory-derived ratios by a fact or of 1.8 or more, although the ratios showed somewhat closer agreement when elevated sources were excluded from the analysis.

Across all sites, emissions inventory-derived TNMOC/NO x 

# ratios were higher in 2008 than in 2005, which resulted from decreases in on-road NO x 

# emissions that were greater than decreases in on-road VOC emissions. At the two sites for which both 2005 and 2008 data were available, ambient-derived TNMOC/NO x 

# ratios were also higher in 2008 than in 2005. The following sections show TNMOC/NO x 

# ratio charts by wind quadra nt and day of week and discuss the results of the analysis for each site. Additional charts (e.g., TNMOC/NO x 

# ratios by month) can be found in Appendix D

.

23 

## Emissions from elevated sources may be injected above the mixed layer and, hence, may not affect surface-level ambient concentrations—especially during morning hours. Pollutant ratios were calculated with and without elevated sources to characterize the potential effects of this phenomenon.
24 

## Because of the inherent uncertaintie s associated with this analysis method, ambient- and emissions inventoryderived ratios that are within approximately 25-50% of each other are considered to be in good agreement (California Air Resources Board, 1997).

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-2 Table 3-1. TNMOC/NO x 

## ratios by site for the hours 0600 to 0900 (emission ratios for full grid extent around each site; ambient ratios for 2005 based on 2004–2006 data).



# Emissions Inventory Ratios Site Ambient Ratios Low Level Only Low Level + Elevated Ambient/EI (Low Level) Ambient/EI (Low Level + Elevated)

2005 Data Chicago-Jardine 1.6 1.7 1.6 0.9 1.0 Chicago-Northbrook 2.2 1.8 1.8 1.2 1.2 Gary 6.0 1.6 1.1 3.6 5.4
Detroit-E7 Mile 6.3 2.3 2.2 2.7 2.9
Milwaukee 3.5 2.0 1.5 1.8 2.3
2008 Data Chicago-Jardine -- 2.5 2.2 -- -- Chicago-Northbrook 2.6 2.9 2.9 0.9 0.9 Gary -- 1.8 1.1 -- -- Detroit-E7 Mile -- 2.7 2.4 -- -- Milwaukee 5.1 2.1 1.7 2.4 2.9



# 3.1.1 Ratio Comparison Results for Chicago-Jardine

Figure 3-1 shows 2005 TNMOC/NO x 

# ratios by wind quadrant 25 

# and day of week for the Jardine site in Chicago, Illinois. Overall, there is good agreement between the ambient- and emissions inventory-derived ratios at this site across all wind quadrants an d days of week. For wind quadrant 1, however, the agreement between ambient- and emissions inventory-derived ratios is poorer than for the remaining wind quadrants, with the emissions inventory-derived ratio about 40% higher than the ambient- derived ratio. However, it s hould be noted that because wind quadrant 1 lies northeast of the site, over Lake Michigan (see Figure 2-4), emission levels in that quadrant are very low compared to the other wind quadrants.

Also, the agreement between ambient- a nd emissions inventory-derived TNMOC/NO x 

# ratios is poorer on weekend days than on weekdays. This is particularly true for Sundays, when the ambient-derived TNMOC/NO x 

# ratio is about 40% higher than the corresponding emissions-derived ratio. Sunday TNMOC and NO x 

# concentrations at Ja rdine are both about 20% higher than Saturday concentrations , making the ambient-derived TNMOC/NO x 

# ratios at that site virtually the same on Saturdays and Sundays. However, the emissions inventory shows decreases in both VOC and NO x 

# emissions on Sundays relative to Saturdays, and the somewhat sharper decrease in VOC emissions lowers the emissions invent ory-derived TNMOC/NO x 

# ratio.

25 

## On all bar charts, the ambient value represen ts the median, and error bars represent the 25 th 

## and 75 th 

## percentiles.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-3 0 1 2 3 4

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 1 2 3 4

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.6

0.9
0.9 0.8 0.9 0.9 1.3 1.4

0 1 2 3 4

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 1 2 3 4

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.6

0.9
0.9 0.8 0.9 0.9 1.3 1.4

Figure 3-1. TNMOC/NO x 

## ratios by wind quadrant and day of week for the Jardine site, 2004-2006 (note that for this figure and subsequent ratio comparison figures, values above each ratio group represent the ambient ratio divided by the low-level emissions only ratio).



# 3.1.2 Ratio Comparison Resu lts for Chicago-Northbrook

Figure 3-2 shows 2005 TNMOC/NO x 

# ratios by wind quadrant and day of week for the Northbrook site in Chicago, Il linois. Generally, there is good agreement between the ambient- and emissions inventory- derived ratios at this site; however, the agreement between ambient- and emissions inventory-derived ratios is poorer for wind quadrants 1 and 3 than for the remaining wind quadrants. Much of wind quadrant 1 lies over Lake Michigan (see Figure 2-5), and emission levels are thus relatively low in that quadrant. For wind quadrant 3, NO x 

# emission levels are 40% higher than in neighboring wi nd quadrant 2, while VOC emission levels are virtually identical for those two wind quadrants. These higher NO x 

# emissions in wind quadrant 3 are driven by heavy-duty mobile source emissions, suggesting that emissions from this source may be overestimated in wind quadrant 3.

0 1 2 3 4 5

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 1 2 3 4 5

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.6

1.1 1.8 1.4 1.2 1.3 1.4 2.0

0 1 2 3 4 5

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 1 2 3 4 5

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.6

1.1 1.8 1.4 1.2 1.3 1.4 2.0



## Figure 3-2. TNMOC/NO x 

## ratios by wind quadrant and day of week for the Northbrook site, 2004–2006.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-4 

# The ambient-derived TNMOC/NO x 

# ratio for Sundays is a factor of 2 higher than the emissions inventory-derived ratio for Sundays at the Northbrook site, whereas the ambientderived ratio for weekdays and Saturdays ar e only about 30% highe r than the emissions inventory-derived ratios. Because TNMOC co ncentrations are higher (by about 10%) and NO x 

# concentrations are lower (by about 30%) on Sund ays than on Saturdays, the ambient-derived TNMOC/NO x 

# ratio is higher on Sundays than on Saturdays. However, the emissions inventory-derived rati os do not capture this trend, as both VOC 26 

# and NO x 

# emissions decrease on Sundays relative to Saturdays, with VOC decr easing somewhat more sharply and lowering the emissions inventory-derived TNMOC/NO x 

# ratio.

Ambient- and emissions i nventory-derived TNMOC/NO x 

# ratios for the Northbrook site were also prepared using 2008 data (see Figure 3-3 ), and the overall (all days and wind quadrants) ambient-derived TNMOC/NO x 

# ratio for this site increased from 2.2 in 2004–2006 to 2.6 in 2008 (an 18% increase). This higher 2008 ratio reflects th e increasing TNMOC concentrations and decreasing NO x 

# concentrations at this site (see Section 2.1.4). The emissions data for Northbrook showed a small VOC increase from 2005 to 2008 and a large NO x 

# decrease. As a result, the emissions inventory-derived TNMOC/NO x 

# ratio increased by 61%, and the ambient- and emissions inventory-derived rati os showed somewhat closer agreement for 2008 than for 2005.

It should also be noted that, when examined by day of week and wind quadrant, the 2008 TNMOC/NO x 

# ratios show a sharper increase relativ e to 2004–2006 ratios in wind quadrants 1 and 4 and on weekdays. 27 

# . These results suggest that the increase in TNMOC emissions around this site between 2004–2006 and 2008 largely ca me from the area north of the site.

0 1 2 3 4 5

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source



### 0 1 2 3 4 5

1234

Wind QuadrantTNMOC/NOx Ratio 

## 1.1

1.0 1.1 1.0 1.0 1.1 1.1 1.1

0 1 2 3 4 5

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source



### 0 1 2 3 4 5

1234

Wind QuadrantTNMOC/NOx Ratio 

## 1.1

1.0 1.1 1.0 1.0 1.1 1.1 1.1

Figure 3-3. TNMOC/NO x 

## ratios by wind quadrant and day of week for the Northbrook site, 2008.

26 

## The organic species in the ambient data are referred to as TNMOC and in the emissions inventory as VOC. For simplicity, all hydrocarbon-to-NO x 

## ratios are referred to as “TNMOC/NO x 

## .”
27 

## For analyses involving 2008 data, Saturdays and Sundays were grouped together as weekend days because of the relatively small number of Saturday/Sunday samples.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-5 

# 3.1.3 Ratio Comparison Results for Gary

Figure 3-4 shows 2005 TNMOC/NO x 

# ratios by wind quadrant and day of week for the Gary, Indiana, site. Agreement between ambient- and emissions inventory-derived TNMOC/NO x 

# ratios is poor at the Gary site, with the ambient-derived ratios 3.4 to 5.0 times higher than the emissions-based ratios across all wind quadrants and days of week. This discrepancy may largely be driven by an undere stimate of VOC emissions around the Gary site (see Section 2.2.2), which is near several large industrial sour ces—including the Burns Harbor Steel Plant. Among days of the week, agreem ent between ambient- and emissions inventoryderived TNMOC/NO x 

# ratios is poorest on Sundays, as the 40% decrease in ambient NO x 

# concentrations between Saturdays and Sundays is not reflected in the emissions data.

0 5 10 15

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 5 10 15

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 3.5 3.5 3.8 4.6 3.6 3.9 3.4 5.0

0 5 10 15

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 5 10 15

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 3.5 3.5 3.8 4.6 3.6 3.9 3.4 5.0

Figure 3-4. TNMOC/NO x 

## ratios by wind quadrant and day of week for the Gary site, 2004–2006.



# 3.1.4 Ratio Comparison Results for Detroit-East 7 Mile

Figure 3-5 shows the 2005 TNMOC/NO x 

# ratios by wind quadrant and day of week for the East 7 Mile site in Detroit, Michiga n. Agreement between ambient- and emissions inventory-derived TNMOC/NO x 

# ratios is poor at the East 7 M ile site, with the ambient-derived ratios 2.5 to 4.0 times higher than the emissions-b ased ratios across all wind quadrants and days of week. Ambient-derived TNMOC/NO x 

# ratios are lowest when winds are from wind quadrant 3, reflecting the impact of la rge industrial sources of NO x 

# southwest of this site (Brown, 2006).

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-6 0 5 10 15

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 5 10 15

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 2.7 4.0

2.5 2.6 2.7 3.4 2.6 3.4

0 5 10 15

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 5 10 15

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 2.7 4.0

2.5 2.6 2.7 3.4 2.6 3.4



## Figure 3-5. TNMOC/NO x 

## ratios by wind quadrant and day of week for the East 7 Mile site, 2004–2006.



# Ambient TNMOC concentrations are highest at the East 7 Mile site among all sites, although VOC emissions levels around the East 7 Mile site are 18% lowe r than they are around the Chicago-Jardine site (see Table 2-6). This discrepancy suggests th at VOC emissions are underestimated around the East 7 Mile site.

3.1.5 Ratio Comparison Results for Milwaukee

Figure 3-6 shows the 2005 TNMOC/NO x 

# ratios by wind quadrant and day of week for the Milwaukee, Wisconsin, site. Agreement betw een ambient- and emissions inventory-derived TNMOC/NO x 

# ratios is mediocre at the Milwaukee site, with the ambi ent-derived ratios 1.5 to 2.2 times higher than the emissions-based ratios across all wind quadrants and days of week. Milwaukee was the only site where agreement between ambient- and emissions inventoryderived TNMOC/NO x 

# ratios was better on Sundays than on weekdays or Saturdays, as Milwaukee was the only site with lower TNMOC concentrations on Sundays than on Saturdays (reflected in the VOC emissi ons levels for the site).

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-7 0 1 2 3 4 5 6

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 2 4 6

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 1.7 2.0

1.9 1.7 1.8 2.2 1.9 1.5

0 1 2 3 4 5 6

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 2 4 6

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 1.7 2.0

1.9 1.7 1.8 2.2 1.9 1.5



## Figure 3-6. TNMOC/NO x 

## ratios by wind quadrant and day of week for the Milwaukee site, 2004–2006.



# Ambient- and emissions i nventory-derived TNMOC/NO x 

# ratios for the Milwaukee site were also prepared using 2008 data (see Figure 3-7 ), and the overall (all days and wind quadrants) ambient TNMOC/NO x 

# ratio for this site increased from 3.5 in 2004–2006 to 5.1 in 2008 (a 46% increase). This higher 2008 ratio reflects the increasing TNMOC concentrations and decreasing NO x 

# concentrations at this site (see Section 2.1.4). The emissions data for Milwaukee showed significant decreases in both VOC and NO x 

# emissions from 2005 to 2008, and emissions-inventory derived TNMOC/NO x 

# ratios were slightly higher for 2008 than for 2005. As a result, the ambient- and emissions in ventory-derived ratios showed poorer agreement for 2008 than for 2005.

0 2 4 6 8

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 2 4 6 8

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 3.4 2.8 2.7 2.5 2.6 2.7 3.1 3.1

0 2 4 6 8

1234

Wind QuadrantTNMOC/NOx Ratio



### 0 2 4 6 8

All WD SAT SUN
Day of WeekTNMOC/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 3.4 2.8 2.7 2.5 2.6 2.7 3.1 3.1

Figure 3-7. TNMOC/NO x 

## ratios by wind quadrant and day of week for the Milwaukee site, 2008.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-8 

# 3.2 CO/NO x 

# Ratio Comparisons

CO/NO x 

# ratios were calculated by day of week, month, and season. For 2005, comparisons between ambient- and emissions inventor y-derived CO/NO x 

# ratios were made for four sites: Chicago-Mannheim, Chicago-Fran klin, Detroit-Linwood, and Milwaukee. Also, CO/NO x 

# ratios were calculated by wind quadrant at the Milwaukee and Chicago-Mannheim sites 28 

# . For 2008, comparisons were made for the three sites for which ambient CO measurements were available: the Mannheim, Franklin, and Northbrook sites in Chicago (and emissions inventory-derived ratios were calc ulated for the remaining sites as well).

Table 3-2 shows calculated ratios for the full grid extent around each monitoring site for all summer and winter days. For 2005, these ca lculations show that ambient- and emissions inventory-derived ratios ag ree within ±30% at all sites. Agre ement is generally closer for winter months when CO concentrations are much higher than in summer months, and agreement is also generally closer when elevated sources are ex cluded from the calculations. For 2008, ambientderived CO/NO x 

# ratios at the Mannheim and Franklin site s were 5% to 39% lower than for 2005; however, emissions inve ntory-derived CO/NO x 

# ratios increased by up to 35% at those sites. As a result, the ambient- and emissions-inventory derived ratios show poorer agreement for 2008 than for 2005.

The following sections show CO/NO x 

# ratio charts by wind quadrant and day of week and discuss the results of the analysis for each site. Additional charts (e.g., CO/NO x 

# ratios by wind quadrant) can be found in Appendix D

.

28 

## The meteorological data needed to support this analysis are not available at the other sites.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-9 Table 3-2. CO/NO x 

## ratios by site (emission ratios for full grid extent around each site; ambient ratios for 2005 based on 2004–2006 data).



# Emissions Inventory Ratios Site Season Ambient Ratios Low Level Only Low Level + Elevated Ambient/EI (Low Level) Ambient/EI (Low Level + Elevated)

2005 Data

Winter 6.4 8.2 8.2 0.8 0.8ChicagoMannheim Summer 8.2 11.2 11.2 0.7 0.7

Winter 7.3 8.0 7.6 0.9 1.0ChicagoFranklin Summer 8.6 10.9 10.3 0.8 0.8

Winter 9.9 10.1 8.0 1.0 1.2 Linwood (Detroit) Summer 12.5 11.6 9.1 1.1 1.4

Winter 10.0 11.2 8.9 0.9 1.1 Milwaukee Summer 13.6 11.9 9.3 1.2 1.5

2008 Data

Winter 4.2 11.1 10.9 0.4 0.4ChicagoMannheim Summer 5.0 15.0 13.6 0.3 0.4

Winter 5.9 9.6 9.2 0.6 0.6ChicagoFranklin Summer 8.2 11.6 10.3 0.7 0.8

Winter 8.6 11.9 11.9 0.7 0.7ChicagoNorthbrook Summer 16.7 16.0 16.0 1.0 1.0

Winter -- 11.5 9.2 -- -- Linwood (Detroit) Summer -- 12.7 9.5 -- --

Winter -- 11.3 9.8 -- -- Milwaukee Summer -- 12.0 9.8 -- --



# 3.2.1 Ratio Comparison Results for Chicago-Mannheim

Figure 3-8 shows 2005 CO/NO x 

# ratios by season, wind quadran t, and day of week for the Mannheim site in Chicago, Illinois. Overall, there is good agreement between the ambient- and emissions inventory-derived ratios at this site across all wind quadrants and days of week.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-10 

# However, there is poorer agreement between am bient- and emissions i nventory-derived CO/NO x 

# ratios on Sundays than on weekdays or Saturd ays, as the magnitude of the decrease in NO x 

# concentrations from Saturdays to Sundays is not completely reflected in the emissions data.

0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source

0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio 

### 0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.8 0.8 0.8 0.8 0.6 0.9 1.4

0.9 0.6 0.7 0.6 0.7 0.7 0.8 1.5

0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source

0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio 

### 0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.8 0.8 0.8 0.8 0.6 0.9 1.4

0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.8 0.8 0.8 0.8 0.6 0.9 1.4

0.9 0.6 0.7 0.6 0.7 0.7 0.8 1.5



## Figure 3-8. CO/NO x 

## ratios by season (top is winter and bottom is summer), wind quadrant, and day of week for the Chicago-Mannheim site, 2004–2006.



# Ambient- and emissions inventory-derived CO/NO x 

# ratios for the Mannheim site were also prepared using 2008 data (see Figure 3-9 ), and for ambient data, the overall (all days and wind quadrants) wintertime CO/NO x 

# ratio for this site decreased from 6.4 in 2004–2006 to 4.2 in 2008 (a 34% decrease). This lower 2008 ratio refl ects the decreasing CO c oncentrations at this site (see Section 2.1.4). However, the wint ertime emissions inventory-derived CO/NO x 

# ratios for this site increased by 35% from 2005 to 2008; as a result, the agreemen t between ambient- and emissions inventory-derived CO/NO x 

# ratios is much poorer for 2008 than for 2005. Because 2005 to 2008 reductions in CO emissions are similar to reductions in CO concentrations (both around 40%) while NO x 

# emission reductions (50%) are much larger than NO x 

# concentration reductions (13%), this discrepancy indicates that NO x 

# reductions from 2005 to 2008 in the emissions inventory are too large.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-11 

# It should also be noted that the ambient-derived CO/NO x 

# ratios for 2008 increase on weekend days, as was the case with the ratios calculated from 2004–2006 ambient data. However, the 2008 emissions inventory-derived CO/NO x 

# ratios show little variation from weekdays to weekend days (see Figure 3-9).

0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.4 0.3 0.3 0.3 0.4 0.3 0.5 0.5

0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.4 0.3 0.3 0.3 0.3 0.3 0.5 0.4 0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.4 0.3 0.3 0.3 0.4 0.3 0.5 0.5

0 5 10 15 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.4 0.3 0.3 0.3 0.3 0.3 0.5 0.4



## Figure 3-9. CO/NO x 

## ratios by season (top is winter and bottom is summer), wind quadrant, and day of week for the Chicago-Mannheim site, 2008.



# 3.2.2 Ratio Comparison Results for Chicago-Franklin

Figure 3-10 shows 2005 CO/NO x 

# ratios by season and day of week 29 

# for the Franklin site in Chicago, Illinois. Overall, there is good agreement between the ambient- and emissions inventory-derived ratios at this site across all days of week. However, there is poorer agreement between ambient- and emissi ons inventory-derived CO/NO x 

# ratios on Sundays than on weekdays or Saturdays, as the magnitude of the decrease in NO x 

# concentrations from Saturdays to Sundays is not completely reflected in the emissions data.

29 

## Pollutant ratios by wind quadrant could not be calculated for the Franklin site beca use of a lack of wind data.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-12 0 2 4 6 8 10 12 14 16 18

All WD SAT SUN
Day of WeekCO/NOx Ratio 

## 0.9 0.7 1.0 1.6

0 2 4 6 8 10 12 14 16 18

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.8 0.9 1.3

0 2 4 6 8 10 12 14 16 18

All WD SAT SUN
Day of WeekCO/NOx Ratio 

## 0.9 0.7 1.0 1.6

0 2 4 6 8 10 12 14 16 18

All WD SAT SUN
Day of WeekCO/NOx Ratio 

## 0.9 0.7 1.0 1.6

0 2 4 6 8 10 12 14 16 18

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.8 0.9 1.3



## Figure 3-10. CO/NO x 

## ratios by season (left is winter and right is summer) and by day of week for the Chicago-Franklin site, 2004–2006.



# Ambient- and emissions inventory-derived CO/NO x 

# ratios for the Franklin site were also prepared using 2008 data (see Figure 3-11 ); for ambient data, the overall (all days and wind quadrants) wintertime CO/NO x 

# ratio for this site decreased from 7.3 in 2004–2006 to 5.9 in 2008 (a 19% decrease). This lower 2008 ratio reflects the decreasing CO concentrations at this site (see Section 2.1.4). However, the winter time emissions inventory-derived CO/NO x 

# ratios for this site increased by 20% from 2005 to 2008; as a result, the agreemen t between ambient- and emissions inventory-derived CO/NO x 

# ratios is generally poorer for 2008 than for 2005. Although 2005 to 2008 reductions in CO emissions are similar to reductions in CO concentrations (both around 25%), reductions in NO x 

# emissions (37%) are much larger than reductions in NO x 

# concentrations (6%). This discrepancy indicates that NO x 

# reductions from 2005 to 2008 in the emissions inventory are too large.

0 2 4 6 8 10 12 14

All WD SAT SUN

Da y of WeekCO/NOx Ratio 

## 0.6 0.5 0.9 0.9

0 5 10 15 20 25

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.7 0.6 1.3 1.3

0 2 4 6 8 10 12 14

All WD SAT SUN

Da y of WeekCO/NOx Ratio 

## 0.6 0.5 0.9 0.9

0 5 10 15 20 25

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.7 0.6 1.3 1.3

Figure 3-11. CO/NO x 

## ratios by season (left is winter and right is summer) and by day of week for the Chicago-Franklin site, 2008.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-13 

# It should be noted that CO/NO x 

# ratios calculated for Sundays are an exception to the trend described above, as emissions inventory- derived ratios show cl oser agreement with ambient-derived ratios for 2008 than for 2005, partic ularly for winter months (see Figure 3-11). This occurs, in part, because ambient-derived CO/NO x 

# ratios for 2008 do not increase sharply from Saturdays to Sundays, as wa s the case with the ratios for 2005.

3.2.3 Ratio Comparison Resu lts for Chicago-Northbrook

Figure 3-12 shows 2008 CO/NO x 

# ratios by season, wind quadrant, and day of week for the Northbrook site in Chicago, Illinois (no ambi ent CO measurements were available for this site from 2004–2006). Generally, the ambient- and emi ssions inventory-derived ratios at this site show good agreement (±50%) across all wind quadrants and days of week. However, the ambient- and emissions inventory-derived CO/NO x 

# ratios show poorer agreement on weekend days than on weekdays, particularly during summer months. During both winter and summer months, the ambient-derived CO/NO x 

# ratios increase sharply on weekend days compared to weekdays, while the emissions inventory-derived ratios rema in relatively constant from weekdays to weekend days. Although weekday to weekend re ductions in CO emissions are similar to reductions in CO concentrati ons (both around 25% for winter months), NO x 

# emission reductions (14% for winter months) are much smaller than NO x 

# concentration reductions (72% for winter months). This discrepancy indicates that NO x 

# reductions from weekdays to weekend days in the emissions inventory are too small.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-14 0 2 4 6 8 10 12 14 16 18 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20 25 30 35

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.7 0.7 0.8 0.6

0.7 0.6 1.5 1.4

0 5 10 15 20 25 30 35 40

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20 25 30 35 40 45 50

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 1.2 0.9 1.0 1.5

1.0 0.9 1.6 1.6 0 2 4 6 8 10 12 14 16 18 20

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20 25 30 35

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.7 0.7 0.8 0.6

0.7 0.6 1.5 1.4

0 5 10 15 20 25 30 35 40

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20 25 30 35 40 45 50

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 1.2 0.9 1.0 1.5

1.0 0.9 1.6 1.6



## Figure 3-12. CO/NO x 

## ratios by season (top is winter and bottom is summer), wind quadrant, and day of week for the Chicago-Northbrook site, 2008.



# 3.2.4 Ratio Comparison Results for Detroit-Linwood

Figure 3-13 shows CO/NO x 

# ratios by season and day of week 30 

# for the Linwood site in Detroit, Michigan. Overall, there is good ag reement between the ambient- and emissions inventory-derived ratios at this site across all days of wee k, particularly during winter months.

30 

## Pollutant ratios by wind quadrant co uld not be calculated for the Linwood s ite because of a lack of wind data.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-15 0 5 10 15 20 25 30

All WD SAT SUN
Day of WeekCO/NOx Ratio



## 1.0 1.0 0.9 1.0

0 5 10 15 20 25 30

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 1.1 1.4 0.8 1.3

0 5 10 15 20 25 30

All WD SAT SUN
Day of WeekCO/NOx Ratio



## 1.0 1.0 0.9 1.0

0 5 10 15 20 25 30

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 1.1 1.4 0.8 1.3



## Figure 3-13. CO/NO x 

## ratios by season (left is winter and right is summer) and by day of week for the Detroit-Linwood site, 2004–2006.



# 3.2.5 Ratio Comparison Results for Milwaukee

Figure 3-14 shows CO/NO x 

# ratios by season, wind quadrant, and day of week for the Milwaukee site in Wisconsin. Overall, ther e is good agreement between the ambient- and emissions inventory-derived ratios at this site across all wind quadrants and days of week for both winter and summer months.

### Upper Midwest Emissions Inventory Evaluation Pollutant Ratio Comparisons



## 3-16 0 5 10 15 20 25

All WD SAT SUN

Da y of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source

0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio 

## 0.8 1.3

1.3 1.2 0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20 25

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.9 0.8 1.0 0.9 0.8 1.1 1.1

1.2 1.5 1.0 1.0

0 5 10 15 20 25

All WD SAT SUN

Da y of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source

0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio 

## 0.8 1.3

1.3 1.2 0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20 25

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.9 0.8 1.0 0.9 0.8 1.1 1.1

0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio



### 0 5 10 15 20 25

All WD SAT SUN
Day of WeekCO/NOx Ratio 

### Ambient

EI - Low Level Only

EI - With Elevated Source 

## 0.8 0.9 0.8 1.0 0.9 0.8 1.1 1.1

1.2 1.5 1.0 1.0



## Figure 3-14. CO/NO x 

## ratios by season (top is winter and bottom is summer), wind quadrant, and day of week for the Milwaukee site, 2004–2006.

### Upper Midwest Emissions Inventory Evaluatio n Hydrocarbon Composition Comparisons



## 4-1 

# 4. Hydrocarbon Composition Comparison Results

Comparisons of ambient- and emissions inventory-derived hydrocarbon compositions were based on the 55 individual species that we re detected and identified by the ambient measurement systems. In addition, STI also com puted and compared the relative reactivity of the organic species in the emissions inventory an d ambient data. The reactivity of each species was estimated according to published MIR values that represent the ozone formation potential of various organic compounds (Carter, 2003).


# 4.1 Relative Hydrocarbon Composition Comparisons

Relative hydrocarbon composition comparisons were performed by day of week, season, and wind quadrant. For 2005, hydrocarbon compositi on comparisons were performed for five sites: Chicago-Jardine, Chi cago-Northbrook, Gary, Detroit-East 7 Mile, and Milwaukee. For 2008, comparisons were made for the two sites for which ambient TNMOC measurements were available: Chicago-Northbrook and Milwaukee. 31 

# Figures 4-1 through 4-5 show comparisons of the ambient- and emissions inventory-derived relative compositions of 15 of the most abundant species in the ambient data. Th ese hydrocarbon composition plots show that:

 The speciation of the emissions inventory is representative of the TNMOC composition detected by ambient monitoring sites for some species groups, including C4+ alkanes, C8+ aromatics, styrenes, and propylene.

 The speciation of the emissions inventory is representative of the TNMOC composition detected by ambient monitoring sites for C6 + alkanes at the Chicago and Milwaukee sites; however, this species is overestimated in the emissions inventory at the Gary and Detroit sites. C6+ alkanes are present in gasoline exha ust and evaporative emissions.

 The speciation of the emissions inventory tends to overestimate the contribution of acetylene, ethylene, toluene, and isoprene co mpared to the ambient data. Isoprene is highly reactive and short-lived in the atmosphere, and therefore it may be under-represented in the ambient data. The dominant source of acetylene and toluene 32 

# in the summer emissions inventory is gas-power ed lawn and garden equipment, and the contribution of these species to overall hydr ocarbon emissions increases on weekends, when lawn and garden equipment are mo st active (see day of week plots in Appendix E ). The speciation profile assigned to this sour ce in the LADCO invent ories is based on a 1997 study on emissions from four-stroke lawn mower emissions covering ten mowers with two types of gasoline (Battye and Harris, 2005), and the same profile is assigned to lawn and garden equipment in the latest version of EPA’s SPECIATE database (U.S. Environmental Protection Agenc y, 2008). Commercial aircraft are the dominant source of ethylene in the LADCO emissions data. A 1984 EPA speciation profile for turbine engine exhaust is assigned to this source category in the LADCO inventories.

31 

## Per LADCO’s instructions, the same speciation profiles were assigned to both the 2005 and 2008 inventories, so the speciation of the emissions data did not change from year to year. The hydrocarbon composition of the ambient data also showed little year-to-year variation.
32 

## For the Gary site, petroleum storage evaporative losses are another significant source of toluene. This is not true at the other sites.

### Upper Midwest Emissions Inventory Evaluatio n Hydrocarbon Composition Comparisons



## 4-2 

#  Compared to the ambient data, the speciati on of the emissions inventory overestimates the contribution of pentanes at some sites, es pecially Detroit East 7 Mile. At the Detroit site, surface coating solvents are the dominant source of pentane emissions.

 The speciation of the emissions inventory underestimates the contribution of ethane, propane, and C6-C11 alkanes at all sites and butane at the Chicago sites. However, ethane and propane are long-lived in the atmo sphere and tend to accumulate; therefore, it is likely that the ambient monitors det ected aged ethane and propane emissions.

0% 5% 10% 15% 20% 25%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure 4-1. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Chicago-Jardine site.

0% 5% 10% 15% 20% 25%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

## Ambient 2005
Ambient 2008
Emissions



## Figure 4-2. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Chicago-Northbrook site.

### Upper Midwest Emissions Inventory Evaluatio n Hydrocarbon Composition Comparisons



## 4-3 0% 5% 10% 15% 20% 25%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure 4-3. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Gary site.

0% 5% 10% 15% 20% 25%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure 4-4. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Detroit-East 7 Mile site.

### Upper Midwest Emissions Inventory Evaluatio n Hydrocarbon Composition Comparisons



## 4-4 0% 5% 10% 15% 20% 25%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient 2005
Ambient 2008
Emissions



## Figure 4-5. Comparison of 0600–0900 ambient- and emissions inventory-derived TNMOC compositions for the Milwaukee site.



# 4.2 Hydrocarbon Reactivity Comparisons

Hydrocarbon reactivity comparisons were pe rformed by day of week, month, season, and wind quadrant for five sites using 2004–2006 ambient data and 2005 emissions data: 33 

# ChicagoJardine, Chicago-Northbrook, Gar y, Detroit-East 7 Mile, and Milw aukee. Across all sites, the overall weighted reactivity values for the emissi ons inventory for the summer season are 16% to 80% higher than the weighted reactivity values for the ambient data. The ambient- and emissions inventory-derived reactivity values show the closest agreement at the Milwaukee site and the greatest disparity at the Northbrook site . The emissions invent ory-derived reactivity values are consistently higher for Saturday and Sunday emissions data than for weekday emissions data, while the ambient-derived reactivity values show little change across days of the week. Tables 4-1 and 4-2 show reactivity data for the five sites.

The hydrocarbon composition analysis in the prev ious section showed that the emissions inventory and the ambient data differ significantly between several species or group of species. At all sites, ethane and propane make up a highe r percentage of the TNMO C concentration in the ambient data than in the emissions inventory, while the more reactive ethylene and acetylene make up a higher percentage in the emissions inventory. (Ethane and propane have MIR values of 0.3 and 0.6, respectively, while ethylene and acety lene are far more reactive, with MIR values of 9.1 and 1.2, respectively.) These differences resu lt in higher weighted reactivity values for the emissions data than for the ambient data.

33 

## These analyses were not repeated for 2008 because the 2008 hydrocarbon compositions were very similar to the 2005 versions for both the ambient and emissions data.

## 4-5Table 4-1.Reactivity values by site,day of week, month, and season.OverallWeekdaySaturdaySundaySiteNameMonthEmissionsInventoryAmbientEmissionsInventoryAmbientEmissionsInventoryAmbientEmissionsInventoryAmbientJune3.92.83.72.84.03.04.02.9July3.92.73.72.74.02.93.92.7August3.72.73.62.63.82.83.82.6ChicagoJardineSummer3.82.73.72.73.92.93.92.7June4.52.54.32.54.52.44.62.4July4.42.54.32.64.52.54.52.4August4.42.54.12.54.32.44.32.3ChicagoNorthbrookSummer4.52.54.22.54.42.54.42.4June4.53.34.22.64.32.54.72.5July4.53.34.22.84.32.94.72.8August4.33.24.02.84.12.84.42.7GarySummer4.32.84.02.74.22.74.52.7June3.72.53.42.53.92.54.02.3July3.72.53.42.63.82.54.02.6August3.52.53.32.63.72.53.82.5DetroitE7MileSummer3.62.53.42.63.82.53.92.5June3.73.13.43.13.83.03.93.0July3.73.03.42.93.82.93.93.0August3.63.13.43.03.73.03.73.0MilwaukeeSummer3.63.13.43.03.83.03.83.0

## 4-6Table 4-2.Reactivity values by wind quadrant (all summer months included).WQ1WQ2WQ3WQ4SiteNameEmissionsInventoryAmbientEmissionsInventoryAmbientEmissionsInventoryAmbientEmissionsInventoryAmbientChicagoJardine3.92.73.72.73.92.83.82.7ChicagoNorthbrook4.22.53.92.64.62.54.62.4Gary4.42.84.32.84.12.73.92.6DetroitE7Mile3.42.73.52.53.72.53.82.5Milwaukee3.53.03.53.13.73.13.62.9

### Upper Midwest Emissions Inventory Evaluation Findings and Recommendations



## 5-1 

# 5. Findings and Recommendations

The on-road mobile source component of LADCO’s 2005 emissions inventory was developed using EPA’s MOBILE6.2 model and link-level activity data. The top-down evaluation for the 2005 emissions inve ntory indicates that, in genera l, on-road mobile sources are represented accurately in the emissions data. This conclusion is based on the fact that agreement between ambient- and emissions-inventory-deriv ed pollutant ratios was closest (±20%) for wintertime CO/NO x 

# ratios, and on-road mobile sources accounted for 57% to 80% of wintertime CO and NO x 

# emissions at all sites for which ratios we re calculated. For sites in the Chicago area, agreement between ambient- and emissions inventory-derived pollutant ratios was as close as could be expected, given the limitations of the analysis techniques. However, comparisons with ambient data indicate that the emissions inventory for Sundays may not be representative of actual activity patterns on that day of the wee k, perhaps due to decreases in on-road mobile source emissions from Saturdays to Sundays, as we ll as inaccurate temporal characterizations of other source categories. Also, sources of VOC emissions appear to be missing or underrepresented in the emissions inventory near sites that ar e influenced by industrial and residential emissions, such as the Gary and Detroit- East 7 Mile sites. These results are consistent with previous top-down emissions evaluations for other regions, which show closest agreement between ambient- and emissions inventory-derived pollu tant ratios on weekdays and at sites heavily impacted by on-road mobile s ource emissions (Chinkin and Reid, 2006).

The on-road mobile source component of LADCO’s 2008 emissions inventory was developed using EPA’s M OVES model with default input data , and county-level outputs from MOVES were spatially allocated using spatial surrogate data. 34 

# For the 2008 emissions inventory, agreement between ambient- and emi ssions-inventory derived pollutant ratios was generally poorer than was observed for the 2005 inventory. The greater discrepancy between ambient- and emissions inventory-derived pollu tant ratios from 2005 to 2008 primarily results from large decreases in on-road NO x 

# emissions that outpaced reductions in ambient NO x 

# concentrations. However, the Saturday-to-Sunda y differences in pollutant ratio comparisons observed for the 2005 inventory were not observe d for the 2008 inventory, as there was no variation between Saturday and Sunday on-road mobile source emissions in the 2008 inventory (as was the case for 2005).

For both 2005 and 2008, the speciation of the VOC emissions inventory at all sites does not compare well with the hydrocarbon compositi on of the ambient data , resulting in a VOC emissions inventory that shows significantly more reactivity at all sites than the corresponding ambient data. As a result, ozone modeling e fforts for the region may be influenced by “compensating errors,” as the underestimated magnitude of VOC emissions is offset by the overestimated reactivity of those emissions . The following key findings support these conclusions.

34 

## LADCO plans to update the 2008 inventory with state- specific MOVES inputs and link-level activity data. The 2008 inventory used in this analysis was the most current version as of April 29, 2011.

### Upper Midwest Emissions Inventory Evaluation Findings and Recommendations



## 5-2 

# TNMOC/NO x 

# Ratios

For both 2005 and 2008, the agreement betw een overall ambient- and emissions inventory-derived TNMOC/NO x 

# ratios is good (±20%) for the Jardine (2005 only) and Northbrook sites in Chicago. However, agreement is mediocre for the Milwaukee site, where the ambient-derived ratio is higher than the emissi ons-derived ratio by a factor of 1.8 in 2005 and a factor of 2.4 in 2008. Agreement is poor at th e Detroit-East 7 Mile and Gary sites for 2005, where ambient-derived ratios were higher than emissions inventory- derived ratios by factors of 2.7 and 3.6, respectively.

 For 2005, ambient TNMOC concentrations are hi ghest at the Gary and Detroit-East 7 Mile sites. However, VOC emissions are lo west around the Gary s ite and are 18% lower at the East 7 Mile site than at the Jardin e site (which has the lowest ambient TNMOC concentrations among all sites). These re sults suggest that some VOC sources are missing or underrepresented at Gary and East 7 Mile. At the Gary site, which is in a heavily industrialized area, point source TN MOC emissions may be underestimated. At the East 7 Mile site, which is in a suburban area, both residential sources of TNMOC and industrial sources, which impact the site wh en winds are from the southwest, may be underestimated.

 For 2005, the agreement between ambient- and emissions i nventory-derived TNMOC/NO x 

# ratios is generally be tter on weekdays and Saturdays than on Sundays. The increased discrepancy between ambient- and emissions inventor y-derived ratios on Sundays largely occurs because ambien t TNMOC concentrations are similar on Saturdays and Sundays at most sites, while VOC emissions are consistently lower on Sundays than Saturdays.

 At the Chicago-Northbrook and M ilwaukee sites, overall TNMOC/NO x 

# ratios derived from 2008 ambient data are higher than ra tios derived from 2004–2006 data by 18% and 46%, respectively. The higher 2008 ratios refl ect increasing TNMOC concentrations and decreasing NO x 

# concentrations at these sites.

 For 2008, the overall emissions inventory-derived TNMOC/NO x 

# ratio for ChicagoNorthbrook increased by 61% relative to 2005 an d showed somewhat closer agreement to the ambient-derived ratio than in 2005. However, the overall emissions inventoryderived TNMOC/NO x 

# ratio for the Milwaukee site wa s virtually unchanged from 2005 to 2008, resulting in poorer agreement with the am bient-derived ratio in 2008 than in 2005.

CO/NO x 

# Ratios

For 2005, the agreement between overall ambient- and emissions inventory-derived CO/NO x 

# ratios is good (±30%) across all sites. Howe ver, at the Franklin and Mannheim sites in Chicago, the agreement between ambient- and emissions invent ory-derived CO/NO x 

# ratios is better on weekdays and Saturday s than on Sundays, as the emissions data do not completely account for the magnitude of the decrease in NO x 

# concentrations from Saturdays to Sundays at those sites.

For 2008, the agreement between overall ambient- and emissions inventory-derived CO/NO x 

# ratios is mediocre (±30%) across all sites. At the Mannheim and Franklin sites in

### Upper Midwest Emissions Inventory Evaluation Findings and Recommendations



## 5-3 

# Chicago, ambient-derived CO/NO x 

# ratios were 5% to 39% lower than for 2005; however, emissions inventory-derived CO/NO x 

# ratios increased by up to 35% at those sites. As a result, the ambient- and emissions-inventory derived ratios show poorer agreement for 2008 than for 2005. The large increases in emissions inventory-derived CO/NO x 

# ratios at these sites resulted from sharp decreases in on-road NO x 

# emissions between 2005 and 2008.

Speciation and Reactivity

 The speciation of the emissions inventory tends to overestimate the contribution of acetylene, ethylene, toluene, and isoprene co mpared to the ambient data. Isoprene is highly reactive and short-lived in the atmosphere, and it therefore may be under-represented in the ambient data. The non-road mobile sector of the emissions inventory is the dominant source of acet ylene, ethylene, and toluene emissions.

 The speciation of the emissions inventory underestimates the contribution of ethane, propane, and C6-C11 alkanes at all sites and butane at the Chicago sites. However, ethane and propane are long-lived in the atmo sphere and tend to accumulate; therefore, it is likely that the ambient monitors det ected aged ethane and propane emissions.

 Across all sites, the overall weighted reactivit y value of the emissions inventory for the summer season is 16% to 80% higher than the weighted reactivity va lue of the ambient data.

Based on the findings from this study, we reco mmend that the following steps be taken to further investigate the LADCO 2005 and 2008 em issions inventories and to make specific improvements to those inventories:

 Improve the accuracy of weekend emissions estimates by collecting and analyzing day-specific on-road, non-ro ad, and area source activity da ta to better characterize differences in weekday, Saturday, and Sunday activity levels.

 Collect bottom-up emissions ac tivity data for residential and industrial sources around the Gary, Detroit-East 7 Mile, and Milwa ukee sites to “ground truth” the current VOC emissions inventories for these locations.

 Employ source apportionment techniques, su ch as positive matrix factorization (PMF), to further evaluate the inventor y around the Gary, Detroi t-East 7 Mile, and Milwaukee sites and to identif y specific source types that may be underestimated in the VOC inventories.

 Evaluate the source(s) of large decreases in on-road NO x 

# emissions in the 2008 MOVES-based inventory relative to the 2005 MOBILE6.2-based inventory.

 Review the speciation profiles assigned to on-road mobile sources and key off-road sources, such as lawn and ga rden equipment and aircraft.

 Redo the 2008 pollutant ratio comparisons with additional ambient data (e.g., TNMOC measurements from the Jardine and Gary sites) and revised on-road mobile source inventories (i.e., on-road emissions developed using link-le vel activity data and state-specific MOVES inputs).

### Upper Midwest Emissions Inventory Evaluation References



## 6-1 

# 6. References

Battye W. and Harris J. (2005) Improving modeli ng inventory data: speci ation profiles. Draft technical report prepared for the Lake Michig an Air Directors Cons ortium, Des Plaines, IL, by EC/R Incorporated, Chapel Hill, NC, February. Brown S.G. (2006) Accountability–Tracking a nd evaluating air quality programs, Task 3– Detroit, Michigan. Technical memorandum prepared for the U.S. Environmental Protection Agency, Research Triangle Park, NC, by Sonoma Technol ogy, Inc., Petaluma, CA, STI-905213.05-3040-TM, September. California Air Resources Board (1997) Public m eeting to consider appr oval and verification of the California emissions inventory. Report pr epared by the Technical Support Division, Mobile Source Control Division, Office of Air Quality and Transportation Planning, California Environmental Protection Agenc y, Air Resources Board, Sacramento, CA, November. Carter W.P.L. (2003) The SAPRC-99 chemical mechanism and updated reactivity scales. Revised final report prepared for the California Air Resources Board, Sacramento, CA, by University of California, Center for Environmental Research and Technology, Air Pollution Research Center and College of E ngineering, Riverside, CA, Contracts No. 92- 329 and 95-308, February. Chinkin L.R., Main H.H., and Roberts P.T. ( 2002) Weekday/weekend ozone observations in the South Coast Air Basin volume III: analysis of summer 2000 field measurements and supporting data. Final report prepared fo r National Renewable Energy Laboratory, Golden, CO, by Sonoma Technology, Inc., Petaluma, CA, STI-999670- 2124-FR, April.
Chinkin L.R., Penfold B.M., Brown S.G., a nd Hafner H.R. (2005) Emissions inventory evaluation and reconciliation in the South Coast Air Basi n. Final report prepared for South Coast Air Quality Management District, Diamond Bar, CA, by Sonoma Technology, Inc., Petaluma, CA , STI-904045-2728-FR, August. Chinkin L.R. and Reid S.B. (2006) Emissions reconciliation findings and recommendations – Comparison of ambient measurements to emissions representations for modeling. Technical memorandum prepared for the Ca lifornia Air Resources Board, Sacramento, CA, by Sonoma Technology, Inc., Petaluma, CA, STI-905044.12-3094-TM, December. Desert Research Institute ( 2005) Validation of the U.S. EPA MOBILE6 highway vehicle emission factor model, Task 4: Guidance document for validation of on-road vehicle emissions inventory. Prepared for the Lake Michigan Air Directors Consortium (LADCO), Des Plaines, IL, by Desert Re search Institute, Reno, NV, April. Fujita E.M., Croes B.E., Bennett C.L., Lawson D.R., Lurmann F.W., and Main H.H. (1992) Comparison of emissions invent ory and ambient concentration ratios of CO, NMOG, and NO x 

# in California’s South Coast Air Basin. J. Air Waste Manage. Assoc. 42 , 264-276. LADCO (1998) Comparison of ambi ent and emissions VOC and NO x 

# data in the Lake Michigan region. November. Pollack A.K., Lindhjem C., Stoeckenius T.E., Tr an C., Mansell G., Jimenez M., Wilson G., and Coulter-Burke S. (2004) Evaluation of the U.S. EPA MOBILE6 highway vehicle

### Upper Midwest Emissions Inventory Evaluation References



## 6-2 

# emission factor model. Final report prepar ed for the Coordinating Research Council (CRC), Alpharetta, GA, Emissions Inventor y Improvement Program (EIIP), Research Triangle Park, NC, and U.S. EPA Office of Transportation and Air Quality (OTAQ), Ann Arbor, MI by ENVIRON International Corporation, Novato, CA, CRC Project E-64, March.
Roberts P.T., Brown S.G., Reid S.B., Buhr M.P ., Funk T.H., Stiefer P.S., Hopke P.K., and Kim E. (2004) Emissions inventory evaluation a nd reconciliation in th e Houston-Galveston area. Final report prepared for the Houston Advanced Research Center, Texas Environmental Research Consortium, The Woodlands, TX, by Sonoma Technology, Inc., Petaluma, CA, STI-903640-2490-FR2, June. U.S. Environmental Protection Agency (2008) SPECIATE database, ve rsion 4.2. Available on the Internet at http://www.epa.gov/ttnchie1/s oftware/speciate/index.html . November. U.S. Environmental Protection Agency (2010) Technical guidance on the use of MOVES2010 for emissions inventory prep aration in state implementa tion plans and transportation conformity. Prepared by the EPA's Office of Transportation and Air Quality, Ann Arbor, MI, EPA-420-B-10-023, April. Av ailable on the Internet at http://www.epa.gov/otaq/models/moves/420b10023.pdf

.

### Upper Midwest Emissions Inventory Evaluation Appendix A



## A-1 

# APPENDIX A

Chemical Species Cross-Reference List

### Upper Midwest Emissions Inventory Evaluation Appendix A



## A-3 Table A-1. List of PAMS species used to match emissions and ambient data. Page 1 of 2 

# SAROAD Code CAS Code Species Name Molecular Weight MIR Value

43203 74-85-1 Ethylene 28.054 9.07
45201 71-43-2 Benzene 78.114 0.81
43229 107-83-5 2-Methylpentane 86.178 1.78
43230 96-14-0 3-Methylpentane 86.178 2.06
43248 110-82-7 Cyclohexane 84.162 1.44
43261 108-87-2 Methylcyclohexane 98.189 1.97
43262 96-37-7 Methylcyclopentane 84.162 2.4
43271 108-08-7 2,4-Dimethylpentane 100.205 1.63
43274 565-59-3 2,3-Dimethylpentane 100.205 1.53
43275 591-76-4 2-Methylhexane 100.205 1.36
43276 540-84-1 2,2,4-Trimethylpentane 114.232 1.43
43279 565-75-3 2,3,4-Trimethylpentane 114.232 1.22
43291 75-83-2 2,2-Dimethylbutane 86.178 1.33
43295 589-34-4 3-Methylhexane 100.205 1.84
43298 589-81-1 3-Methylheptane 114.232 1.33
98001 79-29-8 2,3-Dimethylbutane 86.178 1.13
98140 592-27-8 2-Methylheptane 114.232 1.18
43213 106-98-9 1-Butene 56.108 10.22
43216 624-64-6 Trans-2-Butene 56.108 13.9
43217 590-18-1 cis-2-Butene 56.108 13.22
43224 109-67-1 1-Pentene 70.135 7.73
43226 646-04-8 Trans-2-Pentene 70.135 10.23
43227 627-20-3 cis-2-Pentene 70.135 10.23
98005 592-76-7 1-Heptene 98.189 4.2
45107 25551-13-7 Trimethylbenzene 120.195 9.9
45113 141-93-5 1,3-Diethylbenzene 134.222 8.39
45114 105-05-5 1,4-Diethylbenzene 134.222 3.36
45203 100-41-4 Ethylbenzene 106.168 2.79
45204 95-47-6 o-Xylene 106.168 7.48
45207 108-67-8 1,3,5-Trimethylbenzene 120.195 11.22
45208 95-63-6 1,2,4-Trimethylbenzene 120.195 7.18
45209 103-65-1 N-Propylbenzene 120.195 2.2
98043 98-82-8 Isopropylbenzene (Cumene) 120.195 2.32
99914 622-96-8 1-Methyl-4-Ethylbenzene 120.195 3.75
99915 611-14-3 1-Methyl-2-Ethylbenzene 120.195 6.61
43551 67-64-1 Acetone 58.0804 0.43

### Upper Midwest Emissions Inventory Evaluation Appendix A



## A-4 Table A-1. List of PAMS species used to match emissions and ambient data. Page 2 of 2 

# SAROAD Code CAS Code Species Name Molecular Weight MIR Value

45220 100-42-5 Styrene 104.152 1.94
43502 50-00-0 Formaldehyde 30.0264 8.96
43202 74-84-0 Ethane 30.07 0.31
43204 74-98-6 Propane 44.097 0.56
43212 106-97-8 n-Butane 58.124 1.32
43214 75-28-5 Isobutane 58.124 1.34
43220 109-66-0 n-Pentane 72.151 1.53
43242 287-92-3 Cyclopentane 70.135 2.67
98132 78-78-4 Isopentane 72.151 1.67
43205 115-07-1 Propylene 42.081 11.57
45202 108-88-3 Toluene 92.141 3.97
43503 75-07-0 Acetaldehyde 44.0534 6.83
43206 74-86-2 Acetylene 26.038 1.24
43243 78-79-5 Isoprene 68.119 10.68
43231 110-54-3 n-Hexane 86.178 1.43
43233 111-65-9 n-Octane 114.232 1.09
43235 111-84-2 n-Nonane 128.259 0.93
43238 124-18-5 n-Decane 142.286 0.81
43241 1120-21-4 n-Undecane 156.313 0.72

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-1 

# APPENDIX B

Monitoring Site Photographs

## B-3 Upper Midwest Emissions Inventory Evaluation Appendix BLooking NorthLooking EastLooking WestLooking SouthFigure B-1.Photographs taken around the Chicago-Jardine monitoring site.

## B-4 Upper Midwest Emissions Inventory Evaluation Appendix BLooking NorthLooking EastLooking WestLooking SouthFigure B-2.Photographs taken around the Chicago-Northbrook monitoring site.

## B-5 Upper Midwest Emissions Inventory Evaluation Appendix BLooking NorthLooking EastLooking WestLooking SouthFigure B-3.Photographs taken around the Chicago-Mannheim monitoring site.

## B-6 Upper Midwest Emissions Inventory Evaluation Appendix BLooking NorthLooking EastLooking WestLooking SouthFigure B-4.Photographs taken around the Gary, Indiana, monitoring site.

## B-7 Upper Midwest Emissions Inventory Evaluation Appendix BLooking NorthLooking EastLooking WestLooking SouthFigure B-5.Photographs taken around the Milwaukee, Wisconsin, monitoring site.

## B-8 Upper Midwest Emissions Inventory Evaluation Appendix BLooking NorthLooking EastLooking WestLooking SouthFigure B-6.Photographs taken around the Detroit-East 7 Mile monitoring site.

## B-9 Upper Midwest Emissions Inventory Evaluation Appendix BLooking NorthwestLooking NortheastLooking SouthwestLooking SoutheastFigure B-7.Photographs taken around the Detroit-Linwood monitoring site.

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-10 Figure B-8. Photograph of the Chicago-Franklin monitoring site.

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-11 Figure B-9. Image of the area around the Jardine and Franklin sites in Chicago.

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-12 Figure B-10. Image of the area around the Northbrook site in Chicago.

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-13 Figure B-11. Image of the area around the Mannheim site in Chicago.

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-14 Figure B-12. Image of the area around the Gary site.

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-15 Figure B-13. Image of the area around the East 7 Mile and Linwood sites in Detroit.

### Upper Midwest Emissions Inventory Evaluation Appendix B



## B-16 Figure B-14. Image of the area around the Milwaukee site.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-1 

# APPENDIX C

Diurnal Concentration Plots for 2008 and 2009

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-3 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300

T N M O C ( p p b C )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300

T N M O C ( p p b C )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300

T N M O C ( p p b C )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )



## Figure C-1. Hourly TNMOC and NO x 

## concentrations for the Ch icago-Northbrook site for summer weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-4 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

T N M O C ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

T N M O C ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

T N M O C ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 10 20 30 40

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 10 20 30 40

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 10 20 30 40

N O x ( p p b )



## Figure C-2. Hourly TNMOC and NO x 

## concentrations for the Ch icago-Northbrook site for summer weekdays (left), Saturdays (center), and Sundays (right), 2009.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300

T N M O C ( p p b C )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300

T N M O C ( p p b C )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300

T N M O C ( p p b C )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )



## Figure C-3. Hourly TNMOC and NO x 

## concentrations for the Milwaukee site for summer weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-6 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 

### Hour 0 50 100 150 200

N O x ( p p b )



## Figure C-4. Hourly CO and NO x 

## concentrations for the Chica go-Franklin site for summer weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-7 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 300 600 900

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )



## Figure C-5. Hourly CO and NO x 

## concentrations for the Chica go-Franklin site for summer weekdays (left), Saturdays (center), and Sundays (right), 2009.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-8 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )



## Figure C-6. Hourly CO and NO x 

## concentrations for the Chicago-Mannheim site for summer weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-9 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )



## Figure C-7. Hourly CO and NO x 

## concentrations for the Chicago-Mannheim site for summer weekdays (left), Saturdays (center), and Sundays (right), 2009.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800 1000

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800 1000

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800 1000

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )



## Figure C-8. Hourly CO and NO x 

## concentrations for the Chicago-Northbrook site for summer weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-11 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300 400 500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300 400 500 600 700

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300 400 500 600 700

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 10 20 30 40

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 10 20 30 40

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 10 20 30 40

N O x ( p p b )



## Figure C-9. Hourly CO and NO x 

## concentrations for the Chicago-Northbrook site for summer weekdays (left), Saturdays (center), and Sundays (right), 2009.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-12 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )



## Figure C-10. Hourly CO and NO x 

## concentrations for the Chicago-Mannheim site for winter weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-13 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 40 80 120

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 40 80 120

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 40 80 120

N O x ( p p b )



## Figure C-11. Hourly CO and NO x 

## concentrations for the Chicago-Mannheim site for winter weekdays (left), Saturdays (center), and Sundays (right), 2009.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-14 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 500 1000 1500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 50 100 150 200

N O x ( p p b )



## Figure C-12. Hourly CO and NO x 

## concentrations for the Chicago-Franklin site for winter weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-15 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 300 600 900

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 40 80 120

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 40 80 120

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 40 80 120

N O x ( p p b )



## Figure C-13. Hourly CO and NO x 

## concentrations for the Chicago-Franklin site for winter weekdays (left), Saturdays (center), and Sundays (right), 2009.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-16 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800 1000

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800 1000

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 200 400 600 800 1000

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80 100

N O x ( p p b )



## Figure C-14. Hourly CO and NO x 

## concentrations for the Chicago-Northbrook site for winter weekdays (left), Saturdays (center), and Sundays (right), 2008.

### Upper Midwest Emissions Inventory Evaluation Appendix C



## C-17 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300 400 500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300 400 500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 100 200 300 400 500

C O ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0 20 40 60 80

N O x ( p p b )



## Figure C-15. Hourly CO and NO x 

## concentrations for the Chicago-Northbrook site for winter weekdays (left), Saturdays (center), and Sundays (right), 2009.

### Upper Midwest Emissions Inventory Evaluation Appendix D



## D-1 

# APPENDIX D

Additional Comparisons of Pollutant Ratios

### Upper Midwest Emissions Inventory Evaluation Appendix D



## D-3 0 2 4 6

678678678678678

E7Mile Gary Jardine Northbrook Milw aukeeAmbient Ratio Median/Emission Ratio



### All

WD
SAT
SUN



## Figure D-1. Ratios of ambient-derived TNMOC/NO x 

## ratios to emissions-derived TNMOC/NO x 

## ratios by month and day of week for 2005 1 

## (the 1:1 agreement line is shown as a dashed red line).

1 

## Because the 2005 emissions inventory was compared to ambient data from a three-y ear period (2004-2006), the large number of ambient samples allowe d for month-specific (and other) analyses that were not possible with the 2008 ambient-to-emissions comparisons.

### Upper Midwest Emissions Inventory Evaluation Appendix D



## D-4 0 1 2 3 4

1234

Wind QuadrantTNMOC/NOx Ratio

0 1 2 3 4

1234

Wind Quadrant 0 1 2 3 4

1234

Wind Quadrant Ambient

EI - Low Level Only

EI - With Elevated Source



## Figure D-2. Summer 2005 TNMOC/NO x 

## ratios by wind quadrant for the Chicago-Jardine site on weekdays (left), Saturdays (center), and Sundays (right).

0 1 2 3 4 5 6 7

1234

Wind QuadrantTNMOC/NOx Ratio

0 1 2 3 4 5 6 7

1234

Wind Quadrant 0 1 2 3 4 5 6 7

1234

Wind Quadrant Ambient

EI - Low Level Only

EI - With Elevated Source



## Figure D-3. Summer 2005 TNMOC/NO x 

## ratios by wind quadrant for the Chicago-Northbrook site on weekdays (left), Saturdays (c enter), and Sundays (right).

0 5 10 15

1234

Wind QuadrantTNMOC/NOx Ratio

0 5 10 15

1234

Wind Quadrant 0 5 10 15

1234

Wind Quadrant Ambient

EI - Low Level Only

EI - With Elevated Source



## Figure D-4. Summer 2005 TNMOC/NO x 

## ratios by wind quadrant for the Gary site on weekdays (left), Saturdays (center), and Sundays (right).

### Upper Midwest Emissions Inventory Evaluation Appendix D



## D-5 0 5 10 15 20

1234

Wind QuadrantTNMOC/NOx Ratio

0 5 10 15 20

1234

Wind Quadrant 0 5 10 15 20

1234

Wind Quadrant Ambient
EI - Low Level Only

EI - With Elevated Source



## Figure D-5. Summer 2005 TNMOC/NO x 

## ratios by wind quadrant for the Detroit – East 7 Mile site on weekdays (left), Saturdays (c enter), and Sundays (right).

0 1 2 3 4 5 6 7 8 9

1234

Wind QuadrantTNMOC/NOx Ratio

0 1 2 3 4 5 6 7 8 9

1234

Wind Quadrant 0 1 2 3 4 5 6 7 8 9

1234

Wind Quadrant Ambient

EI - Low Level Only

EI - With Elevated Source



## Figure D-6. Summer 2005 TNMOC/NO x 

## ratios by wind quadrant for the Milwaukee site on weekdays (left), Saturdays (center), and Sundays (right).

0 1 2 3

12 1 2 6 7 8 12 1 2 6 7 8 12 1 2 6 7 8 12 1 2 6 7 8

Franklin Linw ood Mannheim Milw aukeeAmbient Ratio Median/Emission Ratio



### All

WD
SAT
SUN



## Figure D-7. Ratios of ambient-derived CO/NO x 

## ratios to emissions-derived CO/NO x 

## ratios by month and day of week for 2005 (the 1:1 agreement line is shown as a dashed red line).

### Upper Midwest Emissions Inventory Evaluation Appendix D



## D-6 0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio

0 5 10 15 20 25

1234

Wind Quadrant 0 5 10 15 20 25

1234

Wind Quadrant Ambient

EI - Low Level Only

EI - With Elevated Source



## Figure D-8. Winter 2005 CO/NO x 

## ratios by wind quadrant for the Chicago-Mannheim site on weekdays (left), Saturdays (center), and Sundays (right).

0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio

0 5 10 15 20 25

1234

Wind Quadrant 0 5 10 15 20 25

1234

Wind Quadrant Ambient
EI - Low Level Only

EI - With Elevated Source



## Figure D-9. Summer 2005 CO/NO x 

## ratios by wind quadrant for the Chicago-Mannheim site on weekdays (left), Saturdays (center), and Sundays (right).

0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio

0 5 10 15 20 25

1234

Wind Quadrant 0 5 10 15 20 25

1234

Wind Quadrant Ambient
EI - Low Level Only

EI - With Elevated Source



## Figure D-10. Winter 2005 CO/NO x 

## ratios by wind quadrant for the Milwaukee site on weekdays (left), Saturdays (center), and Sundays (right).

### Upper Midwest Emissions Inventory Evaluation Appendix D



## D-7 0 5 10 15 20 25

1234

Wind QuadrantCO/NOx Ratio

0 5 10 15 20 25

1234

Wind Quadrant 0 5 10 15 20 25

1234

Wind Quadrant Ambient
EI - Low Level Only

EI - With Elevated Source



## Figure D-11. Summer 2005 CO/NO x 

## ratios by wind quadrant for the Milwaukee site on weekdays (left), Saturdays (center), and Sundays (right).

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-1 

# APPENDIX E

Additional Comparisons of Hydrocarbon Compositions

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-3 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-1. Comparison of 2005 summer weekday ambient- and emissions-derived hydrocarbon compositions for the Chicago-Jardine site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-2. Comparison of 2005 summer Saturday ambient- and emissions-derived hydrocarbon compositions for the Chicago-Jardine site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-4 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-3. Comparison of 2005 summer Sunday ambient- and emissions-derived hydrocarbon compositions for the Chicago-Jardine site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-4. Comparison of June 2005 ambient - and emissions-derived hydrocarbon compositions for the Chicago-Jardine site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-5 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-5. Comparison of July 2005 ambient- and emissions-derived hydrocarbon compositions for the Chicago-Jardine site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-6. Comparison of August 2005 ambient- and emissions-derived hydrocarbon compositions for the Chicago-Jardine site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-6 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-7. Comparison of 2005 summer weekday ambient- and emissions-derived hydrocarbon compositions for the Chicago-Northbrook site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-8. Comparison of 2005 summer Saturday ambient- and emissions-derived hydrocarbon compositions for the Chicago-Northbrook site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-7 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-9. Comparison of 2005 summer Sunday ambient- and emissions-derived hydrocarbon compositions for the Chicago-Northbrook site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-10. Comparison of June 2005 ambient- and emissions-derived hydrocarbon compositions for the Chicago-Northbrook site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-8 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-11. Comparison of July 2005 ambient- and emissions-derived hydrocarbon compositions for the Chicago-Northbrook site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-12. Comparison of August 2005 ambient- and emissions-derived hydrocarbon compositions for the Chicago-Northbrook site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-9 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-13. Comparison of 2005 summer weekday ambient- and emissions-derived hydrocarbon compositions for the Detroit-East 7 Mile site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-14. Comparison of 2005 summer Saturday ambient- and emissions-derived hydrocarbon compositions for the Detroit-East 7 Mile site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-10 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-15. Comparison of 2005 summer Sunday ambient- and emissions-derived hydrocarbon compositions for the Detroit-East 7 Mile site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-16. Comparison of June 2005 ambient- and emissions-derived hydrocarbon compositions for the Detroit-East 7 Mile site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-11 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-17. Comparison of July 2005 ambient- and emissions-derived hydrocarbon compositions for the Detroit-East 7 Mile site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-18. Comparison of August 2005 ambient- and emissions-derived hydrocarbon compositions for the Detroit-East 7 Mile site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-12 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-19. Comparison of 2005 summer weekday ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-20. Comparison of 2005 summer Saturday ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-13 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-21. Comparison of 2005 summer Sunday ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-22. Comparison of June 2005 ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-14 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-23. Comparison of July 2005 ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-24. Comparison of August 2005 ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-15 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-25. Comparison of 2005 summer weekday ambient- and emissions-derived hydrocarbon compositions for the Gary site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-26. Comparison of 2005 summer Saturday ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-16 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-27. Comparison of 2005 summer Sunday ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-28. Comparison of June 2005 ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

## Upper Midwest Emissions Inventory Evaluation Appendix E

E-17 0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-29. Comparison of July 2005 ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.

0% 5% 10% 15% 20% 25% 30%EthyleneBenzeneC6+ AlkanesC4+ AlkenesC8+ AromaticsStyrenesEthanePropaneButanesPentanesPropyleneTolueneAcetyleneIsopreneC6-C11 Alkanes% TNMOC 

### Ambient
Emissions



## Figure E-30. Comparison of August 2005 ambient- and emissions-derived hydrocarbon compositions for the Milwaukee site.