# Y OCKE AND 

# C OMPANY

Final Report
UPDATES TO THE CARBON BOND

CHEMICAL MECHANISM: CB05
RT-04-00675

Prepared for
Deborah Luecken U.S. Environmental Protection Agency

Research Triangle Park, NC 27703

Prepared by Greg Yarwood and Sunja Rao ENVIRON International Corporation 101 Rowland Way, Suite 220 Novato, CA 94945
Mark Yocke Yocke & Company 101 Rowland Way Novato, CA 94945

Gary Z. Whitten

Smog Reyes

112 Mesa Point Reyes Station, CA 94956

December 8, 2005

101 Rowland Way, Suite 220, Novato, CA 94945 415.899.0703H:\EPA_CB4\Report\final\ACKNOWLEDGEMENT.doc 

### ACKNOWLEDGEMENT

The authors gratefully acknowledge contributions from several colla borators in this work. Dr. William Carter of U.C. Riverside (UCR) simu lated smog chamber experiments performed at UCR. Mr. Ken Sexton of the University of North Carolina (UNC) provided assistance in simulating smog chamber experiments performed at UNC. Dr. Deborah Luecken and Dr. Golam Sarwar of U.S. EPA provided advice and review of the data, assumptions and interpretation of results for this study.H:\EPA_CB4\Report\final\ABSTRACT.doc 

### ABSTRACT

Updated versions of the Carbon Bond mechanism were developed for use in EPA atmospheric modeling studies. The new Carbon Bond mechanism is called CB05 because it was developed in 2005. The CB05 is a condensed mechanism of at mospheric oxidant chemistry that provides a basis for computer modeling studies of ozone, part iculate matter (PM), visi bility, acid deposition and air toxics issues. Updates in CB05 compared to earlier CB4 mechanisms are:

• Updated rate constants based on recent (2003 – 2005) IUPAC and NASA evaluations.
• An extended inorganic reaction set for ur ban to remote tropos pheric conditions.
• NOx recycling reactions to represent the fate of NOx over multiple days.
• Explicit organic chemistry for methane and ethane.
• Explicit methylperoxy radical, met hyl hydroperoxide and formic acid.
• Lumped higher organic peroxides, organic acids and peracids.
• Internal olefin (R-HC=CH -R) species called IOLE.
• Higher aldehyde species ALDX making ALD2 explicitly acetaldehyde.
• Higher peroxyacyl nitrate species from ALDX called PANX.
• Lumped terpene species called TERP.
• Optional mechanism extension for reactive chlorine chemistry.
• Optional extended mechanism with e xplicit reactions for air-toxics. The core CB05 mechanism has 51 species and 15 6 reactions. The CB05 was evaluated against smog chamber data from the Universities of No rth Carolina and Californi a at Riverside. An updated wall reaction mechanism was developed for the UNC chamber that improved performance in experiments that are sensitive to chamber radical sources. The addition of higher aldehyde (ALDX) and internal olefin (IOLE) species to CB05 improve mechanism performance for simulating these species groups. The additi on of organic peroxide species improves the simulation of oxidants that are involved in PM sulfate formation. The addition of explicit methylperoxy radical improves the simulation of hydrogen peroxide under low NOx conditions. Two CB05 mechanism extensions were developed. The reactive chlorine chemistry mechanism can be used in conjunction w ith the CB05 core mechanism to model the impact of CL 2 

### and/or HOCl emissions on oxidant formation and VOC decay rates. The explicit species extension can be used in conjunction with the CB05 (or anothe r) core mechanism to model the following toxic species: primary formaldehyde, primary acetal dehyde, 1,3-butadiene, primary and secondary acrolein. Other explicit species are toluene, o-xylene, m-xylene, p-xylene, apha-pinene and betapinene. These include the main precursors to secondary organic aerosol (SOA) and could be used as the basis for refined modeling approach for SOA that is independent of the core mechanism selected (e.g., CB4, CB05 or SAPRC99).December 2005



### i TABLE OF CONTENTS Page

1. INTRODUCTION................................................................................................................ 1-1 History of CB4................................................................................................................. ...... 1-1

2. MECHANISM UPDATES .................................................................................................. 2-1
CB05 Core Mechanism.......................................................................................................... 2- 1 Extended Mechanism with Explicit Species........................................................................ 2-10 Reactive Chlorine Chemistry............................................................................................... 2-13 Chemical Species Mapping for CB05 Mechanisms ............................................................ 2-15

3. CB05 IMPLEMENTATION TESTING............................................................................ 3-1 Comparing CB05 to CB4....................................................................................................... 3-1 Rate Constant Comparisons................................................................................................... 3-5 Box Model Comparisons ....................................................................................................... 3-9

4. MECHANISM EVALUATION.......................................................................................... 4-1
UNC Chamber ................................................................................................................... .... 4-1 UCR Chamber................................................................................................................... ..... 4-9

5. SUMMARY AND RECOMMENDATIONS..................................................................... 5-1

REFERENCES..................................................................................................................... ..... R-1

APPENDICES Appendix A: Assignments from VO C Species to CB05 Model Species Appendix B: Chamber Simulations for the University of North Carolina (UNC) Chamber with CB05 Orga nized by Chemical Compound TypeDecember 2005



### ii TABLES Table 2-1. Species names for the CB05 core mechanism ..................................................... 2-1 Table 2-2. Reactions in the CB05 core mechanism .............................................................. 2-2 Table 2-3. Reactions in the extended CB05 mechanism that may be added to the core mechanism. ............................................................... 2-10 Table 2-4. Reactions in the CB05 reactive chlorine mechanism that may be added to the CB05 core mechanism............................................... 2-13 Table 2-5. Species added to CB05 by the reactive chlorine mechanism ............................ 2-14 Table 3-1. VOC composition used for the box model comparison of CB4 and CB05......... 3-1 Table 3-2. Comparison of CB05 th ermal rate constants calculated by SmogReyes and EPA for three different temperature/pressure conditions (units are ppm and minutes) ............................ 3-6 Table 4-1. Wall reactions from the Jeffries, Voicu and Sexton (2002) UNC chamber mechanisms that were changed for this project........................... 4-2 Table 4-2. New wall reactions for the UNC chamber used in this project............................ 4-2 Table 4-3. Compounds and numbers of UCR experiments included in the comparison between CB05 and SAPRC99 mechanism performance ......... 4-12 Table 4-4. Numbered UCR chamber experiments used to evaluate the CB05 and SAPRC99 mechanisms, by compound ....................................... 4-13

FIGURES Figure 3-1. Comparison of CB4 and CB05 ozone predictions for urban MIR conditions. ......................................................................................... 3-2 Figure 3-2. Comparison of CB4 and CB05 HNO 3 

### predictions for urban MIR conditions .......................................................................................... 3-3 Figure 3-3. Comparison of CB4 and CB05 H 2 

### O 2 

### predictions for urban MIR conditions. ......................................................................................... 3-3 Figure 3-4. Comparison of CB4 and CB05 ozone predictions for urban MOIR conditions ....................................................................................... 3-4 Figure 3-5. Comparison of CB4 and CB05 HNO 3 

### predictions for urban MOIR conditions ....................................................................................... 3-4 Figure 3-6. Comparison of CB4 and CB05 H 2 

### O 2 

### predictions for urban MOIR conditions ....................................................................................... 3-5 Figure 3-7. Comparison of resu lts from the CMAQ and OZIPM box models for NO, NO 2 

### and O 3 

### at 298 K and 1 atmosphere .................................. 3-10 Figure 3-8. Comparison of resu lts from the CMAQ and OZIPM box models for HONO and HO 2 

### at 298 K and 1 atmosphere................................... 3-10 Figure 3-9. Comparison of resu lts from the CMAQ and OZIPM box models for NO, NO 2 

### and O 3 

### at 298 K and 0.5 atmosphere ............................... 3-11 Figure 3-10. Comparison of resu lts from the CMAQ and OZIPM box models for NO, NO 2 

### and O 3 

### at 310K and 1 atmosphere ................................... 3-11 Figure 4-1. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC carbon monoxide experiment August 30, 1993 (red) ......... 4-3 Figure 4-2. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC carbon monoxide experiment August 30, 1996 (blue) ....... 4-4December 2005



### iii Figure 4-3. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experiment of September 4, 1997 (red chamber) with trimethylacetaldehyde and Propionaldehyde............................................... 4-5 Figure 4-4. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experime nt October 16, 1996 (blue chamber) with propene, 1-butene and 1-pentene................................................................. 4-6 Figure 4-5. Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experime nt September 14, 1996 (blue chamber) with an equimolar mixture of all butene isomers (1-butene, cis-2-butene, trans-2-butene, isobutene).............................................................. 4-7 Figure 4-6. SAPRC99 (left) and CB05 (right) simulation of a carbon monoxide experiment in the EPA chamber at UCR .......................................... 4-14 Figure 4-7. SAPRC99 simulation of four formaldehyde experiments in the EPA chamber at UCR .............................................................................. 4-15 Figure 4-8. CB05 simulation of four formaldehyde experiments in the EPA chamber at UCR .............................................................................. 4-16 Figure 4-9. SAPRC99 (left) and CB05 (right) simulation of an ethene experiment in the EPA chamber at UCR................................................ 4-17 Figure 4-10. SAPRC99 (left) and CB05 (right) simulation of a propene experiment in the EPA chamber at UCR ........................................................... 4-17 Figure 4-11. SAPRC99 (left) and CB 05 (right) simulation of a butane experiment in the EPA chamber at UCR ........................................................... 4-18 Figure 4-12. SAPRC99 simulation of two toluene experiments in the EPA chamber at UCR .............................................................................. 4-19 Figure 4-13. CB05 simulation of two toluene experiments in th e EPA chamber at UCR ..... 4-20 Figure 4-14. SAPRC99 simulation of two xylene experiments in the EPA chamber at UCR. ............................................................................. 4-21 Figure 4-15. CB05 simulation of two xylene expe riments in the EPA chamber at UCR. ..... 4-22 Figure 4-16. Bias in oxidant production (O 3 

### -NO) at hours 1-6 in UCR chamber experiments for the CB05 and SAPRC99 mechanisms, by compound................................................................................ 4-23December 2005

H:\EPA_CB4\Report\final\Sec1_Intro.doc 

### 1-1 1. INTRODUCTION

The goals of this study were to develop updated versions of the Carbon Bond mechanism for use in EPA atmospheric modeling studies. The star ting point for this study was version 4 of the Carbon Bond mechanism (CB4) developed in the la te 1980s (Gery et al., 1989) as updated in the mid 1990s for EPA’s “OTAG” study. An overvie w of the development history of CB4 and related mechanisms is given below.
The new version of the Carbon Bond mechanism is called CB05 because it was developed in 2005. The CB05 is a condensed mechanism of at mospheric oxidant chemistry that provides a basis for computer modeling studies of ozone, part iculate matter (PM), visi bility, acid deposition and air toxics issues. The CB05 mechanism update s developed for this study are as follows: 1. Incorporating current kinetic and photo lysis data in the core mechanism. 2. Extending the chemical mechanism to better support PM modeling needs such as formation of secondary or ganic aerosols (SOA). 3. Adding extra species and r eactions to treat a number of volatile organic compounds (VOCs) explicitly for modeling air toxics. 4. Accounting for the role of reactive chlorine emissions in VOC degradation and oxidant chemistry. The CB05 mechanism updates are di scussed further in Section 2.

HISTORY OF CB4 EPA sponsored the development of version IV of the Carbon Bond (CB4) in the late 1980’s for use in urban and regional photochemical m odeling and Gery et al., (1989), published the mechanism. The regional models of the late 1980’s that utilized CB4 were more limited in domain extent than current re gional models (e.g., formulated for the planetary boundary layer and not the upper troposphere) a nd the original CB4 was more appropriate for urban than regional scale modeling. EPA made limited updates to the CB4 mechanism in the early 1990s. The three main updates were to PAN chemistry, radical terminati on reactions and isoprene chemistry and they culminated in the version of CB4 used fo r the Ozone Transport Assessment Group (OTAG) modeling and EPA’s NOx SIP call. Two other vers ions of CB4 that have appeared since the OTAG version are CBM-Z and CB2002. These mechanisms are reviewed briefly below.

The Urban Airshed Model Version of CB4 The EPA’s Urban Airshed Model (UAM-IV; Morris and Myers, 1990) had the first widely used version of the CB4 mechanism. Changes from the Gery et al. (1989) mechanism were the inclusion of explicit chemistry for methanol and ethanol and an update to the PAN chemistry. Dodge (1991) updated the PAN chemistry for CB4 because the Gery et al. (1989) mechanism had incorrect temperature dependencies for PAN formation (Tuazon, Carter and Atkinson, 1991).December 2005

H:\EPA_CB4\Report\final\Sec1_Intro.doc 

### 1-2 The OTAG Version of CB4 The OTAG version of CB4 had two updates were ma de to better represent regional scale oxidant formation in the eastern US where high isoprene le vels occur and rural areas have relatively low NOx concentrations. Yarwood updated the radi cal-radical termination reactions (among HO 2 

### and RO 2 

### radicals) to better represent oxidant fo rmation under conditions of low NOx (Yarwood and Burton, 1994). Whitten updated the isoprene chem istry in the CB4 (Whitten et al., 1996) to reflect newer scientific data on the products a nd mechanisms of isoprene oxidation (Carter and Atkinson, 1996). The updated isoprene mechanism is a translation from SAPRC to CB4 species of Carter’s condensed “1-product” isoprene mechanism (Carter, 1996).

CBM-Z – Pacific Northwest National Laboratory The Pacific Northwest National Laboratory (P NNL) has developed a mechanism based on the Carbon Bond approach called CBM-Z (Zaveri an d Peters, 1999). Changes in CBM-Z were intended to update the mechanism from the publis hed Gery et al., (1989) version and improve performance for regional scale modeling, and included:
• Revised inorganic chemistry.
• Explicit treatment of the lesser re active alkanes - methane and ethane.
• Revised parameterizations of the reactive paraffin, olefin, and aromatic reactions.
• Inclusion of alkyl and acyl peroxy radical interactions a nd their reactions with the NO 3 

### radical.
• Inclusion of organi c hydroperoxides.
• Isoprene chemistry based on the condensed one-product mechanism of Carter (1996). The CBM-Z and CB4 were evaluated against smog chamber data from the TVA chamber and showed improved performance for CBM-Z on thes e chamber experiments. Sensitivity tests showed larger differences between CBM-Z and CB4 for regional modeling conditions than for urban or smog chamber conditions. One factor that contributed to differences under regional conditions (Zaveri and Peters, 1999) was the in clusion in CBM-Z of reactions for organic nitrates that slowly recycle nitr ogen from an inactive form (organic nitrates) to an active form (NOx).

CB2002 – University of North Carolina In late 1990s, UNC started to update and re-e valuate the CB4 mechanism against smog chamber data. UNC’s approach was to retain the overall structure of CB4 but upda te rate constants and some product yields based on recent data. The first mechanism produced by UNC was called CB99. Unfortunately, the CB99 work was completed just as literatur e values for a critical rate constant (OH + NO 2 

### ) changed. UNC repeated the work with the new OH + NO 2 

### rate constant and developed CB2002 to supercede CB99 (Je ffries, Voicu, and Sexton, 2002). The CB2002 was evaluated against UNC smog chamber data as described in detail in Jeffries, Voicu, and Sexton (2002).December 2005

H:\EPA_CB4\Report\final\Sec1_Intro.doc 

### 1-3 The main changes between CB2002 and CB4 were:
• Updated inorganic reaction rate c onstants with new reactions for NO 3 

### reacting with OH, HO 2 

### and itself, and O 3 

### reacting with O( 3 

### P).
• A new HONO photolysis reaction yielding NO 2 

### and H-atoms. IUPAC (2004) now recommends setting this reaction to zero for tropospheric conditions.
• New rate constants for N 2 

### O 5 

### reacting with water (Wahner et al., 1998). This update also includes a reaction of N 2 

### O 5 

### with water dimers (i.e., N 2 

### O 5 

### + H 2 

### O + H 2 

### O).
• Lower rate constants for radical-radical termination reactions involving XO2 and HO 2 

### . • New rate constants for all olefin r eactions involving ETH, OLE and ISOP.
• New products for reactions of ETH and OLE.December 2005

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 

### 2-1 2. MECHANISM UPDATES

The main CB05 mechanism is referred to as the core mechanism. There are two extensions to the core mechanism for modeling explicit species (e.g., toxics) and reactive chlorine chemistry. The core mechanism and extensions are describe d below. Finally, the process for mapping “real species” to CB05 “model species” is disc ussed (e.g., for emission inventory modeling).

CB05 CORE MECHANISM The core CB05 mechanism has 51 chemical species (Table 2-1) and 156 reactions (Table 2-2). The changes in the mechanism from CB4 (Gery et al., 1989) fall into the following categories that are discussed following Tables 2-1 and 2-2.

• Kinetic Updates
• Photolysis Updates
• Extended Inorganic Reaction Set
• Simple Alkanes (Methane and Ethane)
• Higher Aldehydes
• Alkenes with Internal Double Bonds
• Oxygenated Products and Intermediates
• Terpene Chemistry
Table 2-1. Species names for the CB05 core mechanism.

Species Name Description Number of Carbons NO Nitric oxide 0 NO2 Nitrogen dioxide 0 O3 Ozone 0 O Oxygen atom in the O 3 (P) electronic state 0 O1D Oxygen atom in the O 1 (D) electronic state 0 OH Hydroxyl radical 0 HO2 Hydroperoxy radical 0 H2O2 Hydrogen peroxide 0 NO3 Nitrate radical 0 N2O5 Dinitrogen pentoxide 0 HONO Nitrous acid 0 HNO3 Nitric acid 0 PNA Peroxynitric acid (HNO 4 ) 0 CO Carbon monoxide 1 FORM Formaldehyde 1 ALD2 Acetaldehyde 2 C2O3 Acetylperoxy radical 2 PAN Peroxyacetyl nitrate 2 ALDX Propionaldehyde and higher aldehydes 2 CXO3 C3 and higher acylperoxy radicals 2 PANX C3 and higher peroxyacyl nitrates 2 XO2 NO to NO2 conversion from alkylperoxy (RO 2 ) radical 0 XO2N NO to organic nitrate conversion from alkylperoxy (RO 2 ) radical 0 NTR Organic nitrate (RNO 3 ) 1 ETOH Ethanol 2December 2005

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 

### 2-2

Species Name Description Number of Carbons CH4 Methane 1 MEO2 Methylperoxy radical 1 MEOH Methanol 1 MEPX Methylhydroperoxide 1 FACD Formic acid 1 ETHA Ethane 2 ROOH Higher organic peroxide 1 AACD Acetic and higher carboxylic acids 2 PACD Peroxyacetic and higher peroxycarboxylic acids 2 PAR Paraffin carbon bond (C-C) 1 ROR Secondary alkoxy radical 0 ETH Ethene 2 OLE Terminal olefin carbon bond (R-C=C) 2 IOLE Internal olefin carbon bond (R-C=C-R) 4 ISOP Isoprene 5 ISPD Isoprene product (lumped methacrolein, methyl vinyl ketone, etc.) 4 TERP Terpene 10 TOL Toluene and other monoalkyl aromatics 7 XYL Xylene and other polyalkyl aromatics 8 CRES Cresol and higher molecular weight phenols 8 TO2 Toluene-hydroxyl radical adduct 7 OPEN Aromatic ring opening product 4 CRO Methylphenoxy radical 7 MGLY Methylglyoxal and other aromatic products 3 SO2 Sulfur dioxide 0 SULF Sulfuric acid (gaseous) 0



### Table 2-2. Reactions in the CB05 core mechanism. Label Reactants Products Rate Expression Notes R1 NO2 NO + O 1.0 x <NO2_SAPRC99> 20 R2 O+O2+M O3 + M 6.0E–34^–2.4 1 R3 O3+NO NO2 3.0E–12 @ 1500 1 R4 O+NO2 NO 5.6E–12 @ –180 1 R5 O+NO2 NO3 2.5E–31^–1.8 & 2.2E–11^–0.7 1
R6 O+NO NO2 9.0E–32^–1.5 & 3.0E–11 1 R7 NO2+O3 NO3 1.2E–13 @ 2450 1 R8 O3 O 1.0 x <O3_O3P_IUPAC05> 2 R9 O3 O1D 1.0 x <O3_O1D_IUPAC05> 2 R10 O1D+M O + M 2.1E–11 @ –102 1 R11 O1D+H2O 2*OH 2.20E–10 1 R12 O3+OH HO2 1.7E–12 @ 940 1 R13 O3+HO2 OH 1.0E–14 @ 490 1 R14 NO3 NO2 + O 1.0 x <NO3NO2_SAPRC99> 20 R15 NO3 NO 1.0 x <NO3NO_SAPRC99> 20 R16 NO3+NO 2*NO2 1.5E–11 @ –170 1 R17 NO3+NO2 NO + NO 2 4.5E–14 @ 1260 1 R18 NO3+NO2 N2O5 2.0E–30^–4.4 & 1December 2005

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 

### 2-3 Label Reactants Products Rate Expression Notes 1.4E–12^–0.7 R19 N2O5+H2O 2*HNO3 2.50E–22 2 R20 N2O5+H2O+H2O 2*HNO3 1.80E–39 2 R21 N2O5 NO3 + NO2 1E–03^–3.5 @ 11000 & 9.7E14^0.1 @ 11080 & 0.45 & 1.0 2

R22 NO+NO+O2 2*NO2 3.3E–39 @ –530 2 R23 NO+NO2+H2O 2*HONO 5.00E–40 3 R24 NO+OH HONO 7.0E–31^–2.6 & 3.6E–11^–0.1 1 R25 HONO NO + OH 1.0 x <HONO_IUPAC05> 2 R26 OH+HONO NO2 1.8E–11 @ 390 1 R27 HONO+HONO NO + NO2 1.00E–20 4 R28 NO2+OH HNO3 2.0E–30^–3.0 & 2.5E–11 1 R29 OH+HNO3 NO3 %2 2.4E–14 @ –460 & 2.7E–17 @ –2199 & 6.5E–34 @ –1335 1

R30 HO2+NO OH + NO2 3.5E–12 @ –250 1 R31 HO2+NO2 PNA 1.8E–31^–3.2 & 4.7E–12 & 0.6 2 R32 PNA HO2 + NO2 4.1E–5 @ 10650 & 4.8E15 @ 11170 & 0.6 2 R33 OH+PNA NO2 1.3E–12 @ –380 1 R34 HO2+HO2 H2O2 %3 2.3E–13 @ –600 & 1.7E–33 @ –1000 1 R35 HO2+HO2+H2O H2O2 %3 3.22E–34 @ –2800 & 2.38E–54 @ –3200 1 R36 H2O2 2*OH 1.0 x <H2O2_SAPRC99> 20 R37 OH+H2O2 HO2 2.9E–12 @ 160 1 R38 O1D+H2 OH + HO2 1.10E–10 1 R39 OH+H2 HO2 5.5E–12 @ 2000 1 R40 OH+O HO2 2.2E–11 @ –120 1 R41 OH+OH O 4.2E–12 @ 240 1 R42 OH+OH H2O2 6.9E–31^–1.0 & 2.6E–11^0 1 R43 OH+HO2 4.8E–11 @ –250 1 R44 HO2+O OH 3.0E–11 @ –200 1 R45 H2O2+O OH + HO2 1.4E–12 @ 2000 1 R46 NO3+O NO2 1.00E–11 1 R47 NO3+OH HO2 + NO2 2.20E–11 1 R48 NO3+HO2 HNO3 3.50E–12 1 R49 NO3+O3 NO2 1.00E–17 5 R50 NO3+NO3 2*NO2 8.5E–13 @ 2450 1 R51 PNA 0.610*HO2 + 0.610*NO2 + 0.390*OH + 0.390*NO3 1.0 x <HO2NO2_IUPAC05> 2 R52 HNO3 OH + NO2 1.0 x <HNO3_IUPAC05> 2 R53 N2O5 NO2 + NO3 1.0 x <N2O5_IUPAC05> 2 R54 XO2+NO NO2 2.6E–12 @ –365 6December 2005

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 

### 2-4 Label Reactants Products Rate Expression Notes R55 XO2N+NO NTR 2.6E–12 @ –365 6 R56 XO2+HO2 ROOH 7.5E–13 @ –700 7 R57 XO2N+HO2 ROOH 7.5E–13 @ –700 7 R58 XO2+XO2 6.80E–14 8 R59 XO2N+XO2N 6.80E–14 8 R60 XO2+XO2N 6.80E–14 8 R61 NTR+OH HNO3 + HO2 + 0.330*FORM + 0.330*ALD2 + 0.330*ALDX – 0.660*PAR 5.9E–13 @ 360 9
R62 NTR NO2 + HO2 + 0.330*FORM + 0.330*ALD2 + 0.330*ALDX – 0.660*PAR 1.0 x <NTR_IUPAC05> 28
R63 ROOH+OH XO2 + 0.500*ALD2 + 0.500*ALDX 3.01E–12 @ –190 1 R64 ROOH OH + HO2 + 0.500*ALD2 + 0.500*ALDX 1.0 x <COOH_SAPRC99> 20 R65 OH+CO HO2 %3 1.44E–13 @ 0.0 & 3.43E–33 @ 0.0 2 R66 OH+CH4 MEO2 2.45E–12 @ 1775 1 R67 MEO2+NO FORM + HO2 + NO2 2.8E–12 @ –300 1 R68 MEO2+HO2 MEPX 4.1E–13 @ –750 1 R69 MEO2+MEO2 1.370*FORM + 0.740*HO 2 + 0.630*MEOH 9.5E–14 @ –390 1 R70 MEPX+OH 0.700*MEO2 + 0.300*XO2 + 0.300*HO2 3.8E–12 @ –200 1 R71 MEPX FORM + HO2 + OH 1.0 x <COOH_SAPRC99> 20 R72 MEOH+OH FORM + HO2 7.3E–12 @ 620 1 R73 FORM+OH HO2 + CO 9.00E–12 1 R74 FORM 2*HO2 + CO 1.0 x <HCHO_R_SAPRC99> 20 R75 FORM CO 1.0 x <HCHO_M_SAPRC99> 20 R76 FORM+O OH + HO2 + CO 3.4E–11 @ 1600 1 R77 FORM+NO3 HNO3 + HO2 + CO 5.80E–16 1 R78 FORM+HO2 HCO3 9.7E–15 @ –625 2 R79 HCO3 FORM + HO2 2.4E+12 @ 7000 1 R80 HCO3+NO FACD + NO 2 + HO2 5.60E–12 1 R81 HCO3+HO2 MEPX 5.6E–15 @ –2300 1 R82 FACD+OH HO2 4.00E–13 1 R83 ALD2+O C2O3 + OH 1.8E–11 @ 1100 1 R84 ALD2+OH C2O3 5.6E–12 @ –270 1 R85 ALD2+NO3 C2O3 + HNO3 1.4E–12 @ 1900 1 R86 ALD2 MEO2 + CO + HO2 1.0 x <CCHO_R_SAPRC99> 20 R87 C2O3+NO MEO2 + NO2 8.1E–12 @ –270 1 R88 C2O3+NO2 PAN 2.7E–28^–7.1 & 1.2E–11^–0.9 & 0.3 2 R89 PAN C2O3 + NO2 4.9E–3 @ 12100 & 5.4E16 @ 13830 & 0.3 2 R90 PAN C2O3 + NO2 1.0 x <PAN_IUPAC05> 2 R91 C2O3+HO2 0.800*PACD + 0.200* AACD + 0.200*O3 4.3E–13 @ –1040 1 R92 C2O3+MEO2 0.900*MEO 2 + 0.900*HO2 + FORM + 0.100*AACD 2.0E–12 @ –500 1
R93 C2O3+XO2 0.900*MEO2 + 0.100*AACD 4.4E–13 @ –1070 2December 2005

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 

### 2-5 Label Reactants Products Rate Expression Notes R94 C2O3+C2O3 2*MEO2 2.9E–12 @ –500 1 R95 PACD+OH C2O3 4.0E–13 @ –200 10 R96 PACD MEO2 + OH 0.0 x <COOH_SAPRC99> 20 R97 AACD+OH MEO2 4.0E–13 @ –200 1 R98 ALDX+O CXO3 + OH 1.3E–11 @ 870 11 R99 ALDX+OH CXO3 5.1E–12 @ –405 2 R100 ALDX+NO3 CXO3 + HNO3 6.50E–15 2 R101 ALDX MEO2 + CO + HO 2 1.0 x <C2CHO_SAPRC99> 20 R102 CXO3+NO ALD2 + NO2 + HO2 + XO2 6.7E–12 @ –340 2 R103 CXO3+NO2 PANX 2.7E–28^–7.1 & 1.2E–11^–0.9 & 0.3 12 R104 PANX CXO3 + NO2 4.9E–3 @ 12100 & 5.4E16 @ 13830 & 0.3 12 R105 PANX CXO3 + NO2 1.0 x <PAN_IUPAC05> 2 R106 PANX+OH ALD2 + NO2 3.00E–13 13 R107 CXO3+HO2 0.800*PACD + 0.200* AACD + 0.200*O3 4.3E–13 @ –1040 14 R108 CXO3+MEO2 0.900*ALD2 + 0.900*XO2 + HO2 + 0.100*AACD + 0.100*FORM 2.0E–12 @ –500 15 R109 CXO3+XO2 0.900*ALD2 + 0.100*AACD 4.4E–13 @ –1070 16 R110 CXO3+CXO3 2*ALD2 + 2*XO2 + 2*HO2 2.9E–12 @ –500 1 R111 CXO3+C2O3 MEO2 + XO2 + HO2 + ALD2 2.9E–12 @ –500 1 R112 PAR+OH 0.870*XO2 + 0.130*XO2N + 0.110*HO2 + 0.060*ALD2 – 0.110*PAR + 0.760*ROR + 0.050*ALDX 8.10E–13 17

R113 ROR 0.960*XO2 + 0.600*ALD2 + 0.940*HO2 – 2.100*PAR + 0.040*XO2N + 0.020*ROR + 0.500*ALDX 1.0E+15 @ 8000 17

R114 ROR HO2 1.60E+03 17 R115 ROR+NO2 NTR 1.50E–11 17 R116 O+OLE 0.200*ALD2 + 0.300*ALDX + 0.300*HO2 + 0.200*XO2 + 0.200*CO + 0.200*FORM + 0.010*XO2N + 0.200*PAR + 0.100*OH 1.E–11 @ 280 18

R117 OH+OLE 0.800*FORM + 0.330*ALD2 + 0.620*ALDX + 0.800*XO2 + 0.950*HO2 – 0.700*PAR 3.20E–11 21
R118 O3+OLE 0.180*ALD2 + 0.740*FORM + 0.320*ALDX + 0.220*XO2 + 0.100*OH + 0.330*CO + 0.440*HO2 – PAR 6.5E–15 @ 1900 22

R119 NO3+OLE NO2 + FORM + 0.910*XO2 + 0.090*XO2N + 0.560*ALDX + 0.350*ALD2 – PAR 7E–13 @ 2160 23
R120 O+ETH FORM + 1.700*HO2 + CO + 0.700*XO2 + 0.300*OH 1.04E–11 @ 792 4
R121 OH+ETH XO2 + 1.560*FORM + 0.220*AL DX + HO2 1.0E–28^–0.8 & 8.8E–12 1 R122 O3+ETH FORM + 0.630*CO + 0.130*HO2 + 0.130*OH + 0.370*FACD 1.2E–14 @ 2630 1
R123 NO3+ETH NO2 + XO2 + 2. 0*FORM 3.3E–12 @ 2880 2 R124 IOLE+O 1.240*ALD2 + 0.660*ALDX + 0.100*HO2 + 0.100*XO2 + 0.100*CO + 0.100*PAR 2.3E–11 26
R125 IOLE+OH 1.300*ALD2 + 0.700*ALD X + HO2 + XO2 1.0E–11 @ –550 26 R126 IOLE+O3 0.650*ALD2 + 0.350*ALDX + 0.250*FORM + 0.250*CO + 0.500*O + 0.500*OH + 0.500*HO2 8.4E–15 @ 1100 26December 2005

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### 2-6 Label Reactants Products Rate Expression Notes R127 IOLE+NO3 1.180*ALD2 + 0.640*ALD X + HO2 + NO2 9.6E–13 @ 270 26 R128 TOL+OH 0.440*HO2 + 0.080*XO2 + 0.360*CRES + 0.560*TO2 1.8E–12 @ –355 24
R129 TO2+NO 0.900*NO2 + 0.900*HO2 + 0.900*OPEN + 0.100*NTR 8.10E–12 17
R130 TO2 CRES + HO2 4.2 17 R131 OH+CRES 0.400*CRO + 0.600*XO2 + 0.600*HO2 + 0.300*OPEN 4.10E–11 17
R132 CRES+NO3 CRO + HNO3 2.20E–11 17 R133 CRO+NO2 NTR 1.40E–11 17 R134 CRO+HO2 CRES 5.50E–12 25 R135 OPEN C2O3 + HO2 + CO 9.0 x <HCHO_R_SAPRC99> 20 R137 OPEN+O3 0.030*ALDX + 0.620*C2O3 + 0.700*FORM + 0.030*XO2 + 0.690*CO + 0.080*OH + 0.760*HO2 + 0.200*MGLY 5.4E–17 @ 500 17

R138 OH+XYL 0.700*HO2 + 0.500*XO2 + 0.200*CRES + 0.800*MGLY + 1.100*PAR + 0.300*TO2 1.7E–11 @ –116 17
R139 OH+MGLY XO2 + C2O3 1.7E–11 17 R140 MGLY C2O3 + HO2 + CO 1.0 x <MGLY_IUPAC05> 2 R141 O+ISOP 0.750*ISPD + 0.500*FORM + 0.250*XO2 + 0.250*HO2 + 0.250*CXO3 + 0.250*PAR 3.60E–11 19
R142 OH+ISOP 0.912*ISPD + 0.629*FORM + 0.991*XO2 + 0.912*HO2 + 0.088*XO2N 2.54E–11 @ –407.6 19
R143 O3+ISOP 0.650*ISPD + 0.600*FORM + 0.200*XO2 + 0.066*HO2 + 0.266*OH + 0.200*CXO3 + 0.150*ALDX + 0.350*PAR + 0.066*CO 7.86E–15 @ 1912 19

R144 NO3+ISOP 0.200*ISPD + 0.800*NTR + XO2 + 0.800*HO2 + 0.200*NO2 + 0.800*ALDX + 2.400*PAR 3.03E–12 @ 448 19
R145 OH+ISPD 1.565*PAR + 0.167*FORM + 0.713*XO2 + 0.503*HO2 + 0.334*CO + 0.168*MGLY + 0.252*ALD2 + 0.210*C2O3 + 0.250*CXO3 + 0.120*ALDX 3.36E–11 19

R146 O3+ISPD 0.114*C2O3 + 0.150*FORM + 0.850*MGLY + 0.154*HO2 + 0.268*OH + 0.064*XO2 + 0.020*ALD2 + 0.360*PAR + 0.225*CO 7.10E–18 19

R147 NO3+ISPD 0.357*ALDX + 0.282*FORM + 1.282*PAR + 0.925*HO2 + 0.643*CO + 0.850*NTR + 0.075*CXO3 + 0.075*XO2 + 0.150*HNO3 1.00E–15 19

R148 ISPD 0.333*CO + 0.067*ALD2 + 0.900*FORM + 0.832*PAR + 1.033*HO2 + 0.700*XO2 + 0.967*C2O3 0.0036 x <ACROLEIN_SAPRC99> 20

R149 TERP+O 0.150*ALDX + 5.12*PAR 3.60E–11 20 R150 TERP+OH 0.750*HO2 + 1.250*XO2 + 0.250*XO2N + 0.280*FORM + 1.66*PAR + 0.470*ALDX 1.5E–11 @ –449 20
R151 TERP+O3 0.570*OH + 0.070*HO2 + 0.760*XO2 + 0.180*XO2N + 0.240*FORM + 0.001*CO + 7.000*PAR + 0.210*ALDX + 0.390*CXO3 1.2E–15 @ 821 20

R152 TERP+NO3 0.470*NO2 + 0.280*HO2 + 1.030*XO2 + 0.250*XO2N + 0.470*ALDX + 0.530*NTR 3.7E–12 @ –175 20
R153 SO2+OH SULF + HO2 3.0E–31^–3.3 & 1.5E–12 1 R154 OH+ETOH HO2 + 0.900*ALD2 + 0.050*ALDX + 0.100*FORM + 0.100*XO2 6.9E–12 @ 230 1
R155 OH+ETHA 0.991*ALD2 + 0.991*XO2 + 0.009*XO2N + HO2 8.7E–12 @ 1070 1December 2005

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### 2-7 Label Reactants Products Rate Expression Notes R156 NO2+ISOP 0.200*ISPD + 0.800*NTR + XO2 + 0.800*HO2 + 0.200*NO + 0.800*ALDX + 2.400*PAR 1.50E–19 19

Table Notes:

Rate constants are in units of molecules cm -3 and seconds -1 Read rate expressions as follows: A / <J_label> k = A x j A @ E k = A x exp(

– E/T) A ^ B @ E k = A x (T/300) B x exp(

– E/T) A o ^ B o @ E o & A ∞ ^ B ∞ @ E ∞ & F & n 

## [ ] 

## [ ] k k M kM k F o

o G 

### = + ∞

⎡ ⎣ ⎢ ⎤ ⎦ ⎥ 1 / where 

## [ ] 

## ( ) G kM k

n o 

### = + ∞ ⎛ ⎝ ⎜ ⎞ ⎠ ⎟ ⎡ ⎣ ⎢ ⎤ ⎦ ⎥ − − 

### 1 2 1 

### log /

%2 A o @ E o & A 2 @ E 2 & A 3 @ E 3 

## [ ] 

## [ ] k k k M kM k o 

### = + + 3
3 2 

### 1 / %3 A 1 @ E 1 & A 2 @ E 2 k = k 1 + k 2 [M] 1 Rate constant from NASA/JPL (2003) 2 Rate constant from IUPAC (2005) 3 Kaiser and Wu (1977) 4 Jeffries et al. (2002) 5 Hjorth (1992) 6 Based on NASA/JPL (2003) C2H5O2 + NO 7 Based on NASA/JPL (2003) C2H5O2 + HO2 8 Based on NASA/JPL (2003) C2H5O2 + C2H5O2 9 Average based on NASA/JPL (2 003) CH3/C2H5 nitrates 10 Same as AACD+OH 11 Herron (1988) 12 Same as for PAN 13 Average based on NASA/JPL (2 003) CH3/C2H5 nitrate ra tio and IUPAC (2005) PAN+OH 14 NASA/JPL (2003) for CH3C(O)OO + HO2 15 NASA/JPL (2003) for CH3C(O)OO + CH3O2 16 IUPAC (2005) for CH3C(O)OO 17 Gery et al. (1989) 18 Cvetanovic (1987) 19 Atkinson and Carter (1994) single lumped product mechanism for isoprene. 20 SAPRC99 21 Consistent with IUPAC (2005) high-pressure limit for OH + propene. Falloff from the highpressure limit isn’t significant in the troposphe re. Stoichiometric coeffi cients consistent with Atkinson (1997) and those developed and tested by Adelmann (1999). 22 Rate constant consistent with IUPAC (2005) for O3 + propene. Products based on Gery et al. (1989) assuming a 2 to 1 product ratio of hi gher aldehydes (ALDX) to acetaldehyde (ALD2). 23 Rate constant from Canosa-Mas et al. (1991) for minor pathway. May need future adjustment. 24 Rate constant from Le Bras (1997), products from Gery et al. (1989). 25 Adelmann (1999). 26 Ligocki, et al. (2002). 27 Homogeneous gas-phase reactions of N2O5 with water measured by Wahner, Mentel and Sohn (1998) and selected by IUPAC (2005). Rate contributions from heterogeneous reactions (see IUPAC 2005) may be added to the homogeneous rate. 28 IUPAC (2005) photolysis data for isopropyl nitrate.December 2005

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### 2-8 Kinetic Data Kinetic data for rate constant expressions were updated from the most recent evaluations by the IUPAC and NASA/JPL review panels, as detailed in the notes to Table 2-2. In general, values from IUPAC (2005) were selecte d. NASA/JPL (2003) values were used in some cases where IUPAC did not provide evaluated data.

Photolysis Data Mechanism specific data required to calculate phot olysis rates are absorp tion cross-sections and quantum yields. Photolysis data for CB05 are from the IUPAC (2005) evaluation or the SAPRC99 chemical mechanism (Carter, 2000). In general, data were used from SAPRC99 unless the IUPAC (2005) recommendations were found to be significantly different. Using the same data as SAPRC99 simplifies implemen tation in air quality models and promotes consistency between two mechanisms that may be compared.

Extended Inorganic Reaction Set Yarwood, Whitten and Rao (2005) reviewed the inor ganic reaction set in the CB4 to identify reactions that should be added to account for cond itions of temperature, pressure and chemical environment encountered in annual simulations at scales ranging from urban to continental. Seventeen reactions were added as discussed below. The extended inorganic reactions are summarized briefly here and disc ussed in more detail below. Reactions of molecular hydrogen (38 and 39) are somewhat important to odd-hydrogen (OH and HO 2 

### ) for very dry conditions in the upper tropo sphere. Including hydrogen will allow the air quality impacts of hydrogen as an alternative fuel to be evaluated. Hydrogen has a tropospheric background concentration of about 0.6 ppm (Novelli et al, 1999). Reactions 40 to 45 involving odd-oxygen and odd-hydrogen species may be important for pristine conditions such as the upper troposphere . Including these react ions provides a more complete description of hydroxyl radical (OH) chemistry in th e upper troposphere to improve modeling for persistent air toxics and mercury.
Additional NO 3 

### radical reactions (46 to 50) improve nighttime chemistry. NO 3 

### radical is the main driver for atmospheric chemistr y at night and incl uding additional NO 3 

### removal reactions improves the calculation of nighttime destruction rates for several types of reactive hydrocarbons (e.g., aldehydes, olefins) and for NOx (via NO 3 

### and N 2 

### O 5 

### reactions). Additional NOx recycling reactions (51 to 53 and 61 to 62) improve the representation of the fate of NOx over multi-day timescales by slowly recy cling nitrogen from inactive forms of NOz to NOx. Reactions 51 and 53 are poten tially important for very cold conditions such as the upper troposphere. Reactions 52, 61 and 62 of nitric acid and organic nitr ates are potentially important to regional ozone and oxidant chemistry in the lower troposphere (Zaveri and Peters, 1999).December 2005

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### 2-9 Simple Alkanes (Methane and Ethane) Explicit reactions were added fo r OH with methane (CH4) and etha ne (ETHA) to better describe the chemistry in remote atmospheres.

Higher Aldehydes A new higher aldehyde species (ALDX) was added based on propionaldehyde chemistry (Ligocki and Whitten, 1992). Note that ALDX and related species contain two carbon atoms, not three, because this simplif ies. Species related to AL DX are the corresponding peroxyacyl radicals (CXO3), peroxynitrat es (PANX), carboxylic acids (AACD) and peroxycarboxylic acids (PACD). The species ALD2 and related specie s (C2O3 and PAN) now e xplicitly represent the chemistry of acetaldehyde. In important diffe rence between higher aldehydes and acetaldehyde is that they photolyse more rapidly because high er aldehydes have larger quantum yields than acetaldehyde. The benefits of including the lu mped higher aldehyde (ALDX) in CB05 are that acetaldehyde becomes explicit for air toxics mo deling, faster photolysis rates for higher aldehydes are better represented, and the degr adation sequence for higher aldehydes becomes deeper (ALDX to ALD2 to FORM). ALDX also im proves the representation of internal olefins, as discussed next.

Alkenes with Internal Double Bonds A new species (IOLE) was added to represent alkenes with internal double bonds (internal olefins) such as 2-butenes. IO LE is four carbon species. Internal olefins react very rapidly to produce photolytic products (aldeh ydes). Internal olefins were represented by their aldehyde products (e.g., 2-butene was represented as 2 AL D2) in the CB4. Includi ng the explicit species IOLE in CB05 better describes the rate (kinetics) of internal olefin reactions than the CB4 approach. The IOLE chemistry is improved by having both acetaldehyde (ALD2) and lumped higher aldehydes (ALDX) as reaction produc ts (Ligocki and Whitten, 1992).

Oxygenated Products and Intermediates Several oxygenated species were added in conjun ction with methane. Methylperoxy radicals were added as an explicit species (MEO2) rather than representing them by XO2. This change allows explicit representation of the products of the methylperoxy self-reaction (formaldehyde and methanol) and the reaction between met hylperoxy and hydroperoxy radicals (methyl hydroperoxide). This change is expected to impr ove the representation of peroxide products that are important in sulfate production. Other organic peroxides also were added as products of peroxy ra dical reactions. Higher organic peroxides (ROOH) were added as products of XO2 reacting with HO2 with chemistry based on ethyl hydroperoxide reactions. Peroxycarboxylic acids were a dded based on peroxyacetic acid (PACD) as products of the reactions of pe roxyacetyl (C2O3) and higher peroxyacyl (CXO3) radicals with HO2.December 2005

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### 2-10 Two carboxylic acids were added as products of peroxy radical reactions. Formic acid (FACD) is produced by reactions of HO2 with formalde hyde. Higher carboxylic acids were added based on acetic acid (AACD) as products of the r eactions of peroxyacetyl (C2O3) and higher peroxyacyl (CXO3) radicals with HO2.

Terpene Chemistry A new species TERP was added to CB05 to represent terpenes. The CB05 TERP chemistry is based on the SAPRC99 lumped terpene chemistry (Carter, 2000) translated to CB05 species.

EXTENDED MECHANISM WITH EXPLICIT SPECIES An extended version of CB05 was developed by adding explicit reactions for several organic compounds. Explicit chemistry was added for or ganic compounds that ar e air toxics and/or precursors to secondary organic aerosol. The explicit compounds we re added as tracer species that are decayed by oxidants (OH, etc.) without perturbing the oxidant le vels. This approach makes the extended mechanism independent of the core mechanism so that the explicit compounds in the extended mechanism could be used in conjunction with any core mechanism (e.g., CB05, CB4, SAPRC99). The reactions for th e extended organic mechanism are listed in Table 2-3.
Table 2-3. Reactions in the extended CB05 mechanism that may be added to the core mechanism.

Reaction Label Reactants Products Rate Expression T01 PFRM + OH OH 9.0E-12 T02 PFRM + NO3 NO3 5.8E-16 T03 PFRM + O O 3.4E-11 @ 1600 T04 PFRM 1.0/<HCHO_R_SAPRC99> T05 PFRM 1.0/<HCHO_M_SAPRC99> T06 PACT + OH OH 5.6E-12 @ -270 T07 PACT + NO3 NO3 1.4E-12 @ 1900 T08 PACT + O O 1.8E-11 @ 1100 T09 PACT 1.0/<CCHO_R_SAPRC99> T10 BUTD + OH OH + SACR 1.4E-11 @ -424. T11 BUTD + O3 O3 + SACR 8.2E-15 @ 2070. T12 BUTD + NO3 NO3 + SACR 1.79E-13 T13 BUTD + O O3 + SACR 3.99E-12(T/298)**1.45 T14 PACR + OH OH 2.0E-11 T15 PACR + O3 O3 2.61E-19 T16 PACR + NO3 NO3 1.7E-11 @ 3131. T17 PACR 1.0/<ACROLEIN_SAPRC99> T18 SACR + OH OH 2.0E-11 T19 SACR + O3 O3 2.61E-19 T20 SACR + NO3 NO3 1.7E-11 @ 3131. T21 SACR 1.0/<ACROLEIN_SAPRC99> T22 TOLU + OH OH 1.8E-12 @ -355. T23 MXYL + OH OH 1.7E-11 @ -116. T24 OXYL + OH OH 1.22E-11 T25 PXYL + OH OH 1.3E-11 T26 APIN + O O 2.79E-11December 2005

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### 2-11

Reaction Label Reactants Products Rate Expression T27 APIN + OH OH 1.2E-11 @ -440. T28 APIN + O3 O3 6.3E-16 @ 580. T29 APIN + NO3 NO3 1.2E-12 @ -490. T30 BPIN + O O 2.81E-11 T31 BPIN + OH OH 7.51E-11 T32 BPIN + O3 O3 1.74E-15 @ 1260. T33 BPIN + NO3 NO3 2.81E-11



### Explicit Air Toxics The following explicit toxic species are included in the extended mechanism: PFRM = primary formaldehyde PACT = primary acetaldehyde BUTD = 1,3-butadiene PACR = primary acrolein SACR = secondary acrolein from 1,3-butadiene The primary formaldehyde and acetaldehyde specie s allow the contributio ns of these primary aldehydes to be quantified. For example, the species FORM in CB05 is the sum of primary and secondary formaldehyde. If PFRM is included in the mechanism, primary formaldehyde is given directly by PFRM and secondary formaldehyde is the difference FORM – PFRM. For this approach to work, emissions of formaldehyde must be mapped to both PFRM and FORM. This does not double count the oxidant formation potential of formaldehyde emissions because the PFRM species is oxidant neutral. In this ap proach, PFRM is a “tracer” species whereas FORM is an “active” species. The same approach works for distinguishing pr imary from secondary acetaldehyde by using the tracer species PACT and the active species ALD2. Acrolein is explicitly apportioned as primar y and secondary by the tracer species PACR and SACR. SACR is formed in CB05 only by reaction of the BUTD tracer (1,3-butadiene), which is expected to be the dominant source of secondary acrolein in the atmosphere. The mapping of real compounds to model species for tasks such as emissions processing is discussed below.

Explicit Secondary Organic Aerosol Precursors Secondary organic aerosol (SOA) formation is dominated by aromatics and biogenic terpene and sesquiterpene emissions (Odum et al., 1997). Aerosol yields can be attached to the corresponding lumped species in the CB05 core mechanism (TOL, XYL and TERP) to model SOA production. However, including explicit ar omatics and terpene sp ecies in the extended mechanism can permit a more refined treatm ent of SOA production. The following explicit aromatics and terpenes are included in the extended mechanism:December 2005

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### 2-12 TOLU = toluene MXYL = m-xylene OXYL = o-xylene PXYL = p-xylene APIN = alpha-pinene BPIN = beta-pinene The methodology for using the CB05 explicit sp ecies to model SOA formation will depend upon how SOA formation is implemented in the host air quality model. In general, SOA formation is modeled by forming semi-volatile products (SVPs) in VOC reactions. The SVPs are partitioned between the gas and aerosol phase according to the ambient cond itions (e.g., temperature, preexisting aerosols). Yields of SVPs should be added to the CB05 explicit species reactions in a format (i.e., species names and yiel ds) that is compatible with th e host air quality model. Data on SVP yields are available from O dum et al., 1997 and other studies. The explicit aromatic species also ma y be of interest as air toxics.

Rate Constant Data The rate constant data sources for species in the extended mechanism that are not also in the CB05 core mechanism are listed below. OH + BUTD. Liu, A., W.A. Mulac, and C.D. J onah (1992) “Rate constants for the gas phase reactions of OH radicals with 1,3 butadiene and allene at 1 a tmosphere in Ar and over the temperature range 303-1173K” J. Phys. Chem. Vol. 92 O3 + BUTD. Treacy, J., M. ElHag, D. O'Farrell, and H. Sidebottom (1992) “Reactions of ozone with unsaturated organic compounds” Ber. Bunsenges. Phys. Chem., Vol. 96, pp 422-7. NO3 + BUTD. Ellermann, T., O.J. Nielsen, and H. Skov (1992) “Absolute rate constents for the reactions of NO3 radicals with a series of dienes at 295K” Chem. Phy. Lett., Vol. 200, pp. 224-9. O3P + BUTD. Adusei, G.Y.; Fontijn, A 1993 “Kin etics of the reaction between O(3P) atoms and 1,3-butadiene between 280 and 1015 K” J. Phys. Chem, Vol. 97, pp 1406 – 1408. OH + PACR. Orlando, J.J.; Tyndall, G.S. (2002) “Mechanisms for the reactions of OH with two unsaturated aldehydes: Crotonaldehyde a nd acrolein” J. Phys. Chem. A, Vol. 106, pp 12252 – 12259.O3 + PACR. Grosjean, D.; Grosjean, E.; Williams, E.L., II (1993) “Rate constants for the gasphase reactions of ozone with unsaturated al cohols, esters, and carbonyls” Int. J. Chem. Kinet Vol 25, pp 783 – 794. NO3 + PACR. Cabanas, B.; Salgado, S.; Marti n, P.; Baeza, M.T.; Martinez, E. (2001) “Nighttime Atmospheric Loss Process for Unsa turated Aldehydes: Reaction with NO3 Radicals” J. Phys. Chem. A: Vol. 105, pp 4440 – 4445.December 2005

H:\EPA_CB4\Report\final\Sec2_MechUpdates.doc 

### 2-13 OH + OXYL and PXYL. Atkinson, R. and Asch mann S.M (1989) “Rate constants for the gasphase reactions of the OH radical with a seri es of aromatic hydrocarbons at 296K” Int. J. Chem. Kinet., Vol. 21, pp 355-365. OH + MXYL. Atkinson, R. (1986) "Kinetics an d Mechanisms of the Gas Phase Reactions of the Hydroxyl Radical with Organic Co mpounds", Chem. Rev., Vol. 86, pp 69-201. O + APIN and BPIN. Luo, D., J.A. Pierce, I.L. Malkina, and W.P.L. Carter (1996) “Rate constants for the reactions of O(3P) with se lected monoterpenes” Int. J. Chem. Kinet., Vol. 28, pp 1-8. OH, O3 and NO3 + APIN. IUPAC (2005) OH + BPIN. Foster, P., I. Denis and V. Jac ob (1996) “Chap.7: Aerosol surface reactions and photocatalysis” in Vol. 2 of Hetreogene ous and Liquid Phase Processess book, pp 191- 196. O3 + BPIN. Khamaganor, V.G. and R.A. H ites (2001) “Rate Constants for the Gas-Phase Reactions of Ozone with Isoprene, alpha, and beta-Pinene, and Limonene as a Function of Temperature” J. Phys. Chem. A., Vol. 105, pp 815-822. NO3 + BPIN. Kind, I., T. Berndt and O. Boge ( 1998) “Gas-phase rate c onstants for the reaction of NO3 radicals with a series of cyclic al kenes, 2-ethyl-1-bute ne and 2,3-dimethyl-1,3- butadiene” Chem. Phys. Lett., Vol. 288, pp 111-118.

REACTIVE CHLORINE CHEMISTRY Tanaka et al. (2003) developed an extension to the CB4 mechanis m with chlorine chemistry to evaluate the potential impact of r eactive chlorine emissions (i.e., Cl 2 

### and HOCl) on tropospheric ozone formation. The Tanaka chlorine mechanism was reviewed and updated to be compatible with CB05. The reactions in Table 2-4 shoul d be added to the CB05 core mechanism for modeling reactive chlorine. Tabl e 2-5 identifies the species a dded for the reactive chlorine mechanism.
Table 2-4. Reactions in the CB05 reactive chlorine mechanism that may be added to the CB05 core mechanism.

Reaction Label Reactants Products Rate Expression CL1 CL2 2 CL 1.0 x <CL2_CB05> CL2 HOCL OH + CL 1.0 x <HOCL_CB05> CL3 CL + O3 CLO 2.3E-11 @ 200 CL4 CLO + CLO 0.3 CL2 + 1.4 CL 1.63E-14 CL5 CLO + NO CL + NO2 6.4E-12 @ -290 CL6 CLO + HO2 HOCL 2.7E-12 @ -220 CL7 OH + FMCL CL + CO 5.0E-13 CL8 FMCL CL + CO + HO2 1.0 x <FMCL_CB05> CL9 CL + CH4 HCL + MEO2 6.6E-12 @ 1240 CL10 CL + PAR HCL + 0.870*XO2 + 0.130*XO2N + 0.110*HO2 + 0.060*ALD2 - 0.110*PAR + 0.760*ROR + 0.050*ALDX 5.0E-11

CL11 CL + ETHA HCL + 0.991*ALD2 + 0.991*XO2 + 0.009*XO2N + 8.3-11 @ 100December 2005

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### 2-14

Reaction Label Reactants Products Rate Expression HO2 CL12 CL + ETH FMCL + 2.000*XO2 + 1.000*HO2 + 1.000*FORM 1.07E-10 CL13 CL + OLE FMCL + 0.330*ALD2 + 0.670*ALDX + 2.000*XO2 + 1.000*HO2 - 1.000*PAR 2.5E-10
CL14 CL + IOLE 0.300*HCL + 0.700*FMCL + 0.450*ALD2 + 0.550*ALDX + 0.300*OLE + 0.300*PAR + 2.000*XO2 + 1.000*HO2 3.5E-10

CL15 CL + ISOP 0.15HCL + 1. 000*XO2 + 1.000*HO2 + 0.850*FMCL + 1.000*ISPD 4.3E-10 CL16 CL + FORM HCL + 1.000*HO2 + 1.000*CO 8.2E-11 @ 34 CL17 CL + ALD2 HCL + C2O3 7.9-11 CL18 CL + ALDX HCL + CXO3 1.3E-10 CL19 CL + MEOH HCL + 1.000*HO2 + 1.000*FORM 5.5-11 CL20 CL + ETOH HCL + 1.000*HO2 + 1.000*ALD2 8.2-11 @ -45



### Table 2-5. Species added to CB05 by the reactive chlorine mechanism.

Species Name Description CL2 Molecular chlorine HOCL Hypochlorous acid CL Chlorine atom CLO Chlorine monoxide FMCL Formyl chloride (HC(O)Cl)



### Considerations in updating the reactiv e chlorine mechanism for CB05 are: 1. Reaction rate constants were updated from Ta naka et al (2003) us ing the latest IUPAC (2005) recommendations except as described below. 2. CH4 is added as an explicit species and th e Cl + CH4 are products updated to be explicit methylperoxy radical. 3. The Cl + PAR products are updated to be the same as OH + PAR in CB05. The Cl + PAR rate is an average over the absolute rate s (on a per carbon atom basis) of the alkanes listed by in Tanaka et al (2003). 4. The Cl + OLE rate is updated to an average over the absolute rates (on a per C=C basis) for the alkenes presented in Tanaka et al (2003). Reaction products assume that reaction with C=C goes by addition and that the Cl atom ends up in a carbonyl compound, represented by formyl chloride (HC(O)Cl) as a surrogate. Other carbonyl products are ALD2 and ALDX by analogy with OH + OLE react ion. Note that in CB05 there is no need to consider H-abstraction from pa raffinic carbons adjacent to the C=C group because OLE is a 2 carbon species (C=C).
5. The Cl + IOLE reaction is added. The rate is estimated as the rate for Cl reacting with OLE + 2 PAR because IOLE is a 4 carbon spec ies, whereas OLE is a 2 carbon species. The products assume that reaction goes 70% by Cl-addition and 30% by H-abstraction, consistent with the rate constant assumpti on. The products for each channel are assumed to be:December 2005

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### 2-15 C=C addition => FMCL + 0.65 ALD2 + 0.35 ALDX + 2 XO2 + HO2 H-abstraction => HCL + ALDX + OLE + XO2 + HO2 Cl-addition reactions are assumed to form acy l chlorides that are represented by formyl chloride (FMCL) as a surrogate, plus alde hydes that are split between ALD2 and ALDX by analogy with the OH + IOLE reaction. H-abst raction is assumed to form HCl plus unsaturated carbonyls that are represented as ALDX + OLE. 6. The Cl + isoprene chemistry is extensively revised from Tanaka et al. (2003). The goal of Tanaka et al. was to track a unique ma rker for the CL + ISOP reaction to permit comparison with ambient data. The goal for CB 05 is to track the fate of the Cl and the fate of the carbon in isoprene. The HCl a nd FMCL yields reflect the balance between Habstraction and addition pathways of 15% and 85% (Personal communication from Dr. Renyi Zhang, Texas A&M University: manuscrip t submitted). FMCL acts as a surrogate for the fate of all Cl-addition pathways. The lumped isoprene oxidation product from the CB05 mechanism (ISPD) accounts for the carbon containing products. 7. FMCL (formyl chloride) serves as a surr ogate for all products where chlorine is incorporated into a chlorocar bonyl after an addition reacti on, i.e., for olefins. The purpose is to account for sequestration of Cl in an organic molecule (chlorocarbonyl) allowing for the Cl to return later as a Cl -atom after the chlorocar bonyl reacts with OH or photolyses. 8. Reactions of Cl-atoms with aldehydes (A LD2 and ALDX) are included with rate constants from IUPAC (2005) and products the same as corresponding OH reactions. The organic products of Cl + ALDX are uncertain because there may be H-abstraction at the paraffinic carbon atoms of higher aldehydes.
9. No Cl-atom reactions are included for TO L, XYL or TERP because the products are uncertain. Omitting these reactions may not gr eatly alter the fate of Cl-atoms because, unlike OH, Cl-atoms react rapidly with all VOCs. For example, the global background for methane of ~1.7 ppm provides a significant “universal” sink for Cl-atoms because Clatoms react quite rapidly with methane.
10. The self-reaction of ClO radicals is added to account for situations where intense sources of ClO (e.g., high Cl 2 

### emissions) exceed the availability of NO or HO2 to act as sinks for ClO. The products of the CLO self-reacti on are highly condensed to approximate the final products under tropospheric conditions.
11. No Cl-atom reaction with NO 2 

### is included because the product CLNO 2 

### photolyses rapidly.

CHEMICAL SPECIES MAPPING FOR CB05 MECHANISMS An integral part of any condensed chemical mechanism is the assignment from real world organic species to the lumped species of the condensed mechanism. The existing chemical species mapping for CB4 was updated for CB05. The changes were:December 2005

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### 2-16 1. All assignments to 2 ALD2 representing inte rnal olefins were cha nged to IOLE. Note that internal olefins substituted at the double bond are different, as described next. 2. All remaining ALD2 assignments were changed to ALDX except for acetaldehyde, 2- methyl-2-butene and 3-substituted alk-2-en es (which remain assigned to n PAR + ALD2). Alkenes that are branched at th e double bond are represented as aldehyde + PAR because their dominant reaction products (e.g., acetone plus acetaldehyde from 2-methyl2-butene) are less reactive than the IOLE. 3. Terpenes were mapped to TERP A list of mappings from real orga nic species to CB05 model species is provided in Appendix A. The following species mapping cha nges apply specifically to the extended version of the CB05 mechanism: 4. Formaldehyde is mapped to PFRM as well as FORM 5. Acetaldehyde is mapped to PACT as well as ALD2 6. 1,3-Butadiene is mapped to BUTD as well as 2 OLE 7. Acrolein is mapped to PACR as well as 0.5 OLE plus ALDX 8. Toluene is mapped to TOLU as well as TOL 9. p-Xylene is mapped to PXYL as well as XYL 10. o-Xylene is mapped to OXYL as well as XYL 11. m-Xylene is mapped to MXYL as well as XYL
12. α -Pinene is mapped to APIN as well as TERP
13. β - Pinene is mapped to APIN as well as TERP No changes to species mappings for organi c compounds are required for the CB05 reactive chlorine mechanism. However, emission invent ory preparation for the CB05 reactive chlorine mechanism should consider sources of reactive chlorine (CL 2 

### and HOCl).December 2005

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### 3-1 3. CB05 IMPLEMENTATION TESTING

EPA is implementing the CB05 mechanism into the CMAQ air quality model. Tests were performed to confirm that the CMAQ implementa tion is correct. Indepe ndent rate constant calculations performed by SmogReyes and EPA check ed the kinetic rate c onstant expressions. Independent box model simulations by the same groups checked the complete mechanism implementation, i.e., the reactions, photolysis data and rate constant data. Box model calculations also compared the CB05 mechanism to CB4, and these comparisons are discussed first.

COMPARING CB05 TO CB4 The CB05 mechanism was implemented in the OZIPM box model for comparison with CB4 as shown in Figure 3-1. The version of CB4 compar ed is the OTAG version of CB4 (discussed in Section 1). The scenario modeled is an MIR (m aximum incremental reactivity) condition with an urban emissions mix of VOCs and NOx. The MIR condition has low VOC/NOx ratio where adding VOC has the greatest incremental im pact on the ozone production rate. The VOC composition used for CB4 and CB05 is compared in Table 3-1 on a moles carbon basis. The difference from CB4 to CB05 is that ALD2 is disaggregated to ALD2, IOLE and ALDX.
Table 3-1. VOC composition used for the box model comparison of CB4 and CB05. Fractional Contribution to Moles Carbon CB Species CB4 CB05 PAR 0.675 0.675 ETH 0.045 0.045 OLE 0.034 0.034 TOL 0.116 0.116 XYL 0.078 0.078 MEOH 0.001 0.001 ETOH 0.009 0.009 ISOP 0.5 0.5 CRES 0.002 0.002 FORM 0.009 0.009 ALD2 0.027 0.006 IOLE N/A 0.018 ALDX N/A 0.003 Total 1.496 1.496December 2005

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### 3-2 Figure 3-1. Comparison of CB4 and CB05 ozone predictions for urban MIR conditions.



### CB05 forms ozone more rapidly than CB4 for the MIR condition compared in Figure 3-1, but ultimately CB4 and CB05 form the same amount of ozone. The faster ozone formation rate in CB05 results from including ALDX (higher alde hydes) and IOLE (internal olefins) in the mechanism that boost radical production in th e morning. ALDX boosts radical production because higher aldehydes produce more radicals th an acetaldehyde (i.e., have a higher quantum yield for radicals) when they photolyse. IO LE boosts radical production directly via reaction products and indirectly because AL DX is a product of IOLE degradation. The formation of nitric acid and hydrogen peroxi de by CB4 and CB05 is compared in Figures 3- 2 and 3-3 for the MIR condition. Nitric acid formation is similar, but hydrogen peroxide production is slower in CB05. However, note th at very little hydrogen peroxide is formed by either CB05 or CB4 at MIR conditions. Compar ing hydrogen peroxide is more meaningful for MOR than MIR conditions. CB05 and CB4 al so were compared under maximum ozone formation (MOIR) box model conditions (Figures 3-4 to 3-6). The VOC compositions for the MOR simulations were the same as for the MIR simulations (Table 3-1). The MOIR condition differs from the MIR condition in having lowe r NOx levels, resulting in higher ozone. The MOIR VOC/NOx ratio was set for CB4 and not re-adjusted for CB05, so the CB05 result is probably not exactly at the MOIR condition. CB05 produced slightly lower final ozone and nitric acid than CB4, but sli ghtly higher hydrogen peroxide. CB05 had more rapid initial production of ozone, nitric acid and hydrogen peroxide than CB4 due to the ALOX and IOLE changes to CB05.December 2005

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### 3-3 Figure 3-2. Comparison of CB4 and CB05 HNO 3 

### predictions for urban MIR conditions.

Figure 3-3. Comparison of CB4 and CB05 H 2 

### O 2 

### predictions for urban MIR conditions.December 2005

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### 3-4 Figure 3-4. Comparison of CB4 and CB05 ozone predictions for urban MOIR conditions.

Figure 3-5 . Comparison of CB4 and CB05 HNO 3 

### predictions for urban MOIR conditions.December 2005

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### 3-5 Figure 3-6. Comparison of CB4 and CB05 H 2 

### O 2 

### predictions for urban MOIR conditions



### .

RATE CONSTANT COMPARISONS
The CB05 kinetic rate constant expressions were checked by inde pendent calculations for three temperature/pressure conditions: Pressure Temperature (K) 1 atm 298 0.5 atm 298 1 atm 310 Both temperature and pressure were varied because some rate expressions depend upon both parameters. Rate constants were compared in units of ppm and minutes, as used within the CMAQ air quality model, such that units conv ersion from the molecular units (molecules per cm 3 

### and seconds) of the rate expressions also was tested. The rate constant comparison (Table 3- 2) found very good agreement for all reactions. The largest difference of 1.2% was for the reaction of OH with CO that uses a unique rate expression.December 2005

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### 3-6 Table 3-2 . Comparison of CB05 thermal rate cons tants calculated by SmogReyes and EPA for three different temperature/pressure conditions (units are ppm and minutes). SmogReyes EPA Percent Difference 1 Temperature (K) 298 298 310 298 298 310 298 298 310 Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 1 NO2 + hv 2 2 O + O2 + M 2.22E-05 5.55E-06 1.87E-05 2.22E-05 5.55E-06 1.87E-05 0.0% 0.0% 0.2% 3 O3 + NO 2.89E+01 1.44E+01 3.38E+01 2.89E+01 1.44E+01 3.37E+01 0.0% 0.3% 0.2% 4 O + NO2 1.51E+04 7.54E+03 1.42E+04 1.51E+04 7.57E+03 1.42E+04 0.2% 0.4% 0.1% 5 O + NO2 4.85E+03 1.50E+03 4.30E+03 4.85E+03 1.50E+03 4.30E+03 0.1% 0.0% 0.1% 6 O + NO 2.46E+03 6.74E+02 2.18E+03 2.46E+03 6.74E+02 2.18E+03 0.0% 0.0% 0.2% 7 NO2 + O3 4.76E-02 2.38E-02 6.30E-02 4.77E-02 2.38E-02 6.30E-02 0.2% 0.0% 0.1% 8 O3 + hv 2 9 O3 + hv 2 10 O1D + M 4.37E+04 2.19E+04 4.15E+04 4.37E+04 2.19E+04 4.15E+04 0.0% 0.2% 0.1% 11 O1D + H2O 3.25E+05 1.63E+05 3.12E+05 3.25E+05 1.63E+05 3.13E+05 0.0% 0.3% 0.2% 12 O3 + OH 1.07E+02 5.36E+01 1.16E+02 1.07E+02 5.36E+01 1.16E+02 0.2% 0.0% 0.2% 13 O3 + HO2 2.85E+00 1.43E+00 2.92E+00 2.85E+00 1.43E+00 2.92E+00 0.1% 0.2% 0.0% 14 NO3 + hv 2 15 NO3 + hv 2 16 NO3 + NO 3.92E+04 1.96E+04 3.69E+04 3.92E+04 1.96E+04 3.69E+04 0.1% 0.1% 0.1% 17 NO3 + NO2 9.70E-01 4.85E-01 1.10E+00 9.70E-01 4.85E-01 1.10E+00 0.0% 0.0% 0.2% 18 NO3 + NO2 1.74E+03 8.08E+02 1.60E+03 1.74E+03 8.08E+02 1.60E+03 0.1% 0.0% 0.1% 19 N2O5 + H2O 3.70E-07 1.85E-07 3.56E-07 3.69E-07 1.85E-07 3.55E-07 0.1% 0.1% 0.2% 20 N2O5 + H2O + H2O 6.55E-11 1.64E-11 6.06E-1 1 6.55E-11 1.64E-11 6.05E-11 0.0% 0.1% 0.1% 21 N2O5 3.17E+00 2.85E+00 1.31E+01 3.17E+00 2.85E+00 1.31E+01 0.1% 0.1% 0.1% 22 NO + NO + O2 7.11E-10 1.78E-10 6.13E-10 7.11E-10 1.78E-10 6.14E-10 0.0% 0.1% 0.1% 23 NO + NO2 + H2O 1.82E-11 4.55E-12 1.68E-11 1.82E-11 4.55E-12 1.68E-11 0.0% 0.0% 0.1% 24 NO + OH 1.09E+04 3.60E+03 9.69E+03 1.09E+04 3.60E+03 9.69E+03 0.4% 0.1% 0.1% 25 HONO + hv 2 26 OH + HONO 7.19E+03 3.59E+03 7.27E+03 7.19E+03 3.59E+03 7.27E+03 0.0% 0.1% 0.0% 27 HONO + HONO 1.48E-05 7.39E-06 1.42E-05 1.48E-05 7.39E-06 1.42E-05 0.1% 0.0% 0.1% 28 NO2 + OH 1.55E+04 5.56E+03 1.38E+04 1.55E+04 5.56E+03 1.38E+04 0.3% 0.1% 0.2% 29 OH + HNO3 2.28E+02 1.13E+02 1.95E+02 2.28E+02 1.13E+02 1.95E+02 0.0% 0.1% 0.1% 30 HO2 + NO 1.20E+04 5.99E+03 1.11E+04 1.20E+04 5.98E+03 1.11E+04 0.2% 0.1% 0.4% 31 HO2 + NO2 2.05E+03 7.10E+02 1.81E+03 2.05E+03 7.10E+02 1.81E+03 0.2% 0.0% 0.1% 32 PNA 4.99E+00 3.50E+00 2.02E+01 4.99E+00 3.50E+00 2.02E+01 0.1% 0.0% 0.1% 33 OH + PNA 6.88E+03 3.44E+03 6.29E+03 6.88E+03 3.44E+03 6.29E+03 0.0% 0.0% 0.0% 34 HO2 + HO2 4.32E+03 1.72E+03 3.70E+03 4.32E+03 1.72E+03 3.70E+03 0.0% 0.2% 0.1% 35 HO2 + HO2 + H2O 2.39E-01 4.76E-02 1.48E-01 2.39E-01 4.76E-02 1.48E-01 0.2% 0.1% 0.2% 36 H2O2 + hv 2 37 OH + H2O2 2.51E+03 1.25E+03 2.46E+03 2.51E+03 1.25E+03 2.46E+03 0.2% 0.2% 0.0% 38 O1D + H2 1.63E+05 8.13E+04 1.56E+05 1.63E+05 8.13E+04 1.56E+05 0.3% 0.0% 0.2% 39 OH + H2 9.89E+00 4.95E+00 1.23E+01 9.89E+00 4.95E+00 1.23E+01 0.0% 0.1% 0.2% 40 OH + O 4.86E+04 2.43E+04 4.60E+04 4.86E+04 2.43E+04 4.60E+04 0.1% 0.1% 0.1% 41 OH + OH 2.77E+03 1.39E+03 2.75E+03 2.77E+03 1.39E+03 2.75E+03 0.2% 0.2% 0.0% 42 OH + OH 9.30E+03 3.14E+03 8.57E+03 9.30E+03 3.14E+03 8.57E+03 0.0% 0.1% 0.0% 43 OH + HO2 1.64E+05 8.20E+04 1.53E+05 1.64E+05 8.21E+04 1.53E+05 0.0% 0.1% 0.1% 44 HO2 + O 8.68E+04 4.34E+04 8.13E+04 8.67E+04 4.34E+04 8.12E+04 0.1% 0.0% 0.1% 45 H2O2 + O 2.51E+00 1.26E+00 3.14E+00 2.52E+00 1.26E+00 3.14E+00 0.3% 0.3% 0.0% 46 NO3 + O 1.48E+04 7.39E+03 1.42E+04 1.48E+04 7.39E+03 1.42E+04 0.1% 0.0% 0.1% 47 NO3 + OH 3.25E+04 1.63E+04 3.13E+04 3.25E+04 1.63E+04 3.13E+04 0.0% 0.3% 0.1%December 2005

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### 3-7 SmogReyes EPA Percent Difference 1 Temperature (K) 298 298 310 298 298 310 298 298 310 Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 48 NO3 + HO2 5.17E+03 2.59E+03 4.97E+03 5.17E+03 2.59E+03 4.97E+03 0.1% 0.1% 0.0% 49 NO3 + O3 1.48E-02 7.39E-03 1.42E-02 1.48E-02 7.39E-03 1.42E-02 0.1% 0.0% 0.1% 50 NO3 + NO3 3.38E-01 1.69E-01 4.47E-01 3.38E-01 1.69E-01 4.46E-01 0.1% 0.1% 0.2% 51 PNA + hv 2 52 HNO3 + hv 2 53 N2O5 + hv 2 54 XO2 + NO 1.31E+04 6.54E+03 1.20E+04 1.31E+04 6.54E+03 1.20E+04 0.2% 0.0% 0.1% 55 XO2N + NO 1.31E+04 6.54E+03 1.20E+04 1.31E+04 6.54E+03 1.20E+04 0.2% 0.0% 0.1% 56 XO2 + HO2 1.16E+04 5.81E+03 1.02E+04 1.16E+04 5.81E+03 1.02E+04 0.1% 0.1% 0.2% 57 XO2N + HO2 1.16E+04 5.81E+03 1.02E+04 1.16E+04 5.81E+03 1.02E+04 0.1% 0.1% 0.2% 58 XO2 + XO2 1.01E+02 5.03E+01 9.66E+01 1.00E+02 5.02E+01 9.66E+01 0.5% 0.1% 0.0% 59 XO2N + XO2N 1.01E+02 5.03E+01 9.66E+01 1.00E+02 5.02E+01 9.66E+01 0.5% 0.1% 0.0% 60 XO2 + XO2N 1.01E+02 5.03E+01 9.66E+01 1.00E+02 5.02E+01 9.66E+01 0.5% 0.1% 0.0% 61 NTR + OH 2.60E+02 1.30E+02 2.62E+02 2.61E+02 1.30E+02 2.62E+02 0.2% 0.2% 0.1% 62 NTR + hv 2 63 ROOH + OH 8.42E+03 4.21E+03 7.89E+03 8.42E+03 4.21E+03 7.89E+03 0.0% 0.0% 0.1% 64 ROOH + hv 2 65 OH + CO 3.55E+02 1.44E+02 3.41E+02 3.56E+02 1.44E+02 3.37E+02 0.4% 0.1% 1.2% 66 OH + CH4 9.38E+00 4.69E+00 1.14E+01 9.37E+00 4.69E+00 1.13E+01 0.1% 0.0% 0.5% 67 MEO2 + NO 1.13E+04 5.66E+03 1.05E+04 1.13E+04 5.66E+03 1.05E+04 0.2% 0.0% 0.3% 68 MEO2 + HO2 7.51E+03 3.75E+03 6.55E+03 7.51E+03 3.75E+03 6.55E+03 0.0% 0.1% 0.1% 69 MEO2 + MEO2 5.20E+02 2.60E+02 4.75E+02 5.20E+02 2.60E+02 4.75E+02 0.1% 0.1% 0.0% 70 MEPX + OH 1.10E+04 5.49E+03 1.03E+04 1.10E+04 5.49E+03 1.03E+04 0.1% 0.1% 0.0% 71 MEPX + hv 2 72 MEOH + OH 1.35E+03 6.74E+02 1.40E+03 1.35E+03 6.74E+02 1.40E+03 0.2% 0.1% 0.2% 73 FORM + OH 1.33E+04 6.65E+03 1.28E+04 1.33E+04 6.65E+03 1.28E+04 0.0% 0.0% 0.1% 74 FORM + hv 2 75 FORM + hv 2 76 FORM + O 2.34E+02 1.17E+02 2.77E+02 2.34E+02 1.17E+02 2.77E+02 0.0% 0.0% 0.0% 77 FORM + NO3 8.57E-01 4.29E-01 8.24E-01 8.57E-01 4.29E-01 8.24E-01 0.0% 0.1% 0.0% 78 FORM + HO2 1.17E+02 5.84E+01 1.03E+02 1.17E+02 5.84E+01 1.03E+02 0.2% 0.0% 0.5% 79 HCO3 9.05E+03 9.05E+03 2.25E+04 9.05E+03 9.05E+03 2.25E+04 0.0% 0.0% 0.1% 80 HCO3 + NO 8.28E+03 4.14E+03 7.96E+03 8.28E+03 4.14E+03 7.96E+03 0.0% 0.0% 0.0% 81 HCO3 + HO2 1.86E+04 9.30E+03 1.33E+04 1.86E+04 9.30E+03 1.33E+04 0.0% 0.0% 0.2% 82 FACD + OH 5.91E+02 2.96E+02 5.68E+02 5.91E+02 2.96E+02 5.68E+02 0.0% 0.1% 0.0% 83 ALD2 + O 6.63E+02 3.32E+02 7.35E+02 6.63E+02 3.32E+02 7.36E+02 0.1% 0.1% 0.1% 84 ALD2 + OH 2.05E+04 1.02E+04 1.90E+04 2.05E+04 1.02E+04 1.90E+04 0.1% 0.4% 0.0% 85 ALD2 + NO3 3.52E+00 1.76E+00 4.33E+00 3.52E+00 1.76E+00 4.33E+00 0.1% 0.1% 0.0% 86 ALD2 + hv 2 87 C2O3 + NO 2.96E+04 1.48E+04 2.75E+04 2.96E+04 1.48E+04 2.75E+04 0.1% 0.1% 0.1% 88 C2O3 + NO2 1.55E+04 7.50E+03 1.42E+04 1.55E+04 7.49E+03 1.42E+04 0.1% 0.1% 0.0% 89 PAN 1.99E-02 1.93E-02 1.19E-01 1.99E-02 1.93E-02 1.19E-01 0.2% 0.1% 0.4% 90 PAN + hv 2 91 C2O3 + HO2 2.08E+04 1.04E+04 1.75E+04 2.08E+04 1.04E+04 1.75E+04 0.2% 0.2% 0.0% 92 C2O3 + MEO2 1.58E+04 7.91E+03 1.43E+04 1.58E+04 7.91E+03 1.43E+04 0.2% 0.1% 0.3% 93 C2O3 + XO2 2.36E+04 1.18E+04 1.97E+04 2.36E+04 1.18E+04 1.97E+04 0.1% 0.1% 0.1% 94 C2O3 + C2O3 2.30E+04 1.15E+04 2.07E+04 2.29E+04 1.15E+04 2.07E+04 0.2% 0.2% 0.1% 95 PACD + OH 1.16E+03 5.78E+02 1.08E+03 1.16E+03 5.78E+02 1.08E+03 0.3% 0.1% 0.3% 96 PACD + hv 2December 2005

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### 3-8 SmogReyes EPA Percent Difference 1 Temperature (K) 298 298 310 298 298 310 298 298 310 Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 97 AACD + OH 1.16E+03 5.78E+02 1.08E+03 1.16E+03 5.78E+02 1.08E+03 0.3% 0.1% 0.3% 98 ALDX + O 1.04E+03 5.18E+02 1.12E+03 1.04E+03 5.18E+02 1.12E+03 0.3% 0.1% 0.1% 99 ALDX + OH 2.93E+04 1.47E+04 2.67E+04 2.93E+04 1.47E+04 2.68E+04 0.1% 0.2% 0.3% 100 ALDX + NO3 9.61E+00 4.80E+00 9.24E+00 9.61E+00 4.80E+00 9.23E+00 0.0% 0.1% 0.1% 101 ALDX + hv 2 102 CXO3 + NO 3.10E+04 1.55E+04 2.85E+04 3.10E+04 1.55E+04 2.85E+04 0.0% 0.0% 0.0% 103 CXO3 + NO2 1.55E+04 7.50E+03 1.42E+04 1.55E+04 7.49E+03 1.42E+04 0.1% 0.1% 0.0% 104 PANX 1.99E-02 1.93E-02 1.19E-01 1.99E-02 1.93E-02 1.19E-01 0.2% 0.1% 0.4% 105 PANX + hv 2 106 PANX + OH 4.43E+02 2.22E+02 4.26E+02 4.43E+02 2.22E+02 4.26E+02 0.1% 0.1% 0.0% 107 CXO3 + HO2 2.08E+04 1.04E+04 1.75E+04 2.08E+04 1.04E+04 1.75E+04 0.2% 0.2% 0.0% 108 CXO3 + MEO2 1.58E+04 7.91E+03 1.43E+04 1.58E+04 7.91E+03 1.43E+04 0.2% 0.1% 0.3% 109 CXO3 + XO2 2.36E+04 1.18E+04 1.97E+04 2.36E+04 1.18E+04 1.97E+04 0.2% 0.2% 0.2% 110 CXO3 + CXO3 2.30E+04 1.15E+04 2.07E+04 2.29E+04 1.15E+04 2.07E+04 0.2% 0.2% 0.1% 111 CXO3 + C2O3 2.30E+04 1.15E+04 2.07E+04 2.29E+04 1.15E+04 2.07E+04 0.2% 0.2% 0.1% 112 PAR + OH 1.20E+03 5.99E+02 1.15E+03 1.20E+03 5.99E+02 1.15E+03 0.2% 0.1% 0.1% 113 ROR 1.32E+05 1.32E+05 3.72E+05 1.32E+05 1.32E+05 3.72E+05 0.3% 0.3% 0.0% 114 ROR 9.60E+04 9.60E+04 9.60E+04 9.60E+04 9.60E+04 9.60E+04 0.0% 0.0% 0.0% 115 ROR + NO2 2.22E+04 1.11E+04 2.13E+04 2.22E+04 1.11E+04 2.13E+04 0.1% 0.1% 0.1% 116 O + OLE 5.78E+03 2.89E+03 5.76E+03 5.78E+03 2.89E+03 5.76E+03 0.1% 0.1% 0.0% 117 OH + OLE 4.73E+04 2.36E+04 4.55E+04 4.73E+04 2.36E+04 4.55E+04 0.0% 0.2% 0.1% 118 O3 + OLE 1.63E-02 8.13E-03 2.01E-02 1.64E-02 8.18E-03 2.01E-02 0.9% 0.6% 0.2% 119 NO3 + OLE 7.36E-01 3.68E-01 9.37E-01 7.36E-01 3.68E-01 9.37E-01 0.0% 0.0% 0.0% 120 O + ETH 1.08E+03 5.39E+02 1.15E+03 1.08E+03 5.39E+02 1.15E+03 0.2% 0.0% 0.1% 121 OH + ETH 1.20E+04 5.90E+03 1.16E+04 1.20E+04 5.90E+03 1.16E+04 0.4% 0.1% 0.3% 122 O3 + ETH 2.61E-03 1.30E-03 3.53E-03 2.61E-03 1.30E-03 3.52E-03 0.2% 0.2% 0.3% 123 NO3 + ETH 3.10E-01 1.55E-01 4.33E-01 3.10E-01 1.55E-01 4.33E-01 0.1% 0.1% 0.0% 124 IOLE + O 3.40E+04 1.70E+04 3.27E+04 3.40E+04 1.70E+04 3.27E+04 0.0% 0.0% 0.0% 125 IOLE + OH 9.36E+04 4.68E+04 8.38E+04 9.36E+04 4.68E+04 8.38E+04 0.0% 0.0% 0.0% 126 IOLE + O3 3.10E-01 1.55E-01 3.44E-01 3.10E-01 1.55E-01 3.43E-01 0.1% 0.1% 0.2% 127 IOLE + NO3 5.73E+02 2.87E+02 5.71E+02 5.73E+02 2.87E+02 5.71E+02 0.1% 0.1% 0.1% 128 TOL + OH 8.76E+03 4.38E+03 8.04E+03 8.76E+03 4.38E+03 8.04E+03 0.0% 0.0% 0.0% 129 TO2 + NO 1.20E+04 5.99E+03 1.15E+04 1.20E+04 5.99E+03 1.15E+04 0.2% 0.1% 0.3% 130 TO2 2.52E+02 2.52E+02 2.52E+02 2.52E+02 2.52E+02 2.52E+02 0.0% 0.0% 0.0% 131 OH + CRES 6.06E+04 3.03E+04 5.83E+04 6.06E+04 3.03E+04 5.82E+04 0.0% 0.0% 0.1% 132 CRES + NO3 3.25E+04 1.63E+04 3.12E+04 3.25E+04 1.63E+04 3.13E+04 0.0% 0.3% 0.2% 133 CRO + NO2 2.07E+04 1.03E+04 1.99E+04 2.07E+04 1.03E+04 1.99E+04 0.0% 0.4% 0.0% 134 CRO + HO2 8.13E+03 4.06E+03 7.82E+03 8.13E+03 4.06E+03 7.81E+03 0.0% 0.1% 0.1% 135 OPEN + hv 2 136 OPEN + OH 4.43E+04 2.22E+04 4.26E+04 4.43E+04 2.22E+04 4.26E+04 0.1% 0.1% 0.0% 137 OPEN + O3 1.49E-02 7.45E-03 1.53E-02 1.49E-02 7.45E-03 1.53E-02 0.0% 0.0% 0.1% 138 OH + XYL 3.70E+04 1.85E+04 3.50E+04 3.71E+04 1.85E+04 3.51E+04 0.4% 0.1% 0.2% 139 OH + MGLY 2.66E+04 1.33E+04 2.56E+04 2.66E+04 1.33E+04 2.56E+04 0.0% 0.0% 0.1% 140 MGLY + hv 2 141 O + ISOP 5.32E+04 2.66E+04 5.11E+04 5.32E+04 2.66E+04 5.11E+04 0.0% 0.0% 0.1% 142 OH + ISOP 1.47E+05 7.37E+04 1.34E+05 1.47E+05 7.37E+04 1.34E+05 0.3% 0.0% 0.0% 143 O3 + ISOP 1.90E-02 9.50E-03 2.34E-02 1.90E-02 9.50E-03 2.34E-02 0.0% 0.0% 0.1% 144 NO3 + ISOP 9.96E+02 4.98E+02 1.02E+03 9.96E+02 4.98E+02 1.01E+03 0.0% 0.0% 0.5% 145 OH + ISPD 4.97E+04 2.48E+04 4.77E+04 4.97E+04 2.48E+04 4.77E+04 0.1% 0.1% 0.1%December 2005

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### 3-9 SmogReyes EPA Percent Difference 1 Temperature (K) 298 298 310 298 298 310 298 298 310 Reaction Pressure (Atm) 1 0.5 1 1 0.5 1 1 0.5 1 146 O3 + ISPD 1.05E-02 5.25E-03 1.01E-02 1.05E-02 5.25E-03 1.01E-02 0.1% 0.1% 0.1% 147 NO3 + ISPD 1.48E+00 7.39E-01 1.42E+00 1.48E+00 7.39E-01 1.42E+00 0.1% 0.0% 0.1% 148 ISPD + hv 2 149 TERP + O 5.32E+04 2.66E+04 5.11E+04 5.32E+04 2.66E+04 5.11E+04 0.0% 0.0% 0.1% 150 TERP + OH 1.00E+05 5.00E+04 9.07E+04 1.00E+05 5.00E+04 9.07E+04 0.0% 0.0% 0.0% 151 TERP + O3 1.13E-01 5.64E-02 1.21E-01 1.13E-01 5.64E-02 1.21E-01 0.2% 0.0% 0.1% 152 TERP + NO3 9.84E+03 4.92E+03 9.25E+03 9.84E+03 4.92E+03 9.24E+03 0.0% 0.0% 0.1% 153 SO2 + OH 1.31E+03 5.11E+02 1.20E+03 1.31E+03 5.11E+02 1.20E+03 0.3% 0.0% 0.3% 154 OH + ETOH 4.71E+03 2.36E+03 4.67E+03 4.71E+03 2.36E+03 4.67E+03 0.1% 0.1% 0.0% 155 OH + ETHA 3.55E+02 1.77E+02 3.92E+02 3.55E+02 1.77E+02 3.92E+02 0.1% 0.2% 0.0% 156 NO2 + ISOP 2.22E-04 1.11E-04 2.13E-04 2.22E-04 1.11E-04 2.13E-04 0.1% 0.1% 0.1% Maximum Difference 0.9% 0.6% 1.2% Table Notes 1. Differences are calculated as the absolu te difference between SmogReyes and EPA values divided by the EPA value. 2. Photolysis reactions (with a reactant hv) are not compared.



### BOX MODEL COMPARISONS Comparing the results of box model simulati ons checked the CMAQ implementation of the CB05 mechanism reactions together with photolysis data and rate constant data. SmogReyes implemented CB05 in the OZIPM box model and se t up calculations for the three temperature and pressure conditions as were used for the ra te constant comparison sh own in Table 3-2. EPA set up a box model version of CMAQ to match as closely as possible the conditions of the OZIPM tests. There was generally good agreemen t between the concentra tions predicted by the two box models suggesting that the mechanism im plementation was correct in both models. Example comparisons for 298 K and 1 atmosp here are shown in Figure 3-7 (NO, NO 2 

### and O 3 

### ) and Figure 3-8 (HONO and HO 2 

### ). Figures 3-9 and 3-10 show si milar comparisons at different temperatures and pressures. Th ese comparisons confirm that CB05 is implemented correctly in the CMAQ model.December 2005

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### 3-10 Figure 3-7 . Comparison of results from the CMAQ and OZIPM box models for NO, NO 2 

### and O 3 

### at 298 K and 1 atmosphere.

Figure 3-8 . Comparison of results from the CMAQ and OZIPM box models for HONO and HO 2 

### at 298 K and 1 atmosphere.December 2005

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### 3-11 Figure 3-9 . Comparison of results from the CMAQ and OZIPM box models for NO, NO 2 

### and O 3 

### at 298 K and 0.5 atmosphere.

Figure 3-10 . Comparison of results from the CMAQ and OZIPM box models for NO, NO 2 

### and O 3 

### at 310K and 1 atmosphere.December 2005

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### 4-1 4. MECHANISM EVALUATION

UNC CHAMBER The University of North Carolina (UNC) operate s a smog chamber facility as described in the CB4-2002 report (Jeffries, Voicu and Sexton; 2002). For this project, UNC provided a database of chamber experiments along with software (ca lled Morpho) to simulate chamber experiments and assistance in using the data and software . The CB05 mechanism was implemented in the Morpho software and simulation re sults were compared to experi mental data as shown below and in Appendix B.

Updated UNC Wall Reaction Mechanism
The chemical mechanism used to simulate a cham ber experiment must include reactions for both the gas-phase chemistry taking place in the cham ber and the effects of the chamber walls. Chamber walls can provide both sources and sinks for reactive species. The role of the chamber walls is most apparent in experiments that are sensitive to input of radicals and/or reactive nitrogen species from the chamber walls, such as experiments with carbon monoxide (CO). Jeffries, Voicu and Sexton (2002) revised the UNC chamber mechanism in the process of developing the CB4-2002. Nonetheless, the cham ber characterization experiments from CB4- 2002 still show biases for ozone a nd nitrogen species as shown in CO experiments in Figures 4-1 and 4-2 (from Jeffries, Voicu and Sexton; 2002). We reviewed and updated the chamber wall mechanism, as described below, to improve performance in chamber characterization experiments before beginning the evaluation of the CB05 mechanism. The improvement in the wall reaction mechanism can be seen in Figures 4-1 and 4-2 by comparing the CB05 (top) and CB4-2002 (bottom) simulations. Results of additional UNC cham ber characterization experiments with CB05 are included in Appendix B. The wall mechanism developed by Jeffries, Voicu a nd Sexton (2002) was modifi ed in four ways: (1) The deposition rate of N 2 

### O 5 

### was increased by a factor of 9 in order to more accurately simulate the observed NO 2 

### data in experiments with only NOx and high CO. These experiments have essentially no PAN that no rmally might confound the data analysis. (2) Radicals from wall nitrous acid (HONO) photolysis were changed from a mechanism using N 2 

### O 4 

### on the walls to a mechanism based on NO, NO 2 

### , and water on the walls. (3) A pathway releasing NO 2 

### from nitric acid on the walls (WHNO 3 

### ) was added. (4) Loss of PNA (HO 2 

### NO 2 

### ) to the walls was added. This loss primarily impacts the highest CO experiments. The original Jeffries, Voicu and Sexton (2002) wa ll reactions and the revi sed reactions used in this study are compared in Tables 4-1 and 4-2.December 2005

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### 4-2 Table 4-1. Wall reactions from the Jeffries, Voicu and Sexton (2002) UNC chamber mechanisms that were changed for this project. Label Reactants Products Rate Expression W1 N2O5 + WH2O 2.0 * WHNO3 2.6E-18 W2 NO2 + H2O WNO2 1.0E-22 W3 WNO2 NO2 6.6E-7 W4 WNO2+WNO2 WN2O4 1.0E-10 W5 WN2O4 + WH2O WHONO + WHNO3 1.0E-14

Table 4-2. New wall reactions for the UNC chamber used in this project. Label Reactants Products Rate Expression W1 N2O5 + WH2O 2.0 * WHNO3 2.34E-17 W2 NO2 + H2O WNO2 1.0E-23 W3 WNO2 NO2 1.0E-4 W4 NO + H2O WNO 1.5E-23 W5 WNO NO 1.0E-4 W6 WNO+WNO2 2.0 * WHONO 2.0E-14 W7 WHNO3 NO2 5.0E-6 W8 PNA + WH2O WHNO3 1.0E-17December 2005

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### 4-3 Figure 4-1 . Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC carbon monoxide experiment August 30, 1993 (red).December 2005

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### 4-4 Figure 4-2 . Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC carbon monoxide experiment August 30, 1996 (blue).December 2005

H:\EPA_CB4\Report\final\Sec4_Eval.doc 

### 4-5 ALDX Mechanism Update One of the CB05 updates discussed in Section2 is the inclusion of a highe r aldehyde species in addition to acetaldehyde. The impact of adding a higher aldehyde species (ALDX) to CB05 can be seen in performance for UBC chamber expe riments for aldehydes larger than acetaldehyde. Figure 4-3 compares the performance of CB05 an d CB4-2002 in simulating an experiment from September 4, 1997 (red chamber) with trimethyl acetaldehyde and propi onaldehyde. CB4-2002 represents these aldehydes using ALD2 and pr oduces ozone too slowly, although the final ozone level is simulated quite well. CB05 produces oz one more rapidly becaus e of greater radical production from ALDX photolysis than ALD2 photolysis. The rate of NO to NO 2 

### conversion also is simulated better by CB05 than CB4-2002.

Figure 4-3 . Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experiment of September 4, 1997 (red chamber) with tr imethylacetaldehyde and propionaldehyde.December 2005

H:\EPA_CB4\Report\final\Sec4_Eval.doc 

### 4-6 Including ALDX in CB05 also improves performa nce for olefins larger than propene. For example propionaldehyde is a product of 1–butene reactions and butyralde hyde is a product of 1- pentene reactions. Figure 4-4 compares CB 05 and CB4-2002 performance for an experiment from October 16, 1996 (blue chamber) with propene, 1-butene and 1-pentene. The rate of ozone production and the rate of NO to NO 2 

### conversion are simulated much better by CB05 using ALDX than by CB4-2002 using ALD2 to represent the aldehyde products of olefin reactions.

Figure 4-4 . Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experiment October 16, 1996 (blue chamber) with propene, 1-butene and 1-pentene.December 2005

H:\EPA_CB4\Report\final\Sec4_Eval.doc 

### 4-7 IOLE Mechanism Update Including IOLE in CB05 also improves performa nce for internal olefins (i.e., RHC=CHR) compared to the CB4 surrogate representation of 2 ALD2. Figure 4-5 compares CB05 and CB4- 2002 performance for an experiment from Sept ember 14, 1996 (blue chamber) with an equimolar mixture of all butene isomers (1-butene, cis-2- butene, trans-2-butene, isobutene). CB05 does better than CB4-2002 in simulating the rate of ozone production, the final ozone level and the rate of NO to NO 2 

### conversion. CB05 produces ozone more rapidly because of radical production from IOLE reactions and formation of ALDX as a product in addition to ALD2.

Figure 4-5 . Comparison of CB05 (top) and CB4-2002 (bottom) simulations of UNC experiment September 14, 1996 (blue chamber) with an equimolar mixture of all butene isomers (1-butene, cis-2-butene, trans-2-butene, isobutene).December 2005

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### 4-8 Summary of CB05 Performance for UNC Chamber Experiments Results of CB05 simulations for UNC chamber experiments are shown in Appendix B. Experiments are grouped according to the VOC introduced into the red chamber. Each experiment is identified by date and chamber (re d or blue) and further details on each experiment are given in Jeffries, Vo icu and Sexton (2002). The performance of CB05 against the UNC ch amber data is summarized as follows: Chamber Background. The chamber background expe riments mostly reflect the wall mechanism and performed well. Carbon monoxide. The CO experime nts reflect the wall mechanism and core inorganic chemistry in CB05 and performed well with a coupl e of exceptions that are not understood. Formaldehyde. The formaldehyde experiments test formaldehyde and basic radical chemistry. CB05 performed very well. Methane. Methane experiments are somewhat se nsitive to the chamber wall mechanism and any impurity in the methane because methane has very low reactivity. CB05 performed well with a couple of exceptions that are not understood Acetaldehyde (ALD2). Acetalde hyde experiments add PAN formation and additional radical reactions to the chemistry tested by meth ane and formaldehyde experiments. CB05 performed well for experiments with acet aldehyde and acetaldehyde mixtures. Higher aldehydes (ALDX). CB05 performed we ll for experiments with higher aldehyde mixtures. As discussed above, ALDX is an area of improvement in CB05 over CB4. Ethene (ETH). Ethene experi ments test ethene and formalde hyde chemistry. CB05 performed quite well for ethene experiments. Terminal olefins (OLE). Terminal olefins test the OLE chemistry for alk-1-enes and rely upon ADLX, ALD2 and formaldehyde chemistry. CB05 performed quite well for OLE experiments. Olefin mixtures (IOLE and OLE). Internal olef ins test the IOLE chemistry for alk-2-enes and similar compounds and rely upon ADLX, ALD2 and formaldehyde chemistry. CB05 performed well for IOLE experiments. Alkanes (PAR). Alkane experiments test the PAR chemistry in addition to the aldehyde and inorganic chemistry. CB05 over predicted ozone in one butane experiments but not others. CB05 performed well for alkanes higher than butane. Aromatics (TOL and XYL). Aromatics chemis try is complex and includes several species specific to aromatics, but also reli es upon simpler aldehyde chemistry. CB05 performance showed more scatter for arom atics than other species. CB05 generally under-predicted the initial rise in ozone a nd the peak ozone, but did not show a clearDecember 2005

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### 4-9 trend toward over or under pred iction of the final ozone fo rmation. This result differs from the UCR chamber evaluation presented below. Isoprene. Isoprene is an explic it species in CB05 that involves the aldehyde and basic inorganic chemistry. CB05 tended to under predict ozone formation in isoprene experiments. This result is surprising as the isoprene chemistr y was not overtly changed from the previous CB4 mechanisms (e.g., CB4-2002). The current CB05 isoprene mechanism was implemented as a translation of the SAPR C one-product isoprene mechanism. This should be revisited, possibly by implemen ting a “three product” mechanism with methacorlein and methylvinyl ketone as explicit products (Carter 1996). Urban Mixtures. CB05 tended to under predict oz one formation in many but not all experiments with the UNC synthetic urban mixture. Fu rther investigation would be needed to understand this performance.

UCR CHAMBER The University of California at Riverside (UCR) operates several smog chambers including a new chamber (the “EPA chamber”), described by Carter et al., 2005, which is capable of experiments at lower NOx levels than the earl ier chambers. Dr. Carter of UCR performed chamber simulations to evaluate both the CB05 and the SAPRC99 “fixed parameter” mechanisms (Carter, 2000) for this study. Result s from several simulations in the EPA chamber are shown in Figures 4-6 to 4-15. The result s are summarized as follows. CB05 and SAPRC99 performance was similar for experiments with CO, formaldehyde and ethene. CB05 performed somewhat better than SAPRC99 for propene al though both mechanisms performed quite well. CB05 and SAPRC99 performance was similar and good for butane. The CB05 and SAPRC99 fixed parameter versio n (Carter, 2000) were compared against experiments from several chambers at UCR. Dr. Carter at UCR performed the UCR chamber simulations for both CB05 and SAPRC99 and provided the resu lts to the CB05 mechanism developers. Over 350 UCR experiments for individual com pounds and compound mixtures were used to evaluate the mechanisms as listed in Tables 4-3 and 4-4. Each group of experiments was compared by displaying the bias in predicted oxidant production (O3-NO) with experiment time, as seen in Figure 4-16. The bias values (pre diction minus observation divided by observation) are assigned to ranges (bins) and counted. G ood performance is shown by most of the counts being in the bins with low bias. Separate lines are shown for each hour of the experiment (1 to 6 hours) to reveal biases in the rate of oxidant pr oduction (early hours) vers us biases in the final amount of oxidant (late hours). Different compounds test different parts of the photochemical mechanisms, as discussed above in the evaluation against UNC chamber data. Compounds are ordered in Figure 4-16 and the discussion below so as to involve progressively more of the mechanism in the evaluation. Carbon Monoxide (CO). The CO experiments were used by UCR to adjust the chamber wall mechanism for CB05. The UCR chamber wall mechanisms differ by chamber and wereDecember 2005

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### 4-10 not reevaluated in detail for CB05. A singl e parameter that controls the production of radicals by wall reactions was adjusted (upward) for CB05 compared to SAPRC99. Formaldehyde. CB05 showed a slight under-predict ion bias for formaldehyde in contrast to SAPRC99, which showed neutral bias. This ma y be related to differences in the OH plus NO2 rate constant between CB05 and SAPRC99 ( CB05 rate is slightly higher). Note that CB05 and SAPRC99 are using the same photolysis data for formaldehyde so this is not a factor in the different perfo rmance of the two mechanisms. Acetaldehyde. Both mechanisms performed well for acetaldehyde with CB05 performing exceptionally well. Ethene. CB05 and SAPRC99 performance for ethene was similar with both mechanisms showing a slight positive bias. The sim ilarity in CB05 and SAPRC99 performance for ethane is surprising given the difference in performance for formaldehyde (see above) because ethene experiments are very sens itive to the formaldehyde mechanism. Propene. Both CB05 and SAPRC99 tended to unde r-predict oxidant pro duction for propene in the UCR chambers, especially in the ear ly experiment hours. CB05 had less underprediction of the final oxidant le vels from propene than SAPRC99. Trans-2-butene. This compound tests the new IOLE chemistry in CB05. CB05 performed very well for trans-2-butene. SAPRC99 tended to under-estimate the initial oxidant production rate but then performed similar to CB05 in predicting the final oxidant levels. Isoprene. CB05 and SAPRC99 performed similarly and well for isoprene with near zero bias being the most frequent performance. CB05 ha d a slightly broader bi as distribution than SAPRC99. This may be because SAPRC99 ha s a more complex “3-product” mechanism than the CB05 “1-product” mechanism. Th e CB05 1-product mechanism is a translation of the SAPRC 1-product mechanism. n-Butane. CB05 had a narrower and negative bias distribution whereas SAPRC99 had a broader and positive bias distribution for n-butane. For both mechanisms, near-zero bias was the most frequent outcome for the final oxida nt levels in n-butane experiments.
n-Octane. Both CB05 and SAPRC99 tended to u nder-predict oxidant pro duction from n-octane, with greater negative bias for SAPRC99 than CB05. Toluene. CB05 under-predicted the initial rate of oxidant forma tion from toluene but tended to produce the right final oxidant levels. SAPRC99 tended to slightly under-predict the initial oxidant production rate but slightly over-predict th e final oxidant levels for toluene. Thus, SAPRC99 has closer to zero overall bias for toluene than CB05. m-Xylene. CB05 tended to under-predict the initia l rate of oxidant formation from m-xylene and slightly under-predict the final oxidant le vels. SAPRC99 performance for m-xylene was very good and most often showed zero bias for oxidant levels throughout experiments.December 2005

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### 4-11 o-Xylene. Both CB05 and SAPRC99 showed a lot of scatter in oxidant bias for o-xylene. CB05 had less scatter and tended to under-predict the final oxidants whereas SAPRC99 had more scatter and tended to over-predict the final oxidant levels for o-xylene. 1,2,4-Trimethylbenzene. Both CB05 and SAPRC 99 showed scattered oxidant bias for 1,2,4- Trimethylbenzene. CB05 tended to under-predi ct the final oxidants whereas SAPRC99 tended to over-predict the final oxida nt levels for 1,2,4-trimethylbenzene. Alpha-pinene and beta-pinene. The new CB05 terpene mechanism is a translation of the SAPRC99 lumped terpene mechanism, so CB05 and SAPRC99 are expected to show similar performance for alpha- and beta-pinene, as was the case. Performance for alphapinene was much better than for beta-pinen e illustrating the difficulty in representing oxidant formation from both species using a single lumped terpene mechanism. Surrogate mixtures. Oxidant performance was eval uated for two different types of multi-species mixtures (surrogate mixtures) employed at UCR that are referred to as the “EPA Surrogate” and the “Full Surrogate.” CB 05 and SAPRC99 performance for surrogate mixtures is quite similar. For the “EPA Surrogate” experiments, both mechanisms show scattered negative bias with a greater te ndency to under-predict the early oxidant production rate and lesser bias for the final oxi dant levels. The assessment for the “Full Surrogate” runs is similar except that the CB05 bias is less scattered and marginally closer to neutral than SAPRC99. Overal l, CB05 shows less scatter but SAPRC99 has marginally less negative bias than CB05 for th e final oxidant levels in surrogate mixture experiments. Neither mechanism performed cl early better than the other in the surrogate mixture experiments.
The area of most difference between CB05 a nd SAPRC99 is aromatics chemistry. The SAPRC99 aromatics chemistry performs much bette r than CB05 against the UCR chamber data CB05 predicts less ozone formation from aroma tics than SAPRC99, especially for toluene, and therefore systematically under pr edicts the UCR chamber ozone in aromatics experiments. CB05 showed less tendency to under predict ozone in UNC aromatics chamber experiments than UCR experiments. There appears to be a syst ematic difference in the aromatics experiments between the UCR and UNC chambers that may be re lated to the chambers or the design of the experiments. This could be investigated by evaluating the SAPRC99 mechanism against UNC chamber experiments. Further work is warrant ed to understand differences in the UCR and UNC aromatics experiments and differences between the aromatics mechanisms.December 2005

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### 4-12 Table 4-3 . Compounds and numbers of UCR experiment s included in the comparison between CB05 and SAPRC99 mechanism performance. Compound Number of Experiments Carbon monoxide 18 Formaldehyde 24 Acetaldehyde 12 Ethene 39 Propene 89 t-2-Butene 12 Isoprene 18 Butane 10 Octane 5 Toluene 28 m-Xylene 27 o-Xylene 13 123-trimethylbenzene 9 Alpha-Pinene 11 Beta-Pinene 9 EPA surrogate mixture 25 Full surrogate mixture 18December 2005H:\EPA_CB4\Report\final\Sec4_Eval.doc4-13Table 4-4.Numbered UCR chamber experiments used to evaluate the CB05 and SAPRC99 mechanisms, by compound.COFormaldehydeAcet-aldehydeEthenePropenetrans-2-ButeneIsopreneButaneOctaneToluenem-Xyleneo-Xylene1,2,3-trimethylbenzenea-Pineneb-PineneEPASurrogateFullSurrogate1824123989121810528271391192518CTC031 ITC1549 DTC150A ITC1555 ETC440 XTC081 EC146 ITC511 ETC484 EPA114B ITC534 DTC073A DTC207A DTC201AETC420 ETC421 EPA080A DTC251ACTC061 ITC1554 DTC150B ITC926 ETC449 XTC082 EC147 ITC811 ETC488 EPA095A ITC699 DTC188A DTC207B DTC203AETC443 ETC433 EPA080B DTC251BCTC090A ITC864 DTC152B ITC936 DTC026A XTC097 EC157 ITC812 ETC094 EPA083B ITC828 DTC188B DTC208ADTC203B ETC444 ETC434 EPA081A DTC455ACTC090B ETC378 DTC387B ETC220 DTC026B XTC113 ETC493 DTC053A ETC097 EPA085B DTC042A DTC189A DTC208B DTC204A ETC446 ETC435 EPA081BDTC455BEPA057A ETC441 XTC083 ETC221 DTC128A CTC012 ETC501 DTC053B ETC135 EPA113B DTC042B DTC189B DTC209ADTC204B ETC447 ETC442 EPA082A DTC474AEPA057B DTC149A XTC092 ETC381 DTC128B CTC018 ETC307 DTC056A ETC224 DTC151A DTC191A DTC209B CTC056 XTC095 XTC099 EPA082B DTC474BEPA058A DTC149B CTC014 ETC439 DTC129A CTC023 ETC309 DTC056B ETC389DTC155A DTC191B CTC038 CTC091B OTC318A OTC318B EPA083A DTC488AEPA058B DTC218A CTC015 ETC464 DTC129B CTC049 DTC043B XTC093 ETC393DTC158A DTC192A CTC039 CTC093A ETC508 DTC051B EPA084B DTC488BEPA061A DTC218B CTC032 ETC466 DTC205A CTC059 DTC021B XTC101 DTC019B DTC170A DTC192B CTC046 CTC093B DTC045B DTC048A EPA085A DTC616AEPA061B DTC270A CTC072 ETC467 DTC205B CTC078 DTC069A EC520 DTC031A XTC106 DTC193A CTC068 DTC044A EPA086A DTC616BEPA070A DTC270B EC164 ETC469 DTC246A CTC083A DTC041A EC522 CTC026 DTC193BCTC081 DTC034B EPA095B CTC149AEPA070B DTC387A EC254 ETC471 DTC288ACTC083B DTC033A EC524 CTC034 CTC029 CTC091A EPA096A CTC149BEPA071A XTC086 ETC473 DTC288B CTC086A EC527 CTC048 CTC035 EC288 EPA096B CTC165AEPA071B CTC016 ETC476 DTC301A CTC086B EC669 CTC065 CTC036 EPA097A CTC165BEPA103A CTC024 ETC479 DTC301B CTC115A OTC309A CTC079 CTC066 EPA097B CTC171AEPA103B CTC077 ETC482 DTC331A CTC115B OTC309B EC264 CTC080 EPA098A CTC171BEPA140A CTC095A ETC486 DTC331B CTC132AOTC316A EC266 CTC094A EPA098B OTC277AEPA140B CTC095B ETC497 DTC346A CTC132BOTC316B EC269 CTC094B EPA100A OTC277BCTC116A ETC505 DTC346B CTC147AEC270 ETC196 EPA101ACTC116B DTC041B DTC371A CTC147BEC271 ETC207 EPA101BCTC133A DTC043A DTC371B CTC153AEC273 ETC301 EPA108BCTC133B DTC044B DTC393A CTC153BEC293 DTC025A EPA110BCTC176A DTC045A DTC393B CTC163AEC327 DTC068B EPA113ACTC176B DTC046B DTC405A CTC163BEC340 DTC035A EPA114ADTC047A DTC405B CTC170AOTC299A DTC067B EPA123ADTC048B DTC417A CTC170BOTC299B CTC109ADTC050A DTC417B CTC191AOTC300A CTC128ADTC051A DTC431A CTC191B OTC300BDTC072B DTC431B CTC203AXTC105 DTC443A CTC203BXTC112 DTC443B CTC219AEC142 DTC458A CTC219BEC143 DTC458B CTC234AEC156 DTC472A CTC234BEC285 DTC472B CTC245AEC286 DTC483A CTC245BEC287 DTC483B CTC264AEPA073A DTC503A CTC264BEPA073B DTC503B OTC272ADTC526A OTC272BDTC526B OTC295ADTC578A OTC295BDTC578B OTC298ADTC597A OTC298BDTC597BDecember 2005

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### 4-14 Carbon Monoxide SAPRC99 CB05

Figure 4-6 . SAPRC99 (left) and CB05 (right) simulati on of a carbon monoxide experiment in the EPA chamber at UCR.December 2005

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### 4-15 SAPRC99

Figure 4-7. SAPRC99 simulation of four formaldehyde experiments in the EPA chamber at UCR.December 2005

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### 4-16 CB05

Figure 4-8. CB05 simulation of four formaldehyde experiments in the EPA chamber at UCR.December 2005

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### 4-17 SAPRC99 CB05

Figure 4-9. SAPRC99 (left) and CB05 (right) simulation of an ethene experiment in the EPA chamber at UCR.

SAPRC99 CB05

Figure 4-10. SAPRC99 (left) and CB05 (right) simulation of a propene experiment in the EPA chamber at UCR.December 2005

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### 4-18 SAPRC99 CB05

Figure 4-11. SAPRC99 (left) and CB05 (right) simulation of a butane experiment in the EPA chamber at UCR.December 2005

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### 4-19 SAPRC99

Figure 4-12. SAPRC99 simulation of two toluene experiments in the EPA chamber at UCR.December 2005

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### 4-20 CB05

Figure 4-13. CB05 simulation of two toluene experiments in the EPA chamber at UCR.December 2005

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### 4-21 SAPRC99

Figure 4-14. SAPRC99 simulation of two xylene experiments in the EPA chamber at UCR.December 2005

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### 4-22 CB05

Figure 4-15. CB05 simulation of two xylene experiments in the EPA chamber at UCR.December 2005

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### 4-23 CB05 SAPRC99

Figure 4-16. Bias in oxidant production (O 3 

### -NO) at hours 1-6 in UCR chamber experiments for the CB05 and SAPRC99 mechanisms, by compound.December 2005

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### 4-24 CB05 SAPRC99

Figure 4-16. (continued). Bias in oxidant production (O 3 

### -NO) at hours 1-6 in UCR chamber experiments for the CB05 and SAPRC99 mechanisms, by compound.December 2005

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### 4-25 CB05 SAPRC99

Figure 4-16. (continued). Bias in oxidant production (O 3 

### -NO) at hours 1-6 in UCR chamber experiments for the CB05 and SAPRC99 mechanisms, by compound.December 2005

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### 4-26 CB05 SAPRC99

Figure 4-16. (continued). Bias in oxidant production (O 3 

### -NO) at hours 1-6 in UCR chamber experiments for the CB05 and SAPRC99 mechanisms, by compound.December 2005

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### 4-27 CB05 SAPRC99

Figure 4-16. (concluded). Bias in oxidant production (O 3 

### -NO) at hours 1-6 in UCR chamber experiments for the CB05 and SAPRC99 mechanisms, by compound.December 2005

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### 5-1 5. SUMMARY AND RECOMMENDATIONS

The Carbon Bond mechanism has been updated for use in EPA atmospheric modeling studies. The starting point for this st udy was version 4 of the Carbon Bond mechanism (CB4) developed in the late 1980s (Gery et al., 1989) as updated in the mid 1990s for EPA’s “OTAG” ozone transport assessment study. The new version of the Carbon Bond mechanism is called CB05 because it was developed in 2005. The CB05 is a condensed mechanism of atmospheri c oxidant chemistry that provides a basis for computer modeling studies of oz one, particulate matter (PM), visi bility, acid deposition and air toxics issues. Updates in CB05 compar ed to earlier CB4 mechanisms are:

• Updated rate constants based on recent (2003 – 2005) IUPAC and NASA evaluations.
• An extended inorganic reaction set for urban to remote tropospheric conditions.
• NOx recycling reactions to represent the fate of NOx over multiple days.
• Explicit organic chemistry for methane and ethane.
• Explicit methylperoxy radical, met hyl hydroperoxide and formic acid.
• Lumped higher organic peroxides, organic acids and peracids.
• Internal olefin (R-HC=CH -R) species called IOLE.
• Higher aldehyde species ALDX making ALD2 explicitly acetaldehyde.
• Higher peroxyacyl nitrate species from ALDX called PANX.
• Lumped terpene species called TERP.
• Optional mechanism extension for reactive chlorine chemistry.
• Optional extended mechanism with e xplicit reactions for air-toxics. The core CB05 mechanism has 51 species and 15 6 reactions. The CB05 was evaluated against smog chamber data from the Universities of No rth Carolina (UNC) and Ca lifornia at Riverside (UCTR). An updated wall reaction mechanism was developed for the UNC chamber that improved performance in experiments that are sensitive to chamber radical sources. The addition of higher aldehyde (ALDX) and inte rnal olefin (IOLE) sp ecies to CB05 improved mechanism performance for simulating these specie s groups. The addition of organic peroxide species improves the simulation of oxidants that are involved in PM sulfate formation. The addition of explicit methylper oxy radical improves the simula tion of hydrogen peroxide under low NOx conditions. Two CB05 mechanism extensions were develope d. The optional reactive chlorine chemistry mechanism can be used in conjunction with the CB05 core mechanism to model the impact of Cl 2 

### and/or HOCl emissions on oxidant formation and VOC decay rates. The optional explicit species extension can be used in conjunction with the CB05 (or another) core mechanism to model the following toxic species: primary formaldehyde, primary acetaldehyde, 1,3-butadiene, primary and secondary acrolein. Other optional e xplicit species are toluen e, o-xylene, m-xylene, p-xylene, apha-pinene and beta-pinene. These include the ma in precursors to secondary organic aerosol (SOA) and could be used as the basis for refined mode ling approach for SOA that is independent of the core mechanism se lected (e.g., CB4, CB05 or SAPRC99).December 2005

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### 5-2 Recommendations

• Terpene experiments from UNC should be implemented in the UNC “Morpho” chamber simulation software and used to evalua te, and possibly update, the CB05 terpene mechanism.

• The SAPRC99 mechanism should be evaluate d against UNC chamber experiments using the Morpho software and updated UNC chamber wall mechanisms.

• There should be a comparative study of UCR and UNC chamber experiments, especially for aromatics, to understand apparent chamber differences.December2005

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### R-1 REFERENCES

Adelman Z.E., 1999. “A Reevaluation Of The Carbon Bond-IV Photochemical Mechanism.” School of Public Health,University of Nort h Carolina, Chapel Hill, North Carolina, Canosa-Mas, C.E., S.J. Smith, S.J. Waygood, and R.P. Wayne. 1991. “Study of the temperature dependence of the reaction of the nitrate radical with propene.” J. Chem. Soc. Faraday Trans ., 87, 3473-3478. Carter, W.P.L. 2000. “Programs and Files Implementing the SAPRC-99 Mechanism and its Associated Emissions Processing Procedures for Models-3 and Other Regional Models.” January. http://pah.cert.ucr.edu/~carter/SAPRC99.htm Carter W. P. L. 1996. “Condensed atmosphe ric photooxidation mechanisms for isoprene.” Atmospheric Environment , 30, 4275-4290. Carter, W. P. L., and R. Atkinson. 1996. “Devel opment and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx.” Int. J. Chem. Kinet , 28, 497-530. Carter, W. P. L., D.R. Cocker III, D. R. Fitz, I.L. Malkina, K. Bumiller, C. G. Sauer, J.T. Pisano , 

### C. Bufalino , 

### and C. Song. 2005. “A new environmental chamber for evaluation of gasphase chemical mechanisms and secondary ae rosol formation.” Accepted for publication in Atmospheric Environment , July 15, 2005. Cvetanovic, R.J. 1987. “Evaluated chemical kine tic data for the reacti ons of atomic oxygen O(3P) with unsaturated hydrocarbons.” J. Phys. Chem. Ref. Data , 16, 261. Dodge, M.C. 1991. “Updating of the CB4 Mechanism.” Memorandum to Shao-Hang Chu, Environmental Protection Agency, Office of Air Quality Planning and Standards, Research Triangle Park, NC. March. Gery, M.W., G.Z. Whitten, J.P. Killus, and M. C. Dodge. 1989. “A Photochemical Kinetics Mechanism for Urban and Regional Scale Computer Modeling.” J. Geophys. Res ., 94, 925-956. Herron, J.T. 1988 “Evaluated chemical kinetic da ta for the reactions of atomic oxygen O(3P) with saturated organic compounds in the gas phase” J. Phys. Chem. Ref. Data , 17, 967. Hjorth, J., J. Notholt, and G. Restelli 1992 “A spectroscopic study of the equilibrium NO2 + NO3 + M = N2O5 + M and the kinetics of the O3/N2O5/NO3/NO2/air system” Int. J. Chem. Kinet ., 24, 51-65. IUPAC. 2005. R. Atkinson, D.L. Baulch, R.A. C ox, J.N. Crowley, R.F. Hampson, R.G. Hynes, M.E. Jenkin, J.A. Kerr, M.J. Rossi, and J. Troe. “Evaluated kinetic and photochemical data for atmospheric chemistry - IUPAC subc ommittee on gas kinetic data evaluation for atmospheric chemistry.” July 2005 web ve rsion available from http://www.iupackinetic.ch.cam.ac.uk/index.htmlDecember2005

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### R-2 Jeffries, H.E., I. Voicu, and K. Sexton. 2002. “Experimental Tests of Reactivity and Reevaluation of The Carbon Bond Four Photoche mical Reaction Mechanism.” Final report for Cooperative Agreement No. R828906, U.S. EPA, RTP, NC. Kaiser, E.W. and C.H. Wu. 1977. “A Kine tic study of the Gas Phase Formation and Decomposition Reactions of Nitrous Acid.” J. Phys Chem . 81, 1701-1706. Ligocki, M. P. and G. Z. Whitten. 1992. “Mode ling of Air Toxics with the Urban Airshed Model.” Presented at the Air and Waste Ma nagement Association 85th Annual Meeting and Exhibition, Kansas City, Missouri. Paper 92-84.12. Ligocki, M.P., R.R. Schulhof, R.E. Jackson, M. M. Jimenez, G.Z. Whitten, G.M. Wilson, T.C. Myers, and J.L. Fieber. 1992. “Modeling th e Effects of Reformulated Gasolines on Ozone and Toxics Concentrations in the Ba ltimore and Houston Areas,” Final Report to U.S. EPA, Systems Applications International, San Rafael, CA. Luo, D., J.A. Pierce, J.L. Malkina, and W.P.L. Carter. 1996. “Rate Constants for the Reactions of O(3P) with Selected Monoterpenes.” Int. J. Chem. Kinet ., 28, 1-8. Morris, R. E. and T. C. Myers. 1990. “User's Guide for the Urban Airshed Model. Volume I: User's Manual for UAM (CB-IV).” Prepared for the U.S. Environmental Protection Agency (EPA-450/4-90-007a), Systems Appli cations International, San Rafael, CA. NASA/JPL 2003. S.P. Sander, R.R. Fr iedl, D. M. Golden, M. J. Kurylo, R. E. Huie, V. L. Orkin, G. K. Moortgat, A. R. Ravishankara, C. E. Ko lb, M. J. Molina, and B. J Finlayson-Pitts. Chemical Kinetics and Photochemical Data fo r use in Atmospheric Studies, Evaluation Number 14. NASA Jet Propul sion Laboratory. Februa ry. Available from http://jpldataeval.jpl.nasa.gov/download.html. Novelli, P.C., P.M. Lang, K.A. Masarie, D.F. Hurst, R. Myers, and J.W. Elkins. 1999. “Molecular hydrogen in the tropospher e: global distribution and budget.” J. Geophys. Res . 104, 30,427-30,444. Odum, J.R., T.P.W. Jungkamp, R.J. Griffin, R.C. Flagan a nd J.H. Seinfeld. 1997. “The Atmospheric Aerosol-Forming Potential of Whole Gasoline Vapor.” Science , 276, 96-99. See also Environmental Science & Technology , 31, 1890-1897. Tanaka P.L., D.T. Allen, E.C. McDonald-Buller, S. Chang, Y. Kimura, G. Yarwood and J.D. Neece. 2003. “Development of a chlorine mechanism for use in the carbon bond IV chemistry model.” Journal of Geophysical Research. Vol. 108(D4), 4145. Troe J., 2001. “Analysis of the temperature and pressure dependence of the reaction HO + NO2 + M → HONO2 + M.” Int. J. Chem. Kinet ., 33, 878-889. Tuazon, E.C, W.P.L. Carter, and R. Atkinson. 1991. “Thermal decomposition of peroxyacetyl nitrate and reactions of acetyl peroxy radicals with NO and NO 2 

### over the temperature range 283-313 K.” J. Phys. Chem ., 95, 2434-2437.December2005

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### Appendix A Assignments from VOC Species to CB05 Model SpeciesTable 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsALKANES - examplesmethane0000000000001000016.04 1propane 0 1.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 044.1 1.5ethane0000000000000100030.07 2n-butane0400000000000000058.12 42,2-dimethylpropane0400000000010000072.15 42-methylpropane; isobutane0400000000000000058.12 42-methylpropane; isobutane0400000000000000058.12 4n-pentane0500000000000000072.15 52-methyl-butane0500000000000000072.15 52,2-dimethylbutane0500000000010000086.18 5isomers of pentane0500000000000000072.15 5cyclopentane0500000000000000070.14 5c5 paraffin0500000000000000072.15 5dimethylbutane 0 5.750000000000.250000086.18 5.75isomers of hexane 0 5.830000000000.170000086.18 5.832,3-dimethylbutane0600000000000000086.18 6cyclohexane0600000000000000084.16 61,6-Diisocyanatohexane06000000000200000168.2 62-methylpentane0600000000000000086.18 63-methylpentane0600000000000000086.18 6methylcyclopentane0600000000000000084.16 6methylpentane0600000000000000086.18 63,3-dimethylpentane06000000000100000100.21 6n-hexane0600000000000000086.18 6dimethylpentane 0 6.750000000000.2500000100.21 6.75c7 paraffins 0 6.810000000000.1900000100.21 6.81isomers of heptane 0 6.810000000000.1900000100.21 6.81n-octane07000000000100000114.23 7c7 cycloparaffins0700000000000000098.19 7methyl hexane07000000000000000100.21 7n-decane07000000000300000142.29 7n-heptane07000000000000000100.21 7methylcyclohexane0700000000000000098.19 72,4-dimethylpentane07000000000000000100.21 72,2,4-trimethylpentane07000000000100000114.23 72,3-dimethylpentane07000000000000000100.21 72,3,3-trimethylpentane07000000000100000114.23 7dimethylcyclopentane0700000000000000098.19 7ethylcyclopentane0700000000000000098.19 7n-nonane07000000000200000128.26 72-methylhexane07000000000000000100.21 72,2-dimethylhexane07000000000100000114.23 73-methylhexane07000000000000000100.21 7trimethylpentane 0 7.330000000000.6700000114.23 7.33isomers of octane (c8 paraffin) 0 7.620000000000.3800000114.23 7.62Page 1 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsmethylnonane 0 7.750000000002.2500000142.29 7.75dimethylhexanes 0 7.830000000000.1700000114.23 7.83c8 cycloparaffins08000000000000000112.22 83-methylheptane08000000000000000114.23 82-methylheptane08000000000000000114.23 84-methylheptane08000000000000000114.23 8methylheptane08000000000000000114.23 8n-undecane08000000000300000156.31 8n-dodecane08000000000400000170.34 8ethylcyclohexane08000000000000000112.22 8cis-1,4-dimethylcyclohexane08000000000000000112.22 82,3,4-trimethylpentane08000000000000000114.23 8cis-1-methyl-3-ethylcyclopentane08000000000000000112.22 8isopropylcyclopentane08000000000000000112.22 8trimethylcyclopentane08000000000000000112.22 8c8 alkyl cyclohexanes08000000000000000112.22 8dimethylcyclohexanes08000000000000000112.22 82,2,4-trimethylhexane08000000000100000128.26 82,4-dimethylhexane08000000000000000114.23 82,5-dimethylhexane08000000000000000114.23 82,3-dimethylhexane08000000000000000114.23 8ethylhexane08000000000000000114.23 82,2,5-trimethylhexane08000000000100000128.26 8cis-bicyclo[3.3.0]octane08000000000000000110.2 8aliphatics 0 8.080000000000.6200000122.89 8.08diethylcyclohexane 0 8.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 0140.27 8.5isomers of nonane (c9 paraffin) 0 8.750000000000.2500000128.26 8.75trimethylhexanes 0 8.80 0 0 0 0 0 0 0 0 0.2 0 0 0 0 0128.26 8.8propenylcyclohexane07100000000000000124.23 9methyloctanes09000000000000000128.26 9c9 cycloparaffins09000000000000000126.24 9methyldodecanes09000000000400000184.37 92,4-dimethylheptane09000000000000000128.26 93,5-dimethylheptane09000000000000000128.26 92,5-dimethylheptane09000000000000000128.26 92,3-dimethylheptane09000000000000000128.26 9ethylheptane09000000000000000128.26 9ethylbicycloheptane09000000000000000124.23 9dimethylheptanes09000000000000000128.26 92-methyloctane09000000000000000128.26 93-methyloctane09000000000000000128.26 94-methyloctane09000000000000000128.26 9propylcyclohexane09000000000000000126.24 91,1,3-trimethylcyclohexane09000000000000000126.24 9ethyldimethylpentane09000000000000000128.26 9tetramethylcyclopentane09000000000000000126.24 9c9 alkyl cyclohexanes09000000000000000126.24 9Page 2 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsethylmethylcyclohexanes09000000000000000126.24 92,3,5-trimethylhexane09000000000000000128.26 9ethylmethylhexane09000000000000000128.26 9n-tridecane09000000000400000184.37 9isopropylcyclohexane (2-methylethyl cycloh09000000000000000126.24 9Bicyclo[4.3.0]nonane (octahydroindene)09000000000000000124.23 9unk c9 paraffin09000000000000000128.26 9methylcyclooctane09000000000000000126.24 9isomers of decane (c10 paraffins) 0 9.250000000000.7500000142.29 9.25c6 substituted cyclohexane 0 9.330000000002.6700000168.32 9.33isomers of undecane (c11 paraffins) 0 9.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 0156.31 9.5methyldecanes 0 9.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 0156.31 9.5dimethyloctanes 0 10000000000000000142.29 10n-tetradecane 0 10000000000400000198.39 10n-pentadecane 0 10000000000500000212.42 10isomers of tridecane (c13 paraffins) 0 10000000000300000184.37 102,4,5-trimethylheptane 0 10000000000000000142.29 10methylethylheptane 0 10000000000000000142.29 10trimethylheptanes 0 10000000000000000142.29 10ethyloctane 0 10000000000000000142.29 102,4-dimethyloctane 0 10000000000000000142.29 103,4-dimethyloctane 0 10000000000000000142.29 102,3-dimethyloctane 0 10000000000000000142.29 102,6-dimethyloctane 0 10000000000000000142.29 10dimethylethylcyclohexane 0 10000000000000000140.27 10isopropylmethylcyclohexane 0 10000000000000000140.27 10butylcyclohexane 0 10000000000000000140.27 10cyclopentylcyclopentane 0 10000000000000000138.25 10c10 alkyl cyclohexanes 0 10000000000000000140.27 10methyl propylcyclohexanes 0 10000000000000000140.27 10tetramethylhexane 0 10000000000000000142.29 10decalins (mixed cis,trans) 0 10000000000000000138.25 10c5 substituted cyclohexane 0 10.250000000000.7500000154.3 10.25dimethylnonanes 0 10.40 0 0 0 0 0 0 0 0 0.6 0 0 0 0 0156.31 10.4isomers of dodecane (c12 paraffins) 0 10.670000000001.3300000170.34 10.67isomers of tetradecane (c14 paraffins) 0 10.750000000003.2500000198.39 10.75trimethyloctanes 0 11000000000000000156.31 11hexadecane 0 11000000000500000226.45 11n-heptadecane 0 11000000000600000240.48 11c16 branched alkanes 0 11000000000500000226.45 11dimethylundecanes 0 11000000000200000184.37 11ethylmethyloctane 0 11000000000000000156.31 11n-pentylcyclohexane 0 11000000000000000154.3 11ethyl propylcyclohexanes 0 11000000000000000154.3 11diethylmethylcyclohexanes 0 11000000000000000154.3 11dimethyldecane 0 11000000000100000170.34 112-methyldecane 0 11000000000000000156.31 11Page 3 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsmethyldecalins 0 11000000000000000152.28 11methylundecane 0 11.20 0 0 0 0 0 0 0 0 0.8 0 0 0 0 0170.34 11.2isomers of pentadecane (c15 paraffins) 0 11.250000000003.7500000212.42 11.25ethyldimethyloctane 0 12000000000000000170.34 12dimethylbutylcyclohexane 0 12000000000000000168.32 12c2 alkyl decalin 0 12000000000000000166.31 12nonadecane 0 13000000000600000268.53 13trimethyldecane 0 13000000000000000184.37 13methylpropylnonane 0 13000000000000000184.37 13eicosane 0 14000000000600000282.56 14isomers of heptadecane (c17 paraffins) 0 15000000000200000240.48 15isomers of octadecane (c18 paraffins) 0 16.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 0254.5 16.5ALKENES - examplesethylene0000000100000000028.05 2propylene0110000000000000042.08 31,2-propadiene 0 0 1.50000000000000040.07 3trans-2-butene0000000000000010056.11 4cis-2-butene0000000000000010056.11 42-methylpropene (isobutene)0300010000000000056.11 4isomers of butene 0 1 0.50000000000001056.11 41-butene0210000000000000056.11 44-vinylcyclohexene02100000000000000108.18 41,2-butadiene {methylallene} 0 1 1.50000000000000054.09 41,3-butadiene0020000000000000054.09 4methylbutene 0 3.33 0.33 0 0 0.330000000000.33 0 70.14 4.981,3-cyclopentadiene000000000000001.25 0 0 66.1 5methylbutadiene0000000010000000068.12 5isoprene0000000010000000068.12 5trans-2-pentene0100000000000010070.14 5cis-2-pentene0100000000000010070.14 52-methyl-2-butene0300001000000000070.14 52-methyl-1-butene0400010000000000070.14 5isomers of pentene 0 2.4 0.2 0 0 0.20000000001070.14 53-methyl-1-butene0310000000000000070.14 51-pentene0310000000000000070.14 51,4-pentadiene0120000000000000068.12 5cyclopentene0100000000000010068.12 5normal pentene isomers0310000000000000070.14 5piperylene {1,3-pentadiene} (mixed isomers 0 0 0.50000000000010068.12 5cyclohexene0200000000000010082.15 6cis-3-hexene0200000000000010084.16 62-hexenes0200000000000010084.16 64-methyl-trans-2-pentene0200000000000010084.16 6trans-3-hexene0200000000000010084.16 6trans-2-hexene0200000000000010084.16 6cis-2-hexene0200000000000010084.16 6Page 4 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbons1-methylcyclopentene0200000000000010082.15 6dimethylbutene 0 3.5 0 0 0 0.50000000001084.16 62-methyl-2-pentene0400000000000001084.16 63-methyl-trans-2-pentene0400001000000000084.16 62,3-dimethyl-1-butene0500010000000000084.16 62-ethyl-1-butene0500010000000000084.16 62-methyl-1-pentene0500010000000000084.16 6c6 olefins (hexene isomers) 0 3 0.330000000000001.17 0 84.16 6methylpentenes 0 3.5 0.50000000000000.75 0 84.16 6hexadiene0010000000000010082.15 6methylcyclopentadiene0010000000000010080.13 61-hexene0410000000000000084.16 63-methyl-1-pentene0410000000000000084.16 64-methyl-1-pentene0410000000000000084.16 6methylcyclohexene0300000000000010096.17 7methylhexadiene0300000000000010096.17 73-ethyl-2-pentene0500001000000000098.19 71-methyl cyclohexene0500000000000001096.17 72,4,4-trimethyl-1-pentene06000100000100000112.22 7c7 olefins 0 4 0.50000000000001098.19 7ethylpentene 0 5 0.50 0 0 0 0 0 0 0 0 0 0 0 0.5 098.19 7dimethylpentene 0 4.5 0.750 0 0 0 0 0 0 0 0 0 0 0 0.5 098.19 7methylcyclohexadiene0110000000000010094.16 71-heptene0510000000000000098.19 7ethylcyclopentene0510000000000000096.17 7dimethylcyclopentenes0510000000000000096.17 73-heptene (mixed cis,trans)0300000000000010098.19 7methylhexenes 0 4 0.50000000000001098.19 7heptenes 0 3.33 0.170000000000001.67 0 98.19 7.01c8 olefins 0 4.67 0.5000000000.3300010112.22 7.67cis-2-octene04000000000000100112.22 82,4,4-trimethyl-2-pentene (beta diisobutyl06000010000000000112.22 8dimethylhexadiene02100000000000100110.2 8tetramethylcyclobutene06100000000000000110.2 81-octene06100000000000000112.22 8butoxybutene06100000000000000128.22 8octatriene00200000000000100108.18 8trimethylpentadiene04200000000000000110.2 8methyl heptene 0 5.33 0.670000000000000.67 0 112.22 8.01trans-2-nonene05000000000000100126.24 94-nonene (mixed isomers)05000000000000100126.24 9c9 olefins 0 6 0.500000000000010126.24 9nonadiene03100000000000100124.23 9ethylheptene07100000000000000126.24 9trimethylhexene07100000000000000126.24 91-nonene07100000000000000126.24 9c10 olefins 0 6.17 0.330 0 0 0 0 0 0 0 0.5 0 0 01.33 0 140.27 9.49Page 5 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbons3-carene00000000000000001136.24 10d-limonene00000000000000001136.24 10a-pinene00000000000000001136.24 10b-pinene00000000000000001136.24 10terpinene00000000000000001136.24 10myrcene00000000000000001136.24 10dimethyloctenes06000000000000100140.27 10propylheptenes 0 7 0.500000000000010140.27 10methylnonenes 0 7 0.500000000000010140.27 10ethyloctenes 0 7 0.500000000000010140.27 10c12 olefins 0 7 0.500000000200010168.32 104-phenyl-1-butene01110000000000000132.21 10trans-1-phenylbutene01110000000000000132.21 101-decene08100000000000000140.27 10b-phellandrene {1(7)-2-p-menthadiene}00000000000000001136.24 10dl-limonene {dipentene}00000000000000001136.24 10terpene00000000000000001136.24 10methyldecenes 0 8 0.500000000000010154.3 11c11 olefins 0 8 0.500000000000010154.3 111-undecene09100000000000000154.3 11trimethylnonene 0 10100000000000000168.32 121-Dodecene 0 10100000000000000168.32 12trimethyldecenes 0 10 0.500000000000010182.35 13caryophyllene09300000000000000204.36 15ALKYNES - examplesacetylene0100000000010000026.04 11-propyne0100000000000001040.07 31-butyne (ethylacetylene)0200000000000001054.09 42-butyne0200000000000001054.09 41-pentyne0300000000000001068.12 5pentenyne0110000000000001066.1 5hexyne0400000000000001082.15 6methylheptyne (6-methyl-2-heptyne)06000000000000010110.2 8dimethyloctyne08000000000000010138.25 10ALDEYHDES - examplesbenzaldehyde00000000000700000106.12 0p-tolualdehyde {4-methylbenzaldehyde}00000000000800000120.15 0formaldehyde0000010000000000030.03 1acetaldehyde0000001000000000044.05 2glyoxal0100010000000000058.04 2total c2-c5 aldehydes 0 0.6500000000000001053.11 2.65acrolein (2-propenal) 0 0 0.50000000000001056.06 3propionaldehyde0100000000000001058.08 3methyl glyoxal0000010000000001072.06 3butyraldehyde0200000000000001072.11 4Page 6 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsisobutyraldehyde0200000000000001072.11 4crotonaldehyde0010000000000001070.09 4n-pentanal (n-valeraldehyde)0300000000000001086.13 5isovaleraldehyde (3-methylbutanal)0300000000000001086.13 52-furfural0110000000000001096.09 52-Hexenal0210000000000001098.15 6hexanal (hexanaladehyde)04000000000000010100.16 62,4-hexadienal0010000000000010096.13 6methylhexanal05000000000000010114.19 7trans, trans-2,4-heptadienal01100000000000100110.16 7ethylhexaldehyde06000000000000010128.22 8ALCOHOLS - examplescarvomenthol (2-p-menthanol) (2-methyl-5-(0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0156.27 0methyl alcohol0000000001000000032.04 1phenol (carbolic acid)0100000000050000094.11 1ethyl alcohol0000000000100000046.07 2ethylene glycol0200000000000000062.07 22-Methylaminoethanol0100000000000001075.11 3n-propyl alcohol0300000000000000060.1 3isopropyl alcohol0300000000000000060.1 3tert-butyl alcohol0300000000010000074.12 3propylene glycol0300000000000000076.1 3glycerol0300000000000000092.1 32-methoxyethanol {methyl cellosolve} {egme0300000000000000076.1 3diglycolamine (2-(2-aminoethoxy)ethanol)02000000000000010105.14 4n-butyl alcohol0400000000000000074.12 4isobutyl alcohol0400000000000000074.12 4sec-butyl alcohol0400000000000000074.12 41,4-butanediol0400000000000000090.12 4butandiol0400000000000000090.12 4diethylene glycol (2,2'-oxybisethanol)04000000000000000106.12 42-ethoxyethanol {cellosolve} {egee}0400000000000000090.12 4misc. alcohols 0 4.740 0 0 0 0 0 0 0 0 0.1 0 0 0 0 085.64 4.74amyl alcohols0500000000000000088.15 5furfuryl alcohol0120000000000000098.1 5n-pentanol0500000000000000088.15 51-ethoxy-2-propanol05000000000000000104.15 5isoamyl alcohol (3-methyl-1-butanol)0500000000000000088.15 5bis-phenol a0 5 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0228.29 5methyl carbitol {2-(2-methoxyethoxy)ethano05000000000000000120.15 5diisopropylene glycol02000000000000020134.18 6diethyl aminoethanol04000000000000010117.19 62-Ethyl-1,3-hexanediol06000000000200000146.23 6triethylene glycol06000000000000000150.18 62-Hexyloxyethanol06000000000200000146.23 6cyclohexanol06000000000000000100.16 6Page 7 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonshexylene glycol (2-methylpentane-2,4-diol)06000000000000000118.18 61-hexanol (n-hexanol)06000000000000000102.18 64-methyl-2-pentanol (methyl isobutyl carbi06000000000000000102.18 6diacetone alcohol (4-hydroxy-4-methyl-2-pe06000000000000000116.16 6butyl cellosolve {2-butoxyethanol} {egbe}06000000000000000118.18 6carbitol {degee} {2-(2-ethoxyethoxy)ethano06000000000000000134.18 6benzyl alcohol00010000000000000108.14 72,2,4-Trimethyl-1,3-Pentanediol07000000000100000146.23 71-heptanol07000000000000000116.2 7dimethylpentanol (2,3-dimethyl-1-pentanol)07000000000000000116.2 7o-cresol (2-methyl-benzenol)00010000000000000108.14 7biphenylol {2-phenylphenol}00010000000500000170.21 7cresols00010000000000000108.14 7octanol isomers 0 7.250000000000.7500000130.23 7.25c8 phenols01010000000000000122.17 8xylenol01010000000000000122.17 82-(2-butoxyethoxy)ethanol {butyl carbitol08000000000000000162.23 8methylheptanol08000000000000000130.23 82-ethyl-1-hexanol08000000000000000130.23 8dimethylbenzylalcohol01001000000000000136.19 9c9 phenols02010000000000000136.19 9trimethylcyclohexanol09000000000000000142.24 9dimethylheptanol (2,6-dimethyl-2-heptanol)09000000000000000144.26 9ethyldimethylphenol02001000000000000150.22 10c10 alkylphenols03010000000000000150.22 102-N,N-Dibutylaminoethanol08000000000000010173.3 101-decanol 0 10000000000000000158.29 103,7-dimethyl-1-octanol 0 10000000000000000158.29 10a-terpineol00000000000000001154.25 10c11 alkylphenols04010000000000000164.25 11nonylphenol08010000000000000220.36 15ETHERS - examplesethylene oxide0100000000010000044.05 1dimethyl ether0200000000000000046.07 2propylene oxide0200000000010000058.08 2dimethoxymethane (methylal)0300000000000000076.1 3ethyl ether0400000000000000074.12 4methyl t-butyl ether (mtbe)0400000000010000088.15 4tetrahydrofuran0200000000000001072.11 41,4-dioxane0400000000000000088.11 4propylene glycol methyl ether {1-methoxy-20200000000000001090.12 4ethyl t-butyl ether03000000000100010102.18 5ethyl isopropyl ether0500000000000000088.15 5t-amylmethylether (tame)05000000000100000102.18 5ethylene glycol propyl ether {2-propoxyet05000000000000000104.15 54,4-Dimethyl-3-oxahexane04000000000100010116.2 6Page 8 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsdiisopropyl ether06000000000000000102.18 6propylene glycol n-propyl ether06000000000000000118.18 6acetal (1,1-diethoxyethane)02000000000000020118.18 6ethylfuran0220000000000000096.13 6di(propylene glycol) methyl ether05000000000000010148.2 7dibutyl ether08000000000000000130.23 82-butyltetrahydrofuran06000000000000010128.22 8KETONES - examplescarvone0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0150.22 0acetone0300000000000000058.08 3methyl ethyl ketone (mek) (2-butanone)0400000000000000072.11 41-methyl-2-pyrrolidinone0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0.5 099.13 5Methyl Isopropyl Ketone0500000000000000086.13 5methyl n-butyl ketone06000000000000000100.16 6methyl isobutyl ketone06000000000000000100.16 6cyclohexanone0600000000000000098.15 6dimethylcyclobutanone0600000000000000098.15 6methyl amyl ketone07000000000000000114.19 72-methyl-3-hexanone07000000000000000114.19 7propylcyclohexanone07000000000200000140.23 7heptanone07000000000000000114.19 7methylacetophenone01010000000100000134.18 8trimethylcyclopentanone08000000000000000126.2 8dihydroxynapthalenedione02010000000100000190.16 9nonenone07100000000000000140.23 92,2,4,4-tetramethyl-3-pentanone09000000000000000142.24 9c4 substituted cyclohexanone 0 10000000000000000154.25 109,10-anthraquinone00020000000000000208.22 141-aminoanthraquinone00020000000000000223.23 14ORGANIC ACIDS - examplesformic acid0000000000010000046.03 0oxalic acid0000000000020000090.04 0acetic acid0100000000010000060.05 1benzoic acid01000000000600000122.12 1terephthalic acid (p-benzenedicarboxylic a01000000000700000166.13 1propionic acid0200000000010000074.08 2acrylic acid0010000000010000072.06 2methyacrylic acid0110000000010000086.09 3butanoic acid0300000000010000088.11 33-Methylbutanoic acid03000000000200000102.13 3isobutyric acid0300000000010000088.11 3adipic acid04000000000200000146.14 42-ethylhexanoic acid07000000000100000144.21 7Phenylacetic Acid00010000000100000136.15 7dimethylethylbenzoic acid01001000000000000150.18 9Page 9 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsESTERS - examplesmethyl formate0100000000010000060.05 1phthalic anhydride01000000000700000148.12 1acetic anhydride02000000000200000102.09 2methyl acetate0200000000010000074.08 2vinyl acetate0110000000010000086.09 3ethyl acetate0300000000010000088.11 3methyl acrylate0110000000010000086.09 3dimethylterephthalate03000000000700000194.19 3dimethyl phthalate03000000000700000194.19 3Isopropyl Formate0300000000010000088.11 3maleic anhydride0020000000000000098.06 4propyl acetate04000000000100000102.13 4isopropyl acetate04000000000100000102.13 4ethyl acrylate02100000000100000100.12 4methyl methacrylate02100000000100000100.12 4hydroxypropyl acrylate02100000000200000130.14 4dimethyl succinate (dimethyl butaneoate)04000000000200000146.14 4misc. esters 0 4.1100000000010000.01 0 104.38 4.13c5 ester 0 4.330000000000.6700000102.13 4.33propylene glycol monomethyl ether acetate03000000000100010132.16 5n-butyl acetate05000000000100000116.16 5isobutyl acetate05000000000100000116.16 52-ethoxyethyl acetate {cellosolve acetate}05000000000100000132.16 5pentanedioic acid, dimethyl ester (dimethy05000000000200000160.17 5n-Propyl Propionate05000000000100000116.16 5n-butyl benzoate05000000000600000178.23 5methyl isobutyrate05000000000000000102.13 5amyl acetate06000000000100000130.19 6n-butyl acrylate04100000000100000128.17 6dimethyl adipate (dimethylhexanedioate)06000000000200000174.2 6isobutyl acrylate {2-propenoic acid}04100000000100000128.17 6butyl methacrylate05100000000100000142.2 7dipropyl phthalate07000000000700000250.3 72-butoxyethyl acetate (ethylene glycol but05000000000100010160.21 7ethylhexanoate (ethyl n-hexanoate)07000000000100000144.21 7substituted c9 ester (c12)07000000000500000216.32 7substituted c7 ester (c12)07000000000500000216.32 7methylethylpentanoate07000000000100000144.21 7methyl amyl acetate (4-methyl-2-pentanol a07000000000100000144.21 7isobutyl isobutyrate07000000000100000144.21 7dipropylene glycol methyl ether acetate06000000000100010190.24 82-Ethyl-Hexyl Acrylate06100000000300000184.28 8butylisopropylphthalate08000000000700000264.32 8dibutyl phthalate09000000000700000278.35 9diethylene glycol butyl ether acetate {2-209000000000100000204.27 9Page 10 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsisoamyl isobutyrate09000000000000000158.24 9methyl c11 ester 0 11000000000200000212.33 11methyl dodecanoate {methyl laurate} 0 12000000000100000214.35 12methyl c12 ester 0 12000000000200000228.38 12methyl myristate {methyl tetradecanoate} 0 14000000000100000242.4 14methyl c13 ester 0 14000000000100000242.4 14methyl c15 ester 0 16000000000100000270.46 16AROMATIC COMPOUNDS - examplesbenzene0100000000050000078.11 1nitrobenzene01000000000500000123.11 1aniline {aminobenzene}00000.7500000000000093.13 6toluene0001000000000000092.14 7methylphenanthrenes00010000000800000192.26 7c2 alkylphenanthrenes00010000000300000206.28 7c2 alkylanthracenes00010000000300000206.28 7biphenyl {phenyl benzene}00010000000500000154.21 7o-xylene00001000000000000106.17 8m-xylene00001000000000000106.17 8p-xylene00001000000000000106.17 8m-xylene and p-xylene00001000000000000106.17 8benzo[ghi]fluoranthene0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 0 0226.28 8benzo(a)anthracene0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 0 0228.29 8chrysene0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 0 0228.29 8benzo(c)phenanthrene0 0 0 0 1 0 0 0 0 0 0 10 0 0 0 0 0228.29 8methylbenzphenanthrene0 0 0 0 1 0 0 0 0 0 0 11 0 0 0 0 0242.32 8styrene 0 0 0.510000000000000104.15 8methylbenzanthracenes0 0 0 0 1 0 0 0 0 0 0 11 0 0 0 0 0242.32 8isomers of xylene 0 0.25 0 0.25 0.75000000000000106.17 8ethylbenzene01010000000000000106.17 8methyl biphenyl (mixed) {phenyltoluene}00001000000500000168.24 8methylchrysenes0 0 0 0 1 0 0 0 0 0 0 11 0 0 0 0 0242.32 8indene 0 0 0.501000000000000116.16 91,3,5-trimethylbenzene01001000000000000120.2 91,2,4-trimethylbenzene01001000000000000120.2 91,2,3-trimethylbenzene01001000000000000120.2 9trimethylbenzenes01001000000000000120.2 9ethyltoluenes {methylethylbenzenes}01001000000000000120.2 9o-ethyltoluene01001000000000000120.2 9m-ethyltoluene01001000000000000120.2 9p-ethyltoluene01001000000000000120.2 9c9 alkyl benzenes 0 1.38 0 0.38 0.62000000000000120.2 9t-butylbenzene02010000000100000134.22 9Isomers of propylbenzene02010000000000000120.2 9n-propylbenzene02010000000000000120.2 9cumene (isopropyl benzene)02010000000000000120.2 9methyl styrene (mixed) {vinyl toluene}00110000000000000118.18 9Page 11 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsindan01001000000000000118.18 9cumene hydroperoxide02010000000000000152.19 9Butylbenzene isomers 0 2.90 1 0 0 0 0 0 0 0 0.1 0 0 0 0 0134.22 9.9c3/c4/c5 alkylbenzenes 0 2.25 0 0.32 0.68000000000000133.24 9.93methylindans02001000000000000132.21 10camphene00000000000000001136.24 10methylindene00101000000000000130.19 10divinyl benzene {vinyl styrene}00101000000000000130.19 101,3-diethylbenzene (meta)02001000000000000134.22 101,2-diethylbenzene (ortho)02001000000000000134.22 101,2,3,4-tetramethylbenzene02001000000000000134.22 10ethyldimethylbenzenes02001000000000000134.22 10tetramethylbenzenes02001000000000000134.22 101-methyl-2-tert-butylbenzene02001000000100000148.25 101-methyl-4-isopropylbenzene02001000000000000134.22 101-methyl-3n-propylbenzene02001000000000000134.22 101-methyl-3-isopropylbenzene02001000000000000134.22 10napthalene02001000000000000128.17 10dihydronaphthalene02001000000000000130.19 101-methyl naphthalene02001000000100000142.2 10diethylbenzenes02001000000000000134.22 10(1-methylpropyl)benzene (sec-butyl benzene03010000000000000134.22 10n-butylbenzene03010000000000000134.22 10(2-methylpropyl)benzene03010000000000000134.22 10ethyl styrene {ethylvinyl benzene}01110000000000000132.21 10c4 alkylstyrenes01110000000200000160.26 101,3-diethylbenzene (meta)02001000000000000134.22 101,2-diethylbenzene (ortho)02001000000000000134.22 10c10 aromatics 0 2.25 0 0.25 0.75000000000000134.22 10methylnaphthalenes 0 2.50 0 1 0 0 0 0 0 0 0.5 0 0 0 0 0142.2 10.5dimethylindans03001000000000000146.23 11dimethylindene01101000000000000144.22 11c3 alkylstyrene01101000000000000146.23 11c11 unsaturated alkylbenzenes01101000000000000146.23 111-(1,1-dimethylethyl)-3,5-dimethylbenzene03001000000100000162.28 11methoxynaphthalene03001000000000000158.2 11methyldihydronaphthalene03001000000000000144.22 11c11 alkylbenzenes 0 3.33 0 0.33 0.67000000000000148.25 11n-pentylbenzene04010000000000000148.25 11c2 alkyl indan03001000000000000146.23 11ethylindan03001000000000000146.23 11diisopropyl benzene (mixed isomers)04001000000000000162.28 12acenaphthylene00201000000000000152.2 12c2 alkylnaphthalene04001000000000000156.23 12acenaphthene04001000000000000154.21 12c12 dialkyl benzenes04001000000000000162.28 12dimethyl napthalenes04001000000000000156.23 12Page 12 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsethylnaphthalenes04001000000000000156.23 12trimethylindan04001000000000000160.26 12propylnaphthalene05001000000000000170.26 13trimethylnaphthalene05001000000000000170.26 13fluorene05001000000000000166.22 13c13 alkyl benzenes 0 5.33 0 0.33 0.67000000000000176.3 13anthracene02201000000000000178.23 14diphenyl ethane {bibenzyl}00020000000000000182.27 14methylanthracenes00011000000000000192.26 15fluoranthene00002000000000000202.26 16pyrene00002000000000000202.26 16cyclopentaphenanthrenes00002000000000000204.27 16cyclopentaanthracenes00002000000000000204.27 16phenylnaphthalenes01011000000000000204.27 16ethyl-phenyl-phenyl-ethane01011000000000000210.32 16methylfluoranthenes01002000000000000216.28 17di(ethylphenyl)ethane04020000000000000238.37 18cyclopenta[cd]pyrene02002000000000000228.29 18HALOGENATED COMPOUNDS - examplesmethyl chloride0000000000010000050.49 0carbon tetrachloride00000000000100000153.82 0dichlorodifluoromethane (f-12)00000000000100000120.91 0chlorotrifluoromethane (f-13)00000000000100000104.46 01,1-dichloroethane0000000000020000098.96 01,1,1-trichloroethane00000000000200000133.41 01,1,2-trichloroethane00000000000200000133.41 0dichlorotetrafluoroethane00000000000200000170.92 0ethyl chloride0000000000020000064.52 0ethylene dichloride0000000000020000098.96 0chloropentafluoroethane (f115)00000000000200000154.47 0hexafluoroethane {f-116}00000000000200000138.01 0methylene bromide00000000000100000173.85 0ethylene dibromide00000000000200000187.87 0methyl bromide0000000000010000094.94 01,2-dichloro-1,1,2,2-tetrafluoroethane {cf00000000000200000170.92 0chlorodifluoromethane (f-22)0000000000010000086.47 0trifluoromethane (f-23)0000000000010000070.01 0chlorofluorohydrocarbons00000000000200000187.38 0trichlorotrifluoroethane-f11300000000000200000187.38 0chloroform00000000000100000119.38 0trichlorofluoromethane00000000000100000137.37 0Iodomethane00000000000100000141.94 0dichloromethane {methylene chloride}0000000000010000084.93 0tetrafluoromethane {carbon tetrafluoride}0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 88 0perchloroethylene00000000000200000165.83 02,2-dichloronitroaniline01000000000500000207.02 1Page 13 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsbromodinitroaniline {2,4-dinitro-6-bromoan01000000000500000262.03 1bromodinitrobenzene01000000000500000247.01 1chlorobenzene01000000000500000112.56 1o-dichlorobenzene0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 147 11,3-dichlorobenzene {m-dichlorobenzene}0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 147 1p-dichlorobenzene0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 147 1dichlorobenzenes0 1 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 147 1trichlorobenzenes (mixed)01000000000500000181.45 1tetrachlorobenzenes01000000000500000215.89 1propylene dichloride 0 1.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 0112.99 1.51,3-Dichloropropane 0 1.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 0112.99 1.5vinyl chloride0000000100000000062.5 21,1-dichloroethene {vinylidene chloride}0200000000000000096.94 2trichloroethylene (tce)00000001000000000131.39 2Chloropropane0300000000000000078.54 3epichlorohydrin0300000000000000092.53 3Glycerol alpha-monochlorohydrin03000000000000000110.54 3chloroprene (2-chloro-1,3-butadiene)0020000000000000088.54 41-chlorobutane0400000000000000092.57 4benzyl chloride00010000000000000126.59 7Benzoyl chloride00010000000000000140.57 73-(chloromethyl)-heptane08000000000000000148.68 8NITROGEN containing compounds - examplesnitroethane 0 0.40 0 0 0 0 0 0 0 0 1.6 0 0 0 0 075.07 0.4methylamine0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.5 031.06 1pyridine0100000000040000079.1 1phenyl isocyanate01000000000600000119.12 1acetonitrile0100000000010000041.05 1hydroxyacetonitrile0100000000010000057.05 1Monomethyl Hydrazine0100000000000000046.07 1Nitropropanes 0 1.50 0 0 0 0 0 0 0 0 1.5 0 0 0 0 089.09 1.5dimethyl formamide0200000000010000073.1 2ethylene diamine0000000100000000060.1 2ethanolamine0000000000000001061.08 2ethylamine0000000000000001045.09 2dimethylamine0000000000000001045.09 2ethyleneamines0000000000000001043.07 2trimethyl amine0100000000000001059.11 3tert-butyl amine0100000000010001073.14 3isopropylamine0100000000000001059.11 3dimethyl alkyl amines0100000000000001059.11 3acrylonitrile0110000000000000053.06 3Isobutyronitrile0300000000010000069.11 3butyronitrile0300000000010000069.11 3N,N-Dimethylacetoacetamide02000000000200010129.16 4dimethylacetamide0000000000000002087.12 4Page 14 of 15Table 1. Matrix of Assignments from Real Compounds to Carbon Bond 05 (CB05) Model Speciesname NASN PAROLE TOLXYL FORMALD2 ETH ISOP MEOH ETOH NR CH4 ETHAIOLEALDXTERP MW# carbonsN-(2-Hydroxyethyl)ethylenediamine02000000000000010104.15 4diethanolamine04000000000000000105.14 4n,n-dimethylethanolamine0400000000000000089.14 4diethylenetriamine02000000000000010103.17 4diethylamine0200000000000001073.14 4n-Butylamine0200000000000001073.14 42-methyl-3-butenenitrile0210000000010000081.12 4methyl glutaronitrile04000000000200000108.14 4morpholine (tetrahydro-1,4-oxazin)0400000000000000087.12 4caprolactam05000000000100000113.16 51,4-Diazabicyclo[2.2.2]octane04000000000000010112.18 6hexamethylenediamine04000000000000010116.21 6cyclohexamine0400000000000001099.18 6hexamethyleneimine0400000000000001099.18 6Diisopropanolamine04000000000000010133.19 6triethanolamine04000000000000010149.19 6triethylene tetramine04000000000000010146.24 6triethylamine02100000000000010101.19 6n-Hexylamine04000000000000010101.19 6N-aminoethylpiperazine04000000000000010129.21 6n-phenylaniline {diphenylamine}00010000000500000169.23 74-methylaniline00010000000000000107.16 7toluene isocyanate00010000000100000133.15 72,4-toluene diisocyanate {tdi}00010000000200000174.16 72,4-Dinitrotoluene00010000000000000182.14 7benzothiazole00010000000000000135.19 7Tetraethylenepentamine06000000000000010189.31 84,4-methylene dianiline01010000000500000198.27 8dimethylnaphthyridine03010000000000000158.2 10SULFUR containing compounds - examplescarbonyl sulfide0000000000010000060.07 0carbon disulfide0100000000000000076.14 1methyl mercaptan0100000000000000048.11 1dimethyl sulfide0200000000000000062.13 2dimethyl disulfide0200000000000000094.2 2ethyl mercaptan0200000000000000062.13 2Diethyl Sulfate04000000000000000154.19 4Thiophene0000000000000010084.14 4Page 15 of 15

### Appendix B Chamber Simulations for the University of North Carolina (UNC)

Chamber with CB05 Organized by Chemical Compound Type

### Chamber Background

Au 07 97 OC 10 965 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 07, 1997 Background

● O 3 , (L)

● ● ● ● ● ● ● ● NO, (L) NO 2 , (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 07, 1997 Background

O 3 , (L)

● ● ● ● ● ● ● ● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Background5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 07, 1997

Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 07, 1997

● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TNO, NO2, ppmO3, ppm



## October 10, 1996 Background

O 3 , (L)

● ● ● ● ● ● ● ● ● NO, (L)
● NO 2 , (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TNO, NO2, ppmO3, ppm



## October 10, 1996 Background

O 3 , (L)

● ● ● ● ● ● ●

NO, (L)
● NO 2 , (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Background Chamber Test5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## October 10, 1996

● ● ● ● ● ● Total Solar Radiation

● ● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## October 10, 1996

● ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (L)
CCl4, (L)

● ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (R)
CCl4, (R)

### Carbon Monoxide (CO)

JL 07 01 JL 22 01 AU 30 93 ST 20 00 OC 03 955 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Jul 07, 2001 170 ppm Carbon Monoxide

O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Jul 07, 2001 500 ppm Carbon Monoxide

● ● ● ● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Delta CO (filtered); NOx Matched5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Jul 07, 2001

● Total Solar Radiation Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## Jul 07, 2001

● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Jul 22, 2001 400 ppm Carbon Monoxide O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Jul 22, 2001 400 ppm Carbon Monoxide

● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Matched Carbon Monoxide; Delta NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Jul 22, 2001

Total Solar Radiation Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## Jul 22, 2001

● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 30, 1993 250 ppm CO

O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 30, 1993 100 ppm CO

O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Delta CO5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 30, 1993

● ● Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 20, 2000 250 ppm Carbon Monoxide

● O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 20, 2000 500 ppm Carbon Monoxide

O 3 , (L)

● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## 500 vs 250 ppm CO; matched 0.33 NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Sep 20, 2000

● ● ● ● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## Sep 20, 2000

● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## October 03, 1995 250 ppm CO Filtered

O 3 , (L)

NO, (L) NO 2 , (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## October 03, 1995 250 ppm CO Non-filtered

O 3 , (L)

NO, (L) NO 2 , (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Matched CO and NOx; BLUE CO filtered with 13x Molesieve5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## October 03, 1995

● ● ● ● ● ● ● ● Total Solar Radiation

● ● ● ● ● ● ● ●

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## October 03, 1995

● ● ● ● ● ● ● ● ● ●

CCl 4 , (L) CCl4, (L) ● ● ● ● ● ● ● ● ●

CCl 4 , (R) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 20, 2000 250 ppm Carbon Monoxide

● O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 20, 2000 500 ppm Carbon Monoxide

O 3 , (L)

● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## 500 vs 250 ppm CO; matched 0.33 NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Sep 20, 2000

● ● ● ● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## Sep 20, 2000

● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (R)

CCl4, (R)

### Formaldehyde (FORM)
JL 08 86 JL 15 88 ST 23 97 ST 30 975 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 8, 1986 0.54 ppm Formaldehyde

O 3 , (L)

NO, (L) NO 2 , (L)

0.54 PPM FORMALDEHYDE (HCHO)-RED

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 8, 1986 1.03 ppm Formaldehyde

O 3 , (L)

● NO, (L) NO 2 , (L)

1.03 PPM FORMALDEHYDE (HCHO)-BLUE

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Delta HCHO at 0.17 NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## July 8, 1986

Total Solar Radiation Eppley Ultraviolet Radiation ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● Chamber Temperature

NO2 toO3P FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 15, 1988 ● ● ● ● ●
● ● ● ● ● ● ● ●

● ● ● ● ● ● ● ● Formaldehyde-PKD

FORM

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TVOC, ppmCCCCHO, HCHO, ppmC



## July 15, 1988

● ● ● ● ● ● ● ● ● ● ● ● ● ● ● Formaldehyde-PKD

FORM5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 15, 1988 0.79 ppmC Formaldehyde

O 3 , (L)

● ● ● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 15, 1988 0.43 ppmC Formaldehyde

O 3 , (L) NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Delta HCHO at 0.3 ppm NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## July 15, 1988

● ● ● ● Total Solar Radiation

● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TCCl4, relativeCCl4, relative



## July 15, 1988

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 23, 1996 0.5 ppm Formaldehyde

✕

✕ ✕ ✕ ✕
✕

✕ ✕

✕ ✕

✕ ✕ ✕ ✕ ✕

HCHO 0.4951 PPM FORMALDEHYDE (HCHO)-RED

FORM CO

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 23, 1996 1.0 ppm Formaldehyde ✕

✕ ✕ ✕ ✕

✕ ✕

✕

✕

✕ ✕

✕ ✕ ✕ ✕ HCHO

1 PPM FORMALDEHYDE (HCHO)-BLUE

FORM5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 23, 1996 0.5 ppm Formaldehyde

O 3 , (L) NO, (L)

NO 2 , (L)

0.4951 PPM FORMALDEHYDE (HCHO)-RED

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 23, 1996 1.0 ppm Formaldehyde O 3 , (L)

● ● ● ● ● NO, (L)
NO 2 , (L)

1 PPM FORMALDEHYDE (HCHO)-BLUE O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Delta Formaldehyde5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 23, 1996

● ● ● ● Total Solar Radiation

● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 23, 1996

● ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 30, 1997 2.0 ppm Formaldehyde O 3 , (L)

● ● NO, (L) NO 2 , (L)

CB05 Morpho Model Simulaton O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 30, 1997 250 ppm CO

O 3 , (L) NO, (L) NO 2 , (L)

CB05 Morpho Model Simulaton

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Characterization: Formaldehyde vs CO; matched NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 30, 1997

● ● ● ● ● Total Solar Radiation

● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 30, 1997

● ● CCl4, (L) ●

● CCl4, (R)

### Methane (CH4)

JL 21 91 AU 01 97 AU10 92 ST 07 90 ST 19 96 ST 20 935 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 21, 1991

▲ ▲ ▲ ▲

▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲
▲ ▲ ▲
▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲
▲ ▲

▲ ▲ ▲

▲ ▲ ▲
▲ ▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ CO, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Formaldehyde, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 21, 1991

▲

▲ ▲ ▲

▲ ▲ ▲

▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲
▲ ▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲
▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲

▲
▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ CO, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Formaldehyde, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 21, 1991 500 ppmC Methane

O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 21, 1991 250 ppmC Methane

O 3 , (L) NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)



## Run C1-- Delta Methane5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## July 21, 1991

● ●

● Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TCCl4, relativeCCl4, relative



## July 21, 19915 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 01, 1997 500 ppm Methane

● ● O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 01, 1997 250 ppm Methane

● ● ● ● O 3 , (L) NO, (L)
NO 2 , (L)

CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)



## 250 vs 500 ppm Methane; 0.35 NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 01, 1997

Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0.00 0.10 0.20 0.30 0.40 0.50 0.60



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 10, 1992 500 ppm Methane

● ● ● O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0.00 0.10 0.20 0.30 0.40 0.50 0.60



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 10, 1992 250 ppm Methane

● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## CRC Run C1-- Delta Methane5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 10, 1992

Total Solar Radiation

● ● ●

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 10, 1992

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 7, 1990 250 ppm Methane

O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)
NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 7, 1990 394 ppm Methane O 3 , (L) NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Matched Methane5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 7, 1990

● ● ● ● ● ● Total Solar Radiation

● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 7, 1990

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0.00 0.10 0.20 0.30 0.40 0.50 0.60



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 19, 1996 300 ppmC Methane

O 3 , (L)

● NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0.00 0.10 0.20 0.30 0.40 0.50 0.60



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 19, 1996 600 ppmC Methane O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Delta Methane5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 19, 1996

● ● ● ●

● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 19, 1996

● ● ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (L)

CCl4, (L)

● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (R)
CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 20, 1993 250 ppm Methane

O 3 , (L) NO, (L)

NO 2 , (L) CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 20, 1993 500 ppm Methane

O 3 , (L) NO, (L)
NO 2 , (L)

CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)



## 500 vs 250 Methane5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 20, 1993

● ● Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

### Acetaldehyde (ALD2)

JL 09 97 JL 18 97 AU 17 785 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 09, 1997 ● ● ●

●

●

●

●
● ● ● Isobutyraldehyde, (L)

● ● ● ● ● ● ● ● ● ● ● HCHO, (L) FORM, (L)

ALDX, (L)
CO, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 09, 1997

■ ■ ■ ■ ■ ■
■
■
■ ■ ■

Acetaldehyde, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ HCHO, (L)
FORM, (L) ALD2, (L) CO, (L)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 09, 1997 4.64 ppmC IsoButyraldehyde

● O 3 , (L)

● ● ● ● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 09, 1997 2.23 ppmC Acetaldehyde O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

1.12 PPM ACETALDEHYDE-BLUE O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Acetaldehyde vs Isobutyraldehyde5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## July 09, 1997

Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TCCl4, relativeCCl4, relative



## July 09, 1997

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 18, 1997 0.4 ppmv Valeraldehyde + 0.4 ppmV Propionaldehyde

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Butyraldehyde

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ Acetaldehyde

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ HCHO

FORM

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 18, 1997 0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Propionaldehyde

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ HCHO

FORM5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 18, 1997 0.4 ppmv Valeraldehyde + 0.4 ppmV Propionaldehyde

● ● ●
● ●

●
●

● ● ● ● Valeraldehyde

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Propionaldehyde CB05 Simulation

ALDX ● ● ● ● ● ● ● ● ● ● ● ● CCl4

CCl4

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## July 18, 1997 0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde

■ ■ ■ ■ ■ ■
■

■
■ ■ ■ ■ Butyraldehyde

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ Acetaldehyde

ALDX ALD2 ● ● ● ● ● ● ● ● ● ● ● CCl4

CCl45 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 18, 1997 0.4 ppmv Valeraldehyde + 0.4 ppmV Propionaldehyde O 3 , (L)

● ● ● ● ● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 18, 1997 0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

ALDX Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Aldehyde Mix and NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 18, 1997 0.4 ppmv Valeraldehyde + 0.4 ppmV Propionaldehyde O 3 , (L)

● ● ● ● ● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 18, 1997 0.4 ppmV Butyraldehyde + 0.4 ppmV Acetaldehyde O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

ALDX Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Aldehyde Mix and NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.00 0.10 0.20 0.30 0.40 0.50 0.60



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 17, 1978

■ ■ ■ ■ ■ ■

■ ■ ■ ■ ■

Acetaldehyde, (L)

ALD2, (L) ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ CO, (R) CO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 17, 1978 ■

■ ■ Acetaldehyde, (L)

ALD2, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ CO, (R) CO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 17, 1978 0.96 ppmC Acetaldehyde

O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 17, 1978 4.00 ppmC Acetaldehyde O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Delta HC at 0.70 ppm NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 17, 1978

Total Solar Radiation ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● Chamber Temperature

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 17, 1978

CCl4, (L) CCl4, (R)

### Higher Aldehydes (ALDX)

JL 03 97 AU 12 97 ST 04 97 OC 04 965 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0



### H o u r s, L D TAld, ppmCAld, ppmC



## July 03, 1997 ▲ ▲ ▲
▲

▲

▲

▲

▲
▲ ▲ ▲ Propionaldehyde

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ Acetaldehyde

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ HCHO ALD2

FORM ALDX

● ●

● ● CCl 4

CCl4

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TALD2, ppmCFORM, ppmC



## July 03, 1997

▼ ▼ ▼ ▼ ▼ ▼
▼

▼
▼ ▼ ▼ Acetaldehyde, (L)

ALD2, (L)

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ HCHO, (R)

FORM, (R)

CCl45 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 03, 1997 3.000 ppmC Propionaldehyde O 3 , (L)

● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## July 03, 1997 1.888 ppmC Acetaldehyde O 3 , (L)

● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Acetaldehyde vs Propionaldehyde5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## July 03, 1997

● Total Solar Radiation Eppley Ultraviolet Radiation

Chamber Temperture

NO2 toO3P FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 12, 1997

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Acetaldehyde, (L)

ALD2, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 12, 1997

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Acetaldehyde, (L)

ALD2, (L) ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R) CO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 12, 1997 0.4 ppm Valeraldehyde + 0.4 ppm Propionaldehyde O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 12, 1997 1.0 ppm 2-hexanone + 1.0 ppm 2-butanone O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Aldehydes Mix vs Ketones Mix5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 12, 1997

● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 12, 1997

● CCl4, (L)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 04, 1997 0.5 ppmV Trimethylacetaldehyde + 0.5 ppmV propionaldehyde

O 3 , (L)

● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 04, 1997 0.5 ppmV Isobutyraldehyde + 0.5 ppmV propionaldehyde

O 3 , (L)

● ● ● ● ● ● NO, (L) NO 2 , (L)

ALDX Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Aldehyde Mix run5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 04, 1997

● Total Solar Radiation

● ● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 04, 1997

CCl4, (L)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## Oct 04, 1996

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼

Acetaldehyde

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ Formaldehyde ALD2

FORM

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCCCCHO, HCHO, ppmC



## Oct 04, 1996

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Priopionaldehyde

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ Acetaldehyde

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ Formaldehyde ALDX

ALD2

FORM ▲ ▲ Priopionaldehyde

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Formaldehyde FORM5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Oct 04, 1996 2.1 ppmC Acetaldehyde

O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Oct 04, 1996 1.0 ppmC Acetaldehyde + 1.5 ppmC Propionaldehyde

O 3 , (L)

● ● ● ● ● ● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## 1 ppm Acetaldehyde vs 0.5 ppm Acetaldehyde and 0.5 ppm Propionaldehyde Mix5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Oct 04, 1996

● ● ● ●

● Total Solar Radiation

● ● ● ● ●

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

### Ethene (ETH)

AU 16 88 Au 24 975 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D THCHO, ppmCH2, ppm



## August 16, 1988

■ ■ ■ ■ ■

■ ■

■ ■
■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Formaldehyde-PKD

FORM ▲ ▲ ▲ ▲ ▲

H 2 H2 ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4

CCl4

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TETHENE FORM, ppmCH2, ppm



## August 16, 1988 ▼ ▼ ▼ ▼ ▼ ▼

▼

▼

▼

▼ ▼ Ethene

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕

Formaldehyde-PKD

ETH FORM H2

● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 CCl45 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 16, 1988 0.80 ppmC Formaldehyde

O 3 , (L)

● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 16, 1988 1.94 ppmC Ethene O 3 , (L)

● ● ●

NO, (L) NO 2 , (L) CB05 Simulation O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## HC Reactivity at 0.39 NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 16, 1988

● ● ● ● ● Total Solar Radiation

● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 24, 1997

■ ■ ■ ■

■

■ ■ ■ ■ Ethene, (L)

ETH, (L)

▲ ▲ ▲ ▲

HCHO, (R) FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 24, 1997

■ ■ ■ ■ ■

■

■
■ ■ ■ Ethene, (L)

ETH, (L)

▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 24, 1997 3.84 ppmC Ethene O 3 , (L)

● ● ● ● ● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 24, 1997 3.68 ppmC Ethene

● ● O 3 , (L)

● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Matched 4 ppmC Ethene5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 24, 1997

● Total Solar Radiation

● ● ● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 24, 1997

### Terminal Olefins (OLE)

JN 23 92 ST 19 955 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## June 23, 1992

■ ■ ■ ■ ■ ■
■
■
■ ■ ■ ■ Propene, (L)

OLE, (L) ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲
▲ ▲

▲

▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲

▲ ▲ ▲ ▲
▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲
▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲

▲ CO, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## June 23, 1992

■ ■ ■ ■ ■
■
■
■ ■ ■ ■ ■ Propene, (L)

OLE, (L) ▲

▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲

▲

▲ ▲ ▲ ▲

▲
▲ ▲

▲ ▲

▲ ▲ ▲

▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲

▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲

▲ ▲

▲ ▲

▲
▲ ▲
▲ ▲

▲ ▲ ▲ ▲ ▲ ▲
▲

▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲

▲ ▲ ● CO, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## June 23, 1992 1 ppmC Propylene

● ● ● O 3 , (L)

● NO, (L)

NO 2 , (L)

PAN, (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## June 23, 1992 1 ppmC Propylene

● ● O 3 , (L)

NO, (L)

NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Matched Propylene; Matched NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## June 23, 1992

● Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## June 23, 1992

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 19, 1995 6.12 ppmC Propene O 3 , (L)

● ● ● ● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 19, 1995 4.00 ppmC Ethene O 3 , (L)

● ● ● ● ● ● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Propene vs Ethene run; Matched NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 19, 1995 6.12 ppmC Propene

● ● ● ● ● ● ● ● ●
●

●

●

●

● ● ● ● ● ● ● ● ● ● ●

PROPENE

▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ▼ ACETALDEHYDE

✕ ✕ ✕ ✕ ✕ ✕ ✕ Formaldehyde CB05 Simulation

OLE ALD2 FORM CO

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 19, 1995 4.00 ppmC Ethene

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■
■

■

■ ■ ■ ■ ■ ■ ■ ■ ■ ETHENE

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ Formaldehyde CB05 Simulation

ETH FORM CO

### Olefin Mixtures (OLE and IOLE)

AU 13 97 ST 13 02 ST 14 96 OC 16 965 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0

0.0 1.0 2.0 3.0 4.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 13, 1997 1.0 ppm Propene

● ● ●

●

●

●

● ● ● ● ● ● Propene

✕ ✕ ✕ ✕ ✕ HCHO 1.0 ppm Propene

OLE ALD2 FORM CO

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0

0.0 1.0 2.0 3.0 4.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 13, 1997 0.2 ppm Propene, Isobutene, 1-Pentene, 1-Hexene

■ ■ ■ ■ ■ ■
■ ■ ■ ■ ■ ■ Propene ▲ ▲ ▲ ▲ ▲

▲
▲ ▲ ▲ ▲ ▲ ▲ Isobutene

▼ ▼ ▼ ▼ ▼

▼

▼ ▼ ▼ ▼ ▼ ▼ 1-Pentene ◆ ◆ ◆ ◆ ◆

◆

◆ ◆ ◆ ◆ ◆ ◆ 1-Hexene

✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ ✕ HCHO 0.2 ppm Propene, Isobutene, 1-Pentene, 1-Hexene

PAR

OLE ALD2 ALDX FORM CO5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 13, 1997 1.0 ppm Propene O 3 , (L)

NO, (L) NO 2 , (L) PAN, (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 13, 1997 0.2 ppm Propene, Isobutene, 1-Pentene, 1-Hexene O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## C 3 

## alkene vs. C 3 

## , C 4 

## , C 5 

## , C 6 

## alkenes5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 13, 1997

● ● Total Solar Radiation

● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 13, 1997

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 13, 2002 1.5 ppmC SynUrban Terminal Alkenes

O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 13, 2002 3.0 ppmC SynUrban Terminal Alkenes O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Delta SynUrban Mix Terminal Alkenes5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 13, 2002

● ● Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0.00 0.10 0.20 0.30 0.40 0.50 0.60



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 14, 1996 1.0 ppmC All Butenes (equal molar)

● O 3 , (L)

● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60

0.00 0.10 0.20 0.30 0.40 0.50 0.60



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 14, 1996 2.0 ppmC All Butenes (equal molar) O 3 , (L)

● ● ● ● ● ● ● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Delta Equal Molar Butenes Mix5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 14, 1996

● ● ● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## October 16, 1996 2.88 ppmC Propene

● ● ● ● O 3 , (L)

● ● ● ● ● ● ● NO, (L) NO 2 , (L)
PAN, (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## October 16, 1996 0.98 ppmC Propene + 1.32 ppmC 1-Butene + 1.66 ppmC 1-Pentene

● ● ● O 3 , (L)

● ● ● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Propene vs Propene, 1-Butene, 1-Pentene5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## October 16, 1996

● ● ● ● ● ● ● ● Total Solar Radiation

● ● ● ● ● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0

0.0 1.0 2.0 3.0 4.0 5.0



### H o u r s, L D TCCl4, relativeCCl4, relative



## October 16, 1996

● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L) CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (R) CCl4, (R)

### Alkanes (PAR)

MY 22 92 MY 23 92 AU 16 96 AU 19 83 OC 11 015 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## May 22, 1992 ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ N-Butane, (L)

PAR, (L) CO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 5 10 15 20 25 30

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## May 22, 1992

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ N-Butane, (L)

PAR, (L) CO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## May 22, 1992 46 ppmC Butane O 3 , (L)

● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## May 22, 1992 24 ppmC Butane

O 3 , (L)

● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Delta Butane Run5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## May 22, 1992

● ● Total Solar Radiation Eppley Ultraviolet Radiation

Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## May 22, 19925 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## May 23, 1992

■

■ N-Butane, (L)

PAR, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Acetaldehyde, (R)

FORM, (R) ALD2, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 5 10 15 20 25

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## May 23, 1992

■

■ N-Butane, (L)

PAR, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Acetaldehyde, (R)

FORM, (R) ALD2, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## May 23, 1992 33.4 ppmC Butane O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## May 23, 1992 19.7 ppmC Butane

O 3 , (L) NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Delta Butane Run5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## May 23, 1992

● ● ● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## May 23, 19925 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 16, 1996

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Ethane, (L) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Butane, (L) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Hexane, (L) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Octane, (L) PAR, (L)

ETHA, (L) CO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 5 10 15 20

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 16, 1996

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Ethane, (L) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Butane, (L) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Hexane, (L) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Octane, (L) PAR, (L)

ETHA, (L) CO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 16, 1996 2.0 ppmV each of C2, C4, C6, C8 n-Alkane Mix

O 3 , (L)

● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 16, 1996 1.0 ppmV each of C2, C4, C6, C8 n-Alkane Mix

O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## 40 ppmC Alkane Mix vs 20 ppmC Alkane Mix5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 16, 1996

Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 19, 1983 4.6 ppmC Isopentane

O 3 , (L) NO, (L)

NO 2 , (L)

PAN, (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 19, 1983 4.0 ppmC 2,2,4-Trimethylpentane

O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)
NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## HC Reactivity at 0.37 NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 19, 1983

Total Solar Radiation Eppley Ultraviolet Radiation ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 19, 1983

● ● ●

CCl 4 , (L)

CCl4, (L) ● ● ● ●

CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Oct 11, 2001 600 ppm Methane

● ● ● O 3 , (L) NO, (L)
NO 2 , (L) CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Oct 11, 2001 40 ppmC n-Butane

● ● O 3 , (L) NO, (L) NO 2 , (L) CB05 Simulation

O3, (L) NO, (L) NO2, (L) TotNO3, (L)



## Characterization Experiment: CH4 vs Butane5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Oct 11, 2001

● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TCCl4, relativeCCl4, relative



## Oct 11, 2001

CCl4, (L) CCl4, (R)

### Aromatics (TOL and XYL)

AU 01 83 AU 03 95 AU 17 88 AU 22 97 AU 30 95 ST 13 93 ST 14 81 ST 24 965 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 1, 1983 ■ ■ ■ ■
■

■

■
■ ■ ■ ■ Toluene, (L)

TOL, (L) ▲ ▲

▲ ▲ ▲ ▲ CO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 1, 1983

■ ■ ■
■

■

■ ■ ■ ■ ■ o-Xylene, (L)

XYL, (L) ▲ ▲ ▲

▲ ▲

● CO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 1, 1983 4.6 ppmC Toluene

● O 3 , (L)

● ● NO, (L)
NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 1, 1983 2.6 ppmC o-Xylene

O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## HC Reactivity at 0.38 pm NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 1, 1983

Total Solar Radiation Eppley Ultraviolet Radiation
● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 1, 1983

● ● ● ● ●

● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 03, 1995

■ ■ ■ ■

■

■
■ ■ ■ p-xylene, (L)

XYL, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ FORMALDEHYDE, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 03, 1995

■

■

■

■

■
■ ■ ■ 1,3,5-trimethylbenzene, (L)

XYL, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲
▲ FORMALDEHYDE, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 03, 1995 1 ppm p-Xylene

O 3, (L)

NO, (L) NO 2, (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3 , (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 03, 1995 1 ppm 1,3,5-Trimethylbenzene

● ● O 3, (L)

NO, (L) NO 2, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3 , (L)



## Aromatics Experiments;5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 03, 1995

● Total Solar Radiation

● ●

● Eppley Ultraviolet Radiation Chamber Temperture

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 03, 1995

● ● ● ● ● ● ● ● ● CCL4, (L) CCl4, (L) ● ● ● ● ● ● ● ● CCL4, (R) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0 6.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 17, 1988
■ ■ ■ ■

■

■

■ ■ ■ ■ ■ Toluene, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Formaldehyde-PKD, (L) TOL, (L)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 17, 1988 ■ ■ ■

■

■
■ ■ ■ ■ ■ m-Xylene, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Formaldehyde-PKD, (L) XYL, (L) FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 17, 1988 4.926 ppmC Toluene

O 3 , (L)

NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 17, 1988 1.715 ppmC m-Xylene O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## HC Reactivity at 0.36 ppm NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 17, 1988

● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 17, 1988

● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

● ● ● ● ● ● ● ● ● ● ● ● ● ●

CCl 4 , (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 22, 1997

TOL, (L)

ISOP, (L) ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)

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

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 22, 1997

TOL, (L) ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 22, 1997 10.11 ppmC Toluene

● ● O 3 , (L)

● NO, (L)
NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 22, 1997 2.22 ppmC Toluene, 2.84 ppmC p-xylene, 3.08 ppmC 1,3,5-trimethbenzene O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Toluene vs 1,3,5-trimethylbenzene, p-xylene and Toluene5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 22, 1997

● ● Total Solar Radiation

● ● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 22, 1997

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.9 1.9 2.8 3.8 4.7 5.7 6.6 7.6 8.5

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 30, 1995 ■ ■

■

■

■

■ ■ ■ ■ ■ ■ ■ M-XYLENE, (L)

XYL, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Formaldehyde, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.9 1.9 2.8 3.8 4.7 5.7 6.6 7.6 8.5

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## August 30, 1995 ■ ■ ■ ■
■

■

■
■ ■ ■ ■ ■ ■ TOLUENE, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ACETALDEHYDE, (L) TOL, (L)

ALD2, (L) ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Formaldehyde, (R)
FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 30, 1995 8 ppmC m-Xylene

● ● ● ● O 3 , (L)

NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 30, 1995 7 ppmC Toluene

● ● ● ● ● ● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Toluene vs m-Xylene;5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 30, 1995

● ● Total Solar Radiation

● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## August 30, 1995

● ● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L) CCl4, (L) ● ● ● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (R) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 13, 1993

■ ■
■

■

■

■ ■ ■ ■ ■ ■ MXYLENE, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ FORMALDEHYDE, (L)

XYL, (L) ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲

▲ ▲
▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲
▲

▲ ▲ ▲
▲ ▲ ▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲
▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲
▲
▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ CO, (R) CO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 13, 1993 ■ ■ ■ ■

■

■

■ ■ ■ ■ ■ TOLUENE, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ FORMALDEHYDE, (L) TOL, (L) ▲ ▲ ▲ ▲
▲ ▲
▲ ▲

▲ ▲ ▲ ▲

▲ ▲
▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲

▲ ▲

▲ ▲ ▲ ▲
▲ ▲

▲

▲ ▲ ▲ ▲

▲ ▲ ▲

▲ ▲ ▲

▲ ▲ CO, (R) CO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 13, 1993 0.789 ppmC m-Xylene

● O 3 , (L)

● ● NO, (L)

NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L)
PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 13, 1993 1.909 ppmC Toluene

● ● ● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Toluene vs m-Xylene5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 13, 1993

Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperture

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 13, 1993

● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L) CCl4, (L) ● ● ● ● ● ● ● ● ● ●

CCl 4 , (R) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 14, 1981

■ ■ ■ ■

■

■

■

■ m-Xylene, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Propene, (L)

XYL, (L) OLE, (L) ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R) FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 14, 1981

■ ■ ■ ■ ■ ■ ■ ■ Toluene, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Propene, (L) TOL, (L)

OLE, (L) ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R) CO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 14, 1981 1.58 ppmC UNCMIX80, 0.61 ppmC m-Xylene O 3 , (L)

NO, (L)

● NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 14, 1981 1.65 ppmC UNCMIX80, 0.52 ppmC Toluene

O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## HC Reactivity at 0.25 ppm NO x5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 14, 1981

● Total Solar Radiation
Eppley Ultraviolet Radiation ● ● ● ● ● ● ● ● ● ● ● ● ● Chamber Temperature

Dewpoint

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

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

0 1 2 3 4 5 6 7 8 9 10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 14, 1981

● ● ● ● ● CCl 4 , (L) ● ● ● ● ● CCl 4 , (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 24, 1996

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

■

■

■ ■ ■ ■ ■ ■ Isoprene, (L)

TOL, (L) ISOP, (L) ● ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ CO, (R)

FORM, (R)

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

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 24, 1996 ■ ■ ■

■

■ ■ ■ ■ ■ ■ Toluene, (L)

TOL, (L) ●

● ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ CO, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 24, 1996 10.341 ppmC Isoprene

● O 3 , (L)

● ● ● ● ● ● ● ● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 24, 1996 13.37 ppmC Toluene

O 3 , (L)

● ● ● ● ● NO, (L)
NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Toluene vs Isoprene5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 24, 1996

● ● ● Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 24, 1996

● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● CCl 4 , (R) CCl4, (R)

### Isoprene (ISOP)

JN 26 97 AU 06 96 ST 11 99 ST 24 965 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## June 26, 1997

● ●
●

●

● ● ● ● ● ● ● Isoprene, (L)

◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆

HCHO, (L)

ISOP, (L) FORM, (L) ● ● ● ● ● ● ● ● ● ● ● Acetaldehyde, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲

▲ ▲ PAN, (R) ALD2, (R) PAN, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## June 26, 1997 ■ ■ ■

■

■

■ ■ ■ ■ ■ ■ ■ Isoprene, (L)

ISOP, (L) ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆

◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ ◆ HCHO, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ PAN, (R)

FORM, (R)

CO, (R)

PAN, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## June 26, 1997 6.43 ppmC Isoprene
O 3 , (L)

● ● ● ● ● ● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## June 26, 1997 1.92 ppmC Isoprene O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

CB05 Simulation O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Delta Isoprene5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## June 26, 1997

● Total Solar Radiation Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 06, 1996 1.5 ppmC SynUrban

O 3 , (L)

● NO, (L)

NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## August 06, 1996 1.5 ppmC SynUrban + 0.15 ppmC Isoprene

O 3 , (L)

● ● NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Matched SynUrban and NOx with Isoprene added BLUE5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## August 06, 1996

● ● Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D6 7 8 9 10 11 12 13 14 15 16 17 0 1 2 3 4 5 6 7 8 9 10

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TVOC, ppmCVOC, ppm



## September 11, 1999

▲ ▲ ▲

▲

▲

▲ ▲ ▲ ▲ Isoprene

ISOP ALD2 FORM ● ● ● ● ● ● ● ● ● ● Formic Acid ,ppm

● ● ● ● ● ● ● ● ● ● Acetic Acid ,ppm ● Methacrolein

6 7 8 9 10 11 12 13 14 15 16 17 0 1 2 3 4 5 6 7 8 9 10

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TVOC, ppmCVOC, ppm



## September 11, 1999

▲ ▲ ▲

▲

▲ ▲ ▲ ▲ Isoprene

ISOP ● ● ● ● ● ● ● ● ● Formic Acid ,ppm

● ● ● ● ● ● ● ● ● Acetic Acid ,ppm6 7 8 9 10 11 12 13 14 15 16 17 0 1 2 3 4 5 6 7 8 9 10

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 11, 1999

▲ ▲ ▲

▲

▲

▲ ▲ ▲ ▲ Isoprene

ISOP FORM ● ● ● ● ● ● ● ● ● Methacrolein

● ● ● ● ● ● ● ● ● Methylvinylketone

● ● ● ● ● ● ● ● ● ● Formic Acid ,ppm

6 7 8 9 10 11 12 13 14 15 16 17 0 1 2 3 4 5 6 7 8 9 10

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 11, 1999

▲ ▲ ▲

▲

▲ ▲ ▲ ▲ Isoprene

ISOP ● ● ● ● ●

●

●

● Methacrolein

● ● ● ● ●

●

●
● Methylvinylketone

● ● ● ● ● ● ● ● ● Formic Acid ,ppm5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 11, 1999 7.79 ppmC Isoprene

O 3 , (L)

● ● ● ● NO, (L) NO 2 , (L) PAN, (L)

7.79 ppmC Isoprene RED

O3, (L)
NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 11, 1999 7.47 ppmC Isoprene

O 3 , (L)

● ● NO, (L)

NO 2 , (L)

7.47 ppmC Isoprene BLUE

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Matched Isoprene; Delta NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 11, 1999

● Total Solar Radiation Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 11, 1999

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 24, 1996

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

■

■

■ ■ ■ ■ ■ ■ Isoprene, (L)

TOL, (L) ISOP, (L) ● ▲

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ CO, (R)

FORM, (R)

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

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 24, 1996 ■ ■ ■

■

■ ■ ■ ■ ■ ■ Toluene, (L)

TOL, (L) ●

● ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ CO, (R)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 24, 1996 10.341 ppmC Isoprene

● O 3 , (L)

● ● ● ● ● ● ● ● ● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 24, 1996 13.37 ppmC Toluene

O 3 , (L)

● ● ● ● ● NO, (L)
NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) PAN, (L) TotNO3, (L)



## Toluene vs Isoprene5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 24, 1996

● ● ● Total Solar Radiation

● ● ● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## September 24, 1996

● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ● ● CCl 4 , (R) CCl4, (R)

### Urban Mixture

JN 19 97 AU 26 01 ST 10 99 ST 12 94 ST 14 00 ST 14 94 ST 15 94 ST 26 995 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## June 19, 1997 1.96 ppmC SynUrban O 3 , (L)

● NO, (L)

NO 2 , (L)

PAN, (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40 0.50

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TNO, NO2, ppmO3, ppm



## June 19, 1997 1.96 ppmC SynUrban O 3 , (L)

● ● NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Matched SynUrban and NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## June 19, 1997 Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Aug 26, 2001 1.474 ppmC SynUrban

● ● ● ● O 3 , (L)

● NO, (L)

● ● NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Aug 26, 2001 1.474 ppmC SynUrban

● ● ● ● ● ● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Matched SynUrban; Matched NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Aug 26, 2001

Total Solar Radiation

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 5 6 7 8 9 10 11 12

5 6 7 8 9 10 11 12



### H o u r s, L D TCCl4, relativeCCl4, relative



## Aug 26, 2001

● ● ● ● ● ● ● ● ● ● ● ● CCl 4 , (L)

CCl4, (L) ● ● ● ● ● ● ● ● ●
● ● CCl 4 , (R)

CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 10, 1999 1.474 ppmC SynUrban

O 3 , (L)

● ● NO, (L)

NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 10, 1999 1.474 ppmC SynUrban

● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Matched SynUrban and NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Sep 10, 1999

● ● ● ● ● Total Solar Radiation Eppley Ultraviolet Radiation

Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TCCl4, relativeCCl4, relative



## Sep 10, 1999

CCl4, (L) CCl4, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 12, 1994 2.0 ppmC SynURB O 3 , (L)

● NO, (L) NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 12, 1994 2.0 ppmC SynURB O 3 , (L)

● NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## Matched SynURB5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.00 0.05 0.10 0.15 0.20



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 12, 1994

PAR, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

OLE, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.5 1.0 1.5 2.0

0.00 0.05 0.10 0.15 0.20



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 12, 1994

PAR, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

OLE, (R) FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## Sep 14, 2000

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Acetaldehyde, (L)

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ Propanal, (L)

ALD2, (L)

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Formaldehyde, (R) FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

0.00 0.10 0.20 0.30 0.40 0.50



### H o u r s, L D TVOC, ppmCVOC, ppmC



## Sep 14, 2000

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ Formaldehyde, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 14, 2000 6.0 ppmC Butyraldehyde

O 3 , (L)

● ● ● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 14, 2000 6.0 ppmC SynUrban

O 3 , (L)

NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L) TotNO3, (L)



## Butyraldehyde vs SynUrban; matched NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Sep 14, 2000

● ● Total Solar Radiation
Eppley Ultraviolet Radiation

Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 14, 1994

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 14, 1994

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 14, 1994 1.0 ppmC SynURB + 1.0 ppmC SynE85E

● ● O 3 , (L)

● NO, (L)

● NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.10 0.20 0.30 0.40

0.00 0.10 0.20 0.30 0.40



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 14, 1994 2.0 ppmC SynURB

● ● ● ● O 3 , (L)

● ● NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## SynURB vs SynURB/SynE855 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 14, 1994

● ● Total Solar Radiation

● ● ● ●

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 15, 1994

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TVOC, ppmCVOC, ppmC



## September 15, 1994

▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ HCHO, (R)

FORM, (R)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 15, 1994 1.0 ppmC SynURB + 1.0 ppmC SynE85E (minus EtOH)

O 3 , (L) NO, (L)
NO 2 , (L)

PAN, (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## September 15, 1994 2.0 ppmC SynURB

● O 3 , (L)

● NO, (L) NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## SynURB vs SynURB/SynE85 (no EtOH)5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## September 15, 1994

Total Solar Radiation

● ● ●

● Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 26, 1999 1.414 ppmC SynUrban

● ● O 3 , (L) NO, (L)

NO 2 , (L)

PAN, (L) CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.05 0.10 0.15 0.20 0.25 0.30

0.00 0.05 0.10 0.15 0.20 0.25 0.30



### H o u r s, L D TNO, NO2, ppmO3, ppm



## Sep 26, 1999 1.474 ppmC SynUrban

● ● O 3 , (L) NO, (L)

NO 2 , (L)

CB05 Simulation

O3, (L)

NO, (L) NO2, (L)

PAN, (L) TotNO3, (L)



## 4% SynUrban Difference; Matched NOx5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0 10 20 30 40 50 60 70 80 90 100

0.0 0.5 1.0 1.5 2.0



### H o u r s, L D TTemp., Dew Pt.°F; UV, mLy-min-1; min-1/100TSR, Ly-min-1; 1000 x min-1



## Sep 26, 1999

Total Solar Radiation Eppley Ultraviolet Radiation Chamber Temperature

Dewpoint

NO2 toO3P

FORM toHO2 O3 toO1D

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10



### H o u r s, L D TCCl4, relativeCCl4, relative



## Sep 26, 1999