Evaluation of Atmospheric Impacts

INVESTIGATION OF VOC REACTIVITY EFFECTS USING EXISTING REGIONAL AIR QUALITY MODELS SUMMARY OF PROGRESS MAY 15-16, 2002

WILLIAM CARTER* PRINCIPAL INVESTIGATOR

GAIL TONNESEN* AND GREG YARWOOD** CONTRIBUTING INVESTIGATORS

*CE-CERT, UNIVERSITY OF CALIFORNIA, RIVERSIDE ** ENVIRON, INTERNATIONAL OBJECTIVES

ASSESS VOC REACTIVITY EFFECTS USING AN EXISTING REGIONAL MODELING DATABASE REPRESENTING THE EASTERN U.S. ASSESS RELATIVE INCREMENTAL OZONE IMPACTS OF VOC MODEL SPECIES WITH RESPECT TO:  VARIATION WITHIN THE MODELING DOMAIN  DERIVATION OF VARIOUS REACTIVITY METRICS  COMPARISON WITH REACTIVITIES CALCULATED USING EKMA MODELS  PREDICTIONS OF EFFECTS OF SELECTED LARGE SCALE SUBSTITUTIONS ASSESS APPROACHES FOR DERIVING A GENERAL REACTIVITY SCALE REPRESENTING REGIONAL O3 IMPACTS CRC-NARSTO MODELING DATABASE

36 KM GRIDS

MODEL: CAMx VERSION 3.01 WITH DDM EPISODE DATES: JULY 7-15, 1995 (DATA FOR 11th- 14th USED IN ASSESSMENT) EMISSIONS: EPA NET96 MET DATA: MM5 MECHANISM: UPDATED CB4 (ETHANE ADDED) (Analysis of fine grid data still underway. Current analysis uses 4 and 12 km data averaged into the 36 KM grids.) CARBON BOND 4 MECHANISM

ADVANTAGES  LEAST EXPENSIVE TO USE FOR INITIAL STUDY  WIDELY USED  REPRESENTS MOST OF THE IMPORTANT CLASSES OF REACTIVE VOCs

DISADVANTAGES  OUT-OF-DATE (DEVELOPED IN1989)  HIGHLY CONDENSED. CANNOT BE USED TO ASSESS MOST INDIVIDUAL VOCs  INAPPROPRIATE OR NO REPRESENTATION OF SOME IMPORTANT TYPES OF VOCs:  INTERNAL ALKENES (only products represented; effects of initial OH and O3 reaction ignored)  TOLUENE (reactivity characteristics significantly different than predicted using current mechanisms)  RADICAL INHIBITING VOCs (not represented)  MAY BE MORE SENSITIVE TO RADICAL EFFECTS THAN CURRENT MECHANISM

NEVERTHELESS, CB4 PROBABLY SUITABLE FOR INITIAL QUALITATIVE ASSESSMENT OF VARIABILITY OF REACTIVITY WITH MODELING DOMAIN PHASE1: DDM CALCULATIONS

DECOUPLED DIRECT METHOD (DDM) USED TO CALCULATE SENSITIVITIES OF SURFACE O3 CONCENTRATIONS TO CHANGES IN EMISSIONS SENSITIVITIES CALCULATED AS FUNCTION OF TIME AND SPACE AND OUTPUT AS HOURLY AVERAGES FOR ALL GROUND LEVEL CELLS. FIRST DDM CALCULATION:

 SENSITIVITY TO TOTAL VOC AND NOx EMISSIONS

 RESULTS GIVE PPM O3 CHANGE RESULTING FROM 100% CHANGE IN EMISSIONS (IF LINEAR) SECOND DDM CALCULATION:  SENSITIVITY TO SURFACE EMISSIONS OF CO AND 9 VOC MODEL SPECIES VARIED.  SAME TIME AND SPACE DISTRIBUTION AS TOTAL ANTHROPOGENIC VOC

 RESULTS GIVE PPM O3 CHANGE FROM 100% CHANGE IN ANTHROPOGENIC VOC CARBON EMISSIONS AS THE SPECIES (IF LINEAR)

THE SENSITIVITIES OF O3 TO MODEL SPECIES EMISSIONS ARE THE SAME AS THE INCREMENTAL REACTIVITIES OF THESE MODEL SPECIES CARBON BOND 4 MODEL SPECIES WHOSE OZONE SENSITIVITIES WERE DETERMINED

SPECIES APPROXIMATELY REPRESENTATIVE OF

PAR C4 - C6 ALKANES ETH ETHENE (EXPLICIT) OLE PROPENE (PRIMARILY) TOL NO SPECIFIC COMPOUND. MAY BE INDICATIVE OF COMPOUNDS WITH VERY NOx SENSITIVE REACTIVITIES (E.G., PHENOLS, STYRENES) XYL XYLENES FORM FORMALDEHYDE (EXPLICIT) ALD2 ACETALDEHYDE (EXPLICIT) ETOH ETHANOL (EXPLICIT) ETHA ETHANE (ADDED FOR THIS STUDY) CO CARBON MONOXIDE (EXPLICIT) OZONE IMPACT METRICS USED IN INITIAL ANALYSIS

IMPACTS BASED ON EFFECTS OF SPECIES ON DAILY MAXIMUM 1-HOUR AND 8-HOUR AVERAGE O3 FOLLOWING CELLS NOT INCLUDED IN ANALYSIS:

 CELLS WHERE MAXIMUM O3 LESS THAN CUTOFF  80 PPB CUTOFF FOR 1-HOUR AVERAGE  60 PPB CUTOFF FOR 8-HOUR AVERAGE  CELLS WITH ZERO ANTHROPOGENIC EMISSIONS (I.E., CELLS OVER WATER) REACTIVITIES DERIVED RELATIVE TO REACTIVITIES OF TOTAL ANTHROPOGENIC VOC EMISSIONS MIXTURE (BASE ROG)  GIVES BENEFITS OF REDUCING A SINGLE VOC COMPARED TO REDUCING ALL VOCs EQUALLY  BASE ROG SENSITIVITIES DERIVED FROM SENSITIVITIES OF COMPONENT SPECIES  BASE ROG COMPOSITION DERIVED FROM EPA REGIONAL EMISSIONS DATABASE  TOTAL VOC SENSITIVITIES COULD NOT BE USED BECAUSE THEY INCLUDED BIOGENIC VOCs 4 GLOBAL RELATIVE REACTIVITY METRICS DERIVED  MINIMUM SUBSTITUTION ERROR (2 METHODS)  REGIONAL MIR  REGIONAL MAXIMUM O3 COMPOSITION OF BASE ROG MIXTURE USED TO DERIVE RELATIVE REACTIVITIES

MEOH 1% XYL 6% HCHO 1% TOL 9% CB4 MODEL SPECIES: OLE 4% ETH 4% CARBON BASIS ALD2 4% PAR 55% ETOH 4%

Unreact. 12%

MEOH 0% XYL 15% PAR 20% CB4 MODEL SPECIES: HCHO 6% Unreact. 0% REACTIVITY ETOH 3% TOL 5% BASIS (EKMA MIR ALD2 12% SCALE) OLE 20% ETH 10%

(BASED ON NEW EMISSIONS ASSIGNMENTS 5/02) GLOBAL RELATIVE REACTIVITY METRIC #1 MINIMUM SUBSTITUTION ERROR: BASE ROG FOR SPECIES

DEFINITION RELATIVE REACTIVITY TO MINIMIZE SUBSTITUTION ERROR FROM REACTIVITY-BASED SUBSTITUTION OF THE BASE ROG FOR THE MODEL SPECIES SUBSTITUTION ERROR = 2 Σcells [RR(Species)·IRcell(Base ROG) - IRcell(Species)]

ADVANTAGES  WEIGHS CELLS THAT ARE SENSITIVE TO VOCs MORE HIGHLY WHILE TAKING THE MANY CELLS WITH LOWER SENSITIVITIES INTO ACCOUNT  REPRESENTATIVE OF STRATEGIES INVOLVING REPLACING HIGHLY REACTIVE VOCs WITH VOCs OF AVERAGE REACTIVITY  REACTIVITIES OF MIXTURES ARE LINEAR SUMS OF REACTIVITIES OF COMPONENTS

DISADVANTAGES  MAY NOT OPTIMALLY WEIGH CONTRIBUTIONS OF DIFFERENT TYPES OF REGIONS  NOT A PARTICULARLY REALISTIC SUBSTITUTION FOR EXEMPTION ISSUES GLOBAL RELATIVE REACTIVITY METRIC #2 MINIMUM SUBSTITUTION ERROR: SPECIES FOR BASE ROG

DEFINITION RELATIVE REACTIVITY TO MINIMIZE SUBSTITUTION ERROR FROM REACTIVITY-BASED SUBSTITUTION OF THE MODEL SPECIES FOR THE BASE ROG SUBSTITUTION ERROR = 2 Σcells [IRcell(Base ROG) - IRcell(Species)/RR(Species)]

ADVANTAGES  WEIGHS CELLS THAT ARE SENSITIVE TO VOCs MORE HIGHLY WHILE TAKING THE MANY CELLS WITH LOWER SENSITIVITIES INTO ACCOUNT  REPRESENTATIVE OF STRATEGIES INVOLVING SUBSTITUTIONS OF CURRENT EMISSIONS WITH LOW REACTIVITY VOCs

DISADVANTAGES  MAY NOT OPTIMALLY WEIGH CONTRIBUTIONS OF DIFFERENT TYPES OF REGIONS  REACTIVITIES OF MIXTURES ARE NOT LINEAR SUMS OF THOSE OF COMPONENTS  DIVERGENT RESULTS OBTAINED FOR VOCs WHOSE REACTIVITIES ARE SCATTERED AROUND ZERO GLOBAL RELATIVE REACTIVITY METRIC #3 REGIONAL MAXIMUM INCREMENTAL REACTIVITY

DEFINITION USE REACTIVITIES AT THE LOCATION WHERE THE INCREMENTAL REACTIVITY OF THE BASE ROG AT THE TIME OF THE O3 MAXIMUM IS THE HIGHEST

ADVANTAGES  COMPARABLE TO THE WIDELY-USED CARTER (1994) MIR SCALE  REPRESENTATIVE OF IMPACTS IN REGIONS MOST SENSITIVE TO ANTHROPOGENIC VOC CONTROLS

DISADVANTAGES  NOT A TRUE GLOBAL METRIC. DERIVED FROM IMPACTS IN ONLY ONE TYPE OF REGION  REPRESENTS ONLY A SMALL FRACTION CELLS IN MODELING DOMAIN  DOES NOT REPRESENT IMPACTS IN CELLS WITH THE HIGHEST O3  DOES NOT REPRESENT IMPACTS IN THE MANY NOx-LIMITED CELLS GLOBAL RELATIVE REACTIVITY METRIC #4 REGIONAL MAXIMUM OZONE REACTIVITY

DEFINITION USE REACTIVITIES AT THE TIME AND LOCATION OF THE DOMAIN-WIDE O3 MAXIMUM

ADVANTAGES

 ADDRESSES NEEDS TO REDUCE PEAK O3, WHICH IS OF REGULATORY INTEREST  SIMPLEST METRIC TO IMPLEMENT

PROBLEMS  NOT A TRUE GLOBAL METRIC. DERIVED FROM IMPACTS IN ONLY ONE LOCATION  NOT NECESSARILY REPRESENTATIVE OF “MOIR” CONDITIONS AS DEFINED BY CARTER (1994)  REACTIVITY CHARACTERISTICS OF THE HIGHEST O3 CELL CAN VARY SIGNIFICANTLY DEPENDING ON THE EPISODE

 THE DOMAIN-WIDE MAXIMUM O3 MAY BE INSENSITIVE TO ANTHROPOGENIC VOCs EKMA REACTIVITY SCALES FOR COMPARISON WITH REGIONAL MODEL REACTIVITIES

SAME EKMA SCENARIOS AND CALCULATION METHODS AS USED TO DERIVE “CARTER” REACTIVITY SCALES (CARTER, 1994; CARTER, 2000) SAME VERSION OF CB4 AS USED IN THE CAMx REGIONAL MODEL CALCULATIONS RELATIVE REACTIVITIES USE SAME BASE ROG MIXTURE AS USED FOR REGIONAL METRICS MIR SCALE  AVERAGES OF INCREMENTAL REACTIVITIES IN THE SCENARIOS WITH NOx ADJUSTED TO YIELD MAXIMUM BASE ROG REACTIVITY  ANALOGOUS TO REGIONAL MIR METRIC MOIR SCALE  AVERAGES OF INCREMENTAL REACTIVITIES IN THE SCENARIOS WITH NOx ADJUSTED TO YIELD MAXIMUM PEAK O3 CONCENTRATIONS  NOT NECESSARILY ANALOGOUS TO REGIONAL MAXIMUM O3 METRIC BASE CASE SCALES  RELATIVE REACTIVITIES DERIVED TO MINIMIZE SUBSTITUTION ERRORS IN THE BASE CASE (UNADJUSTED NOx) SCENARIOS  ANALOGOUS TO MINIMUM SUBSTITUTION ERROR METRICS #1 AND #2 FOR 1-HOUR AVG. GEOGRAPHICAL DOMAIN FOR MAXIMUM 1-HOUR AVERAGE O3 AND ANTHROPOGENIC VOC SENSITIVE REGIONS

JULY 11 60

20 O3 > 0.08 Emit >0 MIR to EBIR Max O3 Cell MIR Cell

0 0 20 40 60 80 GEOGRAPHICAL DOMAIN FOR MAXIMUM 1-HOUR AVERAGE O3 AND ANTHROPOGENIC VOC SENSITIVE REGIONS

JULY 14 60

0 0 20 40 60 80 GEOGRAPHICAL DOMAIN FOR MAXIMUM 8-HOUR AVERAGE O3 AND ANTHROPOGENIC VOC SENSITIVE REGIONS JULY 14 60

0 0 20 40 60 80 MAXIMUM 1-HOUR AVERAGE OZONE SENSITIVITIES TO VOC AND NOx Maximum 1-HOUR AVERAGE QUANTIFICATION 7/11 7/12 7/13 7/14 -0.5 0.15 0.15

R -0.5 E I N

O 0.15 I MOIR to EBIR

MIR L M C 0.12 Conditions O (21% of cells) V

o 0.09 T EBIR o t

LINE y t i 0.06 v i t i s n

e MIR to MOIR

S 0.03 Conditions (6% of cells) 0.00 -0.12 -0.08 -0.04 0.00 0.04 0.08 NOx Sensitive -0.03 Conditions (73% of cells) Sensitivity to Total NOx

(Cells with Maximum 1-Hour Average O3 < 80 ppb and with Zero Emissions are Excluded) SENSITIVITIES TO BASE ROG (REPRESENTING ANTHROPOGENIC VOCs) VS. SENSITIVITIES TO TOTAL VOCs 1-HOUR AVERAGE QUANTIFICATION ALL CELLS WHERE MAXIMUM 1-HOUR O3 > 80 PPB

0.05 7/11 -0.5 7/12 0.15 7/13 -0.5 G 0.04 0.15 O 7/14 R

a 0.03 B

v 0.02 i t i s n e

S 0.01

0.00 -0.05 0.00 0.05 0.10 0.15 Sensitivity to total VOC DISTRIBUTION OF BASE ROG (ANTHROPOGENIC) / TOTAL VOC SENSITIVITY RATIO

[O3 SENSITIVITY TO BASE ROG]

[O3 SENSITIVITY TO ALL VOCs]

Y 45-50% T I V I 40-45% T I

S 35-40% N E S

30-35% C

O 25-30% V

A 20-25% T O

T 15-20%

G 10-15% O R 5-10% E S

A 0-5% B <0

0% 5% 10% 15% 20% 25% FRACTION OF CELLS (MAXIMUM 1-HOUR AVERAGE QUANTIFICATION) Cells with total VOC sensitivity < 0.001 excluded REACTIVITY CHARACTERISTICS OF EPISODE DAYS

EPISODE DAY 7/11 7/12 7/13 7/14

DOMAIN-WIDE OZONE MAXIMUM (ppb)

Peak 1-Hr Avg. O3 165 162 187 175

Peak 8-Hr Avg. O3 127 126 139 139

HIGH OZONE CELLS 1-Hr Avg. > 80 ppb 18% 22% 25% 25% 1-Hr Avg. > 120 ppb 1% 1% 2% 4%

8-Hr Avg. > 60 ppb 32% 37% 38% 36% 8-Hr Avg. > 80 ppb 7% 7% 10% 12%

CELLS MORE SENSITIVE TO VOCs THAN NOx 1-Hour Avg. Quant. 32% 23% 27% 25% 8-Hour Avg. Quant. 25% 29% 33% 24% ETHANE VS. BASE ROG SENSITIVITIES

1-HOUR DAILY MAXIMUM O3 0.010

0.008 e n a h t 0.006 E

y t i v i

t 0.004

i 7/11 s

n 7/12 e

S 7/13 0.002 7/14 ROG for VOC VOC for ROG 0.000 0.00 0.01 0.02 0.03 0.04 0.05 0.06 Sensitivity to Base ROG

e 0.005 n a h t E

0.004 o t

y t i v

i 0.003 t i 7/11 s n

e 7/12

S 0.002 7/13 7/14 0.001 ROG for VOC VOC for ROG 0.000 0.00 0.01 0.02 0.03 0.04 Sensitivity to Base ROG 1-HOUR MAXIMUM O3 SENSITIVITY EXAMPLES XYLENE VS BASE ROG 0.150 7/11 7/12 7/13

s 0.125

e 7/14 i c

e ROG for VOC p 0.100

S VOC for ROG

l e d o 0.075 M

L Y X 0.050 o t

y t i v i

t 0.025 i s n e

S 0.000 0.00 0.01 0.02 0.03 0.04 0.05 0.06 -0.025 Sensitivity to Base ROG

FORMALDEHYDE VS BASE ROG 0.30 7/11 7/12

s 7/13 e

i 0.25 c 7/14 e

p ROG for VOC S

l 0.20 VOC for ROG e d o M 0.15 O H C H

0.10 o t

y t i v i 0.05 t i s n e

S 0.00 0.00 0.01 0.02 0.03 0.04 0.05 0.06 -0.05 Sensitivity to Base ROG CB4 “TOL” SPECIES VS. BASE ROG SENSITIVITIES

s 0.020 e i c e p S

l 0.010 e d o M

L 0.000 O T

-0.01 0.00 0.01 0.02 0.03 0.04 0.05 0.06 o t

t -0.010 i

v 7/11 i t i

s 7/12 n e -0.020 7/13 S 7/14 ROG for VOC -0.030 VOC for ROG Sensitivity to Base ROG

0.015 s e i c

e 0.010 p S

d 0.005 o M

L 0.000 O T

-0.01 0.00 0.01 0.02 0.03 0.04 o t

-0.005 y t i

v 7/11 i t i -0.010

s 7/12 n

e 7/13 S -0.015 7/14 ROG for VOC -0.020 VOC for ROG Sensitivity to Base ROG EthanePAR HCHO ALD2

ROG / VOC SUBST ROG / VOC SUBST EKMA 7/11 1-hr 8-hr S 7/12 1-hr C

I 8-hr

R 7/13 1-hr

T 8-hr

E 7/14 1-hr

M 8-hr

Y VOC / ROG SUBST VOC / ROG SUBST T I EKMA V

I 7/11 1-hr T 8-hr C 7/12 1-hr A 8-hr E 7/13 1-hr R

E 7/14 1-hr V

I 8-hr

L EKMA

E 7/11 1-hr R

F 7/12 1-hr

O 8-hr 7/13 1-hr N 8-hr O 7/14 1-hr S

I 8-hr R

A MOIR or MAX O3 MOIR or MAX O3

P EKMA (negative) M 7/11 1-hr (negative)

O 8-hr

C 7/12 1-hr 8-hr 7/13 1-hr 8-hr 7/14 1-hr 8-hr

0.00.0 0.50.3 1.00.6 1.50.9 0 2 4 6 0 2 4 6 8

PARTOL XYL HCHO

ROG / VOC SUBST ROG / VOC SUBST EKMA 7/11 1-hr 8-hr S 7/12 1-hr C

I 8-hr

R 7/13 1-hr

T 8-hr

E 7/14 1-hr

M 8-hr

Y VOC / ROG SUBST VOC / ROG SUBST T I EKMA V I 7/11 1-hr T 8-hr C 7/12 1-hr (All off scale) A 8-hr E 7/13 1-hr R

E 7/14 1-hr V

I 8-hr

T MIR MIR A

L EKMA

E 7/11 1-hr R

F 7/12 1-hr

O 8-hr 7/13 1-hr N 8-hr O 7/14 1-hr S

I 8-hr R MOIR or MAX O3

A MOIR or MAX O3

P EKMA (off scale) M 7/11 1-hr (negative)

O 8-hr (Most off scale)

C 7/12 1-hr 8-hr 7/13 1-hr 8-hr 7/14 1-hr 8-hr

0.0-2.0 0.50.0 1.02.0 4.01.5 0 5 10 15 20 25

SUMMARY OF EKMA AND SELECTED REGIONAL RELATIVE REACTIVITIES FOR CB4 SPECIES

Relative Reactivities (Carbon Basis) Effect on Maximum 1-Hour O3 Model Minimum Subst. Error: Species MIR Scales ROG for VOC EKMA Regional EKMA Regional PAR 0.40 0.65 ± 0.08 0.59 0.76 ± 0.07 ETH 2.7 2.8 ± 0.2 3.0 2.9 ± 0.1 OLE 5.6 5.1 ± 0.4 5.8 5.0 ± 0.3 TOL 0.6 0.33 ± 0.07 -3.0 -0.12 ± 0.12 XYL 2.7 2.0 ± 0.2 2.2 1.6 ± 0.2 HCHO 6.6 4.1 ± 0.6 5.9 3.5 ± 0.5 ALD2 3.5 2.6 ± 0.3 3.7 2.6 ± 0.2 Ethane 0.09 0.17 ± 0.03 0.16 0.23 ± 0.03 Ethanol 0.76 0.7 ± 0.2 1.10 0.89 ± 0.08 CO 0.03 0.06 ± 0.01 0.06 0.09 ± 0.01

Regional data are averages of the results for the four episode-days SUMMARY OF EKMA AND SELECTED REGIONAL RELATIVE REACTIVITIES SELECTED COMPOUNDS

Relative Reactivities - Mass Basis MIR Min Subst. Err. #1 Compound SAPRC CB4 CB4 Regional Regional EKMA EKMA EKMA Average Average Ethane 0.11 0.10 0.19 0.16 0.26 n-Butane 0.46 0.47 0.76 0.65 0.89 Ethylene 3.2 3.2 3.5 3.6 3.6 Propene 4.0 4.6 4.3 4.9 4.4 m-Xylene 3.7 3.5 2.7 2.6 2.1 Formaldehyde 3.1 3.7 2.4 3.1 2.0 Acetaldehyde 2.4 2.7 2.1 2.8 2.0 Ethanol 0.59 0.56 0.58 0.76 0.66 CO 0.020 0.020 0.039 0.034 0.055 Note:  Only compounds that are reasonably well represented in the CB4 calculations are listed.  “SAPRC” is SAPRC-99  CB4 n-butane is 4 PAR, propene is OLE + PAR  “Min. Subst. Error #1” is ROG for VOC substitution EFFECT OF KINETIC REACTIVITY ON DIFFERENCES BETWEEN REGIONAL AND EKMA RELATIVE REACTIVITIES MIR or Regional MIR Min. Err. ROG / VOC Sub. ETH, OLE 1.0 ALD2, XYL > - t 0.9 s a HCHO F

0.8 ) R I TOL O 0.7 M

M 0.6 K E (

y ETOH t

i 0.5 v i t c a 0.4 e R c i t 0.3 e n i K

w PAR o l S

< Ethane, CO 0.0 0.0 0.5 1.0 1.5 2.0

EKMA / Regional Relative Reactivity (Max. 1-Hr Average Quantification) PRELIMINARY LARGE SCALE SUBSTITUTION CALCULATIONS

CALCULATION 1  ALL ANTHROPOGENIC VOCS REMOVED  RESULTS ARE COMPARED WITH PREDICTIONS USING LINEAR APPROXIMATION AND BASE ROG REACTIVITIES FROM DDM CALCULATION

CALCULATION 2  ALL ANTHROPOGENIC VOCs REPLACED BY ETHANE ON A CARBON FOR CARBON BASIS  RESULTS ARE COMPARED WITH CALCULATION WITH ALL ANTHROPOGENIC VOCs REMOVED TO DETERMINE EFFECT OF ETHANE ADDITION  RESULTS ARE COMPARED WITH EFFECTS OF ETHANE ADDITION PREDICTED BY DDM CALCULATION OF ETHANE REACTIVITY ONLY DATA FOR JULY 13 AND 14 ARE CURRENTLY ANALYZED MAXIMUM 1-HOUR AVERAGE O3 REDUCTION FROM REMOVING ALL ANTHROPOGENIC VOCs

JULY 14

>1 ppb (35%) >5 ppb (9%) >15 ppb (2%) Max= 69 ppb PLOT OF CHANGE IN MAXIMUM 1-HOUR O3 FROM REMOVING ANTHROPOGENIC VOCs

VS. O3 PREDICTED BY BASE ROG REACTIVITY

o 0.08 h r t n A l

f a 0.06 v o

o n m o i t e 0.04 a R l

u C c l 7/14 O a V

C 0.02

c 7/13 e r i

D 0.00 0.00 0.02 0.04 0.06 0.08

Predicted by Base ROG Sensitivity From DDM

DEPENDENCE OF RATIO ON BASE ROG REACTIVITY /

e 10 7/14 g M n 7/13 a D h D

O d 1 e c t l c a i d C

e t r c P e r i

D 0.1 0.00 0.01 0.02 0.03 0.04 0.05 Base ROG Sensitivity ERROR IN LINEAR APPROXIMATION PREDICTION

OF O3 FOR ANTHROPOGENIC VOC REMOVAL [DIRECT CALC] – [DDM ESTIMATE (BASE ROG)] [DIRECT CALC]

(FOR CELLS WHERE O3 > 1 PPB ONLY)

>1 ppb O3 ch. <-30% (17%) >30% (12%) >75% (2%) Maximum Minimum MAXIMUM 1-HOUR AVERAGE O3 INCREASE FROM ADDING BACK ETHANE TO REPLACE THE ANTHROPOGENIC VOCs THAT WERE REMOVED

JULY 14

>0.5 ppb (47%) >2 ppb (8%) >4 ppb (2%) Max= 8 ppb ERROR IN LINEAR APPROXIMATION PREDICTION

OF O3 FOR ADDING BACK ETHANE AFTER ANTHROPOGENIC VOCs REMOVED [DIRECT CALC] – [ETHANE I.R. ESTIMATE] [DIRECT CALC]

(FOR CELLS WHERE O3 > 0.5 PPB ONLY)

>0.5 ppb O3 ch. <-30% (2%) >30% (17%) >60% (3%) Maximum Minimum SPATIAL DISTRIBUTION OF O3 CHANGES CAUSED BY REPLACING EACH CARBON IN THE BASE ROG WITH 3.9 CARBONS OF ETHANE THE OPTIMUM FACTOR WAS DERIVED FROM THE MINIMUM ETHANE-FOR-VOC SUBSTITUTION ERROR FOR ALL CELLS (INCLUDING OVER H2O AND LOW O3)

O3 CHANGE IN PPB IF 100% SUBSTITUTED (IF LINEAR)

>-0.5 ppb (6%) >0.5 ppb (52%) >2 ppb (11%) >5 ppb (0%) Max= 5 ppb Min= -39 ppb PRELIMINARY CONCLUSIONS

NOx CONTROL IS MORE EFFECTIVE THAN VOC CONTROL IN MOST OF THIS MODELING DOMAIN BIOGENIC VOCs DOMINATE OVER ANTHROPOGENICS IN MOST IN MOST OF THIS MODELING DOMAIN RELATIVE REACTIVITIES ARE HIGHLY VARIABLE, BUT VARIABILITY IS LESS IN MORE VOC-SENSITIVE CELLS RELATIVE REACTIVITIES VARY FROM DAY TO DAY IN ANY GIVEN REGION THE MINIMUM SUBSTITUTION ERROR (MSE) METHOD PROVIDES A MEANS TO DERIVE REACTIVITY METRICS BASED ON VARYING REGIONAL IMPACTS THE MINIMUM SUBSTITUTION ERROR AND REGIONAL MIR METRICS GIVE CONSISTENT RESULTS FOR MOST CB4 SPECIES EXCEPT TOL

THE REGIONAL MAXIMUM O3 METRIC DOES NOT GIVE CONSISTENT REACTIVITY RESULTS EKMA-BASED REACTIVITY SCALES ARE REASONABLY CONSISTENT WITH REGIONAL MSE AND MIR METRICS, BUT SOME BIASES EXIST  EKMA SCALES OVERESTIMATE AROMATIC AND FORMALDEHYDE REACTIVITIES (but this needs to be verified using current mechanisms)  EKMA SCALES UNDERESTIMATES REACTIVITIES OF SLOWLY REACTING SPECIES (E.G., ETHANE) PRELIMINARY CONCLUSIONS (CONTINUED)

NEED TO VERIFY THESE CONCLUSIONS WITH ANALYSIS OF FINE GRID DATA NEED TO TEST THE ASSUMPTION THAT THE BASE ROG SENSITIVITIES CAN BE USED TO ESTIMATE SENSITIVITIES TO TOTAL ANTHROPOGENIC VOCs PRELIMINARY CONCLUSIONS FROM 100% ANTHROPOGENIC VOC REMOVAL CALCULATION

 MAXIMUM O3 IS ~70 PPB, BUT ONLY ~10% OF

THE CELLS HAVE O3 > ~5 PPB, 2%>15 PPB.  EFFECT PREDICTED REASONABLY WELL BY DDM EXCEPT SOME CELLS LOW BASE ROG

SENSITIVITY PREDICTED TO HAVE LARGE O3. PRELIMINARY CONCLUSIONS FROM 100% ETHANE SUBSTITUTION CALCULATION ON EFFECT OF ADDING BACK ETHANE AFTER ANTHRO. VOCs REMOVED

 MAXIMUM O3 IS ~8 PPB, BUT ONLY ~10% OF

THE CELLS HAVE O3 > 2 PPB  INCREMENTAL REACTIVITY ANALYSIS PREDICTS

O3 REASONABLY WELL IN ~95% OF THE CELLS PREDICTIONS OF EFFECTS OF “OPTIMUM” SUBSTITUTIONS BASED ON INCREMENTAL REACTIVITY ANALYSIS STILL NEED TO BE TESTED WITH LARGE SCALE SUBSTITUTION CALCULATIONS NEED TO FINALIZE WHICH OF THE LARGE SCALE SUBSTITUTION CALCULATIONS WILL BE CONDUCTED