YIELDS AND REACTIONS OF

INTERMEDIATE COMPOUNDS FORMED

FROM

THE INITIAL ATMOSPHERIC REACTIONS

OF SELECTED VOCs

California Air Resources Board Contract No. 96-306

Roger Atkinson and Janet Arey Co-Principal InvestigatorsMarcia C. Dodge Sub-contracter

William P. HargerPatricia McElroy

Patricia T. Phousongphouang

Air Pollution Research CenterUniversity of CaliforniaRiverside, CA 92521

Sacramento, CAAugust 9, 2002

PROJECT ELEMENT NO. 1:

INVESTIGATION OF

AMBIENT NO3 RADICAL LEVELS

IN THE LOS ANGELES AIR BASIN

DURING THE SCOS97 STUDY

PROJECT ELEMENT NO. 2:

CRC DATA REVIEW PANEL FOR

ATMOSPHERIC CHEMISTRY OF VOCS

PROJECT ELEMENT NO. 3:

CRITICAL REVIEW PAPERS ON

ATMOSPHERIC CHEMISTRY

AND

CHEMICAL KINETIC MECHANISMS

FOR THE

1998 NARSTO OZONE ASSESSMENT

GAS-PHASE CHEMICALS

Major Atmospheric Loss Processes Are:

• Photolysis

• Reaction with Hydroxyl (OH) Radical(during daylight hours)

• Reaction with Nitrate (NO3) Radical(during nighttime hours)

• Reaction with Ozone (O3)

OH Radical - Daytime ubiquitous

O3 + hν → O* + O2

O* + H2O → 2OH

NO3 Radical - Nighttime, no NO

O3 + NO2 → NO3 + O2

NO3 + NO2 ↔ N2O5

NO3 + hν → NO2 + O (photolyzes during day)

NO3 + NO → 2NO2 (reacts with vehicle NO)

Coastal plain bounded by inland mountains inthe presence of a strong temperature inversion.

From: Lu and Turco (1994) J. Atmos. Sci., Vol.

51, p. 2306.

Pine

Mt.

PER

C/A

zusa

PER

C

0.0

0.2

0.4

0.6

0.8

PDT

Ozo

ne (p

pbv)

0

20

40

60

80

100

120O3 Azusa O3 Pine Mtn.

NO

x at A

zusa

(ppb

v)

0

20

40

60

80NO NO2

20 24 04 08 12 16 20 24 04 08 12 16 20 24 04 08

20 24 04 08 12 16 20 24 04 08 12 16 20 24 04 08

17-2

0

20-2

4

00-0

303

-06

06-0

909

-12

13-1

6

17-2

0

20-2

4

00-0

303

-06

06-0

909

-12

13-1

6

17-2

0

20-2

4

00-0

303

-06

06-0

9

Sept. 4-7, 1997

NOx and O3transportedto elevatedsite

Elevated siteisolatedfrom NO

Evening:

At Azusa: O3 + NO → NO2 + O2

In Inversion layer: NO2 + O3 → NO3 + O2

Isop

rene

(ppb

v)

0.0

0.4

0.8

1.2

1.6

2.0

α-P

inen

e (p

ptv)

0

5

10

15

20

25

30Isoprene α−Pinene

MAC

R, M

VK (p

pbv)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

PER

C, 1

0 x

Cam

phor

(ppt

v)

0

50

100

150

200

250

300MACR MVK Camphor PERC

PDT

17-2

0

20-2

4

00-0

303

-06

06-0

909

-12

13-1

6

17-2

0

20-2

4

00-0

303

-06

06-0

909

-12

13-1

6

17-2

020

-24

00-0

303

-06

06-0

9

17-2

0

20-2

4

00-0

303

-06

06-0

909

-12

13-1

6

17-2

0

20-2

4

00-0

303

-06

06-0

909

-12

13-1

6

17-2

0

20-2

4

00-0

303

-06

06-0

9

Pine Mountain - Sept. 4-7, 1997

Ozo

ne (p

pbv)

0

40

80

120

160O3 AzusaO3 Mt. Baldy

NO

2 M

t. Ba

ldy

(

ppbv

)

0

4

8

12 NO2 Mt. Baldy

04 08 12 16 20 24 04 08 12 16 20 24

Sept. 28-29, 1997

Gas-Phase Polycyclic Aromatic Compounds

Major Atmospheric Loss Processes Are:

• Photolysis

Important for nitro-PAHs

MNNs: τ = 0.1 - 3 hrs

• Reaction with OH Radical

τ < 1 day for most PAHs

C1- and C2- Alkylnaphthalenes τ = 2-4 hrs

• Reaction with NO3 Radical

Forms nitro-PAHs in high yields

• Reaction with O3

only for e.g., τ = 2.5 hrs

CH3

NO2

Nitro-PAH can serve as unique markers of

OH radical and NO3 radical reactions.

NO2

NO2

NO2

NO2

NO2 NO2

1-NP

electrophilic

2-NP

OH rxn. (0.5% yield)

4-NP

NO3 rxn. (trace)

3-NF

electrophilic

2-NF

OH rxn. (3% yield)

2-NF

NO3 rxn. (24% yield)

20

80

60

40

20

80

60

40

20

80

60

40

39 4443413837 4240 45

Time (min)

Abu

ndan

ce

1NF

2NF

3NF4NP

8NF1NP

2NP

7NF

3NF

8NF

1NP

Standard

Ambient

Diesel

2NP

2NF

[M]+ = 247

OH Radical ChemistryDaytime

Torrance, CA

NO3 Radical ChemistryNighttime

Claremont, CA

Diesel Particles

Ambient PAH Concentrations (ng/m3)

PAH SamplingMedia

VehicleTrafficImpacted

WoodSmokeImpacted

IndustrialEmissions

Naphthalene Tenax 4,800 1,400 4,600

1-Methylnaph. Tenax 390 210 370

2-Methylnaph. Tenax 730 340 780

Phenanthrene Tenax 51 230 79

Fluoranthene PUF(filter) 6.2 (0.3) 16 (30) 18 (0.5)

Pyrene PUF(filter) 5.5 (0.3) 12 (30) 16 (0.6)

B[a]P Filter 1.5 8 4.2

B[e]P Filter 0.6 12 6.2

CHOH

CH=CHCHO

H OH

H OHH

NO2

H OHH

O

OH

NO2

CH=CHCHO

CHO

OH +

O2

HO2 +

-H2O-HONO

+

H

OH

NO2NO2 O2 , NO (and other

pathways)

H

OH

O2

OO

O2 , NO

H

OH

H O

OO

+ HC(O)CHOH

(CHO)2 + HO 2

O2

CHO

CHO

20

80

60

40Abu

ndan

ce

4744 4645 48

Time (min)

49 50

2-EN

2,6-DMN

1,6-DMN 1,3-DMN

1,7-DMN

2,3-DMN

1,4-DMN

2,7-DMN

1,5-DMN

1,2-DMN

1-EN

1,8-DMN

Riverside, CA Nighttime Tenax Sample

GC/MS-SIM Analysis for

Dimethyl- and Ethyl-naphthalenes

H ONO2

NO3 +

H ONO2

H

NO2 H O

OH OH

NO2

NO2

+ NO2

+ HNO3

NO2 O2k NO2 k O2

(and other isomer)

Naphthalene + OH ProductsM

olar

Yie

ld (%

)

0

10

20

30

40

Naphthalene + NO3 Products

Mol

ar Y

ield

(%)

0

10

20

30

40

NNs HNNs Dione

ring-opened

Epox OLs decomp NNs HNNs Dione

NO2

NO2

O

O

OH

NO2

OH

O

OHH

H

H

O

CHO

CH=CHCHO

CHO

CHO

Methylnitronaphthalenes (MNNs)

from OH and NO3 Radical Reactions

OH

NO3 2M4NN

1M5NN

1M4NN+

1M6NN

2M1NN 1M3NN

OH Rxn.

Azusa Day

Azusa Night

2M1NN

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

1M8NN

2M1NN

1M4NN

1M2NN

1M3NN

1M6NN

2M6NN

2NN

1NN

2M8NN

1M5NN

2M4NN

2M5NN

6

10

22

31

71

88

133

177

24

31

38

41

49

NO2 on C1 NO2 on C2 Lifetime (min) Lifetime (min)

Calculated Photolysis Lifetimes (min) ofNitronaphthalenes & Methylnitronaphthalenes

NO3 Rxn.

Azusa Night

2M4NN

Banning Night

2M1NN 1M3NN

MAP SHOWING AZUSA,RIVERSIDE, MOUNTAIN SITESAND BANNING

Riverside Night

Azusa Night

Banning Night

Nitro-PAH Markers of OH Radicaland NO3 Radical Reactions

PAH OH Rxn. NO3 Rxn.

Naphthalene 1-NN (1%)2-NN (1%)

1-NN (24%)2-NN (11%)

1-Methyl-Naphthalene

1M5NN1M4+6NNΣ MNNs 0.4%

1M3NNΣ MNNs 30%

2-Methyl-Naphthalene

2M5NNΣ MNNs 0.2%

2M4NN2M1NNΣ MNNs 30%

Biphenyl 3-NBPh (5%) No rxn.

Banning NightAzusa Day

m/z 173

m/z 187MNNs

m/z 187MNNs

m/z 173

m/z 199

m/z 199

3-NO2-biphenyl

3-NO2-biphenyl

1M5NN

2M4NN

1NN

2NN1NN

2NN

NO3 +

H ONO2

O2kc kdke

ka

kb

Products ProductsProducts

H

kobs = kakc[NO2]/(kb + kc[NO2]) k akc [NO2]

kb=

(including nitro-products)

NO2

when kb >> kc[NO2]

2-MN kobs = 1 x 10-27 cm-6 molecule-2 s-1

Yield 2M4NN = 0.1[2-MN] = 60 ng/m3

[2M4NN] = 0.3 ng/m3

t = 2.2 x 104 s

k akc [NO2] kb

= [2M4NN] Yield [NO3] [2-MN] t

[NO2] [NO3] = 2.3 x 1021 molecule2 cm-6

Assume [NO2] = 10 ppbv, then [NO 3] = 1 x 1010molecule cm-3

[NO2]

OH

NO3

Dimethylnitronaphthalenes (DMNNs)from OH and NO3 Radical Reactions

of Volatilized Diesel Fuel

OH Rxn

20.00

Azusa

Dimethylnitronaphthalenes (DMNNs)from OH Reaction of Volatilized Diesel Fuel

and Ambient Sample from Azusa

Ambient NighttimePUF sample

Redlands, CA

Chamber NO3Radical Reaction

CH3

NO2

Vapor Phase Mutagrams - Redlands, CA

1 2 3 4 5 6 7 8 9

Rev

erta

nts

per c

ubic

met

er

0

5

10

15

20

1 2 3 4 5 6 7 8 9

Rev

erta

nts

per c

ubic

met

er

0

5

10

15

20

Day23 Rev m-3

Night31 Rev m-3MNNs

1NN + 2NN

MNNs

1NN + 2NN

HPLC Fraction NumberIncreasing Polarity

ACKNOWLEDGEMENTS

Patricia Phousongphouang

Fabienne Reisen

Pamela Gupta

Jennifer Sasaki

Eric Kwok

EPA SUPERSITE

DOE

1 2 3 4 5 6 7 8 9

Rev

erta

nts

per c

ubic

met

er

0

20

40

60

80

100

Ambient Mutagrams - Claremont, CA

1 2 3 4 5 6 7 8 9

Rev

erta

nts

per c

ubic

met

er

0

20

40

60

80

100

HPLC Fraction NumberIncreasing Polarity

Vapor Phase210 Rev m-3

Particles160 Rev m-3

CH3

NO2

NO2

O

NO2

O

NO2

O

NO2

O

O

O

NO2