PhotochemicalPropertiesof

C1C5AlkylNitratesinthe
LosAngelesBasin

Advisor:Dr.DonBlake
Mentor:JulieLee

EvanJohnson

UniversityofCalifornia,LosAngeles

WhatAreAlkylNitrates?
Organicnitratesthatcanbefoundintroposphericair
Representasmallbutsignicantpartofthe

troposphericreactivenitrogenpool(NOY)

WhystudyAlkylNitrates?
Naturalindicatorsoftropospheric
ozoneproduction
Indicatorsofphotochemicalsmog
Normallyassociatedwithpollutedair

AlkylNitratesandSources
MethylNitrate(MeONO2)
FormedfromareactionwithMethane(CH4)
EthylNitrate(EtONO2)
FormedfromareactionwithEthane
PropylNitrate(iPrONO2,nPrONO2)
FormedfromareactionwithPropane
ButylNitrate(2BuONO2)
FormedfromareactionwithButane
PentylNitrate(2PeONO2,3PeONO2)
FormedfromareactionwithPentane

Objec9ve
AnalyzetheconcentrationsoftheC1C5alkyl

nitratesalongtheightpathfortheLAXmissed
approach
Usealkylnitratesasabasisfordeterminingtheageof
theair
Determinethesourceofeachalkyl
nitrate
Geographicallocation
Specicsource

Photochemistry
Chemicalreactionsthatoccurundertheinuenceof

visibleorultravioletlight

Alkylnitratesaretheproductsofphotochemical

reactions

AlkylNitrateFormation
Minor Pathway
Major Pathway

RONO2

RO

Alkyl Nitrate

NO2+h

NO
OH

RH

Hydrocarbon

H 2O

O2

ROO

ROOR

NO + O(3P)

NO

Alkylperoxy
radical

ROO.

HO2

O2
ROOH

O3

M + NO2
ROONO2

Methods
Samplescollected

alongtheLAX
MissedApproach
Thursday,June
30,2011
HighResolution
Samples

36.0

34.0

32.0

28.0

26.0

24.0

20.0

18.0

16.0

12.0
10.45.79
6.00
6.20
6.40
6.60
6.80
16* - EtONO2 (D) - 6.984
17* - CFC-112 (D) - 7.042

30.0

22.0

7.00
7.20
7.40
7.60
7.80
8.00
8.20
8.40
8.60
8.80
9.00
9.20
9.40
9.60

33* - 3-PeONO2 (D) - 9.978

34 - 2-PeONO2 (D) - 10.066

32* - 3-Methyl-2-BuONO2 (D) - 9.717

29 - 9.363

28* - CHBr2Cl (D) - 9.220

27 - 2-BuONO2 (D) - 8.829

25* - C2Cl4 (D) - 8.543

21* - CH2Br2 (D) - 7.822

22* - CHBrCl2 (D) - 7.901

19* - i-PrONO2 (D) - 7.609

23* - n-PrONO2 (D) - 8.169

24* - CH2ClI (D) - 8.198

30 - 9.518
31 - 9.582

38.0

26* - 8.579

40.0

15* - CHCl3 (D) - 6.691

46.6 mV

18* - C2HCl3 (D) - 7.354

42.0

13* - MeONO2 (D) - 5.931

44.0

14* - 5.998

Chromatography

14.0

min
9.80 10.00

TheTheory
Theageofanairmasscanbeestimatedbypentyl

nitratemixingratios

Ratioof3pentylnitrateto2pentylnitrate
Slopeoflineusedasrelativemeasurement

Basedupontheageoftheair,wecansuggestpossible

sources

Life9meofAlkylNitrates

Methane

MethylNitrate

Ethane

EthylNitrate

Pentane

PentylNitrate

Rela9onshipof3Pentyland
2PentylNitrate
3PentylNitratevs.2PentylNitrate

Verystrong

Rsquared

valueof.99

y=0.52x+0.0969
R=0.9935

10.0
3PentylNitrate

linear
relationship

12.0

8.0
6.0
4.0
2.0
0.0
0.0

5.0

10.0

15.0

2PentylNitrate

20.0

25.0

1stSetofPoints

Methanevs.Time

Slope=0.51x
Indicatesrelativelyyoungair

MethanePPM

LocatedoverOntarioAirport

1.95
1.90
1.85
1.80
22:55:12 23:02:24 23:09:36 23:16:48 23:24:00 23:31:12
Time(Military)

3Pentylvs.2PentylNitrateMixingRatio
4.0

y=0.51x+0.1483
R=0.95

3PentylNitrate

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.0

1.0

2.0

3.0

4.0
2PentylNitrate

5.0

6.0

7.0

8.0

2ndSetofPoints
Slope=0.51x
Indicatesrelativelyyoungair

1.95
MethanePPM

JustbeforeLAX

Methanevs.Time
1.90
1.85
1.80
22:55:12 23:02:24 23:09:36 23:16:48 23:24:00 23:31:12
Time(Military)

3PentylNitratevs.2PentylNitrate
12.0

y=0.51x+0.1502
R=0.99

3PentylNitrate

10.0
8.0
6.0
4.0
2.0
0.0
0.0

5.0

10.0

15.0

2PentylNitrate

20.0

25.0

3rdSetofPoints
LAXmissedapproach
Slope=0.55x
Indicatesrelativelyolderair

1.95
MethanePPM

Justocoastfollowing

Methanevs.Time
1.90
1.85
1.80
22:55:12 23:02:24 23:09:36 23:16:48 23:24:00 23:31:12
Time(Military)

3PentylNitratevs.2PentylNitrate
4.0

y=0.55x0.0248
R=0.90

3PentylNitrate

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.0

1.0

2.0

3.0

4.0

2PentylNitrate

5.0

6.0

7.0

Conclusion
Alkylnitratesareindicatorsofphotochemicalsmog

andozone
Itispossibletopredicttheageofanairmassbased
uponthepentylnitratemixingratio
AlkylnitratesdisplayinterestingtrendsintheLos
Angelesbasin
Wecancombinechemicallyagedairwith
meteorologicaltrajectoriestoidentifysourcesofalkyl
nitratesinair

Acknowledgements
Dr.DonBlake
JulieLee
Dr.EmilySchaller
Dr.RickShetter
TheAirTeam
NASADC8Crew

References
Blake,N.J.,D.R.Blake,A.Swanson,E.Atlas,F.Flocke,andF.S.Rowland

Latitudinal,Vertical,andSeasonalVariationsofC1C4AlkylNitratesintheTroposphereoverthe
PacicOceanduringPEMTropicsAandB:OceanicandContinentalSources
JournalofGeophysicalResearch,108,(D2),8242,doi:10.1029/2001JD001444,2003.
Simpson,I.J.,F.Flocke,E.Atlas,F.S.Rowland,S.Meinardi,T.Wang,H.Guo,Y.H.Kwok,andD.R.
Blake,CommentonLongtermatmosphericmeasurementsofC1C5alkylnitratesinthePearlRiver
DeltaregionofsoutheastChinabyArchibaldetal."Atmos.Environ.,2007,inpress.
Simpson,I.J.,N.J.Blake,D.R.Blake,E.Atlas,F.kFlocke,J.H.Crawford,H.E.Fuelberg,C.M.Kiley,
S.Meinardi,andF.S.Rowland
PhotochemicalProductionandEvolutionofSelectedC2C5AlkylNitratesinTroposphericAir
InuencedbyAsianOutowJournalofGeophysicalResearch,108,8808,(D20),
DOI10.1029/2002JD002830,2003

Ques%ons?