Olivia Clifton University of Wisconsin-Madison

ANs are produced photochemically through oxidation of their parent hydrocarbons } Typically, ANs < 10% NOy
} }

Reservoir species for long-range transport of NOx and thus promote ozone production

ANs have low reactivity compared to other components of NOy

n-pentane

2-pentyl nitrate (2-PeONO2) 3-pentyl nitrate (3-PeONO2)

isopentane

3-methyl-2-butyl nitrate (3-Me-2-BuONO2)

Modeling time evolution of daughter alkyl nitrates to parent hydrocarbons in an air mass Mixing ratios of sister alkyl nitrates can be related to look at measured ratio = predicted ratio
Flocke et al., 1998 Bertman et al., 1995

Want to find an indicator species of oil fields

Why ANs?

Natural gas and oil boom in the last ten years Legislation passed by President Obama on April 18, 2012 setting a cap on VOC emissions from natural gas and oil facilities Time evolution, air mass aging Reservoir species of NOx Why C5s?

Looking at the ratio of sister alkyl nitrates cannot be applied to alkyl nitrates <C4 because they are formed from the decomposition of the other (Flocke et al., 1998) Ratio of isopentane to n-pentane is ~2.5 to 1

Predicted ratio: 0.685

STEP 1 STEP 2

RH + OH R + O2

R + H2O RO2

STEP 3 can go in two directions

a) b)

RO2 + NO RO + NO2 RO2+ NO RONO2

 Photolysis RONO2 + hv RO + NO2 Reaction with OH RONO2 + OH products

3-Me-2-BuONO2 vs. 2- + 3- PeONO2

3-Me-2-BuONO2 vs. 2- + 3- PeONO2

STEP 1 STEP 2

RH + OH R + O2

R + H2O RO2

k1, 1 k2

STEP 3 can go in two directions

a) b)

RO2 + NO RO + NO2 RO2+ NO RONO2

k3a (1 2) k3b, 2

 Photolysis RONO2 + hv RO + NO2 Reaction with OH RONO2 + OH products

JRONO2

k4

Simplification

(Bertman et al., 1995)

kA = k1[OH] kB = JRONO2 + k4[OH] = 1 2

}

RH RONO2 kA, RONO2 products kB

Now, we can use [RONO2]/[RH] = kA (1 e(kA- kB)t)/ (kB kA)

J(h) =

JRONO2

I = solar flux intensity

() I (h,) d

Solar zenith angle = 30

= absorption cross section > 295 nm

Actintic flux values at Earths surface Finlayson-Pitts and Pitts, 2000 Average of absorption cross section of i-PeONO2 and 1PeONO2 (Simpson et al., 2003)

Los Angeles area, 10 am, 6/26/12

kB = JRONO2 + k4[OH]
3-Me-2-BuONO2 2-PeONO2 3-PeONO2
k4 = 1.72 x 10-12 cm3 molecules-1 s-1 k4 = 1.85 x 10-12 cm3 molecules-1 s-1 k4 = 1.12 x 10-12 cm3 molecules-1 s-1

Room temperature, Atkinson et al., 1990 Estimated [OH] = 8.8 x 105 molecules cm-3
Simpson et al., 2003

kA = k1 [OH]
k1
3-Me-2-BuONO2: k1 = ksecondary F(CH) F(CH3) 2-PeONO2: k1 = ksecondary F(CH2) F(CH3) 3-PeONO2: k1 = ksecondary F(CH2) F(CH2) Atkinson, 1987a F(X) = eEx/t
Kwok and Atkinson, 1995

[OH] = 8.8 x 105 molecules cm-3

Average temperature over oilfields: 293 K

[parent alkane]0 = [parent alkane]/ e-k t

A

[parent alkane]0= Average mixing ratio of the parent alkane } Two sets of data
}

Mixing ratios averaged for air samples over oil fields Mixing ratios averaged for air samples not over oil fields

= 12

1 = k1/ktotal

ktotal is the sum of each rate constant for OH removing a H from each of the carbons in an alkane isopentane
ktotal = kprimaryF(CH2) + kprimaryF(CH) + ksecondaryF(CH)F(CH3) + ktertiaryF(CH2)F(CH3)F(CH3) + kprimaryF(CH) k is temperature dependent

Atkinson et al., 1987b

Measured slope: 0.44 <- Modeled slope: 0.47

Measured slope: 0.68 Modeled slope: 0.84 ->

Measured slope and predicted slope are very close

Legitimate model for air mass aging Distinguishing oil fields and non-oil fields
Lagrangian experiment: finding a plume and tracking it

We still dont know what is going on with the LAX R1 air samples

Gregory Hartt } Dr. Don Blake } Dr. Emily Schaller } WAS Group } Rowland-Blake Group } Mr. Rick Shetter } P-3 Crew and NSERC Engineers } SARP 2012
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Atkinson, R. (1990). Gas-Phase Tropospheric Chemistry of Organic Compounds: A Review. Atmospheric Environment, 24A(I), 1-41. Atkinson, R., & Arey, J. (2003). Atmospheric degradation of volatile organic compounds. Chemical reviews, 103(12), 4605-38. Atkinson, R. (1987a). A Structure-Activity Relationship for the Estimation of the Rate Constants for the Gas-Phase Reactions of OH Radicals with Organic Compounds. 19, 799-828. Atkinson, R. et al. (1987b). Alkyl Nitrate Formation from the Reaction of a Series of Branched RO2 Radicals with NO as a Function of Temperature and Pressure. Journal of Atmospheric Chemistry, 5(1), 91-102. Atkinson, R. (1997). Gas-Phase Tropospheric Chemistry of Volatile Organic Compounds: 1. Alkanes and Alkenes. Journal of Physics and Chemistry Reference Data, 26, 215-290. Bertman, S. et al. (1995). Evolution of alkyl nitrates with air mass age. Journal of Geophysical Research, 100(D11), 22, 805-822, 813. Clemitshaw, K.C., et al. (1997). Gas-phase ultraviolet absorption cross-sections and atmospheric lifetimes of several C2-C5 alkyl nitrates. Journal of Photochemistry and Photobiology A: Chemistry, 102(2-3), 117-126. Finlayson-Pitts, B.J., and J.N. Pitts, Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications, 969 pp., Academic, San Diego, Calif., 2000. Kwok, E.S., & Atkinson, R. (1995). Estimation of Hydroxyl Radical Reaction Rate Constants for Gas-Phase Organic Compounds Using a Structure-Reactivity Relationship: An Update. Atmospheric Environment, 29(14), 1685-1695. Roberts, J.M. (1990). Chemistry of Organic Nitrates, 24(2), 243-287. Roberts, J.M., & Fajer, R.W. (1989). UV Absorption Cross Sections of Organic Nitrates as Potential Atmospheric Importance and Estimation of Atmospheric Lifetimes, (13), 945-951. Simpson, I.J. (2003). Photochemical production and evolution of selected C2-C5 alkyl nitrates in tropospheric air influenced by Asian outflow. Journal of Geophysical Research, 108(D20). Turberg, M.P. et al. (1990). Atmospheric Photochemistry of Alkyl Nitrates. Journal of Photochemistry and Photobiology, 51, 281-292. Talukdar, R.K. et al. (1997). Atmospheric fate of several alkyl nitrates, 93(16), 2797-2805. Worton, D.R. et al. (2010). Alkyl nitrate photochemistry during the tropospheric organic chemistry experiment. Atmospheric Environment, 44(6), 773-785.