Determination of OH

Concentration in San
Joaquin Valley
Benjamin Nault
SARP 2010
Senior Chemistry Major,
Purdue University
Why San Joaquin Valley?

  Valley has multiple issues from emissions,

topography, agriculture, climate and
population growth

  Valley has been tagged as a non-attainment

area for PM2.5, PM10, and hourly O3
Why OH radical?

  OH radical is said to be the detergent of the

atmosphere
  OH radical is the initial step for oxygenating
hydrocarbons
  How OH is made
  O3 + hv  O(1D) + O2
  O(1D) + H2O  2OH•
  Photolysis of aldehydes (e.g., formaldehyde)
  O3 reaction with alkenes
Simple Reaction Schemes (Atkinson 2000)

  OH• + RH  R• + H2O
  R• + O2  RO2 •
  RO2 • + NO  RO • + NO2
  RO • + O2  carbonyl + HO2
  HO2 + NO  OH • + NO2

  Net: OH • + RH + 2NO  carbonyl + 2NO2 + OH •

  NO2 + hv  NO + O(3P)
  O(3P) + O2 + M  O3 + M
Experimental Procedure

  Two flights in DC-8

  June 29, 2010 and July 1, 2010
  Only used data below 5000 pressure feet
  Collect samples every 2 minutes in 2 liter
evacuated canisters to a pressure of 40 PSIG
Experimental Procedure, cont.

  Two different analysis used for data

Analysis of Chromatograms

  Draw in baselines
  Find area of standard (of known mixing ratio
(MR))
  Response Factor (RF) = areastnd/MRstnd

  Find area of sample

  MRsample = Areasample/RF
Analysis for other necessary parameters

  Went to CARB website (www.arb.ca.gov)

  Temperature data from Eric

Determined Values for other Parameters

June 29 Flight July 1 Flight

Average 303.6(±2.9)K 299.5(±3.7)K

Temperature

Average [O3] 58.9(±9.4)ppb 55.5(±15.7)ppb

1.32x1012 molec/ 1.26x1012 molec/
cm3 cm3
Methodology of determining [OH]

  Fully described in Jobson et al., 1998, 1999,

Williams et al., 2000, Karl et al., 2001 and
Bartenbach et al., 2007

  Junge 1974: RSD = 0.14/ τ

  τ = 1/e = 1/kI[i]*time

  σ(ln(xi)) = A* τ i-b
Determination of [OH]

  Plotted σ(ln(xi)) versus lifetime (τ) in days

  τ = 1/([OH]*kOH,i*86400 s + hv*86400 s)
  τ = 1/([OH]*kOH,i*86400 s + hv*86400 s +
[O3]*kO3,i*86400 s)
  Rate constants from Karl et al., 2001,
Atkinson 2003, Atkinson and Arey 2003,
Martinez et al.,1992, and Atkinson et al.,
2006.
Example of a graphs
Results and Analysis

06/29 Flight 07/01 Flight

[OH] 2.5x106 molec/cm3 2x106 molec/cm3

R2 0.290363 0.367349
F test 5.73 > Fcrit,95 4.60 8.71 > Fcrit,95 4.54
 Discussion—Comparison (σ(ln(x))=A*τ-b
A b
06/29 Flight 0.56±1.10 0.17±0.07
07/01 Flight 0.56±1.13 0.23±0.08
Boulder (Jobson 3.04±0.24 0.28±0.02
1998)
Hohenpessenburg 0.48±0.06 0.24±0.06
(Bartenbach 2007)
PEM-West B (Williams 4.3±0.6 0.53±0.02
2000)
  Only measurement: ~1x107 molec./cm3 (0.44 pptv)
Data from Brune, PSU, 2008 ARTCAS
Conclusion

  To my knowledge, first [OH] estimated in San

Joaquin Valley

  Determined [OH] were 2.5x106 and 2 x106

molec/cm3

  Most compounds lost through transportation

  Relatively well mixed

Future Work

  Have [O3] and [NOx] measured during flight

  In situ measurements of OH for the San

Joaquin Valley

  Try other methods to determine [OH]

Acknowledgements

  Professor Don Blake

  Matthew Gartner
  Eric Buzay
  Grad Mentors
  Blake/Rowland Group
  Air Group
  Rick Shetter
  Jane Peterson
  Speakers
  DC-8 Flight Crew
References
  Atkinson, R. Atmospheric chemistry of VOCs and NOx. Atmos. Environ., 2000, 34, 2063 – 2101.
  Atkinson, R. Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes.
Atmos. Chem. Phys., 2003, 3, 2233 – 2307.
  Atkinson, R., et al. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume
II – gas phase reactions of organic species. Atmos. Chem. Phys., 2006, 6, 3625 – 4055.
  Atkinson, R. and J. Arey. Atmospheric degradation of volatile organic compounds. Chem. Rev.,
2003, 103, 4605 – 4638.
  Bartenbach, S., et al. In-situ measurements of reactive hydrocarbons at Hohenpeissenberg with
comprehensive two-dimensional gas chromatography (GCxGC-FID): use in estimating HO and
NO3. Atmos. Chem. Phys., 2007, 7, 1 – 14.
  California Environmental Protection Agency Air Resource Board.
  Jobson, B. T., et al. Spatial and temporal variability of nonmethane hydrocarbon mixing ratios
and their relation to photochemical lifetime. J. Geophys. Res., 1998, 103, 13,557 – 13,567.
  Karl, T., et al. Variability-lifetime relationship of VOCs observed at the Sonnblick Observatory
1999—estimation of HO-densities. Atmos. Environ., 2001, 35, 5287 – 5300.
  Jobson, B. T., et al. Trace gas mixing ratio variability versue lifetime in the troposphere and
stratosphere: Observations. J. Geophys. Res., 1999, 104, 16,091 – 16,113.
  Junge, C. E. Residence time and variability of tropospheric trace gases. Tellus, 1974, 26, 477 –
488.
  Martinex, R. D., et al. The near U.V. absorption spectra of several aliphatic aldehydes and
ketones at 300K. Atmos. Environ., 1992, 26A, 785 – 792.
  Williams, J., et al. Variability-lifetime relationship for organic trace gases: A novel aid to
compound identification and estimation of HO concentrations. J. Geophys. Res., 2000, 105,
20,473 – 20,486.
Questions?
Extra Material
Checked for other radical chemistry

  Jobson 1994
Derivation of Jobson Method (Jobson
1998)
  At low variability, σ(ln(xi)) = RSD, but for high
variability, σ(ln(xi)) gives simpler behavior

  ln(Xi/Xi0) = - t / τ

  σ y2 = (δ/ δt ln(Xi/Xi0))2 σ t2 = (- t / τ)2 σ t2

  σ y = σ(ln(xi)) = (1/ τ) * σ t
Other Plots
Lifetime
4000000
10.84837 Ethane (E)
0.32252 Ethene (E)
2.526291 Propane (B/E)
0.097568 Propene (E)
1.32801 i-Butane (B/E)
1.188886 n-Butane (B/E)
0.616576 n-Pentane (B/E)
0.541654 n-Hexane (E)
2.343097 Benzene (E)
0.184381 Acetaldhyde
8.711211 Acetone
0.616576 i-Pentane
0.541654 2-Methylpentane

0.541654 3-Methylpentane

0.528785 Toluene

12.05633 CO