Atmospheric Chemistry and Physics Discussions
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2010
10.5194/acpd-10-657-2010
http://www.atmos-chem-phys-discuss.net/10/657/2010/
http://www.atmos-chem-phys-discuss.net/10/657/2010/acpd-10-657-2010.html
http://www.atmos-chem-phys-discuss.net/10/657/2010/acpd-10-657-2010.pdf
657
710
2010-01-14
Potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol in the Mexico City region
A. Hodzic
alma@ucar.edu
J. L. Jimenez
S. Madronich
M. R. Canagaratna
P. F. DeCarlo
L. Kleinman
J. Fast
National Center for Atmospheric Research, Boulder, CO, USA
Dept. of Chemistry and Biochemistry, and CIRES, Univ. of Colorado, Boulder, CO, USA
Aerodyne Research, Billerica, MA, USA
Dept. of Atmospheric and Oceanic Science, Univ. of Colorado, Boulder, CO, USA
Brookhaven National Laboratory, Upton, New York, USA
Pacific Northwest National Laboratory, Richland, WA, USA
now at: Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, Villigen, Switzerland
It has been established that observed local and regional levels of
secondary organic aerosols (SOA) in polluted areas cannot be explained
by the oxidation and partitioning of anthropogenic and biogenic VOC
precursors, at least using current mechanisms and
parameterizations. In this study, the 3-D regional air quality model
CHIMERE is applied to quantify the contribution to SOA formation of
recently identified semi-volatile and intermediate volatility organic
vapors (S/IVOC) in and around Mexico City for the MILAGRO field
experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA),
their gas-particle partitioning and the gas-phase oxidation of the
vapors. Two recently proposed parameterizations, those of Robinson et
al. (2007) ("ROB") and Grieshop et al. (2009) ("GRI") are
compared and evaluated against surface and aircraft measurements. The
3-D model results are assessed by comparing with the concentrations of
OA components from Positive Matrix Factorization of Aerosol Mass
Spectrometer (AMS) data, and for the first time also with
oxygen-to-carbon ratios derived from high-resolution AMS measurements.
<br><br>
The results show a substantial enhancement in predicted SOA concentrations
(3–6 times) with respect to the previously published base case without
S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading
to much reduced discrepancies with the total OA measurements. The predicted
anthropogenic POA levels are found to agree within 20% with the observed
HOA concentrations for both the ROB and GRI simulations, consistent with the
interpretation of the emissions inventory by previous studies. The impact of
biomass burning POA within the city is underestimated in comparison to the
AMS BBOA, presumably due to insufficient nighttime smoldering emissions.
Model improvements in OA predictions are associated with the better-captured
SOA magnitude and diurnal variability. The predicted production from
anthropogenic and biomass burning S/IVOC represents 40–60% of the total
SOA at the surface during the day and is somewhat larger than that from
aromatics, especially at the T1 site at the edge of the city. The SOA
production from the continued multi-generation S/IVOC oxidation products
continues actively downwind. Similar to aircraft observations, the predicted
OA/ΔCO ratio for the ROB case increases from
20–30 μg sm<sup>−3</sup> ppm<sup>−1</sup> up to
60–70 μg sm<sup>−3</sup> ppm<sup>−1</sup> between a fresh and 1-day aged air
mass, while the GRI case produces a 30–40% higher OA growth than
observed. The predicted average O/C ratio of total OA for the ROB case is
0.16 at T0, substantially below observed value of 0.5. A much better
agreement for O/C ratios and temporal variability (<i>R</i><sup>2</sup>=0.63) is
achieved with the updated GRI treatment. Both treatments show a deficiency in
regard to POA evolution with a tendency to over-evaporate POA upon dilution
of the urban plume suggesting that atmospheric HOA may be less volatile than
assumed in these parameterizations. This study highlights the important
potential role of S/IVOC chemistry in the SOA budget in this region, and
highlights the need for improvements in current parameterizations. We note
that our simulations did not include other proposed pathways of SOA formation
such as formation from very volatile species like glyoxal, which can also
contribute SOA mass and especially increase the O/C ratio.
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