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The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles basin aerosol

Hersey, S. P. and Craven, J. S. and Schilling, K. A. and Metcalf, A. R. and Sorooshian, A. and Chan, M. N. and Flagan, R. C. and Seinfeld, J. H. (2011) The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles basin aerosol. Atmospheric Chemistry and Physics, 11 (15). pp. 7417-7443. ISSN 1680-7316. https://resolver.caltech.edu/CaltechAUTHORS:20110906-153541149

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Abstract

The Pasadena Aerosol Characterization Observatory (PACO) represents the first major aerosol characterization experiment centered in the Western/Central Los Angeles Basin. The sampling site, located on the campus of the California Institute of Technology in Pasadena, was positioned to sample a continuous afternoon influx of transported urban aerosol with a photochemical age of 1–2 h and generally free from major local contributions. Sampling spanned 5 months during the summer of 2009, which were broken into 3 regimes on the basis of distinct meteorological conditions. Regime I was characterized by a series of low pressure systems, resulting in high humidity and rainy periods with clean conditions. Regime II typified early summer meteorology, with significant morning marine layers and warm, sunny afternoons. Regime III was characterized by hot, dry conditions with little marine layer influence. Regardless of regime, organic aerosol (OA) is the most significant constituent of nonrefractory submicron Los Angeles aerosol (42, 43, and 55 % of total submicron mass in regimes I, II, and III, respectively). The overall oxidation state remains relatively constant on timescales of days to weeks (O:C = 0.44 ± 0.08, 0.55 ± 0.05, and 0.48 ± 0.08 during regimes I, II, and III, respectively), with no difference in O:C between morning and afternoon periods. Periods characterized by significant morning marine layer influence followed by photochemically favorable afternoons displayed significantly higher aerosol mass and O:C ratio, suggesting that aqueous processes may be important in the generation of secondary aerosol and oxidized organic aerosol (OOA) in Los Angeles. Online analysis of water soluble organic carbon (WSOC) indicates that water soluble organic mass (WSOM) reaches maxima near 14:00–15:00 local time (LT), but the percentage of AMS organic mass contributed by WSOM remains relatively constant throughout the day. Sulfate and nitrate reside predominantly in accumulation mode aerosol, while afternoon SOA production coincides with the appearance of a distinct fine mode dominated by organics. Particulate NH_4NO_3 and (NH_4)_2SO_4 appear to be NH_3-limited in regimes I and II, but a significant excess of particulate NH_4^+ in the hot, dry regime III suggests less SO_4^(2−) and the presence of either organic amines or NH_4^+-associated organic acids. C-ToF-AMS data were analyzed by Positive Matrix Factorization (PMF), which resolved three factors, corresponding to a hydrocarbon-like OA (HOA), semivolatile OOA (SV-OOA), and low-volatility OOA (LV-OOA). HOA appears to be a periodic plume source, while SV-OOA exhibits a strong diurnal pattern correlating with ozone. Peaks in SV-OOA concentration correspond to peaks in DMA number concentration and the appearance of a fine organic mode. LV-OOA appears to be an aged accumulation mode constituent that may be associated with aqueous-phase processing, correlating strongly with sulfate and representing the dominant background organic component. Periods characterized by high SV-OOA and LV-OOA were analyzed by filter analysis, revealing a complex mixture of species during periods dominated by SV-OOA and LV-OOA, with LV-OOA periods characterized by shorter-chain dicarboxylic acids (higher O:C ratio), as well as appreciable amounts of nitrate- and sulfate-substituted organics. Phthalic acid was ubiquitous in filter samples, suggesting that PAH photochemistry may be an important SOA pathway in Los Angeles. Aerosol composition was related to water uptake characteristics, and it is concluded that hygroscopicity is largely controlled by organic mass fraction (OMF). The hygroscopicity parameter κ averaged 0.31 ± 0.08, approaching 0.5 at low OMF and 0.1 at high OMF, with increasing OMF suppressing hygroscopic growth and increasing critical dry diameter for CCN activation (D_d). An experiment-averaged κ_(org) of 0.14 was calculated, indicating that the highly-oxidized organic fraction of aerosol in Los Angeles is appreciably more hygroscopic than previously reported in urban areas. Finally, PACO will provide context for results forthcoming from the CalNex field campaign, which involved ground sampling in Pasadena during the spring and summer of 2010.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-11-7417-2011DOIArticle
http://www.atmos-chem-phys.net/11/7417/2011/acp-11-7417-2011.htmlPublisherArticle
ORCID:
AuthorORCID
Metcalf, A. R.0000-0003-0385-1356
Sorooshian, A.0000-0002-2243-2264
Chan, M. N.0000-0002-2384-2695
Flagan, R. C.0000-0001-5690-770X
Seinfeld, J. H.0000-0003-1344-4068
Additional Information:© 2011 Author(s). Published by Copernicus Publications on behalf of the European Geosciences Union. This work is distributed under the Creative Commons Attribution 3.0 License. Received: 3 February 2011. Published in Atmos. Chem. Phys. Discuss.: 18 February 2011. Revised: 16 June 2011. Accepted: 25 June 2011. Published: 1 August 2011. Funding was provided by the Electric Power Research Institute. The authors would like to thank Jason Surratt for his helpful comments and direction. We would also like to thank Eric Edgerton and the SEARCH network for guidance on high-volume filter sampling and for the use of a sampler during PACO. Edited by: M. C. Facchini
Funders:
Funding AgencyGrant Number
Electric Power Research Institute (EPRI)UNSPECIFIED
Issue or Number:15
Record Number:CaltechAUTHORS:20110906-153541149
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110906-153541149
Official Citation:Hersey, S. P., Craven, J. S., Schilling, K. A., Metcalf, A. R., Sorooshian, A., Chan, M. N., Flagan, R. C., and Seinfeld, J. H.: The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles basin aerosol, Atmos. Chem. Phys., 11, 7417-7443, doi:10.5194/acp-11-7417-2011, 2011
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:25236
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:07 Sep 2011 14:38
Last Modified:03 Oct 2019 03:04

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