Atmospheric Chemistry and Physics
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2006
10.5194/acp-6-5649-2006
http://www.atmos-chem-phys.net/6/5649/2006/
http://www.atmos-chem-phys.net/6/5649/2006/acp-6-5649-2006.html
http://www.atmos-chem-phys.net/6/5649/2006/acp-6-5649-2006.pdf
5649
5666
2006-12-19
Cluster Analysis of the Organic Peaks in Bulk Mass Spectra Obtained During the 2002 New England Air Quality Study with an Aerodyne Aerosol Mass Spectrometer
C. Marcolli
claudia.marcolli@env.ethz.ch
M. R. Canagaratna
D. R. Worsnop
R. Bahreini
J. A. de Gouw
C. Warneke
P. D. Goldan
W. C. Kuster
E. J. Williams
B. M. Lerner
J. M. Roberts
J. F. Meagher
F. C. Fehsenfeld
M. Marchewka
S. B. Bertman
A. M. Middlebrook
Institute for Atmospheric and Climate Science, ETH Zurich, Switzerland
Aerodyne Research Incorporated, Billerica, Massachusetts, USA
National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Chemical Sciences Division, Boulder, Colorado, USA
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA
Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, USA
We applied hierarchical cluster analysis to an Aerodyne aerosol mass
spectrometer (AMS) bulk mass spectral dataset collected aboard the NOAA
research vessel R. H. Brown during the 2002 New England Air Quality
Study off the east coast of the United States. Emphasizing the organic
peaks, the cluster analysis yielded a series of categories that are
distinguishable with respect to their mass spectra and their occurrence as a
function of time. The differences between the categories mainly arise from
relative intensity changes rather than from the presence or absence of
specific peaks. The most frequent category exhibits a strong signal at <i>m/z</i> 44
and represents oxidized organic matter probably originating from both
anthropogenic as well as biogenic sources. On the basis of spectral and
trace gas correlations, the second most common category with strong signals
at <i>m/z</i> 29, 43, and 44 contains contributions from isoprene oxidation products.
The third through the fifth most common categories have peak patterns
characteristic of monoterpene oxidation products and were most frequently
observed when air masses from monoterpene rich regions were sampled. Taken
together, the second through the fifth most common categories represent on
average 17% of the total organic mass that stems likely from biogenic
sources during the ship's cruise. These numbers have to be viewed as lower
limits since the most common category was attributed to anthropogenic
sources for this calculation. The cluster analysis was also very effective
in identifying a few contaminated mass spectra that were not removed during
pre-processing. This study demonstrates that hierarchical clustering is a
useful tool to analyze the complex patterns of the organic peaks in bulk
aerosol mass spectra from a field study.
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