The atmospheric aging of volatile
organic compounds leads to the
formation of complex mixtures of highly oxidized secondary organic
aerosols (SOAs). State-of-the-art mass spectrometry (MS) has become
a pivotal tool for their chemical characterization. In this study,
we characterized the chemical complexity of naphthalene-derived SOA
by three different time-of-flight (TOF) mass spectrometric techniques
applying electron ionization: high-resolution–TOF–aerosol
MS (AMS), direct inlet probe (DIP)–high-resolution TOFMS, and
thermal desorptioncomprehensive two-dimensional gas chromatographyTOFMS
(GC × GC). We discuss AMS as an online, DIP as an atline, and
GC × GC as an offline technique to compare their informative
value for studying the oxidation state, volatility, and molecular
composition of laboratory-generated SOA. For GC × GC, the accessible
organic content was limited to (semi-)volatile compounds and supported
a reliable assignment of the molecular composition. DIP and AMS were
used to derive secondary parameters such as O/C and H/C ratios, the
general functionality of the compound classes and their abundance
upon photochemical aging. Thereby, while the induced pyrolysis in
the AMS extended the accessibility range to polar, high-molecular-weight
compounds, thermal fragmentation also led to limited molecular information.
For DIP, low-volatility compounds could be volatilized and the high
mass resolution was useful to resolve isobaric mass fragments and
assign reliable sum formulas of fragments and molecular ions. Although
no single technique can provide information to describe the full chemical
complexity of the SOA, AMS, DIP, and GC × GC in their complementarity
are well suited to investigate the impact of SOA on health and environment.