1Chemistry Department, Boston College, Chestnut Hill, MA, USA
2Center for Aerosol and Cloud Chemistry, Aerodyne Research Inc., Billerica, MA, USA
3CIRES University of Colorado, Boulder, CO, USA
4Pacific Northwest National Laboratory, Richland, WA, USA
Abstract. We present the first single particle results obtained using an Aerodyne time-of-flight aerosol mass spectrometer coupled with a light scattering module (LS-ToF-AMS). The instrument was deployed at the T1 ground site approximately 40 km northeast of the Mexico City Metropolitan Area (MCMA) as part of the MILAGRO field study in March of 2006. The instrument was operated as a standard AMS from 12–30 March, acquiring average chemical composition and size distributions for the ambient aerosol, and in single particle mode from 27–30 March. Over a 75-h sampling period, 12 853 single particle mass spectra were optically triggered, saved, and analyzed. The correlated optical and chemical detection allowed detailed examination of single particle collection and quantification within the LS-ToF-AMS. The single particle data enabled the mixing states of the ambient aerosol to be characterized within the context of the size-resolved ensemble chemical information.
The particulate mixing states were examined as a function of sampling time and most of the particles were found to be internal mixtures containing many of the organic and inorganic species identified in the ensemble analysis. The single particle mass spectra were deconvolved, using techniques developed for ensemble AMS data analysis, into HOA, OOA, NH4NO3, (NH4)2SO4, and NH4Cl fractions. Average single particle mass and chemistry measurements are shown to be in agreement with ensemble MS and PTOF measurements. While a significant fraction of ambient particles were internal mixtures of varying degrees, single particle measurements of chemical composition allowed the identification of time periods during which the ambient ensemble was externally mixed. In some cases the chemical composition of the particles suggested a likely source. Throughout the full sampling period, the ambient ensemble was an external mixture of combustion-generated HOA particles from local sources (e.g. traffic), with number concentrations peaking during morning rush hour (04:00–08:00 LT) each day, and more processed particles of mixed composition from nonspecific sources. From 09:00–12:00 LT all particles within the ambient ensemble, including the locally produced HOA particles, became coated with NH4NO3 due to photochemical production of HNO3. The number concentration of externally mixed HOA particles remained low during daylight hours. Throughout the afternoon the OOA component dominated the organic fraction of the single particles, likely due to secondary organic aerosol formation and condensation. Single particle mass fractions of (NH4)2SO4 were lowest during the day and highest during the night. In one instance, gas-to-particle condensation of (NH4)2SO4 was observed on all measured particles within a strong SO2 plume arriving at T1 from the northwest. Particles with high NH4Cl mass fractions were identified during early morning periods. A limited number of particles (~5% of the total number) with mass spectral features characteristic of biomass burning were also identified.