Fluorescence spectra of atmospheric aerosol at Adelphi, Maryland, USA: measurement and classification of single particles containing organic carbon

We measured laser-induced fluorescence spectra from individual supermicron-sized atmospheric particles drawn into our laboratory at Adelphi, MD, an urban site in the Washington, DC metroplex. A virtural impactor concentrator is used along with an aerodynamic-focusing-nozzle which forms, within an optical chamber, a focused aerosol jet where single aerosol particles can be interrogated on-the-fly with a pulsed 266-nm-wavelength laser. Sample rates are a few liter per minute, and are size dependent. Crossed-diode laser beams indicate when a particle is traversing the sample region and are used to trigger the UV laser to fire and the gated intensified CCD to record the fluorescence spectrum. Our breadboard fluorescence particle spectrometer measures particles in the 3–10 μm diameter size range. Typical trigger rates are a few per second. The usable spectral range is from about 295 to 605 nm. The majority of the particles have very weak fluorescence (on average 8 percent of particles have fluorescence signals above noise). The spectra were grouped using a heirarchical cluster analysis, with parameters chosen so that spectra typically cluster into 4–12 main categories. From the set of all cluster spectra we chose 8 template spectra for reanalyzing all the data. On average, 92 percent (81–94 percent) of the spectra were similar to these templates (using the same thresholds used for the cluster analysis). The major emission bands of the most commonly occurring spectra have peaks: near 460 nm (28 percent of fluorescent particles on average), a very broad hump, and may be humic acids or humic like substances; near 317 nm (on average 24 percent of fluorescent particles); near 321 and 460 nm (a double hump, 12 percent of fluorescent particles); and near 341 nm (8 percent of fluorescent particles). Some of the fluorescence in spectra peaking in the 317–341 nm range is probably from dicyclic aromatics and heterocyclics, including the amino acid tryptophan in biological particles such as bacteria and spores.