Paper spray mass spectrometry for the analysis of picoliter droplets

Recent experimental efforts have shown that single particle levitation methods may be effectively coupled with mass spectrometry (MS) using paper spray (PS) ionization for compositional analysis of picoliter droplets. In this work, we characterize the response of PS-MS to analytes delivered in the form of picoliter droplets and explore its potential for identification and quantification of these samples. Using a microdroplet dispenser to generate droplets, we demonstrate sensitivity to a range of oxygenated organic molecules typical of compounds found in atmospheric secondary organic aerosol. We assess experimental factors that influence the reproducibility and sensitivity of the method and explore the linearity of the system response to increasing analyte mass in droplets containing single or multicomponent analytes. We show that the ratio of analyte signal from multicomponent samples may be used to characterize the relative composition of the system. These measurements demonstrate that the droplet PS-MS method is an effective tool for qualitative and quantitative analysis of single picoliter droplets containing picogram levels of analyte. The potential applications of this technique for characterizing the composition of levitated particles will be discussed.