Comparison between mass spectra of individual organic particles generated by UV laser ablation and in the IR/UV two-step mode

In ablation-based single particle mass spectrometry it is common to find that the mass spectra of particles with identical compositions exhibit significant particle-to-particle fluctuations and high degree of fragmentation. This is particularly true when it comes to particles containing organic compounds. At laser fluence that is sufficient to ionize sulfates, mass spectra of the identical organic particles are classified into multitude of classes, some of which are indistinguishable from elemental carbon. In contrast, the individual particle mass spectra generated in two-step mode, in which an IR laser pulse is used to evaporate the semivolatile particle components and a time delayed UV laser pulse is used to ionize the evaporating plume, exhibit greatly diminished particle-to-particle fluctuations and significantly improved mass spectral quality. Since individual particle mass spectra must first be classified and only then can be averaged and analyzed, the IR/UV mode greatly improves the capability to properly quantify particle compositions. We present an experimental investigation of the properties and behavior of individual particle mass spectra of organic particles that are generated by ablation and in the two-step mode as function of UV laser fluence and the delay between the two lasers. The study shows that the two-step mode yields highly reproducible mass spectra that contain sufficient detail to allow molecular identification. In addition it produces significantly higher mass spectral intensities that are linearly related to the mass of organics in the particles. In contrast, ablation generated mass spectra were found to exhibit high degree of fragmentation and large particle-to-particle fluctuations.

Individual particle mass spectra generated in IR/UV mode exhibit greatly diminished particle-to-particle fluctuations and significantly improved mass spectral quality than those produced by UV laser ablation.Figure optionsDownload as PowerPoint slide