Single-particle detection efficiencies of aerosol time-of-flight mass spectrometry during the North Atlantic marine boundary layer experiment

During the North Atlantic marine boundary layer experiment (NAMBLEX) sampling campaign at Mace Head, Ireland, both continental and maritime air masses were sampled. Aerosol was characterized both with a TSI 3800 time-of-flight mass spectrometer (ATOFMS) and a MOUDI microorifice impactor, and particle number counts were measured independently with an aerodynamic particle sizer. The data have been analyzed in order to elucidate factors determining the particle detection efficiencies of the ATOFMS. These are broken down according to the efficiency of the inlet system, the hit efficiency on particles which enter the sensing zone of the instrument and the sensitivity of the measured ion signal to the chemical species. A substantial matrix effect depending on the chemical composition of the aerosol sampled at the time was found, which is reflected in variations in the hit efficiency of particles entering the sensing zone of the instrument with the main desorption-ionization laser. This is in addition to the strong inverse power-law dependence of inlet transmission efficiency on particle diameter. The variation in hit efficiency with particle type is likely attributable to differences in the energetics of laser energy absorption, ablation, and ion formation. However, once variations in both inlet transmission and hit efficiencies are taken into account, no additional matrix dependence of ATOFMS response is required to obtain a linear relationship between the ion signal and the concentration of a particular chemical species. The observations show that a constant mass of material is ionized from each particle, irrespective of size. Consequently the integrated ion signal for a given chemical component and particle size class needs to be increased by a factor related to the cube of particle diameter in order to correlate with the airborne mass of that component.