Development of a new corona discharge based ion source for high resolution time-of-flight chemical ionization mass spectrometer to measure gaseous H2SO4 and aerosol sulfate

A new corona discharge (CD) based ion source was developed for a commercial high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) (Aerodyne Research Inc.) to measure both gaseous sulfuric acid (H2SO4) and aerosol sulfate after thermal desorption. Nitrate core ions (NO3−) were used as reagent ions and were generated by a negative discharge in zero air followed by addition of excess nitrogen dioxide (NO2) to convert primary ions and hydroxyl radicals (OH) into NO3− ions and nitric acid (HNO3). The CD-HRToF-CIMS showed no detectable interference from hundreds parts per billion by volume (ppbv) of sulfur dioxide (SO2). Unlike the atmospheric pressure ionization (API) ToF-CIMS, the CD ion source was integrated onto the ion-molecule reaction (IMR) chamber and which made it possible to measure aerosol sulfate by coupling to a filter inlet for gases and aerosols (FIGAERO). Moreover, compared with a quadrupole-based mass spectrometer, the desired HSO4− signal was detected by its exact mass of m/z 96.960, which was well resolved from the potential interferences of HCO3−⋅(H2O)2 (m/z 97.014) and O−⋅H2O⋅HNO3 (m/z 97.002). In this work, using laboratory-generated standards the CD-HRToF-CIMS was demonstrated to be able to detect as low as 3.1 × 105 molecules cm−3 gaseous H2SO4 and 0.5 μg m−3 ammonium sulfate based on 10-s integration time and two times of the baseline noise. The CD ion source had the advantages of low cost and a simple but robust structure. Since the system was non-radioactive and did not require corrosive HNO3 gas, it can be readily field deployed. The CD-HRToF-CIMS can be a powerful tool for both field and laboratory studies of aerosol formation mechanism and the chemical processes that were critical to understand the evolution of aerosols in the atmosphere.