Estimation of sulfuric acid concentration using ambient ion composition and concentration data obtained with atmospheric pressure interface time-of-flight ion mass spectrometer

Sulfuric acid (H2SO4, SA) is the key compound in atmospheric new particle formation. Therefore, it is crucial to observe its concentration with sensitive instrumentation, such as chemical ionisation (CI) inlets coupled to atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometers. However, there are environmental conditions for which and physical reasons why chemical ionisation cannot be used, for example in certain remote places or during flight measurements with limitations regarding chemicals. Here, we propose a theoretical method to estimate the SA concentration based on ambient ion composition and concentration measurements that are achieved by APi-TOF alone. We derive a theoretical expression to estimate the SA concentration and validate it with accurate CI-APi-TOF observations. Our validation shows that the developed estimate works well during daytime in a boreal forest (R-2 = 0.85); however, it underestimates the SA concentration in, e.g. the Antarctic atmosphere during new particle formation events where the dominating pathway for nucleation involves sulfuric acid and a base (R-2 = 0.48).

Automated summary

This study proposes a theoretical method to estimate sulfuric acid concentration based on ambient ion composition and concentration measurements, validated with accurate observations using CI-APi-TOF instruments. The developed estimate works well during daytime in a boreal forest, but underestimates sulfuric acid concentration in the Antarctic atmosphere during new particle formation events.