Technical note: An improved approach to determining background aerosol concentrations with PILS sampling on aircraft

Particle-into-Liquid Samplers (PILS) have become a standard aerosol collection technique, and are widely used in both ground and aircraft measurements in conjunction with off-line ion chromatography (IC) measurements. Accurate and precise background samples are essential to account for gas-phase components not efficiently removed and any interference in the instrument lines, collection vials or off-line analysis procedures. For aircraft sampling with PILS, backgrounds are typically taken with in-line filters to remove particles prior to sample collection once or twice per flight with more numerous backgrounds taken on the ground. Here, we use data collected during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) to demonstrate that not only are multiple background filter samples are essential to attain a representative background, but that the chemical background signals do not follow the Gaussian statistics typically assumed. Instead, the background signals for all chemical components analyzed from 137 background samples (taken from ∼78 total sampling hours over 18 flights) follow a log-normal distribution, meaning that the typical approaches of averaging background samples and/or assuming a Gaussian distribution cause an over-estimation of background samples – and thus an underestimation of sample concentrations. Our approach of deriving backgrounds from the peak of the log-normal distribution results in detection limits of 0.25, 0.32, 3.9, 0.17, 0.75 and 0.57 μg m−3 for sub-micron aerosol nitrate (NO3−), nitrite (NO2−), ammonium (NH4+), sulfate (SO42−), potassium (K+) and calcium (Ca2+), respectively. The difference in backgrounds calculated from assuming a Gaussian distribution versus a log-normal distribution were most extreme for NH4+, resulting in a background that was 1.58× that determined from fitting a log-normal distribution. •Background distributions of PILS + offline IC measurements do not necessarily follow parametric statistics.•Histograms of background distributions can be fit to lognormal distributions for accurate background determination.•This procedure leads to substantially lower calculated limits of detection for ammonium and other inorganic ions.