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The complex distribution of particle charge states resulting from neutralization processes by radioactive or soft X-ray charge neutralizers is a well-documented problem in aerosol science. Here, we demonstrate that non-idealities in the collection efficiency of an impactor allows for the transmission of an unexpected population of multiply charged particles by a differential mobility analyzer that can bias optical measurements. The extinction cross sections ( Cext ) of ammonium sulfate particles were quantified using cavity ring-down spectroscopy and particle counting. Particles were selected by electrical mobility (i.e., a metric of particle size) using a differential mobility analyzer (DMA) or electrical mobility and mass selected by a tandem DMA and aerosol particle mass analyzer (APM), respectively, to elucidate multiple charging artifacts. Measured  Cext  exhibited statistically significant differences at particle sizes near the impactor cut point implying that these multiply charged particles should not be present and could not be confirmed by parallel size distribution measurements. Additionally, comparison of  Cext  with Mie theory demonstrates that misclassification of the multiply charged particles can give rise to numerically accurate results. To understand these observations, the collection efficiency ( CE ) of four impactors from similar electrostatic classifiers was investigated. From these measurements, it was determined that the nominal and actual diameters of the impactors differed by −0.5% (457 μm vs. (455 ± 1) μm, respectively (uncertainty is 1σ standard deviation)) but the average  Stk50  (the Stokes number at the cut-point,  D50 ) values differed by ≈ 23% (0.23 vs. 0.18 ± 0.01, respectively). The measured  CE  as a function of √ Stk  (a metric of particle aerodynamic size) exhibits a long tail toward higher √ Stk  values, allowing for transmission of the larger and multiply charged particles observed in the optical measurements. These measurements highlight the utility of using orthogonal, spectroscopic methods to quantify the presence of multiply charged particles. Copyright © 2023 American Association for Aerosol Research

Impactor collection efficiencies can modify the uncertainty of multiply charged particles in optical extinction measurements