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In this study the charging efficiency of a radioactive and a non-radioactive plasma bipolar diffusion charger (Gilbert Mark I plasma charger) for sub-12 nm particles has been investigated at various aerosol flow rates. The results were compared to classic theoretical approaches. In addition, the chemical composition and electrical mobilities of the charger ions have been examined using an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF MS). A comparison of the different neutralization methods revealed an increased charging efficiency for negatively charged particles using the non-radioactive plasma charger with nitrogen as the working gas compared to a radioactive americium bipolar diffusion charger. The mobility and mass spectrometric measurements show that the generated bipolar diffusion charger ions are of the same mobilities and composition independent of the examined bipolar diffusion charger. It was the first time that the Gilbert Mark I plasma charger was characterized in comparison to a commercial TSI X-Ray (TSI Inc, Model 3088) and a radioactive americium bipolar diffusion charger. We observed that the plasma charger with nitrogen as the working gas can enhance the charging probability for sub-10 nm particles compared to a radioactive americium bipolar diffusion charger. As a result, the widely used classical charging theory disagrees for the plasma charger and for the radioactive chargers with increased aerosol flow rates. Consequently, in-depth measurements of the charging distribution are necessary for accurate measurements with differential or scanning particle sizers for laboratory and field applications.

Condensation particle counters (CPCs) are crucial instruments for detecting sub-10 nm aerosol particles. Understanding the detection performance of a CPC requires thorough characterization under well-controlled laboratory conditions. Besides the size of the seed particles, chemical interactions between the working fluid and the seed particles also influence the activation efficiencies. However, common seed particle materials used for CPC characterizations are not chosen with respect to chemical interactions with vapor molecules of the working fluid by default. Here, we present experiments on the influence of the seed particle material on the detection efficiencies and the 50 % cutoff diameters of commonly used CPCs for the detection of sub-10 nm particles. A remarkable set consisting of six different and commercially available particle detectors, including the newly developed TSI V-WCPC 3789 and a tuned TSI 3776, was tested. The corresponding working fluids of the instruments are n-butanol, diethylene glycol and water. Among other materials we were able to measure detection efficiencies with nanometer-sized organic seed particles reproducibly generated by the oxidation of β-caryophyllene vapor in a flow tube. Theoretical simulations of supersaturation profiles in the condensers were successfully related to measured detection efficiencies. Our results demonstrate the importance of chemical similarities between seed particles and the working fluids used when CPCs are characterized. We anticipate our study to contribute to a deeper understanding of chemical interactions during heterogeneous nucleation processes.

In this study the impact of humidity on heterogeneous nucleation of n-butanol onto hygroscopic and nonabsorbent charged and neutral particles was investigated using a fast expansion chamber and commercial continuous flow type condensation particle counters (CPCs). More specifically, we measured the activation probability of sodium chloride (NaCl) and silver (Ag) nanoparticles by using n-butanol as condensing liquid with the size analyzing nuclei counter (SANC). In addition, the cutoff diameters of regular butanol-based CPCs for both seed materials under different charging states were measured and compared to SANC results. Our findings reveal a strong humidity dependence of NaCl particles in the sub-10 nm size range since the activation of sodium chloride seeds is enhanced with increasing relative humidity. In addition, negatively charged NaCl particles with a diameter below 3.5 nm reveal a charge-enhanced activation. For Ag seeds this humidity and charge dependence was not observed, underlining the importance of molecular interactions between seed and vapor molecules. Consequently, the cutoff diameter of a butanol-based CPC can be reduced significantly by increasing the relative humidity. This finding suggests that cutoff diameters of butanol CPCs under ambient conditions are likely smaller than corresponding cutoff diameters measured under clean (dry) laboratory conditions. At the same time, we caution that the humidity dependence may lead to wrong interpretations if the aerosol composition is not known.