Abstract
Experimental and theoretical uncertainties in the measurement of cloud condensation nuclei (CCN) with a continuous-flow thermal-gradient CCN counter from Droplet Measurement Technologies (DMT-CCNC) have been assessed by model calculations and calibration experiments with ammonium sulfate and sodium chloride aerosol particles in the diameter range of 20?220 nm. Experiments have been performed in the laboratory and during field measurement campaigns, extending over a period of more than one year and covering a wide range of operating conditions (650?1020 hPa ambient pressure, 0.5?1.0 L min?1 aerosol flow rate, 20?30°C inlet temperature, 4?34 K m?1 temperature gradient). For each set of conditions, the effective water vapor supersaturation (Seff) in the CCNC was determined from the measured CCN activation spectra and Köhler model calculations. High measurement precision was achieved under stable laboratory conditions, where relative variations of Seff in the CCNC were generally less than ±2%. During field measurements, however, the relative variability increased up to ±5?7%, which can be mostly attributed to variations of the CCNC column top temperature with ambient temperature. To assess the accuracy of the Köhler models used to calculate Seff, we have performed a comprehensive comparison and uncertainty analysis of the various Köhler models and thermodynamic parameterizations commonly used in CCN studies. For the relevant supersaturation range (0.05?2%), the relative deviations between different modeling approaches were as high as 25% for (NH4)2SO4 and 16% for NaCl. The deviations were mostly caused by the different parameterizations for the activity of water in aqueous solutions of (NH4)2SO4 and NaCl (activity parameterization, osmotic coefficient, and van't Hoff factor models). The uncertainties related to the model parameterizations of water activity clearly exceeded the CCNC measurement precision. Relative deviations caused by different ways of calculating or approximating solution density and surface tension did not exceed 3% for (NH4)2SO4 and 1.5% for NaCl. Nevertheless, they did exceed the CCNC measurement precision under well-defined operating conditions and should not be neglected in studies aimed at high accuracy. To ensure comparability of results, we suggest that CCN studies should always report exactly which Köhler model equations and parameterizations of solution properties were used. Substantial differences between the CCNC calibration results obtained with (NH4)2SO4 and NaCl aerosols under equal experimental conditions (relative deviations of Seff up to ~10%) indicate inconsistencies between widely used activity parameterizations derived from electrodynamic balance (EDB) single particle experiments (Tang and Munkelwitz, 1994; Tang, 1996) and hygroscopicity tandem differential mobility analyzer (HTDMA) aerosol experiments (Kreidenweis et al., 2005). Therefore, we see a need for further evaluation and experimental confirmation of preferred data sets and parameterizations for the activity of water in dilute aqueous (NH4)2SO4 and NaCl solutions. The experimental results were also used to test the CCNC flow model of Lance et al.~(2006), which describes the dependence of Seff on temperature, pressure, and flow rate in the CCN counter. This model could be applied after subtraction of a near-constant temperature offset and derivation of an instrument-specific thermal resistance parameter (RT?1.8 K W?1). At Seff>0.1% the relative deviations between the flow model and experimental results were mostly less than 5%, when the same Köhler model approach was used. At Seff?.1%, however, the deviations exceeded 20%, which can be attributed to non-idealities which also caused the near-constant temperature offset. Therefore, we suggest that the CCNC flow model can be used to extrapolate calibration results, but should generally be complemented by calibration experiments performed under the relevant operating conditions ? during field campaigns as well as in laboratory studies.