We report Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) measurements of the composition of ambient 10–33 nm diameter particles formed from nucleation on 16 March 2006 in Tecamac, Mexico during the Megacity Initiative: Local and Global Research Observations (MILAGRO) field study. On this day, nucleated particles contained far more organics than sulfates: average ion molar ratios with measurement uncertainties for nitrate, organics and sulfur species were 6 ± 2%, 84 ± 5%, and 10 ± 1%, respectively. The measured organic species include nitrogen‐containing organic compounds, organic acids, and hydroxy organic acids. Independent calculations show that sulfuric acid condensation could have accounted for only 10 ± 2% of the growth that was observed on this day, which is consistent with the TDCIMS measurements of composition. It follows that organic compounds play a dominant role the high growth rates that were observed.

The effect of working fluid on size-dependent activation efficiencies with the laminar flow ultrafine condensation particle counter described by Stolzenburg and McMurry (1991) was studied theoretically and experimentally. Criteria considered include tendency to avoid homogeneous nucleation within the condenser and toxicity. The working fluids that were identified have vapor pressures below that of butanol, so particles grow to smaller sizes and are more difficult to detect optically. Therefore we use a second, conventional CPC as a "booster" to grow particles to a detectable size. Experiments were performed to obtain the size-and material-dependent activation efficiencies for ethylene glycol, diethylene glycol, propylene glycol, oleic acid, and DOS. Using diethylene glycol and oleic acid, values of the 50% activation efficiency diameter, D p50 , for negatively charged particles generated by evaporating sodium chloride, ammonium sulfate, and silver were <1.2 (<0.8) nm , 1.4-1.5 (1.0-1.2) nm, and 1.9-2.0 (1.5) nm as mobility (mass) diameter, respectively. The stability of the UCPC for long-term operation using ethylene glycol and propylene glycol as working fluids was tested by monitoring the instrument's response to silver particles having size near D p50 in an air stream at 40-45% relative humidity. The performance was steady (±3%) for several days indicating the instrument performs stably during unattended operation for realistic atmospheric sampling conditions.

[1] Mass identified ion cluster distributions were measured under ambient atmospheric conditions and compared with model predictions based on laboratory ion cluster thermodynamics data. The results are shown from several days where atmospheric sulfur concentrations were high and thus ion-induced cluster growth was anticipated. Atmospheric gas phase sulfuric acid, temperature, relative humidity, SO 2 , mobility distributions of ions and small charged particles, and aerosol size distributions were also measured in support of the model calculations. The relative agreement of measurement and model for the first and second sulfuric acid clusters (HSO 4 À (H 2 SO 4 ) m ) for m = 1 and 2 is quite good but suggests that sulfuric acid clustering may not occur at the collision rate. Clusters for higher m values were not observed, which is also consistent with model predictions for the conditions under which measurements were performed. The lack of both observed and predicted large ion clusters is also consistent with the independent measurements of ion mobility distributions and particle size distributions, which showed similar numbers of positively and negatively charged ultrafine particles, suggesting that neither positive nor negative ion-induced nucleation processes were likely to have contributed significantly to observed new particle formation rates during this study. The relatively low observed concentrations of the bisulfate ion also suggest that the processes leading to the first sulfuric acid/bisulfate cluster (HSO 4 À H 2 SO 4 ) may be more complicated than simple sulfuric acid clustering or exchange reactions. While nucleation was observed on some days, measurements suggest that ion-induced nucleation did not contribute significantly to new particle production or growth during these events. This does not rule out the possibility that ion-induced nucleation could contribute significantly to atmospheric new particle formation under very different atmosphere conditions such as in areas with much lower temperatures and higher ion concentrations.

[1] A method to estimate nanoparticle diameter growth rates (GR) during new particle formation (NPF) events from the measured dependence of charged fraction, f, on size, D p , is introduced. The method is especially useful for observations during intense particle production rates, when the mode in the distribution of newly formed particles does not grow monotonically with time. This method assumes that the observed profile of f versus D p during the nucleation and growth period is controlled by condensational growth, ion-particle combination/recombination, scavenging by preexisting particles, and coagulation among growing nanoparticles. Values of growth rates obtained by this method (GR f ) agree well with independently obtained particle growth rates due to gas-to-particle conversion processes (GR PSD ) during regional NPF events. The method was then applied to characterize the NPF events observed at Tecamac, Mexico. These growth rates were found to range from 15-40 nm/h, which is significantly higher than values reported for other urban areas. The production rates for 1 nm particles calculated from the estimated growth rates and measured Fuchs surface area (J 1nm = 1900-3000 particles/cm 3 s) are comparable to those recently observed in New Delhi. Because critical nuclei are likely close to 1 nm in size, J 1nm should provide a reasonable estimate for nucleation rates.

[1] This paper investigates the role of ion-induced nucleation (IIN) in new particle formation events observed near ground level at a sampling site located near Boulder, Colorado (14 March 2004 to 27 October 2005. Measurements of mobility distributions of small and intermediate ions (0.4-6.3 nm), size distributions of total particles (3 nm to 5 mm), and charged fractions (2.5-25 nm) were carried out. The relative contributions of neutral nucleation and IIN were inferred using both qualitative and quantitative analyses. First, a simple theoretical analysis is performed to show what can be learned about the initial charge state of the nucleated particles from charged fractions measured after they had grown to 3.0-5.5 nm. We found that for much of our data the charge fractions of freshly nucleated particles below 5 nm were significantly below stationary-state values, and that this tendency increased with decreasing size, indicating that neutral nucleation was dominant. However, the data also show that there were occasionally asymmetries between negative and positive charge fractions that we could not explain unless positive or negative IIN occurred to some extent. A quantitative analysis is then performed to estimate the fractional contribution of positive and negative IIN to new particle formation rates for each nucleation event observed during this period. The results show the average contribution of IIN is about 0.5% for both polarities indicating that IIN was a relatively insignificant contributor to new particle formation in this study. This result is consistent with the direct mass spectrometric measurements of sulfuric acid ion cluster compositions and concentrations performed at the same measurement site.Citation: Iida, K., M. Stolzenburg, P. McMurry, M. J. Dunn, J. N. Smith, F. Eisele, and P. Keady (2006), Contribution of ion-induced nucleation to new particle formation: Methodology and its application to atmospheric observations in Boulder, Colorado,