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Different methods of determining formation rates of 3nm particles are compared, basing on analysis of simulated data, but the results are valid for analyses of experimental particle size distribution data as well. The study shows that the method of determining formation rates indirectly from measured number concentration data of 3-6nm particles is generally in good agreement with the theoretical calculation with a systematic error of 0-20%. While this is often accurate enough, a simple modification to the approximative equation for the formation rate is recommended. Additionally, the temporal connection between the concentration of the nucleating vapour and the formation rate is studied. It is concluded that the often used power-law connecting these two is inaccurate. [ABSTRACT FROM AUTHOR]

A dimensionless theory for new particle formation (NPF) was developed, using an aerosol population balance model incorporating recent developments in nucleation rates and measured particle growth rates. Based on this theoretical analysis, it was shown that 5 a dimensionless parameter LΓ, characterizing the ratio of the particle scavenging loss rate to the particle growth rate, exclusively determined whether or not NPF would occur on a particular day. This parameter determines the probability that a nucleated particle will grow to a detectable size before being lost by coagulation with the pre-existing aerosol. Cluster-cluster coagulation was shown to contribute negligibly to 10 this survival probability under conditions pertinent to the atmosphere. Data acquired during intensive measurement campaigns in Tecamac (MILAGRO), Atlanta (ANARChE), Boulder, and Hyytiälä (QUEST II, QUEST IV, and EUCAARI) were used to test the validity of LΓ as an NPF criterion. Measurements included aerosol size distributions down to 3nm and gas-phase sulfuric acid concentrations. The model was applied to 15 seventy-seven NPF events and nineteen non-events (characterized by growth of preexisting aerosol without NPF) measured in diverse environments with broad ranges in sulfuric acid concentrations, ultrafine number concentrations, aerosol surface areas, and particle growth rates (nearly two orders of magnitude). Across this diverse data set, a nominal value of LΓ=0.7 was found to determine the boundary for the occur20 rence of NPF, with NPF occurring when LΓ<0.7 and being suppressed when LΓ> 0.7. Moreover, nearly 45% of measured LΓ values associated with NPF fell in the relatively narrow range of 0.1Γ<0.3. [ABSTRACT FROM AUTHOR]

Atmospheric new particle formation is generally thought to occur due to homogeneous or ion-induced nucleation of sulphuric acid. We compare ambient nucleation rates with laboratory data from nucleation experiments involving either sulphuric acid or oxidized SO2. Atmospheric nucleation occurs at H2SO4 concentrations 2-4 orders of magnitude lower than binary or ternary H2SO4 nucleation. In contrast, the atmospheric nucleation rates and H2SO4 concentrations are very well replicated in the SO2 oxidation experiments. We explain these features by the formation of free HSO5 radicals in pace with H2SO4 during the SO2 oxidation. We suggest that at temperatures above ∼250 K these radicals produce nuclei of new aerosols much more efficiently than H2SO4. These nuclei are activated to further growth by H2SO4 and possibly other trace species. However, at lower temperatures the atmospheric relative acidity is high enough for the H2SO4-H2O nucleation to dominate. [ABSTRACT FROM AUTHOR]

We have performed a series of simulations with an aerosol dynamics box model to study the connection between new particle formation and sulphuric acid concentration. For nucleation either activation mechanism with a linear dependence on the sulphuric acid concentration or ternary H2O-H2SO4-NH3 nucleation was assumed. We investigated the factors that affect the sulphuric acid dependence during the early stages of particle growth, and tried to find conditions which would yield the linear dependence between the particle number concentration at 3-6nm and sulphuric acid, as observed in field experiments. The simulations showed that the correlation with sulphuric acid may change during the growth from nucleation size to 3-6nm size range, the main reason being the size dependent growth rate between 1 and 3 nm. In addition, the assumed size for the nucleated clusters had a crucial impact on the sulphuric acid dependence at 3 nm. The simulations yielded a linear dependence between the particle number concentration at 3 nm and sulphuric acid, when a low saturation vapour pressure for the condensable organic vapour was assumed, or when nucleation took place at ∼2 nm instead of ∼1 nm. Comparison of results with activation and ternary nucleation showed that ternary nucleation cannot explain the experimentally observed linear or square dependence on sulphuric acid. [ABSTRACT FROM AUTHOR]

The contribution of boundary layer nucleation events to total particle concentrations on the global scale has been studied by including a new particle formation mechanism in a global aerosol microphysics model. The mechanism is based on an analysis of extensive observations of particle formation in the boundary layer at a continental surface site. It assumes that molecular clusters form at a rate proportional to the gaseous sulfuric acid concentration to the power of 1. The formation rate of 3nm diameter observable particles is controlled by the cluster formation rate and the existing particle surface area, which acts to scavenge condensable gases and clusters during growth. Modelled sulfuric acid vapour concentrations, particle formation rates, growth rates, coagulation loss rates, peak particle concentrations, and the daily timing of events in the global model agree well with observations made during a 22-day period of March 2003 at the SMEAR II station in Hyytiälä, Finland. The nucleation bursts produce total particle concentrations (>3 nm diameter) often exceeding 104 cm-3, which are sustained for a period of several hours around local midday. The predicted global distribution of particle formation events broadly agrees with what is expected from available observations. Over relatively clean remote continental locations formation events can sustain mean total particle concentrations up to a factor of 8 greater than those resulting from anthropogenic sources of primary organic and black carbon particles. However, in polluted continental regions anthropogenic primary particles dominate particle number and formation events lead to smaller enhancements of up to a factor of 2. Our results therefore suggest that particle concentrations in remote continental are dominated by nucleated particles while concentrations in polluted continental regions are dominated by primary particles. The effect of boundary layer particle formation over tropical regions and the Amazon is negligible. Particle concentrations are enhanced by a factor 3-10 over the remote Southern Ocean (30-70° S), resulting in total concentrations of ∼250-1000 cm-3, in good agreement with observations. Particle formation tends to peak towards the top of the marine boundary layer and there is a lack of obvious burst-like behaviour at the sea surface. This result suggests that new particle formation in the marine boundary layer could be confused with entrainment from the free troposphere. These first global particle formation simulations reveal some interesting sensitivities. We show, for example, that significant reductions in primary particle emissions may lead to an increase in total particle concentration because of the coupling between particle surface area and the rate of new particle formation. This result suggests that changes in emissions may have a complicated effect on global and regional aerosol properties. Overall, our results show that new particle formation is a significant component of the aerosol particle number budget. [ABSTRACT FROM AUTHOR]

We have investigated the formation and early growth of atmospheric secondary aerosol particles building on atmospheric measurements. The measurements were part of the QUEST 2 campaign which took place in spring 2003 in Hyytiälä (Finland). During the campaign numerous new aerosol particle formation events occurred of which were accompanied by gaseous sulphuric acid measurements. Our detailed analysis of these 15 events is focussed on nucleation and early growth (to a diameter of 3 nm) of fresh particles. It revealed that new particle formation seems to be a function of the gaseous sulphuric acid concentration to the power from one to two. The former would be consistent with the recently developed activation theory while the latter would be consistent with the kinetic nucleation theory. We find that some events are dominated by the activation mechanism and some are dominated by the kinetic mechanism. Inferred coefficients for the two nucleation mechanisms are correlated with the product of gaseous sulphuric acid and ammonia concentrations. This indicates that besides gaseous sulphuric acid also ammonia has a role in nucleation. Early growth of fresh particles to a diameter of 3nm has a mean rate of 1.2 nm/h and is clearly correlated with the gaseous sulphuric acid concentration. [ABSTRACT FROM AUTHOR]

This study covers four years of aerosol number size distribution data from Pallas and Värriö sites 250km apart from each other in Northern Finland and compares new particle formation events between these sites. In eastern air masses almost all events were observed to start earlier at the eastern station Värriö, whereas in western air masses most of the events were observed to start earlier at the western station Pallas. This demonstrates that particle formation in a certain air mass type depends not only on the diurnal variation of the parameters causing the phenomenon (such as photochemistry) but also on some properties carried by the air mass itself. The correlation in growth rates between the two sites was relatively good, which suggests that the amount of condensable vapour causing the growth must have been at about the same level in both sites. The value of condensation sink was frequently much higher at the downwind station. It seems that secondary particle formation related to biogenic sources dominate in many cases over the particle sinks during the air mass transport between the sites. Two cases of transport from Pallas to Värriö were further analysed with an aerosol dynamics model. The model was able to reproduce the observed nucleation events 250km down-wind at Värriö but revealed some differences between the two cases. The simulated nucleation rates were in both cases similar but the organic concentration profiles that best reproduced the observations were different in the two cases indicating that divergent formation reactions may dominate under different conditions. The simulations also suggested that organic compounds were the main contributor to new particle growth, which offers a tentative hypothesis to the distinct features of new particles at the two sites: Air masses arriving from Atlantic Ocean typically spent approximately only ten hours over land before arriving at Pallas, and thus the time for the organic vapours to accumulate in the air and to interact with the particles is relatively short. This can lead to low nucleation mode growth rates and even to suppression of detectable particle formation event due to efficient scavenging of newly formed clusters, as was observed in the case studies. [ABSTRACT FROM AUTHOR]