• Energy Research

New particle formation (NPF) events substantially contribute to the number concentration of atmospheric particles and cloud condensation nuclei (CCN) which can further influence radiative balance and Earth's climate. Many short-term studies have found that sulfuric acid (H2 SO4) and highly oxygenated organic molecules (HOM) are critical compounds in the early steps of NPF. However, it is not fully understood how NPF intensity and frequency respond to global warming and declining anthropogenic sulfur dioxide (SO2) emissions, affecting HOM and H2 SO4 formation, respectively. Here, we report the results of long-term (over 20 years) datasets collected at the Station for Measuring Ecosystem-Atmosphere Relations (SMEAR) II (Hyytiälä, Finland). Owing to the significant contribution of HOM in the initial and subsequent particle formation and growth, we have derived a HOM proxy for conducting the long-term trend analysis. Measurement results together with modelled proxies reveal the declining trends of SO2, H2 SO4, Condensation Sink (CS), NPF frequency and particle formation rate (J3) along with increasing trends of monoterpenes and HOM. Peer reviewed

AbstractA list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog1,2, but how it occurs in cities is often puzzling3. If the growth rates of urban particles are similar to those found in cleaner environments (1–10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below −15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid–base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms4,5.