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Aerosols of biogenic and anthropogenic origin affect the total radiative forcing of global climate. Poor knowledge of the pre-industrial aerosol concentration and composition, in particular of particles formed directly in the atmosphere from gaseous precursors, constitutes a large uncertainty in the anthropogenic radiative forcing. Investigations of new particle formation at pre-industrial-like conditions can contribute to the reduction of this uncertainty. Here we present observations taken at the remote Nepal Climate Observatory Pyramid station at 5,079 m above sea level, a few kilometres from the summit of Everest. We show that up-valley winds funnel gaseous aerosol precursors to higher altitudes. During this transport, these are oxidized into compounds of very low volatility, which rapidly form a large number of aerosol particles. These are then transported into the free troposphere, which suggests that the whole Himalayan region may act as an 'aerosol factory' and contribute substantially to the free tropospheric aerosol population. Aerosol production in this region occurs mainly via organic precursors of biogenic origin with little evidence of the involvement of anthropogenic pollutants. This process is therefore likely to be essentially unchanged since the pre-industrial period, and may have been one of the major sources that contributes to the upper tropospheric aerosol population during that time. Newly formed biogenic particles in the Himalaya increase free-tropospheric background aerosol concentration by a factor of up to two.

Atmospheric new-particle formation (NPF) affects climate by contributing to a large fraction of the cloud condensation nuclei (CCN). Highly oxygenated organic molecules (HOMs) drive the early particle growth and therefore substantially influence the survival of newly formed particles to CCN. Nitrogen oxide (NOₓ) is known to suppress the NPF driven by HOMs, but the underlying mechanism remains largely unclear. Here, we examine the response of particle growth to the changes of HOM formation caused by NOₓ. We show that NOₓ suppresses particle growth in general, but the suppression is rather nonuniform and size dependent, which can be quantitatively explained by the shifted HOM volatility after adding NOₓ. By illustrating how NOₓ affects the early growth of new particles, a critical step of CCN formation, our results help provide a refined assessment of the potential climatic effects caused by the diverse changes of NOₓ level in forest regions around the globe.

The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nanoparticle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e., in conditions in which neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.5 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion–ion recombination before they grew to 2.5 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.5 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy., published version, peerReviewed

Cirrus clouds and their effects on earth’s radiative balance are major sources of uncertainties in predicting future climate. These clouds also dehydrate air ascending to the tropopause, thereby reducing water content in the stratosphere. However, the formation of cirrus clouds is not well understood. Data from field sites and campaigns have shown that organic aerosols (OAs) is a major component of the non-refractory aerosols in the free troposphere where ice cirrus clouds typically form. Measurements by aerosol mass spectrometers in the free troposphere above forests indicate a high mass fraction of these OAs are derived from the atmospheric oxidation of isoprene and other volatile organic compounds (VOCs). Despite their abundance, the effects of these OAs on ice nucleation (IN) is controversial. Previously, these OAs were assumed to be homogeneously mixed liquids, which limits their INabilities. Recent studies have shown that depending on the ambient humidity and temperature, OAs can exist in semi-solid or solid phase states, which can potentially increase INactivity. This laboratory study systematically examines the effects of aerosol-phase state on IN properties of secondary organic aerosols (SOA) produced by the environmental chamber by simultaneously measuring their chemical composition and ice nucleation properties. Selected types of SOA particles were generated by reacting the respective volatile organic compounds (VOCs) with either ozone and/or OH radicals in the MIT environmental chamber and a potential aerosol mass (PAM) oxidation flow reactor. Four kinds of SOA, namely a-pinene SOA, toluene SOA, -caryophyllene SOA, and IEPOX-derived SOA were generated and passed through a temperature control apparatus, where the temperature of the aerosols can be varied between -42°C and 20°C before entering the spectrometer for ice nucleation (SPIN, Droplet Measurement Technologies, Inc.) for determining ice nucleation activity. A scanning mobility particle sizer (SMPS) and an aerosol mass spectrometer (AMS, Aerodyne Inc.) measured the number-diameter distribution and chemical composition of the particles upstream of the SPIN. An optical particle counter downstream of the SPIN measured the optical signatures of the ice particles and some of the large bare organic particles. The SPIN operating temperature was between -38°C and -46°C. Our results show that pre-cooling the aerosol particles to -25 to -42°C enhances the IN onset relative humidity (RH) and the active fraction of IN when compared with non-pre-cooling conditions only for -caryophyllene SOA and IEPOX-derived SOA. Coupled with viscosity and glass transition temperature calculations, we show that the aerosol phase state changes due to the pre-cooling explains this enhancement. By combining the ice nucleation results with chemical analysis of the SOA, our study suggests that the chemical composition influences of these organic aerosols alter the hygroscopicity and the phase state of these organic aerosols, which eventually affects their INproperties. As the phase state of the organic aerosols changes from liquid to semi-solid or solid, their INonset relative humidity decreases, suggesting certain types of SOA (including b-caryophyllene and isoprene SOA) could be potentially important ice nuclei in the free troposphere., 100th American Meteorological Society Annual Meeting, 11-16 January, 2020, Boston, MA, USA

Atmospheric organic aerosols are generally classified as primary and secondary (POA and SOA) according to their formation processes. An actual separation, however, is challenging when the timescales of emission and gas-to-particle formation overlap. The presence of SOA formation in biomass burning plumes leads to scientific questions about whether the oxidized fraction of biomass burning aerosol is rather of secondary or primary origin, as some studies would suggest, and about the chemical compositions of oxidized biomass burning POA and SOA. In this study, we apply nuclear magnetic resonance (NMR) spectroscopy to investigate the functional group composition of fresh and aged biomass burning aerosols during an intensive field campaign in the Po Valley, Italy. The campaign was part of the EUCAARI project and was held at the rural station of San Pietro Capofiume in spring 2008. Factor analysis applied to the set of NMR spectra was used to apportion the wood burning contribution and other organic carbon (OC) source contributions, including aliphatic amines. Our NMR results, referred to the polar, water-soluble fraction of OC, show that fresh wood burning particles are composed of polyols and aromatic compounds, with a sharp resemblance to wood burning POA produced in wood stoves, while aged samples are clearly depleted of alcohols and are enriched in aliphatic acids with a smaller contribution of aromatic compounds. The comparison with biomass burning organic aerosols (BBOA) determined by high-resolution aerosol mass spectrometry (HR-TOF-AMS) at the site shows only a partial overlap between NMR BB-POA and AMS BBOA, which can be explained by either the inability of BBOA to capture all BB-POA composition, especially the alcohol fraction, or the fact that BBOA account for insoluble organic compounds unmeasured by the NMR. Therefore, an unambiguous composition for biomass burning POA could not be derived from this study, with NMR analysis indicating a higher O/C ratio compared to that measured for AMS BBOA. The comparison between the two techniques substantially improves when adding factors tracing possible contributions from biomass burning SOA, showing that the operational definitions of biomass burning organic aerosols are more consistent between techniques when including more factors tracing chemical classes over a range of oxidation levels. Overall, the non-fossil total carbon fraction was 50-57%, depending on the assumptions about the 14C content of non-fossil carbon, and the fraction of organic carbon estimated to be oxidized organic aerosol (OOA) from HR-TOF-AMS measurements was 73-100% modern

In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state (OSC) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H2O+ and CO+ ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H2O+, CO+, and CO2+ fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO+ and especially H2O+ produced from many oxidized species. Combined AMS–vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion fragments as markers to correct for molecular functionality-dependent systematic biases and reproduces known O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C (H : C) values is smaller for theoretical standard mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The OSC values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 OSC units). This indicates that OSC is a more robust metric of oxidation than O : C, likely since OSC is not affected by hydration or dehydration, either in the atmosphere or during analysis.