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Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOxeffect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements. publishedVersion

Highly oxygenated organic molecules (HOMs) are a major source of new particles affecting Earth’s climate1,2. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both day and night, and can lead to new particle formation (NPF)3,4. However, NPF involving organic vapors has been reported much more often during daytime3-6 than during nighttime7,8. Here, we show that the nitrate radicals (NO3) - which arise predominantly at night – inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD chamber at CERN; radical chemistry experiments using an oxidation flow reactor; and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultra-low volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound RO2 dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene-rich environments.

The Portable Ice Nucleation Chamber 2 (PINCii) is a newly developed continuous flow diffusion chamber (CFDC) for measuring ice nucleating particles (INPs). PINCii is a vertically-oriented parallel plate CFDC that has been engineered to improve upon limitations of previous generations of portable CFDCs. This work presents a detailed description of the PINCii instrument and the upgrades that make it unique compared to other operational CFDCs. The PINCii design offers several possibilities for improved INP measurements. Notably, a specific icing procedure results in low background particle counts, which demonstrates the potential for PINCii to measure INPs in very low concentrations. High spatial resolution walltemperature mapping enables the identification of temperature inhomogeneities on the chamber walls. This feature is used to introduce and discuss a new method to analyze CFDC data. A temperature gradient can be maintained throughout the evaporation section in addition to the main chamber, which enables PINCii to be used to study droplet activation processes or to extend ice crystal growth. A series of both liquid droplet activation and ice nucleation experiments were conducted at temperature and saturation conditions that span the spectrum of PINCii’s operational conditions (−50 ≤ temperature ≤ −15 °C and 100 ≤ relative humidity with respect to ice ≤ 160 %) to demonstrate the capabilities of PINCii. In addition, typical sources of uncertainty in CFDCs, including particle background, particle loss, and variations in aerosol lamina temperature and relative humidity, are quantified and discussed for PINCii.

The formation of ice particles in Earth's atmosphere strongly influences the dynamics and optical properties of clouds and their impacts on the climate system. Ice formation in clouds is often triggered heterogeneously by ice-nucleating particles (INPs) that represent a very low number of particles in the atmosphere. To date, many sources of INPs, such as mineral and soil dust, have been investigated and identified in the low and mid latitudes. Although less is known about the sources of ice nucleation at high latitudes, efforts have been made to identify the sources of INPs in the Arctic and boreal environments. In this study, we investigate the INP emission potential from high-latitude boreal forests in the mixed-phase cloud regime. We introduce the HyICE-2018 measurement campaign conducted in the boreal forest of Hyytiala, Finland, between February and June 2018. The campaign utilized the infrastructure of the Station for Measuring Ecosystem-Atmosphere Relations (SMEAR) II, with additional INP instruments, including the Portable Ice Nucleation Chamber I and II (PINC and PINCii), the SPectrometer for Ice Nuclei (SPIN), the Portable Ice Nucleation Experiment (PINE), the Ice Nucleation SpEctrometer of the Karlsruhe Institute of Technology (INSEKT) and the Microlitre Nucleation by Immersed Particle Instrument (mu L-NIPI), used to quantify the INP concentrations and sources in the boreal environment. In this contribution, we describe the measurement infrastructure and operating procedures during HyICE-2018, and we report results from specific time periods where INP instruments were run in parallel for inter-comparison purposes. Our results show that the suite of instruments deployed during HyICE-2018 reports consistent results and therefore lays the foundation for forthcoming results to be considered holistically. In addition, we compare measured INP concentrations to INP parameterizations, and we observe good agreement with the Tobo et al. (2013) parameterization developed from measurements conducted in a ponderosa pine forest ecosystem in Colorado, USA., Atmospheric Chemistry and Physics, 22 (8), ISSN:1680-7375, ISSN:1680-7367

Currently, the complete chemical characterization of nanoparticles (< 100 nm) represents an analytical challenge, since these particles are abundant in number but have negligible mass. Several methods for particle-phase characterization have been recently developed to better detect and infer more accurately the sources and fates of sub-100 nm particles, but a detailed comparison of different approaches is missing. Here we report on the chemical composition of secondary organic aerosol (SOA) nanoparticles from experimental studies of α-pinene ozonolysis at −50, −30, and −10 ∘C and intercompare the results measured by different techniques. The experiments were performed at the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). The chemical composition was measured simultaneously by four different techniques: (1) thermal desorption–differential mobility analyzer (TD–DMA) coupled to a NO3- chemical ionization–atmospheric-pressure-interface–time-of-flight (CI–APi–TOF) mass spectrometer, (2) filter inlet for gases and aerosols (FIGAERO) coupled to an I− high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS), (3) extractive electrospray Na+ ionization time-of-flight mass spectrometer (EESI-TOF), and (4) offline analysis of filters (FILTER) using ultra-high-performance liquid chromatography (UHPLC) and heated electrospray ionization (HESI) coupled to an Orbitrap high-resolution mass spectrometer (HRMS). Intercomparison was performed by contrasting the observed chemical composition as a function of oxidation state and carbon number, by estimating the volatility and comparing the fraction of volatility classes, and by comparing the thermal desorption behavior (for the thermal desorption techniques: TD–DMA and FIGAERO) and performing positive matrix factorization (PMF) analysis for the thermograms. We found that the methods generally agree on the most important compounds that are found in the nanoparticles. However, they do see different parts of the organic spectrum. We suggest potential explanations for these differences: thermal decomposition, aging, sampling artifacts, etc. We applied PMF analysis and found insights of thermal decomposition in the TD–DMA and the FIGAERO.

Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O3 → IOIO4 and (R2) IOIO4 + H2O → HIO3 + HOI + (1)O2. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.

A new bubble-generating glass chamber with an extensive set of aerosol production experiments is presented. Compared to the experiments described in the literature since the ground-setting works of Edward C.​​​​​​​ Monahan et al. in 1980s, the current setup is among the medium-sized installations allowing for accurate control of the air discharge, water temperature, and salinity. The size and material of the chamber offer a variety of applications due to its portability, measurement setup adjustability, and sterilization option. The experiments have been conducted in a cylindrical bubbling tank of 10 L volume that was filled by ∼ 30 %–40 % with water of controlled salt content and temperature and covered with a hermetic lid. The chamber was used to study the characteristics of aerosols produced by bursting bubbles under different conditions. In line with previous findings, the sea spray aerosol production was shown to depend linearly on the surface area covered by the bubbles, which in turn is a near-linear function of the air discharge through the water. Observed dependencies of the aerosol size spectra and particle fluxes on water salinity and temperature, being qualitatively comparable with the previous experiments, substantially refined the existing parameterizations. In particular, the bubble size was practically independent from the air discharge through the water body, except in the case of very small flows. Also, the dependence of aerosol spectrum and amount on salinity was much weaker than suggested in some previous experiments. The temperature dependence, to the contrary, was significant and consistent, with a transition in the spectrum shape at ∼ 10 ∘C. Theoretical analysis based on the basic conservation laws supported the main results of the experiments but also highlighted the need for a better understanding of the aerosol production from a cold water surface.

The occurrence of new particle formation (NPF) events detected in a coastal agricultural site, at Qvidja, in Southwestern Finland, was investigated using the data measured with a nitrate ion-based chemical-ionization atmospheric-pressure-interface time-of-flight (CI-APi-TOF) mass spectrometer. The binned positive matrix factorization method (binPMF) was applied to the measured spectra. It resulted in eight factors describing the time series of ambient gas and cluster composition at Qvidja during spring 2019. The most interesting factors related to the observed NPF events were the two factors with the highest mass-to-charge ratios, numbered 7 and 8, both having profiles with patterns of highly oxygenated organic molecules with one nitrogen atom. It was observed that factor 7 had elevated intensities during the NPF events. A variable with an even better connection to the observed NPF events is fF7, which denotes the fraction of the total spectra within the studied mass-to-charge ratio range between 169 and 450 Th being in a form of factor 7. Values of fF7 higher than 0.50±0.05 were observed during the NPF events, of which durations also correlated with the duration of fF7 exceeding this critical value. It was also observed that factor 8 acts like a precursor for factor 7 with solar radiation and that the formation of factor 8 is associated with ozone levels.

A new bubble-generating glass chamber design with an extensive set of aerosol production experiments is presented. Compared to the experiments described in the literature, current setup is among the medium-sized installations allowing precise control over the air discharge, water temperature and salinity. The size and material of the chamber offer variety of applications due to its portability, measurement setup adjustability and sterilization option. The experiments have been conducted in a cylindrical bubbling tank of 10 l volume filled by ~30–40 % with water of controlled salt content and temperature and covered with a hermetic lid. The chamber was used to study the characteristics of the aerosols produced by bursting bubbles under different conditions. In line with previous findings, the sea spray aerosol production was shown to depend linearly on the surface area covered by the bubbles, which in turn is a near-linear function of the air discharge through the water. Observed dependencies of the aerosol size spectra and particle fluxes on water salinity and temperature, being qualitatively comparable with the previous experiments, substantially refined the existing parameterizations. In particular, the bubble size was practically independent from the air discharge through the water body, except for very small flows. Also, the dependence of aerosol spectrum and amount on salinity was much weaker than suggested in some previous experiments. The temperature dependence, to the contrary, was significant and consistent, with a transition in the spectrum shape at ~10 °C. Theoretical analysis based on the basic conservation laws supported the main results of the experiments but also highlighted the need of better understanding of the aerosol production from a cold water surface.

Short summary We summarize results during the last 5 years in the northern Eurasian region, especially from Russia, and introduce recent observations of the air quality in the urban environments in China. Although the scientific knowledge in these regions has increased, there are still gaps in our understanding of large-scale climate–Earth surface interactions and feedbacks. This arises from limitations in research infrastructures and integrative data analyses, hindering a comprehensive system analysis. The Pan-Eurasian Experiment (PEEX) Science Plan, released in 2015, addressed a need for a holistic system understanding and outlined the most urgent research needs for the rapidly changing Arctic-boreal region. Air quality in China, together with the long-range transport of atmospheric pollutants, was also indicated as one of the most crucial topics of the research agenda. These two geographical regions, the northern Eurasian Arctic-boreal region and China, especially the megacities in China, were identified as a “PEEX region”. It is also important to recognize that the PEEX geographical region is an area where science-based policy actions would have significant impacts on the global climate. This paper summarizes results obtained during the last 5 years in the northern Eurasian region, together with recent observations of the air quality in the urban environments in China, in the context of the PEEX programme. The main regions of interest are the Russian Arctic, northern Eurasian boreal forests (Siberia) and peatlands, and the megacities in China. We frame our analysis against research themes introduced in the PEEX Science Plan in 2015. We summarize recent progress towards an enhanced holistic understanding of the land–atmosphere–ocean systems feedbacks. We conclude that although the scientific knowledge in these regions has increased, the new results are in many cases insufficient, and there are still gaps in our understanding of large-scale climate–Earth surface interactions and feedbacks. This arises from limitations in research infrastructures, especially the lack of coordinated, continuous and comprehensive in situ observations of the study region as well as integrative data analyses, hindering a comprehensive system analysis. The fast-changing environment and ecosystem changes driven by climate change, socio-economic activities like the China Silk Road Initiative, and the global trends like urbanization further complicate such analyses. We recognize new topics with an increasing importance in the near future, especially “the enhancing biological sequestration capacity of greenhouse gases into forests and soils to mitigate climate change” and the “socio-economic development to tackle air quality issues”.

A 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., Measurements in the CLOUD chamber at CERN show that the rapid condensation of ammonia and nitric acid vapours could be important for the formation and survival of new particles in wintertime urban conditions, contributing to urban smog.

Atmospheric new particle formation (NPF), which is observed in many environments globally, is an important source of boundary-layer aerosol particles and cloud condensation nuclei, which affect both the climate and human health. To better understand the mechanisms behind NPF, chamber experiments can be used to simulate this phenomenon under well-controlled conditions. Recent advancements in instrumentation have made it possible to directly detect the first steps of NPF of molecular clusters (~1–2 nm in diameter) and to calculate quantities such as the formation and growth rates of these clusters. Whereas previous studies reported particle formation rates as the flux of particles across a specified particle diameter or calculated them from measurements of larger particle sizes, this protocol outlines methods to directly quantify particle dynamics for cluster sizes. Here, we describe the instrumentation and analysis methods needed to quantify particle dynamics during NPF of sub-3-nm aerosol particles in chamber experiments. The methods described in this protocol can be used to make results from different chamber experiments comparable. The experimental setup, collection and post-processing of the data, and thus completion of this protocol, take from months up to years, depending on the chamber facility, experimental plan and level of expertise. Use of this protocol requires engineering capabilities and expertise in data analysis. This protocol describes the instrumentation and analysis methods needed to quantify particle dynamics during new particle formation of sub-3-nm aerosol particles in chamber experiments.

Measurements of aerosol particles and clusters smaller than 3 nm in diameter are performed by many groups in order to detect recently formed or emitted nanoparticles and for studying the formation and early growth processes of aerosol particles. The Airmodus nano-Condensation Nucleus Counter (nCNC), consisting of a Particle Size Magnifier (PSM) and a Condensation Particle Counter (CPC) is a versatile tool to detect aerosol particles and clusters as small as ca. 1 nm in mobility diameter. It offers several different operation modes: fixed mode to measure the total particle number concentration with a fixed, but adjustable lower cut-off size and stepping and scanning modes for retrieving size-resolved information of ca. 1–4 nm particles. The size analysis is based on changing the supersaturation of the working fluid (diethylene glycol) inside the instrument, which changes the lowest detectable size. Here we present a standard operating procedure (SOP) for setting up, calibrating and operating the instrument for atmospheric field measurements. We will also present recommendations for data monitoring and analysis, and discuss some of the uncertainties related to the measurements. This procedure is the first step in harmonizing the use of the PSM/nCNC for atmospheric field measurements of sub-3 nm clusters and particles. Measurements of aerosol particles and clusters smaller than 3 nm in diameter are performed by many groups in order to detect recently formed or emitted nanoparticles and for studying the formation and early growth processes of aerosol particles. The Airmodus nano-Condensation Nucleus Counter (nCNC), consisting of a Particle Size Magnifier (PSM) and a Condensation Particle Counter (CPC) is a versatile tool to detect aerosol particles and clusters as small as ca. 1 nm in mobility diameter. It offers several different operation modes: fixed mode to measure the total particle number concentration with a fixed, but adjustable lower cut-off size and stepping and scanning modes for retrieving size-resolved information of ca. 1–4 nm particles. The size analysis is based on changing the supersaturation of the working fluid (diethylene glycol) inside the instrument, which changes the lowest detectable size. Here we present a standard operating procedure (SOP) for setting up, calibrating and operating the instrument for atmospheric field measurements. We will also present recommendations for data monitoring and analysis, and discuss some of the uncertainties related to the measurements. This procedure is the first step in harmonizing the use of the PSM/nCNC for atmospheric field measurements of sub-3 nm clusters and particles.

At SMEAR II research station in Hyytiälä, located in the Finnish boreal forest, the process of new particle formation and the role of ions has been investigated for almost 20 years near the ground and at canopy level. However, above SMEAR II, the vertical distribution and diurnal variation of these different atmospheric ions are poorly characterized. In this study, we assess the atmospheric ion composition in the stable boundary layer, residual layer, mixing layer, and free troposphere, and the evolution of these atmospheric ions due to photochemistry and turbulent mixing through the day. To measure the vertical profile of atmospheric ions, we developed a tailored set-up for online mass spectrometric measurements, capable of being deployed in a Cessna 172 with minimal modifications. Simultaneously, instruments dedicated to aerosol properties made measurements in a second Cessna. We conducted a total of 16 measurement flights in May 2017, during the spring, which is the most active new particle formation season. A flight day typically consisted of three distinct flights through the day (dawn, morning, and afternoon) to observe the diurnal variation and at different altitudes (from 100 to 3200 m above ground), to capture the boundary layer development from the stable boundary layer, residual layer to mixing layer, and the free troposphere. Our observations showed that the ion composition is distinctly different in each layer and depends on the air mass origin and time of the day. Before sunrise, the layers are separated from each other and have their own ion chemistry. We observed that the ions present within the stable layer are of the same composition as the ions measured at the canopy level. During daytime when the mixing layer evolved and the compounds are vertically mixed, we observed that highly oxidized organic molecules are distributed to the top of the boundary layer. The ion composition in the residual layer varies with each day, showing similarities with either the stable boundary layer or the free troposphere. Finally, within the free troposphere, we detected a variety of carboxylic acids and ions that are likely containing halogens, originating from the Arctic Sea.

Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.

The formation of ice particles in Earth’s atmosphere strongly influences the dynamics and optical properties of clouds and their impacts on the climate system. Ice formation in clouds is often triggered heterogeneously by ice nucleating particles (INPs) that represent a very low number of particles in the atmosphere. To date, many sources of INPs, such as mineral and soil dust, have been investigated and identified in the lower latitudes. Although less is known about the sources of ice nucleation at higher latitudes, efforts have been made to identify the sources of INPs in the Arctic and boreal environments. In this study, we investigate the INP emission potential from high latitude boreal forests. We introduce the HyICE-2018 measurement campaign conducted in the boreal forest of Hyytiälä, Finland between February and June 2018. The campaign utilized the infrastructure of the SMEAR II research station with additional instrumentation for measuring INPs to quantify the concentrations and sources of INPs in the boreal environment. In this contribution, we describe the measurement infrastructure and operating procedures during HyICE-2018 and we report results from specific time periods where INP instruments were run in parallel for inter-comparison purposes. Our results show that the suite of instruments deployed during HyICE-2018 reports consistent results and therefore lays the foundation for forthcoming results to be considered holistically. In addition, we compare the INP concentration we measured to INP parameterizations, and we show a very good agreement with the Tobo et al. (2013) parameterization developed from measurements conducted in a ponderosa pine forest ecosystem in Colorado, USA.

International audience; Aviation emissions are not limited to greenhouse gases like CO2 but include other gases as well, such as nitrogen oxides (NOx) or sulfur oxides (SOx) and volatile and non-volatile particulate matter (vPM and nvPM respectively). Sulfuric acid formed in the engine exhaust seems to be linked to the formation of vPM. However, the amount of sulfur present in the fuel converted to sulfuric acid in the exhaust is too small to explain the amount of vPM observed (Vancassel et al. 2004). Organic compounds emitted by the engine are among the most suitable candidates to explain the formation of vPM in the engine exhaust (Sorokin et al. 2001), but the molecular mechanisms behind this phenomenon are still unknown.

New particle formation in the upper free troposphere is a major global source of cloud condensation nuclei (CCN)

In order to effectively predict the formation of ice in clouds we need to know which subsets of aerosol particles are effective at nucleating ice, how they are distributed and where they are from. A large proportion of ice-nucleating particles (INPs) in many locations are likely of biological origin, and some INPs are extremely small, being just tens of nanometres in size. The identity and sources of such INPs are not well characterized. Here, we show that several different types of virus particles can nucleate ice, with up to about 1 in 20 million virus particles able to nucleate ice at −20 ∘C. In terms of the impact on cloud glaciation, the ice-nucleating ability (the fraction which are ice nucleation active as a function of temperature) taken together with typical virus particle concentrations in the atmosphere leads to the conclusion that virus particles make a minor contribution to the atmospheric ice-nucleating particle population in the terrestrial-influenced atmosphere. However, they cannot be ruled out as being important in the remote marine atmosphere. It is striking that virus particles have an ice-nucleating activity, and further work should be done to explore other types of viruses for both their ice-nucleating potential and to understand the mechanism by which viruses nucleate ice.

Co-auteur étranger; International audience; Volcanic emissions can significantly affect the Earth's radiation budget by emitting aerosol particles and gas‐phase species that can result in the new particle formation (NPF). These particles can scatter solar radiation or modify cloud properties, with consequences on health, weather, and climate. To our knowledge, this is the first dedicated study detailing how gas‐phase precursors emitted from volcanic plumes can influence the NPF. A series of airborne measurements were performed around the Etna and Stromboli volcanoes within the framework of the CLerVolc and STRAP projects. The ATR‐42 aircraft was equipped with a range of instrumentation allowing the measurement of particle number concentration in diameter range above 2.5 nm, and gaseous species to investigate the aerosol dynamics and the processes governing the NPF and their growth within the volcanic plumes. We demonstrate that NPF occurs within the volcanic plumes in the Free Troposphere (FT) and Boundary Layer (BL). Typically, the NPF events were more pronounced in the FT, where the condensational sink was up to two orders of magnitude smaller and the temperature was ~20°C lower than in the BL. Within the passive volcanic plume, the concentration of sulfur dioxide, sulfuric acid, and N2.5 were as high as 92 ppbV, 5.65×108 and 2.4×105 cm–3, respectively. Using these measurements, we propose a new parameterization for NPF rate (J2.5) within the passive volcanic plume in the FT. These results can be incorporated into mesoscale models to better assess the impact of the particle formed by natural processes, i.e. volcanic plumes, on climate.

The Pan-Eurasian Experiment (PEEX) Science Plan, released in 2015, addressed a need for a holistic system understanding and outlined the most urgent research needs for sustainable development in the Artic-boreal region. Air quality in China and long-range transport of the atmospheric pollutants was also indicated as one of the most crucial topics of the research agenda. This paper summarizes results obtained during the last five years in the Northern Eurasian region. It also introduces recent observations on the air quality in the urban environments in China. The main regions of interest are the Russian Arctic, Northern Eurasian boreal forests (Siberia) and peatlands and on the mega cities in China. We frame our analysis against research themes introduced in 2015. We summarize recent progress in the understanding of the land – atmosphere – ocean systems feedbacks. Although the scientific knowledge in these regions has increased, there are still gaps in our understanding of large-scale climate-Earth surface interactions and feedbacks. This arises from limitations in research infrastructures and integrative data analyses, hindering a comprehensive system analysis. The fast-changing environment and ecosystem changes driven by climate change, socio-economic activities like the China Silk Road Initiative, and the global trends like urbanization further complicate such analyses. We recognize new topics with an increasing importance in the near future, such as enhancing biological sequestration capacity of greenhouse gases into forests and soils to mitigate the climate change and the socio-economic development to tackle air quality issues.

Aerosol particles negatively affect human health while also having climatic relevance due to, for example, their ability to act as cloud condensation nuclei. Ultrafine particles (diameter Dp < 100 nm) typically comprise the largest fraction of the total number concentration, however, their chemical characterization is difficult because of their low mass. Using an extractive electrospray time-of-flight mass spectrometer (EESI-TOF), we characterize the molecular composition of freshly nucleated particles from naphthalene and β-caryophyllene oxidation products at the CLOUD chamber at CERN. We perform a detailed intercomparison of the organic aerosol chemical composition measured by the EESI-TOF and an iodide adduct chemical ionization mass spectrometer equipped with a filter inlet for gases and aerosols (FIGAERO-I-CIMS). We also use an aerosol growth model based on the condensation of organic vapors to show that the chemical composition measured by the EESI-TOF is consistent with the expected condensed oxidation products. This agreement could be further improved by constraining the EESI-TOF compound-specific sensitivity or considering condensed-phase processes. Our results show that the EESI-TOF can obtain the chemical composition of particles as small as 20 nm in diameter with mass loadings as low as hundreds of ng m−3 in real time. This was until now difficult to achieve, as other online instruments are often limited by size cutoffs, ionization/thermal fragmentation and/or semi-continuous sampling. Using real-time simultaneous gas- and particle-phase data, we discuss the condensation of naphthalene oxidation products on a molecular level., Using real-time simultaneous gas- and particle-phase data, the condensation of naphthalene and β-caryophyllene oxidation products on a molecular level is discussed.

Sulfuric acid (H2SO4) is commonly accepted as a key precursor for atmospheric new particle formation (NPF). However, direct measurements of [H2SO4] remain challenging, thus preventing the determination of this important quantity, and, consequently, a complete understanding of its contribution to the NPF process. Several proxies have been developed to bridge the gaps, but their ability to predict [H2SO4] in very specific conditions such as those encountered in volcanic plumes (including in particular high sulphur dioxide mixing ratios) has not been evaluated so far. In this context, the main objective of the present study was to develop new proxies for daytime [H2SO4] in volcanic plume conditions and compare their performance to that of the proxies available in the literature. In specific, the data collected at Maïdo during the OCTAVE 2018 campaign, in the volcanic eruption plume of the Piton de la Fournaise, were first used to derive seven proxies based on the knowledge of sulphur dioxide (SO2) mixing ratio, global radiation, condensation sink (CS) and relative humidity (RH). In three of the seven proxies (F1–F3), all variables were given equal weight in the prediction of [H2SO4], while adjusted powers were allowed for the different variables in the other four proxies (A1–A4). Proxies A1–A4 were overall found to perform better compared to F1–F3, with, in specific, improved predictive ability for [H2SO4] > 2 × 108 cm−3. The CS was observed to play an important role in regulating [H2SO4], while, in contrast, the inclusion of RH did not improve the predictions. A last expression accounting for an additional sink term related to cluster formation, S1, was also tested and showed a very good predictive ability over the whole range of measured [H2SO4]. The newly developed proxies were in a second step further evaluated using airborne measurements performed in the passive degassing plume of Etna during the STRAP 2016 campaign. Increased correlations between observed and predicted [H2SO4] were obtained when the dependence of predicted [H2SO4] over CS was the lowest, and when the dependence over [SO2] was concurrently the highest. The best predictions were finally retrieved by the simple formulation of F2 (in which [SO2] and radiation alone were assumed to explain the variations of [H2SO4] with equal contributions), with a pre factor adapted to the STRAP data. All in all, our results illustrate the fairly good capacity of the proxy available in the literature to describe [H2SO4] in volcanic plume conditions, but highlight at the same time the benefit of the newly developed proxies for the prediction of the highest concentrations ([H2SO4] > 2–3 × 108 cm−3). Also, the contrasting behaviours of the new proxies in the two investigated datasets indicate that in volcanic plumes like in other environments, the relevance of a proxy can be affected by changes in environmental conditions, and that location specific coefficients do logically improve the predictions.

Ice-nucleating particles (INPs) trigger the formation of cloud ice crystals in the atmosphere. Therefore, they strongly influence cloud microphysical and optical properties and precipitation and the life cycle of clouds. Improving weather forecasting and climate projection requires an appropriate formulation of atmospheric INP concentrations. This remains challenging as the global INP distribution and variability depend on a variety of aerosol types and sources, and neither their short-Term variability nor their long-Term seasonal cycles are well covered by continuous measurements. Here, we provide the first year-long set of observations with a pronounced INP seasonal cycle in a boreal forest environment. Besides the observed seasonal cycle in INP concentrations with a minimum in wintertime and maxima in early and late summer, we also provide indications for a seasonal variation in the prevalent INP type. We show that the seasonal dependency of INP concentrations and prevalent INP types is most likely driven by the abundance of biogenic aerosol. As current parameterizations do not reproduce this variability, we suggest a new mechanistic description for boreal forest environments which considers the seasonal variation in INP concentrations. For this, we use the ambient air temperature measured close to the ground at 4.2 m height as a proxy for the season, which appears to affect the source strength of biogenic emissions and, thus, the INP abundance over the boreal forest. Furthermore, we provide new INP parameterizations based on the Ice Nucleation Active Surface Site (INAS) approach, which specifically describes the ice nucleation activity of boreal aerosols particles prevalent in different seasons. Our results characterize the boreal forest as an important but variable INP source and provide new perspectives to describe these new findings in atmospheric models. publishedVersion

To better understand the role of aromatic hydrocarbons in new-particle formation, we measured the particle-phase abundance and volatility of oxidation products following the reaction of aromatic hydrocarbons with OH radicals. For this we used thermal desorption in an iodide-adduct Time-of-Flight Chemical-Ionization Mass Spectrometer equipped with a Filter Inlet for Gases and AEROsols (FIGAERO-ToF-CIMS). The particle-phase volatility measurements confirm that oxidation products of toluene and naphthalene can contribute to the initial growth of newly formed particles. Toluene-derived (C7) oxidation products have a similar volatility distribution to that of α-pinene-derived (C10) oxidation products, while naphthalene-derived (C10) oxidation products are much less volatile than those from toluene or α-pinene; they are thus stronger contributors to growth. Rapid progression through multiple generations of oxidation is more pronounced in toluene and naphthalene than in α-pinene, resulting in more oxidation but also favoring functional groups with much lower volatility per added oxygen atom, such as hydroxyl and carboxylic groups instead of hydroperoxide groups. Under conditions typical of polluted urban settings, naphthalene may well contribute to nucleation and the growth of the smallest particles, whereas the more abundant alkyl benzenes may overtake naphthalene once the particles have grown beyond the point where the Kelvin effect strongly influences the condensation driving force. © 2020 American Chemical Society. ISSN:0013-936X ISSN:1520-5851

By triggering the formation of cloud ice crystals in the atmosphere, ice-nucleating particles (INP) strongly influence cloud properties, cloud life cycle and precipitation. Describing the abundance of atmospheric INPs in weather forecasts and climate projections remains challenging, as the global distribution and variability of INPs depend on a variety of different aerosol types and sources. Although widespread field measurements have been conducted, neither short-term variability nor long-term seasonal cycles have yet been well characterized by continuous measurements. In 2018, the University of Helsinki and the Karlsruhe Institute of Technology (KIT) initiated a field campaign HyICE to perform comprehensive long-term INP measurements in the Finnish boreal forest. The campaign took place in Hyytiälä, Southern Finland at the University of Helsinki SMEARII research station (Hari and Kulmala, 2005). KIT provided the INSEKT (Ice Nucleation Spectrometer of the Karlsruhe Institute of Technology) to analyse the INP content of ambient aerosols sampled on filters. INSEKT is able to measure INP concentrations in the immersion-freezing mode at temperatures between 273 K and 248 K. The measurements started in March 2018 and ended in May 2019, which provides a unique continuous long-term time series of INP concentrations for over more than one year with a time resolution of about one to three days. This long-term observation record is used to examine systematic seasonal trends in the INP concentrations and to find meteorological and aerosol related parameters to describe the observed trends and variabilities. These findings will enable to find new parameterizations of atmospheric INP concentrations, as current parameterizations do not reproduce the observed seasonal cycle yet. In addition to INP concentration measurements, heat treatment tests of the aerosol samples have been conducted providing additional indications about the INP types dominating the INP population in the boreal forest, also in dependence on the season. Finally, this contribution will summarize and discuss major findings and implications from the HyICE long-term INP observation. Hari and Kulmala (2005), Boreal Environ Res. 14, 315-322.

Highly-oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role for new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their new-particle formation rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to −50 °C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the new-particle formation rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products and a 2-dimensional volatility basis set model (2D-VBS) provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25 °C to 0.7 % at −50 °C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to three orders of magnitude at −50 °C compared with 25 °C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic new-particle formation at the molecular level. Our measurements therefore improve our understanding of pure biogenic new-particle formation for a wide range of tropospheric temperatures and precursor concentrations.

Ions enhance the formation rate of atmospheric aerosol particles, which play an important role in Earth’s radiative balance. Ion-induced nucleation involves the stepwise accretion of neutral monomers onto a molecular cluster containing an ion, which helps to stabilize the cluster against evaporation. Although theoretical frameworks exist to calculate the collision rate coefficients between neutral molecules and ions, they need to be experimentally confirmed, ideally under atmospherically relevant conditions of around 1000 ion pairs cm−3. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we have measured the collision rate coefficients between neutral iodic acid (HIO3) monomers and charged iodic acid molecular clusters containing up to 11 iodine atoms. Three methods were analytically derived to calculate ion-polar molecule collision rate coefficients. After evaluation with a kinetic model, the 50% appearance time method is found to be the most robust. The measured collision rate coefficient, averaged over all iodine clusters, is (2.4 ± 0.8)×10−9 cm3 s−1, which is close to the expectation from the surface charge capture theory.

NOx is important for particle growth as it can participate in HOM formation and alter the HOM volatility distribution., 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.

Evaporation of sulfuric acid from particles can be important in the atmospheres of Earth and Venus. However, the equilibrium constant for the dissociation of H2SO4 to bisulfate ions, which is the one of the fundamental parameters controlling the evaporation of sulfur particles, is not well constrained. In this study we explore the volatility of sulfate particles at very low relative humidity. We measured the evaporation of sulfur particles versus temperature and relative humidity in the CLOUD chamber at CERN. We modelled the observed sulfur particle shrinkage with the ADCHAM model. Based on our model results, we conclude that the sulfur particle shrinkage is mainly governed by H2SO4 and potentially to some extent by SO3 evaporation. We found that the equilibrium constants for the dissociation of H2SO4 to HSO4−(KH2SO4) and the dehydration of H2SO4 to SO3 (xKSO3) are KH2SO4 = 2–4 × 109 mol kg−1 and xKSO3 ≥ 1.4 × 1010 at 288.8 ± 5 K.

The quality and chemical composition of urban dew collections with dust precipitates without pre-cleaning of the collecting surface WSF (white standard foil) were investigated for 16 out of 20 collected samples with collected volumes ranging from 22 to 230 ml. The collection period was from March to July 2015 at an urban area, Jubaiha, which is located in the northern part of the capital city Amman, Jordan. The obtained results indicated the predominance of Ca2+ and SO42− ions (ratio 2.2:1) that originated from Saharan soil dust; where the collected samples were alkaline (mean pH = 7.35) with high mineralization (429.22 mg/L) exceeding the previously reported dew values in Amman-Jordan. A relocation of NaCl and to a less extent Mg2+ from sea to land by Saharan wind is indicated by the percent sea-salt fraction calculations (over 100 and 52, respectively). The collected samples exhibited high total organic carbon (TOC) values ranging from 11.86 to 74.60 mg/L, presence of particulate settled material with turbidity ranging from 20.10 to 520.00 NTU, and presence of undesired elements like boron (mean = 1.48 mg/L) that made it different in properties from other dew water collections at clean surfaces, and exceeding the standard limits for drinking water for these parameters set by Jordanian Drinking Water standards (JS286/2015)/WHO standard. The quality of this water is more close to that for raw or agricultural water but if it is meant to be used as potable source of water, at least sand and activated charcoal filters are needed to purify it.

In the present-day atmosphere, sulfuric acid is the most important vapour for aerosol particle formation and initial growth. However, the growth rates of nanoparticles (