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The Arctic is a region that is particularly vulnerable to the impacts of climate change, as it is warming at a faster rate than the rest of the world. This warming causes a decline in multiyear sea ice cover, which results in an increasing open-ocean surface with a much lower albedo therefore leading to positive feedback and enhanced warming. Another factor that plays a role in regulating the temperature in the Arctic is the type and extent of cloud cover. Aerosols that can serve as cloud condensation nuclei or ice nucleating particles (INPs) are key for cloud formation. Some microorganisms are known to produce INPs, but it is not well understood which microorganisms are responsible, which environments they inhabit, and how active they are. In this study, we set out to investigate the partitioning of INPs between the Arctic marine and atmospheric environment by combining in situ measurements with laboratory experiments.First, we wanted to determine if sea ice acts as a reservoir for INPs and, if so, whether the INPs are partitioned into the sea ice during its formation or produced by microorganisms within the sea ice. We used a modified ice-finger to grow sea ice using natural samples from West Greenland and found that INPs concentrate into the ice fraction during sea-ice formation, and that these INPs typically are associated with microorganisms.Next, we wanted to understand the temporal and spatial dynamics of INPs in Arctic sea ice. We collected sea ice cores from the Arctic before and during the spring sea ice phytoplankton bloom and analysed them using cold-stage INP measurements, flow-cytometry, and amplicon sequencing. The results showed that there are between 106 · L-1 (at the bottom of the sea ice) INP-10 present in the Arctic sea ice. Finally, we wanted to determine the potential contribution of sea ice to the atmospheric INP pool in the Arctic. We introduced natural samples of bulk water and sea ice from Nuuk and Station Nord into a temperature-controlled sea spray simulation chamber and quantified the microorganisms and INPs present in the bulk water, surface microlayer and air before and after aerosolization. The results showed that the highly active INPs are efficiently aerosolized into the atmosphere during bubble-bursting where they may contribute to the formation of ice in clouds.Overall, this study provides new insight into the role of Arctic sea ice as a reservoir for INPs and the microorganisms that produce them, as well as the mechanisms by which INPs are released into the Arctic atmosphere. This information is important for understanding the impact of climate change on the Arctic region and the potential consequences for the rest of the world.

Clouds have one of the most profound effects on Earth’s climate, yet they are still responsible for some of the biggest uncertainties in climate models. Cloud formation, radiative properties, thickness and lifetime are tightly interlinked with the presence of atmospheric particles (aerosols) and the formation of ice. Biological aerosols (bioaerosols) such as ice-nucleation proteins (INpro) produced by microorganisms are most efficient catalysts in the formation of ice and can trigger heterogenous freezing between -1°C and -15°C. Several studies have demonstrated that Arctic environments are a source of airborne INpro. Sea spray is one of the major sources of aerosols, which aside of the sea salt contain large amounts of organic material. These are ejected into the atmosphere through the process of wave breaking and bubble bursting of small bubbles, which eject drops from the sea surface microlayer (SML) to the atmosphere. Here, we present results derived from droplet freezing assays and amplicon sequencing combined with quantitative PCR, targeting the 16S rRNA gene from sea and aerosol samples collected along a transect from sub- to high Arctic Greenland (Baffin Bay). We demonstrate a positive correlation between INpro concentration and higher latitudes in sea bulk water (SBW) and SML. Additionally, we try to link specific taxonomic groups from the microbial communities to INpro production. Last, we aim to investigate if partitioning of specific taxonomic groups can be observed from SBW to SML and from SML to the atmosphere. Finally, we performed laboratorial sea-spray experiments simulating turbulent sea conditions. This study has the potential to help closing the current knowledge gap in understanding the partitioning of microorganisms from the sea to the atmosphere and unravel which microbes are the major contributors to atmospheric INpro and hence cloud formation.

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.

Dimethyl sulfide (DMS) is emitted by phytoplankton species in the oceans and constitutes the largest source of naturally emitted sulfur to the atmosphere. The climate impact of secondary particles, formed through the oxidation of DMS by hydroxyl radicals, is still elusive. This study investigates the hygroscopicity and cloud condensation nuclei activity of such particles and discusses the results in relation to their chemical composition. We show that mean hygroscopicity parameters, κ, during an experiment for particles of 80 nm in diameter range from 0.46 to 0.52 or higher, as measured at both sub- and supersaturated water vapour conditions. Ageing of the particles leads to an increase in κ from, for example, 0.50 to 0.58 over the course of 3 h (Exp. 7). Aerosol mass spectrometer measurements from this study indicate that this change most probably stems from a change in chemical composition leading to slightly higher fractions of ammonium sulfate compared to methanesulfonic acid (MSA) within the particles with ageing time. Lowering the temperature to 258 K increases κ slightly, particularly for small particles. These κ values are well comparable to previously reported model values for MSA or mixtures between MSA and ammonium sulfate. Particle nucleation and growth rates suggest a clear temperature dependence, with slower rates at cold temperatures. Quantum chemical calculations show that gas-phase MSA clusters are predominantly not hydrated, even at high humidity conditions, indicating that their gas-phase chemistry should be independent of relative humidity.

Introduction:Breaking waves on the ocean surface lead to sea spray aerosol emission to the atmosphere. Sea spray aerosols are a major source of uncertainty in climate models. The physical processes governing sea spray aerosol production play an important part in determining sea spray aerosol emission, size distribution, and chemical composition. Sea spray often contains organic material, but it is unclear how this material affects the ability of particles to act as cloud condensation nuclei (CCN).Methods:We have measured the CCN-derived hygroscopicity of different types of aerosol particles generated from the following seawater proxies and real seawater using a sea spray simulation tank (Christiansen et al., 2019), AEGOR, or an atomizer in a laboratory setup (Christiansen et al., 2020): Artificial seawater Artificial seawater spiked with diatoms cultured in the laboratory Samples of sea surface microlayer (SML) collected during field campaigns in the North Atlantic and Arctic Ocean. A continuous supply of fresh seawater during a three-week field campaign (June 2019) on the Faroe Islands, while following oceanic biogeochemical parameters. Large-eddy simulation (LES) has been used to evaluate the general role of aerosol hygroscopicity in governing mixed-phase low-level cloud properties in the high Arctic.Conclusions: We show that sea spray aerosols generated using diatom cultures and surface microlayer water exhibit CCN activity similar to that of inorganic sea salt (κ value of ∼1.0), independent of dry particle size (50, 75, and 100 nm). The critical supersaturation of dry 80 nm SSA was relatively invariable (0.158±0.04%), corresponding to the overall hygroscopicity parameter κ of 1.08±0.05% derived from CCN during the phytoplankton bloom. This is despite indications that the chemical composition of both the seawater and the SSA were impacted by the presence of the phytoplankton. For accumulation mode aerosol, the simulated mixed-phase cloud properties do not depend strongly on κ, unless κ < 0.4. In addition, the cloud is sustained for all simulated cases. For Aitken mode aerosol, the hygroscopicity is more important changing the microphysical structure of the cloud and its radiative properties; here the particles can sustain the cloud only when κ ≥ 0.4. The experimental and model results combined suggest that the internal mixing of biogenic organic components in SSA does not have a substantial impact on the cloud droplet activation process and the cloud lifetime in Arctic mixed-phase clouds.References:Christiansen et al. (2020). J. Geophys. Res. Atm. https://doi.org/10.1029/2020JD032808Christiansen et al. (2019). Environ. Sci. Technol. https://doi.org/10.1021/acs.est.9b04078

Little is known about the effects of low temperatures on the formation of SOA from α-pinene. In the current work, ozone-initiated oxidation of α-pinene at initial concentrations of 10 and 50 ppb, respectively, is performed at temperatures of 20, 0 and −15 °C in the Aarhus University Research on Aerosol (AURA) smog chamber during the Aarhus Chamber Campaign on highly oxidized multifunctional organic molecules and Aerosol (ACCHA). Here, we show how temperature influences the formation and chemical composition of α-pinene-derived SOA with a specific focus on the formation of organic acids and dimer esters. With respect to particle formation, results show significant increase in both particle formation rates, particle number concentrations and particle mass concentrations at lower temperatures. In particular, the number concentrations of sub-10 nm particles were significantly enhanced at the lower 0 and -15 °C temperatures. Temperatures also affect chemical composition of the formed SOA. Here, detailed off-line chemical analyses show organic acids contributing from 15 to 30 % by mass, with highest contributions observed at the lower temperatures indicative of enhanced condensation of these semi-volatile species. In comparison, 30 identified dimer esters contribute between 4–11 % to SOA mass. No significant differences in the chemical composition (i.e. organic acids and dimer esters) of the α-pinene-derived SOA particles are observed between experiments performed at 10 and 50 ppb initial α-pinene concentrations, thus suggesting a higher influence of reaction temperature compared to that of α-pinene loading on the SOA chemical composition. Interestingly, the effect of temperature on the formation of dimer esters differs between the individual species. The formation of less oxidized (oxygen-to-carbon ratio (O:C) < 0.4) dimer esters is shown to increase at lower temperatures while the formation of the more oxidized (O:C > 0.4) species is suppressed, consequently resulting in temperature-modulated composition of the α-pinene derived SOA. Temperature ramping experiments exposing α-pinene-derived SOA to changing temperatures (heating and cooling) reveal that the chemical composition of the SOA with respect to dimer esters is governed almost solely by the temperature during the initial oxidization and insusceptible to subsequent changes in temperature. Similarly, the resulting SOA mass concentrations were found to be more influenced by the initial α-pinene oxidation temperatures, thus suggesting that the formation conditions to a large extent govern the type of SOA formed, rather than the conditions to which the SOA is later exposed. For the first time, we discuss the relation between the identified dimer ester and the highly oxidized multifunctional organic molecules (HOMs) measured by Chemical Ionization Atmospheric Pressure interface Time-of-Flight mass spectrometer (CI-APi-TOF) during ACCHA experiments. We propose that, although very different in chemical structures and O:C-ratios, dimer esters and HOMs may be linked through the mechanism of RO2 autoxidation, and that dimer esters and HOMs merely represent two different fates of the RO2 radicals.

Secondary organic aerosol (SOA) plays a central role in air pollution and climate. However, the description of the sources and mechanisms leading to SOA is elusive despite decades of research. While stable isotope analysis is increasingly used to constrain sources of ambient aerosol, in many cases it is difficult to apply because neither the isotopic composition of aerosol precursors nor the fractionation of aerosol forming processes is well characterised. In this paper, SOA formation from ozonolysis of α-pinene – an important precursor and perhaps the best-known model system used in laboratory studies – was investigated using position-dependent and average determinations of 13C in α-pinene and advanced analysis of reaction products using thermal-desorption proton-transfer-reaction mass spectrometry (PTR-MS). The total carbon (TC) isotopic composition δ13C of the initial α-pinene was measured, and the δ13C of the specific carbon atom sites was determined using position-specific isotope analysis (PSIA). The PSIA analysis showed variations at individual positions from −6.9 to +10. 5 ‰ relative to the bulk composition. SOA was formed from α-pinene and ozone in a constant-flow chamber under dark, dry, and low-NOx conditions, with OH scavengers and in the absence of seed particles. The excess of ozone and long residence time in the flow chamber ensured that virtually all α-pinene had reacted. Product SOA was collected on two sequential quartz filters. The filters were analysed offline by heating them stepwise from 100 to 400 °C to desorb organic compounds that were (i) detected using PTR-MS for chemical analysis and to determine the O : C ratio, and (ii) converted to CO2 for 13C analysis. More than 400 ions in the mass range 39–800 Da were detected from the desorbed material and quantified using a PTR-MS. The largest amount desorbed at 150 °C. The O : C ratio of material from the front filter increased from 0.18 to 0.25 as the desorption temperature was raised from 100 to 250 °C. At temperatures above 250 °C, the O : C ratio of thermally desorbed material, presumably from oligomeric precursors, was constant. The observation of a number of components that occurred across the full range of desorption temperatures suggests that they are generated by thermal decomposition of oligomers. The isotopic composition of SOA was more or less independent of desorption temperature above 100 °C. TC analysis showed that SOA was enriched in 13C by 0.6–1.2 ‰ relative to the initial α-pinene. According to mass balance, gas-phase products will be depleted relative to the initial α-pinene. Accordingly, organic material on the back filters, which contain adsorbed gas-phase compounds, is depleted in 13C in TC by 0.7 ‰ relative to the initial α-pinene, and by 1.3 ‰ compared to SOA collected on the front filter. The observed difference in 13C between the gas and particle phases may arise from isotope-dependent changes in the branching ratios in the α-pinene + O3 reaction. Alternatively, some gas-phase products involve carbon atoms from highly enriched and depleted sites, as shown in the PSIA analysis, giving a non-kinetic origin to the observed fractionations. In either case, the present study suggests that the site-specific distribution of 13C in the source material itself governs the abundance of 13C in SOA.

Particulate air pollution in China is influencing human health, ecosystem and climate. However, the chemical composition of particulate aerosol, especially of the organic fraction, is still not well understood. In this study, particulate aerosol samples with a diameter &leq; 2.5 μm (PM2.5) were collected in January 2014 in three cities located in Northeast, East and Southeast China, i.e., Changchun, Shanghai and Guangzhou, respectively. Organic aerosol (OA) in the PM2.5 samples was analyzed by ultrahigh performance liquid chromatography (UHPLC) coupled to high-resolution Orbitrap mass spectrometry in both negative mode (ESI−) and positive mode electrospray ionization (ESI+). After a non-target screening including molecular formula assignments, compounds were classified into five groups based on their elemental composition, i.e., CHO, CHON, CHN, CHOS and CHONS. The CHO, CHON and CHN compounds present the dominant signal abundances of 81–99.7 % in the mass spectra and the majority of these compounds were assigned to mono- and polyaromatics, suggesting that anthropogenic emissions are a large source of urban OA in all three cities. However, the chemical characteristics of these compounds varied among different cities. The degree of aromaticity and the number of polyaromatic compounds were significantly higher in samples from Changchun, which could be attributed to the large emissions from residential heating (i.e., coal combustion) during winter time in Northeast China. Moreover, the ESI− analysis showed higher H / C and O / C ratios for organic compounds in Shanghai and Guangzhou compared to samples from Changchun, indicating that OA in lower latitude regions of China experiences more intense photochemical oxidation processes. The majority of sulfur-containing compounds (CHOS and CHONS) in all cities were assigned to aliphatic compounds with low degrees of unsaturation and aromaticity. Again, samples from Shanghai and Guangzhou exhibit a larger chemical similarity but largely differ from those from Changchun.

Highly-oxygenated Organic Molecules (HOM) are important contributors to Secondary Organic Aerosol (SOA) and New-Particle Formation (NPF) in the boreal atmosphere. This newly discovered class of molecules is efficiently formed from atmospheric oxidation of biogenic volatile organic compounds (VOC), such as monoterpenes, through a process called autoxidation. This process, in which peroxy-radical intermediates isomerize to allow addition of molecular oxygen, is expected to be highly temperature-dependent. Here, we studied the dynamics of HOM formation during alpha-pinene ozonolysis experiments performed at three different temperatures, 20 °C, 0 °C and −15 °C, in the Aarhus University Research on Aerosol (AURA) chamber. We found that the HOM formation, under our experimental conditions (50 ppb alpha-pinene, 100 ppb ozone), decreased considerably as temperature decreased, with molar yields dropping by around a factor of 50 when experiments were performed at 0 °C, compared to 20 °C. At −15 °C, the HOM signals were already close to the detection limit of the nitrate-based Chemical Ionization Atmospheric Pressure interface Time Of Flight (CI-APi-TOF) mass spectrometer used for measuring gas-phase HOM. Surprisingly, very little difference was seen in the mass spectral distribution of the HOM molecules of interest at 0 °C and 20 °C, with e.g. the ratios between the typical HOM products C10H14O7, C10H14O9, and C10H14O11 remaining fairly constant. The more oxidized species have undergone more isomerization steps, yet, at lower temperature, they did not decrease more than the less oxidized species. One possible explanation is be that the rate-limiting step forming these HOM occurs before the products become oxygenated enough to be detected by our CI-APi-TOF (i.e. typically seven or more oxygen atoms). The strong temperature dependence of HOM formation was observed under temperatures highly relevant for the boreal forest, but the exact magnitude of this effect in the atmosphere will be much more complex: the fate of peroxy-radicals is a competition between autoxidation (influenced by temperature and VOC type) and bimolecular termination pathways (influenced mainly by concentration of reaction partners). While the temperature influence is likely smaller in the boreal atmosphere than in our chamber, the magnitude and complexity of this effect clearly deserves more consideration in future studies in order to estimate the ultimate role of HOM on SOA and NPF under different atmospheric conditions.

The sources, formation mechanism and amount of organosulfates (OS) in atmospheric aerosol are not yet well understood, partly due to the lack of authentic standards for quantification. In this study, we report an improved robust procedure for the synthesis of organosulfates with different functional groups. Nine authentic organosulfate standards were synthesized and four standards (benzyl sulfate, phenyl sulfate, glycolic acid sulfate, and hydroxyacetone sulfate) were used to quantify their ambient concentrations. The authentic standards and ambient aerosol samples were analyzed using an optimized ultra performance liquid chromatography–electrospray ionization-tandem mass spectrometric method (UPLC–ESI–MS/MS). The recovery ranged from 80.4 to 93.2 %, the limits of detection and limits of quantification obtained were 1.1–16.7 and 3.4–55.6 pg m−3, respectively. Measurements of ambient aerosol particle samples collected in winter 2013/2014 in urban Xi'an, northwestern China, show that glycolic acid sulfate (77.3 ± 49.2 ng m−3) is the most abundant species of the identified organosulfates followed by hydroxyacetone sulfate (1.3 ± 0.5 ng m−3), phenyl sulfate (0.14 ± 0.09 ng m−3), and benzyl sulfate (0.04 ± 0.01 ng m−3). Except for hydroxyacetone sulfate, which seems to form mainly from biogenic emissions in this region, the organosulfates quantified during winter in Xi'an show an increasing trend with an increase in the mass concentrations of organic carbon indicating their anthropogenic origin.

The sources, formation mechanism and amount of organosulfates (OS) in atmospheric aerosol are not yet well understood, partly due to the lack of authentic standards for quantification. In this study, we report an improved robust procedure for the synthesis of organosulfates with different functional groups. Nine authentic organosulfate standards were synthesized and four standards (benzyl sulfate, phenyl sulfate, glycolic acid sulfate, and hydroxyacetone sulfate) were used to quantify their ambient concentrations. The authentic standards and ambient aerosol samples were analyzed using an optimized ultra performance liquid chromatography-electrospray ionization-tandem mass spectrometric method (UPLC–ESI–MS/MS). The recovery ranged from 80.4 % to 93.2 %, the limits of detection and limits of quantification obtained were 1.1–16.7 pg m−3 and 3.4–55.6 pg m−3, respectively. Measurements of ambient aerosol particle samples collected in winter 2013–2014 in urban Xi’an, northwest China, show that glycolic acid sulfate (77.3 ± 49.2 ng m−3) is the most abundant species of the identified organosulfates followed by hydroxyacetone sulfate (1.3 ± 0.5 ng m−3), phenyl sulfate (0.14 ± 0.09 ng m−3), and benzyl sulfate (0.04 ± 0.01 ng m−3). Except for hydroxyacetone sulfate, which seems to form mainly from biogenic emissions in this region, the organosulfates quantified during winter in Xi’an show an increasing trend with an increase in the mass concentrations of organic carbon indicating their anthropogenic origin.

To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well established saturation vapor pressures. However, vapor pressures of semi- and low volatile organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of two. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H–(O–CH2–CH2)n–OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10−7 Pa to 5 · 10−2 Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows to reject outlying data more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressures values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggest that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about one order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest accuracy data allowing subsequent extrapolation to atmospheric temperatures.

In a series of smog chamber experiments, the cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) generated from ozonolysis of β-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, κCCN, from experimental data. Two types of CCN counters, operating at different temperatures, were used. The effect of semi-volatile organic compounds on the CCN activity of SOA was studied using a thermodenuder. Overall, SOA was only slightly CCN active (with κCCN in the range 0.001–0.16), and in dark experiments with no OH scavenger present, κCCN decreased when particles were sent through the thermodenuder (with a temperature up to 50 °C). SOA was generated under different experimental conditions: In some experiments, an OH scavenger (2-butanol) was added. SOA from these experiments was less CCN active than SOA produced in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments with no OH scavenger present) to OH. In all experiments, the derived κCCN consistently increased with time after initial injection of β-caryophyllene, showing that chemical ageing increases the CCN activity of β-caryophyllene SOA. κCCN was also observed to depend on supersaturation, which was explained either as an evaporation artifact from semi-volatile SOA (only observed in experiments lacking light exposure) or, alternatively, by effects related to chemical composition depending on dry particle size. Using the method of Threshold Droplet Growth Analysis it was also concluded that the activation kinetics of the SOA do not differ significantly from calibration ammonium sulphate aerosol for particles aged for several hours.

Secondary organic aerosol (SOA) plays a central role in air pollution and climate. However, an exact description of the sources and mechanisms leading to SOA is elusive despite decades of research. Stable isotope analysis may help to constrain atmospheric SOA budgets but the isotope effects associated with the underlying processes have to be determined in order to do so. In this paper, SOA formation from ozonolysis of α-pinene – an important precursor and perhaps the best-known model system used in laboratory studies – was investigated using stable carbon isotope analysis, position-specific isotope analysis (PSIA), and high-resolution chemical analysis based on a thermal-desorption proton-transfer-reaction mass-spectrometer (PTR-MS). SOA was formed in a constant-flow chamber under dark, dry and low-NOx conditions, with OH scavengers in the absence of seed particles. Product SOA was collected on doubly-stacked quartz filters (front and back filters). During analysis, the filters were heated stepwise over the range of 100–400 °C to desorb organic compounds that were (i) detected using PTR-MS for chemical analysis and to determine the O:C ratio, and (ii) converted to CO2 for 13C analysis. In addition, the total carbon isotopic composition of selected samples was measured. For the first time PSIA has been performed for α-pinene. More than 400 ions in the mass range from 39–800 Da were detected and quantified using the PTR-MS. The largest mass fraction desorbed from the filters at 150 °C. The measured O:C ratio of front filter material increased from 0.18 to 0.25 as the desorption temperature was raised from 100 to 250 °C. The rising trend is consistent with the fact that functionalization decreases the volatility of chemical species. At temperatures above 250 °C the O:C ratio of thermally desorbed material, presumably from oligomeric precursors, was constant. The observation of a number of components across the full range of desorption temperatures suggests that they are generated by thermal decomposition of oligomers. SOA on front filters was enriched in 13C by 0.2–2.9 ‰ relative to the initial α-pinene, at all desorption temperatures. The total carbon isotopic composition was similar to the enrichment of the major fraction desorbing at 150 °C. Gas-phase compounds desorbing from the back filters showed much lower concentrations but were depleted in 13C by 0.7 ‰ compared to the initial α-pinene and by 1.9 ‰ compared to the corresponding front filter. PSIA showed that the isotope enrichment at individual carbon positions in α-pinene ranged from −6.9 to +10.5 ‰ relative to the bulk composition. However, there was not a clear mechanistic connection between those values and the observed isotopic enrichment of bulk SOA. Instead, fragmentation reactions favouring the loss of small, isotopically light products to the gas phase are consistent with the observations. In monoterpene ozonolysis, functionalization is known to follow fragmentation, however it is the fragmentation step that seems to govern the isotope budget. The isotope effect associated with oligomerization is small. The suggested isotope effects are important for the interpretation of isotopic compositions of ambient aerosol.

We have investigated CCN properties of internally mixed particles composed of one organic acid (oxalic acid dihydrate, succinic acid, adipic acid, citric acid, cis-pinonic acid, or Nordic reference fulvic acid) and one inorganic salt (sodium chloride or ammonium sulphate). Surface tension and water activity of aqueous model solutions with concentrations relevant for CCN activation were measured using a tensiometer and osmometry, respectively. The measurements were used to calculate Köhler curves and critical supersaturations, which were compared to measured critical supersaturations of particles with the same chemical compositions, determined with a cloud condensation nucleus counter. Surfactant surface partitioning was not accounted for. For the aqueous solutions containing cis-pinonic acid and fulvic acid, a depression of surface tension was observed, but for the remaining solutions the effect on surface tension was negligible at concentrations relevant for cloud droplet activation. The surface tension depression of aqueous solutions containing both organic acid and inorganic salt was approximately the same as or smaller than that of aqueous solutions containing the same mass of the corresponding pure organic acids. Water activity was found to be highly dependent on the type and amount of inorganic salt. Sodium chloride was able to decrease water activity more than ammonium sulphate and both inorganic salts are predicted to have a smaller Raoult term than the studied organic acids. Increasing the mass ratio of the inorganic salt led to a decrease in water activity. Water activity measurements were compared to results from the E-AIM model and values estimated from both constant and variable van't Hoff factors. The correspondence between measurements and estimates was overall good, except for highly concentrated solutions. Critical supersaturations calculated with Köhler theory based on measured water activity and surface tension, but not accounting for surface partitioning, compared well with measurements, except for the solutions containing sodium chloride and oxalic acid or one of the more surface active organic compounds. In such cases, significantly lower values were obtained from Köhler theory than the measured critical supersaturations with deviations above 50% for a 60 nm particle containing 50% (dry mass) of Nordic reference fulvic acid, suggesting that surfactant partitioning and/or an effect of sodium chloride on solubility of the organic component is important.

The temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of β-pinene was studied in a flow reactor at 263 K–303 K and 1007 hPa under dry and humid conditions (0% and 26%–68% relative humidity, respectively). The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.18–0.39 at high particle mass concentrations (Mo). Under dry conditions, however, the measurement data exhibited significant oscillatory deviations from the predicted linear increase with inverse temperature (up to 50% at high Mo). Under humid conditions the SOA yield exhibited a linear decrease with inverse temperature, which is opposite to modelled temperature dependence and implies that the model substantially overestimates the yield at low temperatures and underestimates it at high temperatures (deviations up to 80% at high Mo). For the atmospherically relevant concentration level of Mo=10 μg m−3 and temperature range 263 K–293 K, the results from humid experiments in this study indicate that the SOA yield of β-pinene ozonolysis may be well represented by an average value of 0.15 with an uncertainty estimate of ±0.05. When fitting the measurement data with a two-product model, both the partitioning coefficients (Kom,i) and the stoichiometric yields (αi) of the low-volatile and semi-volatile model species were found to vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are strongly dependent on temperature and the presence of water vapour. In fact, the oscillatory positive temperature dependence observed under dry conditions and the negative temperature dependence observed under humid conditions indicate that the SOA yield is governed much more by the temperature and humidity dependence of the involved chemical reactions than by vapour pressure temperature dependencies. We suggest that the elucidation and modelling of SOA formation need to take into account the effects of temperature and humidity on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products.

The formation of carboxylic acids and dimer esters from α-pinene oxidation was investigated in a smog chamber and in ambient aerosol samples collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX). Chamber experiments of α-pinene ozonolysis in dry air and at low NOx concentrations demonstrated formation of two dimer esters, pinyl-diaterpenyl (MW 358) and pinonyl-pinyl dimer ester (MW 368), under both low- and high-temperature conditions. Concentration levels of the pinyl-diaterpenyl dimer ester were lower than the assumed first-generation oxidation products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural precursors. However, the sampling time resolution precluded conclusive evidence regarding formation from gas- or particle-phase processes. CCN activities of the particles formed in the smog chamber displayed a modest variation during the course of experiments, with κ values in the range 0.06–0.09 (derived at a supersaturation of 0.19%). The pinyl-diaterpenyl dimer ester was also observed in ambient aerosol samples collected above a ponderosa pine forest in the Sierra Nevada Mountains of California during two seasonally distinct field campaigns in September 2007 and July 2009. The pinonyl-pinyl ester was observed for the first time in ambient air during the 2009 campaign, and although present at much lower concentrations, it was correlated with the abundance of the pinyl-diaterpenyl ester, suggesting similarities in their formation. The maximum concentration of the pinyl-diaterpenyl ester was almost 10 times higher during the warmer 2009 campaign relative to 2007, while the concentration of cis-pinic acid was approximately the same during both periods, and lack of correlation with levels of cis-pinic and terpenylic acids for both campaigns indicate that the formation of the pinyl-diaterpenyl ester was not controlled by their ambient abundance. In 2009 the concentration of the pinyl-diaterpenyl ester was well correlated with the concentration of DTAA, a supposed precursor of diaterpenylic acid, suggesting that the formation of pinyl-diaterpenyl dimer was closely related to DTAA. Generally, the pinyl-diaterpenyl ester was found at higher concentrations under higher temperature conditions, both in the smog-chamber study and in ambient air aerosol samples, and exhibited much higher concentrations at night relative to daytime in line with previous results. We conclude that analysis of pinyl dimer esters provides valuable information on pinene oxidation processes and should be included in studies of formation and photochemical aging of biogenic secondary organic aerosols, especially at high temperatures.

Organic compounds with surfactant properties are commonly found in atmospheric aerosol particles. Surface activity can significantly influence the cloud droplet forming ability of these particles. We have studied the cloud droplet formation by two-component particles comprising one of the organic surfactants sodium octanoate, sodium decanoate, sodium dodecanoate, and sodium dodecyl sulfate, mixed with sodium chloride. Critical supersaturations were measured with a static diffusion cloud condensation nucleus counter (Wyoming CCNC-100B). Results were modeled from Köhler theory applying three different representations of surfactant properties: (1) using concentration-dependent surface tension reduction during droplet growth and explicitly accounting for surfactant surface partitioning in both solute suppression (Raoult effect) and curvature enhancement (Kelvin effect) contributions to the droplet equilibrium water vapor supersaturation, (2) disregarding surfactant partitioning and using a concentration-dependent surface tension for the droplets corresponding to a macroscopic (bulk) aqueous solution of the same overall composition, and (3) disregarding surfactant properties and assuming the constant surface tension of pure water throughout droplet activation. We confirm previous results for single-component organic surfactant particles, that experimental critical supersaturations are greatly underpredicted, if reduced surface tension is applied in Köhler theory while ignoring the effects of surface partitioning in droplets. We further show that assuming the constant surface tension of pure water can also lead to significant underpredictions of experimental critical supersaturations. The full account for surfactant partitioning in activating droplets generally predicts experimental critical supersaturations well. In addition, for mixed particles comprising less than 50% by mass of surfactant, ignoring surfactant properties and simply using the constant surface tension of pure water also provides a good first-order approximation of the observed activation.

The temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of β-pinene was studied in a flow reactor at 263–303 K and 1007 hPa. The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.22–0.39 at high particle mass concentrations. However, the measurement data exhibited significant deviations (up to 50%) from the predicted linear dependence on inverse temperature. When fitting the measurement data with a two-product model, we found that both the partitioning coefficients (Kom,i) and the stoichiometric yields (αi) of the low-volatile and semi-volatile species vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are dependent on temperature. We suggest that the modelling of secondary organic aerosol formation in the atmosphere needs to take into account the effects of temperature on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products.