Showing papers by "Tuukka Petäjä published in 2017"

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Abstract: Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.

The Green Ocean Amazon Experiment (GoAmazon2014/5) Observes Pollution Affecting Gases, Aerosols, Clouds, and Rainfall over the Rain Forest

Abstract: The Observations and Modeling of the Green Ocean Amazon 2014–2015 (GoAmazon2014/5) experiment took place around the urban region of Manaus in central Amazonia across 2 years. The urban pollution plume was used to study the susceptibility of gases, aerosols, clouds, and rainfall to human activities in a tropical environment. Many aspects of air quality, weather, terrestrial ecosystems, and climate work differently in the tropics than in the more thoroughly studied temperate regions of Earth. GoAmazon2014/5, a cooperative project of Brazil, Germany, and the United States, employed an unparalleled suite of measurements at nine ground sites and on board two aircraft to investigate the flow of background air into Manaus, the emissions into the air over the city, and the advection of the pollution downwind of the city. Herein, to visualize this train of processes and its effects, observations aboard a low-flying aircraft are presented. Comparative measurements within and adjacent to the plume followed t...

Atmospheric gas-to-particle conversion: why NPF events are observed in megacities?

Abstract: In terms of the global aerosol particle number load, atmospheric new particle formation (NPF) dominates over primary emissions. The key for quantifying the importance of atmospheric NPF is to understand how gas-to-particle conversion (GTP) takes place at sizes below a few nanometers in particle diameter in different environments, and how this nano-GTP affects the survival of small clusters into larger sizes. The survival probability of growing clusters is tied closely to the competition between their growth and scavenging by pre-existing aerosol particles, and the key parameter in this respect is the ratio between the condensation sink (CS) and the cluster growth rate (GR). Here we define their ratio as a dimensionless survival parameter, P, as P = (CS/10−4 s−1)/(GR/nm h−1). Theoretical arguments and observations in clean and moderately-polluted conditions indicate that P needs to be smaller than about 50 for a notable NPF to take place. However, the existing literature shows that in China, NPF occurs frequently in megacities such as in Beijing, Nanjing and Shanghai, and our analysis shows that the calculated values of P are even larger than 200 in these cases. By combining direct observations and conceptual modelling, we explore the variability of the survival parameter P in different environments and probe the reasons for NPF occurrence under highly-polluted conditions.

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate

Abstract: A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.

Measurements of sub-3 nm particles using a particle size magnifier in different environments: from clean mountain top to polluted megacities

Abstract: . The measurement of sub-3 nm aerosol particles is technically challenging. Therefore, there is a lack of knowledge about the concentrations of atmospheric sub-3 nm particles and their variation in different environments. In this study, the concentrations of ∼ 1–3 nm particles measured with a particle size magnifier (PSM) were investigated at nine sites around the world. Sub-3 nm particle concentrations were highest at the sites with strong anthropogenic influence. In boreal forest, measured particle concentrations were clearly higher in summer than in winter, suggesting the importance of biogenic precursor vapors in this environment. At all sites, sub-3 nm particle concentrations had daytime maxima, which are likely linked to the photochemical production of precursor vapors and the emissions of precursor vapors or particles from different sources. When comparing ion concentrations to the total sub-3 nm particle concentrations, electrically neutral particles were observed to dominate in polluted environments and in boreal forest during spring and summer. Generally, the concentrations of sub-3 nm particles seem to be determined by the availability of precursor vapors rather than the level of the sink caused by preexisting aerosol particles. The results also indicate that the formation of the smallest particles and their subsequent growth to larger sizes are two separate processes, and therefore studying the concentration of sub-3 nm particles separately in different size ranges is essential.

Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument

Abstract: . We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of ∼ 5.0 × 104 molecules cm−3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.

Ambient observations of dimers from terpene oxidation in the gas phase : Implications for new particle formation and growth

Abstract: We present ambient observations of dimeric monoterpene oxidation products (C16–20HyO6–9) in gas and particle phases in the boreal forest in Finland in spring 2013 and 2014, detected with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols employing acetate and iodide as reagent ions. These are among the first online dual-phase observations of such dimers in the atmosphere. Estimated saturation concentrations of 10−15 to 10−6 µg m−3 (based on observed thermal desorptions and group-contribution methods) and measured gas-phase concentrations of 10−3 to 10−2 µg m−3 (~106–107 molecules cm−3) corroborate a gas-phase formation mechanism. Regular new particle formation (NPF) events allowed insights into the potential role dimers may play for atmospheric NPF and growth. The observationally constrained Model for Acid-Base chemistry in NAnoparticle Growth indicates a contribution of ~5% to early stage particle growth from the ~60 gaseous dimer compounds.

A European aerosol phenomenology-6: Scattering properties of atmospheric aerosol particles from 28 ACTRIS sites [Discussion paper]

Abstract: Abstract. This paper presents the light-scattering properties of atmospheric aerosol particles measured over the past decade at 28 ACTRIS observatories, which are located mainly in Europe. The data include particle light scattering (σsp) and hemispheric backscattering (σbsp) coefficients, scattering Ångström exponent (SAE), backscatter fraction (BF) and asymmetry parameter (g). An increasing gradient of σsp is observed when moving from remote environments (arctic/mountain) to regional and to urban environments. At a regional level in Europe, σsp also increases when moving from Nordic and Baltic countries and from western Europe to central/eastern Europe, whereas no clear spatial gradient is observed for other station environments. The SAE does not show a clear gradient as a function of the placement of the station. However, a west-to-east-increasing gradient is observed for both regional and mountain placements, suggesting a lower fraction of fine-mode particle in western/south-western Europe compared to central and eastern Europe, where the fine-mode particles dominate the scattering. The g does not show any clear gradient by station placement or geographical location reflecting the complex relationship of this parameter with the physical properties of the aerosol particles. Both the station placement and the geographical location are important factors affecting the intra-annual variability. At mountain sites, higher σsp and SAE values are measured in the summer due to the enhanced boundary layer influence and/or new particle-formation episodes. Conversely, the lower horizontal and vertical dispersion during winter leads to higher σsp values at all low-altitude sites in central and eastern Europe compared to summer. These sites also show SAE maxima in the summer (with corresponding g minima). At all sites, both SAE and g show a strong variation with aerosol particle loading. The lowest values of g are always observed together with low σsp values, indicating a larger contribution from particles in the smaller accumulation mode. During periods of high σsp values, the variation of g is less pronounced, whereas the SAE increases or decreases, suggesting changes mostly in the coarse aerosol particle mode rather than in the fine mode. Statistically significant decreasing trends of σsp are observed at 5 out of the 13 stations included in the trend analyses. The total reductions of σsp are consistent with those reported for PM2.5 and PM10 mass concentrations over similar periods across Europe.

The role of highly oxygenated molecules (HOMs) in determining the composition of ambient ions in the boreal forest

Abstract: . In order to investigate the negative ions in the boreal forest we have performed measurements to chemically characterise the composition of negatively charged clusters containing highly oxygenated molecules (HOMs). Additionally, we compared this information with the chemical composition of the neutral gas-phase molecules detected in the ambient atmosphere during the same period. The chemical composition of the ions was retrieved using an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF-MS) while the gas-phase neutral molecules (mainly sulfuric acid and HOMs) were characterised using the same mass spectrometer coupled to a nitrate-based chemical ionisation unit (CI-APi-TOF). Overall, we divided the identified HOMs in two classes: HOMs containing only carbon, hydrogen and oxygen and nitrogen-containing HOMs or organonitrates (ONs). During the day, among the ions, in addition to the well-known pure sulfuric acid clusters, we found a large number of HOMs clustered with nitrate (NO3−) or bisulfate (HSO4−), with the first one being more abundant. During the night, the distribution of ions, mainly composed of HOM clustered with NO3−, was very similar to the neutral compounds that are detected in the CI-APi-TOF as adducts with the artificially introduced primary ion (NO3−). For the first time, we identified several clusters containing up to 40 carbon atoms. These ions are formed by up to four oxidised α-pinene units clustered with NO3−. While we know that dimers (16–20 carbon atoms) are probably formed by a covalent bond between two α-pinene oxidised units, it is still unclear what bonding formed larger clusters. Finally, diurnal profiles of the negative ions were consistent with the neutral compounds revealing that ONs peak during the day while HOMs are more abundant at night-time. However, during the day, a large fraction of the negative charge is taken up by the pure sulfuric acid clusters causing differences between ambient ions and neutral compounds (i.e. less available charge for HOM and ON).

A European aerosol phenomenology - 6: Scattering properties of atmospheric aerosol particles from 28 ACTRIS sites

Abstract: This paper presents the light-scattering properties of atmospheric aerosol particles measured over the past decade at 28 ACTRIS observatories, which are located mainly in Europe. The data include particle light scattering (σsp) and hemispheric backscattering (σbsp) coefficients, scattering Angstrom exponent (SAE), backscatter fraction (BF) and asymmetry parameter (g). An increasing gradient of σsp is observed when moving from remote environments (arctic/mountain) to regional and to urban environments. At a regional level in Europe, σsp also increases when moving from Nordic and Baltic countries and from western Europe to central/eastern Europe, whereas no clear spatial gradient is observed for other station environments. The SAE does not show a clear gradient as a function of the placement of the station. However, a west-to-east-increasing gradient is observed for both regional and mountain placements, suggesting a lower fraction of fine-mode particle in western/south-western Europe compared to central and eastern Europe, where the fine-mode particles dominate the scattering. The g does not show any clear gradient by station placement or geographical location reflecting the complex relationship of this parameter with the physical properties of the aerosol particles. Both the station placement and the geographical location are important factors affecting the intraannual variability. At mountain sites, higher σsp and SAE values are measured in the summer due to the enhanced boundary layer influence and/or new particle-formation episodes. Conversely, the lower horizontal and vertical dispersion during winter leads to higher σsp values at all low-altitude sites in central and eastern Europe compared to summer. These sites also show SAE maxima in the summer (with corresponding g minima). At all sites, both SAE and g show a strong variation with aerosol particle loading. The lowest values of g are always observed together with low σsp values, indicating a larger contribution from particles in the smaller accumulation mode. During periods of high σsp values, the variation of g is less pronounced, whereas the SAE increases or decreases, suggesting changes mostly in the coarse aerosol particle mode rather than in the fine mode. Statistically significant decreasing trends of σsp are observed at 5 out of the 13 stations included in the trend analyses. The total reductions of σsp are consistent with those reported for PM2.5 and PM10 mass concentrations over similar periods across Europe. © Author(s) 2018.

Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation

Abstract: . It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1–2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α -pinene at 5 ∘ C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and − 25 ∘ C). Most negative HOM clusters include a nitrate (NO 3 - ) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH 4 + ) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ∼ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature ( − 25 ∘ C), the presence of C 30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.

Analysis of aerosol effects on warm clouds over the Yangtze River Delta from multi-sensor satellite observations

Abstract: . Aerosol effects on low warm clouds over the Yangtze River Delta (YRD, eastern China) are examined using co-located MODIS, CALIOP and CloudSat observations. By taking the vertical locations of aerosol and cloud layers into account, we use simultaneously observed aerosol and cloud data to investigate relationships between cloud properties and the amount of aerosol particles (using aerosol optical depth, AOD, as a proxy). Also, we investigate the impact of aerosol types on the variation of cloud properties with AOD. Finally, we explore how meteorological conditions affect these relationships using ERA-Interim reanalysis data. This study shows that the relation between cloud properties and AOD depends on the aerosol abundance, with a different behaviour for low and high AOD (i.e. AOD 0.35). This applies to cloud droplet effective radius (CDR) and cloud fraction (CF), but not to cloud optical thickness (COT) and cloud top pressure (CTP). COT is found to decrease when AOD increases, which may be due to radiative effects and retrieval artefacts caused by absorbing aerosol. Conversely, CTP tends to increase with elevated AOD, indicating that the aerosol is not always prone to expand the vertical extension. It also shows that the COT–CDR and CWP (cloud liquid water path)–CDR relationships are not unique, but affected by atmospheric aerosol loading. Furthermore, separation of cases with either polluted dust or smoke aerosol shows that aerosol–cloud interaction (ACI) is stronger for clouds mixed with smoke aerosol than for clouds mixed with dust, which is ascribed to the higher absorption efficiency of smoke than dust. The variation of cloud properties with AOD is analysed for various relative humidity and boundary layer thermodynamic and dynamic conditions, showing that high relative humidity favours larger cloud droplet particles and increases cloud formation, irrespective of vertical or horizontal level. Stable atmospheric conditions enhance cloud cover horizontally. However, unstable atmospheric conditions favour thicker and higher clouds. Dynamically, upward motion of air parcels can also facilitate the formation of thicker and higher clouds. Overall, the present study provides an understanding of the impact of aerosols on cloud properties over the YRD. In addition to the amount of aerosol particles (or AOD), evidence is provided that aerosol types and ambient environmental conditions need to be considered to understand the observed relationships between cloud properties and AOD.

Collocated observations of cloud condensation nuclei, particle size distributions, and chemical composition.

Abstract: Cloud condensation nuclei (CCN) number concentrations alongside with submicrometer particle number size distributions and particle chemical composition have been measured at atmospheric observatories of the Aerosols, Clouds, and Trace gases Research InfraStructure (ACTRIS) as well as other international sites over multiple years. Here, harmonized data records from 11 observatories are summarized, spanning 98,677 instrument hours for CCN data, 157,880 for particle number size distributions, and 70,817 for chemical composition data. The observatories represent nine different environments, e.g., Arctic, Atlantic, Pacific and Mediterranean maritime, boreal forest, or high alpine atmospheric conditions. This is a unique collection of aerosol particle properties most relevant for studying aerosol-cloud interactions which constitute the largest uncertainty in anthropogenic radiative forcing of the climate. The dataset is appropriate for comprehensive aerosol characterization (e.g., closure studies of CCN), model-measurement intercomparison and satellite retrieval method evaluation, among others. Data have been acquired and processed following international recommendations for quality assurance and have undergone multiple stages of quality assessment.

The role of ions in new particle formation in the CLOUD chamber

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

Vertical characterization of highly oxygenated molecules (HOMs) below and above a boreal forest canopy

Abstract: . While the role of highly oxygenated molecules (HOMs) in new particle formation (NPF) and secondary organic aerosol (SOA) formation is not in dispute, the interplay between HOM chemistry and atmospheric conditions continues to draw significant research attention. During the Influence of Biosphere-Atmosphere Interactions on the Reactive Nitrogen budget (IBAIRN) campaign in September 2016, profile measurements of neutral HOMs below and above the forest canopy were performed for the first time at the boreal forest SMEAR II station. The HOM concentrations and composition distributions below and above the canopy were similar during daytime, supporting a well-mixed boundary layer approximation. However, much lower nighttime HOM concentrations were frequently observed at ground level, which was likely due to the formation of a shallow decoupled layer below the canopy. Near the ground HOMs were influenced by the changes in the precursors and oxidants and enhancement of the loss on surfaces in this layer, while the HOMs above the canopy top were not significantly affected. Our findings clearly illustrate that near-ground HOM measurements conducted under stably stratified conditions at this site might only be representative of a small fraction of the entire nocturnal boundary layer. This could, in turn, influence the growth of newly formed particles and SOA formation below the canopy where the large majority of measurements are typically conducted.

Solar eclipse demonstrating the importance of photochemistry in new particle formation.

Abstract: Solar eclipses provide unique possibilities to investigate atmospheric processes, such as new particle formation (NPF), important to the global aerosol load and radiative balance. The temporary absence of solar radiation gives particular insight into different oxidation and clustering processes leading to NPF. This is crucial because our mechanistic understanding on how NPF is related to photochemistry is still rather limited. During a partial solar eclipse over Finland in 2015, we found that this phenomenon had prominent effects on atmospheric on-going NPF. During the eclipse, the sources of aerosol precursor gases, such as sulphuric acid and nitrogen- containing highly oxidised organic compounds, decreased considerably, which was followed by a reduced formation of small clusters and nanoparticles and thus termination of NPF. After the eclipse, aerosol precursor molecule concentrations recovered and re-initiated NPF. Our results provide direct evidence on the key role of the photochemical production of sulphuric acid and highly oxidized organic compounds in maintaining atmospheric NPF. Our results also explain the rare occurrence of this phenomenon under dark conditions, as well as its seemingly weak connection with atmospheric ions.

Aerosol optical properties at SORPES in Nanjing, east China

Abstract: . Aerosol optical properties (AOPs) and supporting parameters – particle number size distributions, PM 2.5 mass concentrations, and the concentrations of trace gases (NO x and NO y) – were measured at SORPES, a regional background station in Nanjing, China from June 2013 to May 2015. The aerosol was highly scattering: the average scattering coefficient was σsp=403 ± 314 Mm −1 , the absorption coefficient σap=26 ± 19 Mm −1 , and the single-scattering albedo SSA = 0.93 ± 0.03 for green light. The SSA in Nanjing appears to be slightly higher than published values from several other sites in China and elsewhere. The average Angstrom exponent of absorption (AAE) for the wavelength range 370–950 nm was 1.04 and the AAE range was 0.7–1.4. These AAE values can be explained with different amounts of non-absorbing coating on pure black carbon (BC) cores and different core sizes rather than contribution by brown carbon. The AOPs had typical seasonal cycles with high σsp and σap in winter and low ones in summer: the averages were σsp=544 ± 422 and σap=36 ± 24 Mm −1 in winter and σsp=342 ± 281 and σap=20 ± 13 Mm −1 in summer. The intensive AOPs had no clear seasonal cycles, the variations in them were rather related to the evolution of pollution episodes. The diurnal cycles of the intensive AOPs were clear and in agreement with the cycle of the particle number size distribution. The diurnal cycle of SSA was similar to that of the air photochemical age, suggesting that the darkest aerosol originated from fresh traffic emissions. A Lagrangian retroplume analysis showed that the potential source areas of high σsp and σap are mainly in eastern China. Synoptic weather phenomena dominated the cycle of AOPs on a temporal scale of 3–7 days. During pollution episodes, modeled boundary layer height decreased, whereas PM 2.5 concentrations and σsp and σap typically increased gradually and remained high during several days but decreased faster, sometimes by even more than an order of magnitude within some hours. During the growth phase of the pollution episodes the intensive AOPs evolved clearly. The mass scattering efficiency MSE of PM 2.5 grew during the extended pollution episodes from ∼ 4 to ∼ 6 m 2 g −1 and the mass fraction of BC e decreased from ∼ 10 to ∼ 3 % during the growth phase of the episodes. Particle growth resulted in the backscatter fraction decreasing from more than 0.16 to less than 0.10, SSA growing from less than 0.9 to more than 0.95, and radiative forcing efficiency (RFE) changing from less than − 26 W m −2 to more than − 24 W m −2 , which means that the magnitude of RFE decreased. The RFE probability distribution at SORPES was clearly narrower than at a clean background site which is in agreement with a published RFE climatology.

Observation of incipient particle formation during flame synthesis by tandem differential mobility analysis-mass spectrometry (DMA-MS)

Abstract: While flame aerosol reactor (FLAR) synthesis of nanoparticles is widely used to produce a range of nanomaterials, incipient particle formation by nucleation and vapor condensation is not well understood. This gap in our knowledge of incipient particle formation is caused by limitations in instruments, where, during measurements, the high diffusivity of sub 3 nm particles significantly affects resolution and transport loss. This work used a high resolution differential mobility analyzer (DMA) and an atmospheric pressure interface-mass spectrometer (APi-TOF) to observe incipient particle formation during flame synthesis. By tandemly applying these two instruments, differential mobility analysis-mass spectrometry (DMA-MS) measured the size and mass of the incipient particles simultaneously, and the effective density of the sub 3 nm particles was estimated. The APi-TOF further provided the chemical compositions of the detected particles based on highly accurate masses and isotope distributions. This study investigated the incipient particle formation in flames with and without the addition of synthesis precursors. Results from FLAR using two types of precursors including tetraethyl orthosilicate (TEOS) and titanium isopropoxide (TTIP) are presented. The effect of the precursor feed rates on incipient particle growth was also investigated.

Resolving anthropogenic aerosol pollution types - deconvolution and exploratory classification of pollution events

Abstract: . Mass spectrometric measurements commonly yield data on hundreds of variables over thousands of points in time. Refining and synthesizing this raw data into chemical information necessitates the use of advanced, statistics-based data analytical techniques. In the field of analytical aerosol chemistry, statistical, dimensionality reductive methods have become widespread in the last decade, yet comparable advanced chemometric techniques for data classification and identification remain marginal. Here we present an example of combining data dimensionality reduction (factorization) with exploratory classification (clustering), and show that the results cannot only reproduce and corroborate earlier findings, but also complement and broaden our current perspectives on aerosol chemical classification. We find that applying positive matrix factorization to extract spectral characteristics of the organic component of air pollution plumes, together with an unsupervised clustering algorithm, k-means+ + , for classification, reproduces classical organic aerosol speciation schemes. Applying appropriately chosen metrics for spectral dissimilarity along with optimized data weighting, the source-specific pollution characteristics can be statistically resolved even for spectrally very similar aerosol types, such as different combustion-related anthropogenic aerosol species and atmospheric aerosols with similar degree of oxidation. In addition to the typical oxidation level and source-driven aerosol classification, we were also able to classify and characterize outlier groups that would likely be disregarded in a more conventional analysis. Evaluating solution quality for the classification also provides means to assess the performance of mass spectral similarity metrics and optimize weighting for mass spectral variables. This facilitates algorithm-based evaluation of aerosol spectra, which may prove invaluable for future development of automatic methods for spectra identification and classification. Robust, statistics-based results and data visualizations also provide important clues to a human analyst on the existence and chemical interpretation of data structures. Applying these methods to a test set of data, aerosol mass spectrometric data of organic aerosol from a boreal forest site, yielded five to seven different recurring pollution types from various sources, including traffic, cooking, biomass burning and nearby sawmills. Additionally, three distinct, minor pollution types were discovered and identified as amine-dominated aerosols.

Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber

Abstract: . Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate α -pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H 2 ), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO 2 ) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5–6.5 % for HOM formation and 22–32 % for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20–50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

Mobile Aerosol Measurement in the Eastern Mediterranean - A Utilization of Portable Instruments

Abstract: Air pollution research and reports have been limited in the Middle East, especially in Jordan with respect to aerosol particle number concentrations. In this study, we utilized a simple “mobile setup” to measure, for the first time, the spatial variation of aerosol concentrations in Eastern Mediterranean. The mobile setup consisted of portable aerosol instruments to measure particle number concentrations (cut off sizes 0.01, 0.02, 0.3, 0.5, 1, 2.5, 5, and 10 µm), particle mass concentrations (PM1, PM2.5, and PM10), and black carbon concentration all situated on the back seat of a sedan car. The car was driven with open windows to ensure sufficient cabin air ventilation for reliable outdoor aerosol sampling. Although the measurement campaign was two days long, but it provided preliminary information about aerosols concentrations over a large spatial scale that covered more than three quarters of Jordan. We should keep in mind that the presented concentrations reflect on road conditions. The submicron particle concentrations were the highest in the urban locations (e.g., Amman and Zarqa) and inside cities with heavy duty vehicles activities (e.g., Azraq). The highest micron particle concentrations were observed in the southern part of the country and in places close to the desert area (e.g., Wadi Rum and Wadi Araba). The average submicron concentration was 4.9 × 103 – 120 × 103 cm–3 (5.7–86.7 µg m–3) whereas the average micron particle concentration was 1–11 cm–3 (8–150 µg m–3, assume ρp = 1 g cm–3). The main road passing through Jafr in the eastern part of Jordan exhibited submicron concentration as low as 800 cm–3. The PM10 concentration consisted of about 40–75% as PM1. The black carbon (BC) concentration variation was in good agreement with the PM1 as well as the submicron particle number concentration.

Cluster formation mechanisms of titanium dioxide during combustion synthesis: Observation with an APi-TOF

Abstract: Few studies reported the formation of Ti-containing clusters in the initial stages of TiO2 flame synthesis The conversion from synthesis precursor to TiO2 monomers was commonly assumed to take pla

Characterization of three new condensation particle counters for sub-3 nm particle detection during the Helsinki CPC workshop: the ADI versatile water CPC, TSI 3777 nano enhancer and boosted TSI 3010

Abstract: . In this study we characterized the performance of three new particle counters able to detect particles smaller than 3 nm during the Helsinki condensation particle counter (CPC) workshop in summer 2016: the Aerosol Dynamics Inc. (ADI; Berkeley, USA) versatile water condensation particle counter (vWCPC), TSI 3777 nano enhancer (TSI Inc., Shoreview, USA) and modified and boosted TSI 3010-type CPC from Universite Blaise Pascal called a B3010. The performance of all CPCs was first measured with charged tungsten oxide test particles at temperature settings which resulted in supersaturation low enough to not detect any ions produced by a radioactive source. Due to similar measured detection efficiencies, additional comparison between the 3777 and vWCPC were conducted using electrically neutral tungsten oxide test particles and with positively charged tetradodecylammonium bromide. Furthermore, the detection efficiencies of the 3777 and vWCPC were measured with boosted temperature settings yielding supersaturation which was at the onset of homogeneous nucleation for the 3777 or confined within the range of liquid water for the ADI vWCPC. Finally, CPC-specific tests were conducted to probe the response of the 3777 to various inlet flow relative humidities, of the B3010 to various inlet flow rates and of the vWCPC to various particle concentrations. For the 3777 and vWCPC the measured 50 % detection diameters (d50s) were in the range of 1.3–2.4 nm for the tungsten oxide particles, depending on the particle charging state and CPC temperature settings, between 2.5 and 3.3 nm for the organic test aerosol, and in the range of 3.2–3.4 nm for tungsten oxide for the B3010.

Chemical investigation and quality of urban dew collections with dust precipitates

Abstract: 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 SO4 2− 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.

VH-TDMA: A description and verification of an instrument to measure aerosol particle hygroscopicity and volatility

Abstract: The aim of this study was to provide a description and characterize the performance of a volatility hygroscopicity tandem differential mobility analyzer (VH-TDMA) by calibration measurements. In our investigations, we used the two calibration standards most often used by the TDMA community: ammonium sulfate ((NH4)2SO4) and sodium chloride (NaCl) particles. The hygroscopic growth factors, volatility factors, and the hygroscopic growth factors of the nonvolatile particle core were measured in different relative humidity and thermal denuder temperature conditions. The measured hygroscopic growth and deliquescence relative humidities for ammonium sulfate and sodium chloride particles are in line with theory and results from previous measurements, as are the measurements for volatility and hygroscopicity of the particle core. We summarize the measurement campaigns, where the VH-TDMA has been deployed, and show the instrument is capable of measuring high quality data of atmospheric particle properties i...

Features in air ions measured by an air ion spectrometer (AIS) at Dome C

Abstract: . An air ion spectrometer (AIS) was deployed for the first time at the Concordia station at Dome C (75°06′ S, 123°23′ E; 3220 m a. s. l. ), Antarctica during the period 22 December 2010–16 November 2011 for measuring the number size distribution of air ions. In this work, we present results obtained from this air ion data set together with aerosol particle and meteorological data. The main processes that modify the number size distribution of air ions during the measurement period at this high-altitude site included new particle formation (NPF, observed on 85 days), wind-induced ion formation (observed on 36 days), and ion production and loss associated with cloud/fog formation (observed on 2 days). For the subset of days when none of these processes seemed to operate, the concentrations of cluster ions (0.9–1.9 nm) exhibited a clear seasonality, with high concentrations in the warm months and low concentrations in the cold. Compared to event-free days, days with NPF were observed with higher cluster ion concentrations. A number of NPF events were observed with restricted growth below 10 nm, which were termed as suppressed NPF. There was another distinct feature, namely a simultaneous presence of two or three separate NPF and subsequent growth events, which were named as multi-mode NPF events. Growth rates (GRs) were determined using two methods: the appearance time method and the mode fitting method. The former method seemed to have advantages in characterizing NPF events with a fast GR, whereas the latter method is more suitable when the GR was slow. The formation rate of 2 nm positive ions (J2+) was calculated for all the NPF events for which a GR in the 2–3 nm size range could be determined. On average, J2+ was about 0.014 cm−3 s−1. The ion production in relation to cloud/fog formation in the size range of 8–42 nm seemed to be a unique feature at Dome C, which has not been reported elsewhere. These ions may, however, either be multiply charged particles but detected as singly charged in the AIS, or be produced inside the instrument, due to the breakage of cloud condensation nuclei (CCN), possibly related to the instrumental behaviour under the extremely cold condition. For the wind-induced ion formation, our observations suggest that the ions originated more likely from atmospheric nucleation of vapours released from the snow than from mechanical charging of shattered snow flakes and ice crystals.

Observations of ozone depletion events in a Finnish boreal forest

Abstract: . We investigated the concentrations and vertical profiles of ozone over a 20-year period (1996–2016) at the SMEAR II station in southern Finland. Our results showed that the typical daily median ozone concentrations were in the range of 20–50 ppb with clear diurnal and annual patterns. In general, the profile of ozone concentrations illustrated an increase as a function of heights. The main aim of our study was to address the frequency and strength of ozone depletion events at this boreal forest site. We observed more than a thousand of 10 min periods at 4.2 m, with ozone concentrations below 10 ppb, and a few tens of cases with ozone concentrations below 2 ppb. Among these observations, a number of ozone depletion events that lasted for more than 3 h were identified, and they occurred mainly in autumn and winter months. The low ozone concentrations were likely related to the formation of a low mixing layer under the conditions of low temperatures, low wind speeds, high relative humidities and limited intensity of solar radiation.