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Showing papers by "Tuukka Petäjä published in 2014"


Journal ArticleDOI
27 Feb 2014-Nature
TL;DR: It is found that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies.
Abstract: Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

1,340 citations


Journal ArticleDOI
16 May 2014-Science
TL;DR: It is shown, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere.
Abstract: Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations.

446 citations


Journal ArticleDOI
TL;DR: In this article, the authors focus on the identification of the main organic aerosol sources and define a standardized methodology to perform source apportionment using positive matrix factorization (PMF) with the multilinear engine (ME-2) on Aerodyne aerosol mass spectrometer (AMS) data.
Abstract: . Organic aerosols (OA) represent one of the major constituents of submicron particulate matter (PM1) and comprise a huge variety of compounds emitted by different sources. Three intensive measurement field campaigns to investigate the aerosol chemical composition all over Europe were carried out within the framework of the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) and the intensive campaigns of European Monitoring and Evaluation Programme (EMEP) during 2008 (May–June and September–October) and 2009 (February–March). In this paper we focus on the identification of the main organic aerosol sources and we define a standardized methodology to perform source apportionment using positive matrix factorization (PMF) with the multilinear engine (ME-2) on Aerodyne aerosol mass spectrometer (AMS) data. Our source apportionment procedure is tested and applied on 25 data sets accounting for two urban, several rural and remote and two high altitude sites; therefore it is likely suitable for the treatment of AMS-related ambient data sets. For most of the sites, four organic components are retrieved, improving significantly previous source apportionment results where only a separation in primary and secondary OA sources was possible. Generally, our solutions include two primary OA sources, i.e. hydrocarbon-like OA (HOA) and biomass burning OA (BBOA) and two secondary OA components, i.e. semi-volatile oxygenated OA (SV-OOA) and low-volatility oxygenated OA (LV-OOA). For specific sites cooking-related (COA) and marine-related sources (MSA) are also separated. Finally, our work provides a large overview of organic aerosol sources in Europe and an interesting set of highly time resolved data for modeling purposes.

275 citations


Journal ArticleDOI
TL;DR: The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations, giving a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps.
Abstract: The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3–)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the...

235 citations


Journal ArticleDOI
TL;DR: A summary of the chemistry of atmospheric clustering, growing nanoparticles, and their precursors is presented, particularly on atmospheric gas-to-particle conversion and recent progress in its understanding.
Abstract: The recent development in measurement techniques and theoretical understanding has enabled us to study atmospheric vapor, cluster and nanoparticle concentrations, dynamics, and their connection to atmospheric nucleation. Here we present a summary of the chemistry of atmospheric clustering, growing nanoparticles, and their precursors. In this work, we focus particularly on atmospheric gas-to-particle conversion and recent progress in its understanding.

234 citations


Journal ArticleDOI
TL;DR: Measurements from the Cosmics Leaving Outdoor Droplets chamber reveal the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions, revealing the fundamental processes involved in particle formation and growth.
Abstract: For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus.

203 citations


Journal ArticleDOI
TL;DR: In this paper, side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement.
Abstract: . Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiala United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

107 citations


Journal Article
TL;DR: The Airmodus Particle Size Magnifier has been used at the SMEAR II station in Hyytiälä, southern Finland, and during nucleation experiments in the CLOUD chamber at CERN for measuring particles as small as about 1 nm in mobility diameter as discussed by the authors.
Abstract: The most important parameters describing the atmospheric new particle formation process are the particle formation and growth rates. These together determine the amount of cloud condensation nuclei attributed to secondary particle formation. Due to difficulties in detecting small neutral particles, it has previously not been possible to derive these directly from measurements in the size range below about 3 nm. The Airmodus Particle Size Magnifier has been used at the SMEAR II station in Hyytiälä, southern Finland, and during nucleation experiments in the CLOUD chamber at CERN for measuring particles as small as about 1 nm in mobility diameter. We developed several methods to determine the particle size distribution and growth rates in the size range of 1–3 nm from these data sets. Here we introduce the appearance-time method for calculating initial growth rates. The validity of the method was tested by simulations with the Ion-UHMA aerosol dynamic model.

104 citations


Journal ArticleDOI
01 Jun 2014-Ecology
TL;DR: By evolutionary adjustment of spore size, release height and timing of release, fungi and other organisms with microscopic spores can change the expected distribution of dispersal locations markedly, providing intriguing hypotheses to be tested empirically in future studies.
Abstract: In species that disperse by airborne propagules an inverse relationship is often assumed between propagule size and dispersal distance. However, for microscopic spores the evidence for the relationship remains ambiguous. Lagrangian stochastic dispersion models that have been successful in predicting seed dispersal appear to predict similar dispersal for all spore sizes up to -40 microm diameter. However, these models have assumed that spore size affects only the downwards drift of particles due to gravitation and have largely omitted the highly size-sensitive deposition process to surfaces such as forest canopy. On the other hand, they have assumed that spores are certain to deposit when the air parcel carrying them touches the ground. Here, we supplement a Lagrangian stochastic dispersion model with a mechanistic deposition model parameterized by empirical deposition data for 1-10 microm spores. The inclusion of realistic deposition improved the ability of the model to predict empirical data on the dispersal of a wood-decay fungus (aerodynamic spore size 3.8 microm). Our model predicts that the dispersal of 1-10 microm spores is in fact highly sensitive to spore size, with 97-98% of 1 microm spores but only 12-58% of 10-microm spores dispersing beyond 2 km in the simulated range of wind and canopy conditions. Further, excluding the assumption of certain deposition at the ground greatly increased the expected dispersal distances throughout the studied spore size range. Our results suggest that by evolutionary adjustment of spore size, release height and timing of release, fungi and other organisms with microscopic spores can change the expected distribution of dispersal locations markedly. The complex interplay of wind and canopy conditions in determining deposition resulted in some counterintuitive predictions, such as that spores disperse furthest under intermediate wind, providing intriguing hypotheses to be tested empirically in future studies.

91 citations


Journal ArticleDOI
TL;DR: In this article, the authors reported results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulfuric acid (H2SO4).
Abstract: . Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of the reaction of stabilized Criegee intermediates (sCIs) with SO2, atmospheric oxidation processes were thought to be dominated by a few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulfuric acid (H2SO4). The measured total sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO2, k(loss) /k(sCI + SO2), was determined at relative humidities of 10 and 50%. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene-derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO2) were in the range (2.0–2.4) × 1012 molecules cm−3 and nearly independent of the relative humidity. This fact points to a minor importance of the sCI + H2O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO2) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO2; k(sCI + acid) / k(sCI + SO2) = (2.8 ± 0.3) for formic acid, and k(sCI + acid) / k(sCI + SO2) = (3.4 ± 0.2) for acetic acid. This finding indicates that sCIs can play a role in the formation and loss of other atmospheric constituents besides SO2.

89 citations


Journal ArticleDOI
TL;DR: In this article, a nano-CPC (condensation particle counter) battery, consisting of four ultrafine CPCs optimized for the detection of sub-3 nm particles, was built.
Abstract: . In this study we built a nano-CPC (condensation particle counter) battery, consisting of four ultrafine CPCs optimized for the detection of sub-3 nm particles. Two of the CPCs use diethylene glycol as a working fluid: a laminar type diethlylene glycol CPC and a mixing type Airmodus A09 particle size magnifier. The other two CPCs are a laminar type TSI 3025A and a TSI 3786 with butanol and water as the working fluids, respectively. The nano-CPC battery was calibrated with seven different test aerosols: tetraheptyl ammonium bromide, ammonium sulfate, sodium chloride, tungsten oxide, sucrose, candle flame products and limonene ozonolysis products. The results show that ammonium sulfate and sodium chloride have a higher activation efficiency with the water-based 3786 than with the butanol-based 3025A, whereas the other aerosols were activated better with butanol than with water as the working fluid. It is worthwhile to mention that sub-2 nm limonene ozonolysis products were detected very poorly with all of the CPCs, butanol being the best fluid to activate the oxidation products. To explore how the detection efficiency is affected if the aerosol is an internal mixture of two different chemical substances, we made the first attempt to control the mixing state of sub-3 nm laboratory generated aerosol. We show that we generated an internally mixed aerosol of ammonium sulfate nucleated onto tungsten oxide seed particles, and observed that the activation efficiency of the internally mixed clusters was a function of the internal mixture composition.

Journal Article
TL;DR: In this paper, the authors explore the inter-annual variability and trends in sources and sinks of atmospheric nanoparticles in a boreal forest environment, and find that the probability of new particle formation is connected to both air mass origin, explaining a large part of the year-to-year variability in the number of NPF events, and concentrations of lowvolatile vapours.
Abstract: New-particle formation (NPF) is globally an important source of climatically-relevant atmospheric aerosols. Here we explore the inter-annual variability and trends in sources and sinks of atmospheric nanoparticles in a boreal forest environment. We look into the precursor vapors leading to the aerosol formation, NPF frequency, as well as the formation and growth rates of the freshly-formed particles. The analysis is based on 16 years of data acquired from the Station for Measuring Ecosystem–Atmosphere Relations (SMEAR II) in Hyytiälä, Finland. The results indicate that the probability of NPF is connected to both air mass origin, explaining a large part of the year-to-year variability in the number of NPF events, and concentrations of low-volatile vapours. The probability of NPF increases with increasing gaseous sulphuric acid concentrations, but even better association is found between the NPF probability and product of sulphuric acid and low-volatile organic vapour (proxy) concentrations. While the concentrations of both sulphuric acid (evaluated by proxy) and sulphuric-acid precursor sulphur dioxide decreased over the 16-year measurement period, the new-particle formation and growth rates slightly increased. On the other hand, the proxy concentrations of oxidized organics increased in all seasons except in winter. The contribution of sulphuric acid to the particle growth was minor, and the growth rate had a clear connection with the ambient temperature due to higher emissions of biogenic volatile organic compounds at higher temperatures. For a given sulphuric acid concentration evaluated by proxy, particle formation rates tended to be higher at higher temperatures.

Journal ArticleDOI
TL;DR: A detailed three-dimensional regional chemi- cal transport model (Particulate Matter Comprehensive Air Quality Model with Extensions, PMCAMx) was applied over Europe, focusing on the formation and chemical transforma- tion of organic matter.
Abstract: A detailed three-dimensional regional chemi- cal transport model (Particulate Matter Comprehensive Air Quality Model with Extensions, PMCAMx) was applied over Europe, focusing on the formation and chemical transforma- tion of organic matter. Three periods representative of dif- ferent seasons were simulated, corresponding to intensive field campaigns. An extensive set of AMS measurements was used to evaluate the model and, using factor-analysis results, gain more insight into the sources and transforma- tions of organic aerosol (OA). Overall, the agreement be- tween predictions and measurements for OA concentration is encouraging, with the model reproducing two-thirds of the data (daily average mass concentrations) within a factor of 2. Oxygenated OA (OOA) is predicted to contribute 93 % to total OA during May, 87 % during winter and 96 % dur- ing autumn, with the rest consisting of fresh primary OA (POA). Predicted OOA concentrations compare well with the observed OOA values for all periods, with an average fractional error of 0.53 and a bias equal to 0.07 (mean error = 0.9 µg m 3 , mean bias = 0.2 µg m 3 ). The model

Journal ArticleDOI
TL;DR: In this article, the authors measured air ions in the diameter range 0.8-42 nm using an air ion spectrometer, and a differential mobility particle sizer (DMPS) provided particle number size distributions between 6 and 800 nm.
Abstract: . Aerosols and new particle formation were studied in the western part of the Yangtze River Delta (YRD) at the Station for Observing Regional Processes of the Earth System, Nanjing University (SORPES-NJU). Air ions in the diameter range 0.8–42 nm were measured using an air ion spectrometer, and a differential mobility particle sizer (DMPS) provided particle number size distributions between 6 and 800 nm. Additionally, meteorological data, trace gas concentrations, and PM2.5 values were recorded. During the measurement period from 18 November 2011 to 31 March 2012, the mean total particle concentration was found to be 23 000 cm−3 and the mean PM2.5 value was 90 μg m−3, well above national limits. We observed 26 new particle formation events occurred during the measurement period, producing 6 nm particles at a rate of about 1 cm−3 s−1. Typical particle growth rates were between 6 and 7 nm h−1. On average, new particle formation and growth were estimated to enhance cloud condensation nuclei concentration by about a factor of two during these event days. Ion measurements showed the typical cluster band below 2 nm, with total ion concentrations between about 600 and 1000 cm−3. A peculiar feature of the ion measurements were heightened ion cluster concentrations during the nights before the event days. At 2 nm, the formation rate of charged particles was only about 0.2% of the total rate, pointing towards an only marginal role of ion-induced nucleation. Based on observations, a simple empirical criterion was deducted to estimate particle formation probability. Dominated by radiation and relative humidity, the criterion can predict the occurrence of particle formation with a 90% accuracy. In a similar fashion, a reasonably accurate estimate of particle formation rates was derived. Combined, these parameters allow for a description of particle formation based on a few basic measured variables.

Journal ArticleDOI
TL;DR: In this paper, a Volatility-Hygroscopicity Tandem Differential Mobility Analyzer (VH-TDMA) was applied to study the volatility and volatility properties of submicron atmospheric aerosol particles in a boreal forest environment in Hyytiala, Finland during the summer of 2010.
Abstract: . A Volatility-Hygroscopicity Tandem Differential Mobility Analyzer (VH-TDMA) was applied to study the hygroscopicity and volatility properties of submicron atmospheric aerosol particles in a boreal forest environment in Hyytiala, Finland during the summer of 2010. Aitken and accumulation mode internally mixed particles (50 nm, 75 nm and 110 nm in diameter) were investigated. Hygroscopicity was found to increase with particle size. The relative mass fraction of organics and SO42- is probably the major contributor to the fluctuation of the hygroscopicity for all particle sizes. The Cloud Condensation Nuclei Counter (CCNC)-derived hygroscopicity parameter κ was observed to be slightly higher than κ calculated from VH-TDMA data under sub-saturated conditions, potential reasons for this behavior are discussed shortly. Also, the size-resolved volatility properties of particles were investigated. Upon heating, more small particles evaporated compared to large particles. There was a significant amount of aerosol volume (non-volatile material) left, even at heating temperatures of 280 °C. Using size resolved volatility-hygroscopicity analysis, we concluded that there was always hygroscopic material remaining in the particles at different heating temperatures, even at 280 °C. This indicates that the observed non-volatile aerosol material did not consist solely of black carbon.

Journal ArticleDOI
TL;DR: In this paper, the authors performed two inter-comparison campaigns to investigate the Doppler lidar performance, compare the backscatter signal and wind profiles, and to optimize the lidar sensitivity through adjusting the telescope focus length and data-integration time to ensure sufficient signal-to-noise ratio (SNR) in low-aerosol-content environments.
Abstract: . The Finnish Meteorological Institute, in collaboration with the University of Helsinki, has established a new ground-based remote-sensing network in Finland. The network consists of five topographically, ecologically and climatically different sites distributed from southern to northern Finland. The main goal of the network is to monitor air pollution and boundary layer properties in near real time, with a Doppler lidar and ceilometer at each site. In addition to these operational tasks, two sites are members of the Aerosols, Clouds and Trace gases Research InfraStructure Network (ACTRIS); a Ka band cloud radar at Sodankyla will provide cloud retrievals within CloudNet, and a multi-wavelength Raman lidar, PollyXT (POrtabLe Lidar sYstem eXTended), in Kuopio provides optical and microphysical aerosol properties through EARLINET (the European Aerosol Research Lidar Network). Three C-band weather radars are located in the Helsinki metropolitan area and are deployed for operational and research applications. We performed two inter-comparison campaigns to investigate the Doppler lidar performance, compare the backscatter signal and wind profiles, and to optimize the lidar sensitivity through adjusting the telescope focus length and data-integration time to ensure sufficient signal-to-noise ratio (SNR) in low-aerosol-content environments. In terms of statistical characterization, the wind-profile comparison showed good agreement between different lidars. Initially, there was a discrepancy in the SNR and attenuated backscatter coefficient profiles which arose from an incorrectly reported telescope focus setting from one instrument, together with the need to calibrate. After diagnosing the true telescope focus length, calculating a new attenuated backscatter coefficient profile with the new telescope function and taking into account calibration, the resulting attenuated backscatter profiles all showed good agreement with each other. It was thought that harsh Finnish winters could pose problems, but, due to the built-in heating systems, low ambient temperatures had no, or only a minor, impact on the lidar operation – including scanning-head motion. However, accumulation of snow and ice on the lens has been observed, which can lead to the formation of a water/ice layer thus attenuating the signal inconsistently. Thus, care must be taken to ensure continuous snow removal.

16 Dec 2014
TL;DR: In this article, the surface tension of organosulfates with a molecular weight of 250 Da (L-OS 250) was used for simultaneous measurements with a hygroscopicity tandem differential mobility analyser (H-TDMA) and a cloud condensation nuclei counter (CCNC).
Abstract: Abstract. Organosulfates have been observed as constituents of atmospheric aerosols in a wide range of environments; however their hygroscopic properties remain uncharacterised. Here, limonene-derived organosulfates with a molecular weight of 250 Da (L-OS 250) were synthesised and used for simultaneous measurements with a hygroscopicity tandem differential mobility analyser (H-TDMA) and a cloud condensation nuclei counter (CCNC) to determine the hygroscopicity parameter, κ, for pure L-OS 250 and mixtures of L-OS 250 with ammonium sulfate (AS) over a wide range of humidity conditions. The κ values derived from measurements with H-TDMA decreased with increasing particle dry diameter for all chemical compositions investigated, indicating that κH-TDMA depends on particle diameter and/or surface effects; however, it is not clear if this trend is statistically significant. For pure L-OS 250, κ was found to increase with increasing relative humidity, indicating dilution/solubility effects to be significant. Discrepancies in κ between the sub- and supersaturated measurements were observed for L-OS 250, whereas κ of AS and mixed L-OS 250/AS were similar. This discrepancy was primarily ascribed to limited dissolution of L-OS 250 at subsaturated conditions. In general, hygroscopic growth factor, critical particle diameter and κ for the mixed L-OS 250/AS particles converged towards the values of pure AS for mixtures with ≥ 20 % w / w AS. Surface tension measurements of bulk aqueous L-OS 250/AS solutions showed that L-OS 250 was indeed surface active, as expected from its molecular structure, decreasing the surface tension of solutions with 24 % from the pure water value at a L-OS 250 concentration of 0.0025 mol L−1. Based on these surface tension measurements, we present the first concentration-dependent parametrisation of surface tension for aqueous L-OS 250, which was implemented to different process-level models of L-OS 250 hygroscopicity and CCN activation. The values of κ obtained from the measurements were compared with κ calculated applying the volume additive Zdanovskii–Stokes–Robinson mixing rule, as well as κ modelled from equilibrium Kohler theory with different assumptions regarding L-OS 250 bulk-to-surface partitioning and aqueous droplet surface tension. This study is to our knowledge the first to investigate the hygroscopic properties and surface activity of L-OS 250; hence it is an important first step towards understanding the atmospheric impact of organosulfates.

Journal ArticleDOI
01 Mar 2014-Ecology
TL;DR: By combining laboratory inoculations with wind tunnel and field trials using the wind-dispersed pathogen Podosphaera plantaginis, striking genetic variation affecting the unexplored microscale (< 2 m) of epidemics is demonstrated and confirms that these traits may be targeted by selection.
Abstract: Many devastating pathogens are passively dispersed, and their epidemics are characterized by variation that is typically attributed to environmental factors. Here, by combining laboratory inoculations with wind tunnel and field trials using the wind-dispersed pathogen Podosphaera plantaginis, we demonstrated striking genetic variation affecting the unexplored microscale (<2 m) of epidemics. Recipient and source host genotypes, as well as pathogen strain, explained a large fraction of variation in the three key dispersal phases: departure, movement, and settlement. Moreover, we found genotypic variation affecting group size of the pathogen dispersal unit, ultimately resulting in increased disease development on hosts close to the infection source. Together, our results show that genotypic variation may generate considerable variation in the rate of disease spread through space and time with disease hotspots emerging around initial foci. Furthermore, the extent of genetic variation affecting the entire disp...

Journal ArticleDOI
TL;DR: It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge, and the growth rate is then probably limited by the arrival rate of sulfurIC acid or cluster-cluster collision.
Abstract: We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid−base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster−cluster collision.

Journal Article
TL;DR: In this paper, Manninen et al. presented a list of departments and departments of the University of Helsinki and the Max Planck Institute for Chemistry, respectively, with their corresponding departments of biology and chemistry.
Abstract: 1) Department of Physics, P.O. Box 64, FI-00014 University of Helsinki, Finland (*corresponding author’s e-mail: hanna.manninen@helsinki.fi) 2) Institute of Physics, University of Tartu, Ulikooli 18, EE-50090 Tartu, Estonia 3) Department of Forest Sciences, P.O. Box 27, FI-00014 University of Helsinki, Finland 4) Department of Chemistry and Biochemistry, University of Denver, 2190 E. Illif Ave., Denver, CO 80208, USA 5) Max Planck Institute for Chemistry, P.O. Box 3060, D-55020 Mainz, Germany 6) Department of Biology, FI-20014 University of Turku, Finland 7) Department of Environmental Biology, University of Huelva, ES-21071 Huelva, Spain


Journal Article
TL;DR: In this paper, the authors provided the first quantitative estimate regarding the terrestrial climate feedback loop connecting the increasing atmospheric carbon dioxide concentration, changes in gross primary production (GPP) associated with the carbon uptake, organic aerosol formation in the atmosphere, and transfer of both diffuse and global radiation.
Abstract: Feedbacks mechanisms are essential components of our climate system, as they either increase or decrease changes in climate-related quantities in the presence of external forcings. In this work, we provide the first quantitative estimate regarding the terrestrial climate feedback loop connecting the increasing atmospheric carbon dioxide concentration, changes in gross primary production (GPP) associated with the carbon uptake, organic aerosol formation in the atmosphere, and transfer of both diffuse and global radiation. Our approach was to combine process-level understanding with comprehensive, long-term field measurement data set collected from a boreal forest site in southern Finland. Our best estimate of the gain in GPP resulting from the feedback is 1.3 (range 1.02-1.5), which is larger than the gains of the few atmospheric chemistry-climate feedbacks estimated using large-scale models. Our analysis demonstrates the power of using comprehensive field measurements in investigating the complicated couplings between the biosphere and atmosphere on one hand, and the need for complementary approaches relying on the combination of field data, satellite observations model simulations on the other hand.

Journal ArticleDOI
TL;DR: In this article, atmospheric H2SO4 / H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research -Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas.
Abstract: . Atmospheric H2SO4 / H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research – Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a possible background amine concentration in the order of 107–108 molecule cm−3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm−3. Also the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products in line with the expected growth by organic products using literature data. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~107 molecule cm−3. Furthermore, the findings confirm the appearance of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediates (sCI). A second set of experiments has been performed in the presence of added amines in the concentrations range of a few 107–1010 molecule cm−3 applying photolytic OH radical generation for H2SO4 production without addition of other organics. All amines showed significant nucleation enhancement with increasing efficiency in the order pyridine

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TL;DR: In this paper, the simultaneous mobility and mass measurement of negative ions generated by the ionizing radiation in a 241Am aerosol charger in N2 (5.0), a 1:1-mixture of N2 and synthetic air, pure synthetic air (5.,0), and filtered laboratory air at ∼30% relative humidity was performed using a high-resolution mobility analyzer and an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF).
Abstract: This work concentrates on the simultaneous mobility and mass measurement of negative ions generated by the ionizing radiation in a 241Am aerosol charger in N2 (5.0), a 1:1-mixture of N2 and synthetic air, pure synthetic air (5.0), and filtered laboratory air at ∼30% relative humidity. Therefore, a high-resolution mobility analyzer (UDMA) and an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) were operated in series. Experiments with N2 as carrier gas showed a dominating signal at an electrical mobility of 2.09 cm2/Vs with 90% of the ions being nitrate based. The ion composition was altered after a baking-out to a spectrum with three strong mobility-peaks at Z1 = 2.34 cm2/Vs, Z2 = 1.42 cm2/Vs, Z3 = 1.08 cm2/Vs and a higher diversity of ions in the corresponding mass spectra. The carrier gas was gradually changed from N2 (5.0) to a 1:1-mixture of N2 with synthetic air and pure synthetic air (5.0), having only a minor effect on the overall pattern of the ion spectrum. Using room air...

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TL;DR: In this article, the authors show that sulfur species, namely sulfur dioxide and sulfuric acid, have an important role in both new particle formation and subsequent growth and that the decrease in new particles formation days is a result of the reduction of sulfur emissions originating from Kola Peninsula.
Abstract: . The smelter industry in Kola Peninsula is the largest source of anthropogenic SO2 in the Arctic part of Europe and one of the largest within the Arctic domain. Due to socio-economic changes in Russia, the emissions have been decreasing especially since the late 1990s resulting in decreased SO2 concentrations close to Kola in eastern Lapland, Finland. At the same time, the frequency of new particle formation days has been decreasing distinctively at SMEAR I station in eastern Lapland, especially during spring and autumn. We show that sulfur species, namely sulfur dioxide and sulfuric acid, have an important role in both new particle formation and subsequent growth and that the decrease in new particle formation days is a result of the reduction of sulfur emissions originating from Kola Peninsula. In addition to sulfur species, there are many other quantities, such as formation rate of aerosol particles, condensation sink and nucleation mode particle number concentration, which are related to the number of observed new particle formation (NPF) days and need to be addressed when linking sulfur emissions and NPF. We show that while most of these quantities exhibit statistically significant trends, the reduction in Kola sulfur emissions is the most obvious reason for the rapid decline in NPF days. Sulfuric acid explains approximately 20–50% of the aerosol condensational growth observed at SMEAR I, and there is a large seasonal variation with highest values obtained during spring and autumn. We found that (i) particles form earlier after sunrise during late winter and early spring due to high concentrations of SO2 and H2SO4; (ii) several events occurred during the absence of light, and they were connected to higher than average concentrations of SO2; and (iii) high SO2 concentrations could advance the onset of nucleation by several hours. Moreover, air masses coming over Kola Peninsula seemed to favour new particle formation.

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TL;DR: The Pan-Eurasian Experiment (PEEX) is a new multidisciplinary, global change research initiative focusing on understanding biosphere-ocean-cryosphere-climate interactions and feedbacks in Arctic and boreal regions in the Northern Eurasian geographical domain this article.
Abstract: The Pan-Eurasian Experiment (PEEX) is a new multidisciplinary, global change research initiative focusing on understanding biosphere-ocean-cryosphere-climate interactions and feedbacks in Arctic and boreal regions in the Northern Eurasian geographical domain. PEEX operates in an integrative way and it aims at solving the major scientific and society relevant questions in many scales using tools from natural and social sciences and economics. The research agenda identifies the most urgent large scale research questions and topics of the land-atmosphere-aquatic-anthropogenic systems and interactions and feedbacks between the systems for the next decades. Furthermore PEEX actively develops and designs a coordinated and coherent ground station network from Europe via Siberia to China and the coastal line of the Arctic Ocean together with a PEEX-modeling platform. PEEX launches a program for educating the next generation of multidisciplinary researcher and technical experts. This expedites the utilization of the new scientific knowledge for producing a more reliable climate change scenarios in regional and global scales, and enables mitigation and adaptation planning of the Northern societies. PEEX gathers together leading European, Russian and Chinese research groups. With a bottom-up approach, over 40 institutes and universities have contributed the PEEX Science Plan from 18 countries. In 2014 the PEEX community prepared Science Plan and initiated conceptual design of the PEEX land-atmosphere observation network and modeling platform. Here we present the PEEX approach as a whole with the specific attention to research agenda and preliminary design of the PEEX research infrastructure.

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TL;DR: In this article, a prescribed fire experiment was conducted on 26 June 2009 in Hyytiala, Finland, to study aerosol and trace gas emissions from prescribed fires of slash fuels and the effects of fire on soil properties in a controlled environment.
Abstract: . A prescribed fire experiment was conducted on 26 June 2009 in Hyytiala, Finland, to study aerosol and trace gas emissions from prescribed fires of slash fuels and the effects of fire on soil properties in a controlled environment. A 0.8 ha forest near the SMEAR II measurement station (Station for Measuring Ecosystem-Atmosphere Relations) was cut clear; some tree trunks, all tree tops and branches were left on the ground and burned. The amount of burned organic material was ~46.8 tons (i.e., ~60 tons ha−1). The flaming phase lasted 2 h 15 min, the smoldering phase 3 h. Measurements were conducted on the ground with both fixed and mobile instrumentation, and in the air from a research aircraft. In the middle of the burning area, CO2 concentration peaked around 2000–3000 ppm above the baseline, and peak vertical flow velocities were ~9 m s−1, as measured with a 10 Hz 3-D sonic anemometer placed within the burn area. In the mobile measurements the peak particle number concentrations were approximately 1–2 × 106 cm−3 in the plume at a distance of 100–200 m from the burn area. On the ground at the SMEAR II station the geometric mean diameter of the mode with the highest concentration was 80 ± 1 nm during the flaming phase and in the middle of the smoldering phase, but, at the end of the smoldering phase, the largest mode was 122 nm. In the volume size distributions, geometric mean diameter of the largest volume mode was 153 nm during the flaming phase and 300 nm during the smoldering phase. The lowest single-scattering albedo of the ground-level measurements was 0.7 in the flaming-phase plume and ~0.9 in the smoldering phase. Elevated concentrations of several volatile organic compounds (VOC) (including acetonitrile, a biomass burning marker) were observed in the smoke plume at ground level. Measurements at the forest floor (i.e., a richly organic layer of soil and debris, characteristic of forested land) showed that VOC fluxes were generally low and consisted mainly of monoterpenes, and VOC flux peaked after the burning. After one year, the fluxes had nearly stabilized close to the level before the burning. The clear-cutting and burning of slash increased the total long-term CO2 release from the soil, and altered the physical, chemical and biological properties of the soil, such as increased the available nitrogen contents of the soil, which in turn, affected the long-term fluxes of greenhouse gases.

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TL;DR: In this article, the authors showed that the difference between AAEs calculated using different corrections can lead to conflicting conclusions on the type of aerosol when using the same data set.
Abstract: . Absorption Angstrom exponents (AAEs) calculated from filter-based absorption measurements are often used to give information on the origin of the ambient aerosol, for example, to distinguish between urban pollution and biomass burning aerosol. Filter-based absorption measurements are widely used and are common at aerosol monitoring stations globally. Several correction algorithms are used to account for artefacts associated with filter-based absorption techniques. These algorithms are of profound importance when determining the absolute amount of absorption by the aerosol. However, this study shows that there are substantial differences between the AAEs calculated from these corrections. Depending on the used correction, AAEs can change by as much as 46%. The study also highlights that the difference between AAEs calculated using different corrections can lead to conflicting conclusions on the type of aerosol when using the same data set. The AAE ranged between 1.17 for non-corrected data to 1.96 for the correction that gave the greatest values. Furthermore, the study implies that the AAEs reported for a site depend on at which filter transmittance the filter is changed. In this work, the AAEs were calculated from data measured with a three-wavelength particle soot absorption photometer (PSAP) at Elandsfontein on the South African Highveld for 23 months. The sample air of the PSAP was diluted to prolong filter change intervals, by a factor of 15. The correlation coefficient between the dilution-corrected PSAP and a non-diluted Multi-Angle Absorption Photometer (MAAP) was 0.9. Thus, the study also shows that the applicability of the PSAP can be extended to remote sites that are not often visited or suffer from high levels of pollution.

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TL;DR: In this article, a mathematical model, BUOYANT, was designed for the evaluation of the dispersion of buoyant plumes originated from major warehouse fires and compared with the data of two prescribed wild-land fire experiments.
Abstract: . We have presented an overview of a mathematical model, BUOYANT, that was originally designed for the evaluation of the dispersion of buoyant plumes originated from major warehouse fires. The model addresses the variations of the cross-plume integrated properties of a buoyant plume in the presence of a vertically varying atmosphere. The model also includes a treatment for a rising buoyant plume interacting with an inversion layer. We have compared the model predictions with the data of two prescribed wild-land fire experiments. For the SCAR-C experiment in Quinault (US) in 1994, the predicted vertical extents of the plume at maximum plume rise were between 500 and 800 m and between 200 and 700 m, using two alternative meteorological data sets. The corresponding observed injection heights of the aerosol particles measured using an airborne lidar (light detection and ranging) ranged from 250 to 600 m. For the prescribed burning experiment in Hyytiala (Finland) in 2009, the model predictions were compared with plume elevations and diameters, determined based on particulate matter number concentration measurements onboard an aeroplane. However, the agreement between modelled and measured results substantially depends on how the properties of the source term are evaluated, especially regarding the convective heat fluxes from the fire. The results demonstrate that in field experiments on wild-land fires, there are substantial uncertainties in estimating both (i) the source terms for the atmospheric dispersion computations and (ii) the relevant vertical meteorological profiles.