We found that ambient and laboratory-generated secondary organic aerosols (SOA) form substantial amounts of OH radicals upon interaction with liquid water, which can be explained by the decomposition ...of organic hydroperoxides. The molar OH yield from SOA formed by ozonolysis of terpenes (α-pinene, β-pinene, limonene) is ∼ 0.1 % upon extraction with pure water and increases to ∼ 1.5 % in the presence of Fe2+ ions due to Fenton-like reactions. Upon extraction of SOA samples from OH photooxidation of isoprene, we also detected OH yields of around ∼ 0.1 %, which increases upon addition of Fe2+. Our findings imply that the chemical reactivity and aging of SOA particles is strongly enhanced upon interaction with water and iron. In cloud droplets under dark conditions, SOA decomposition can compete with the classical H2O2 Fenton reaction as the source of OH radicals. Also in the human respiratory tract, the inhalation and deposition of SOA particles may lead to a substantial release of OH radicals, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols.
It has been hypothesized that predecessors of today's bryophytes significantly increased global chemical weathering in the Late Ordovician, thus reducing atmospheric CO2 concentration and ...contributing to climate cooling and an interval of glaciations. Studies that try to quantify the enhancement of weathering by non-vascular vegetation, however, are usually limited to small areas and low numbers of species, which hampers extrapolating to the global scale and to past climatic conditions. Here we present a spatially explicit modelling approach to simulate global weathering by non-vascular vegetation in the Late Ordovician. We estimate a potential global weathering flux of 2.8 (km(3) rock) yr(-1), defined here as volume of primary minerals affected by chemical transformation. This is around three times larger than today's global chemical weathering flux. Moreover, we find that simulated weathering is highly sensitive to atmospheric CO2 concentration. This implies a strong negative feedback between weathering by non-vascular vegetation and Ordovician climate.
Phase transitions of nanoparticles are of fundamental importance in atmospheric sciences, but current understanding is insufficient to explain observations at the nano-scale. In particular, ...discrepancies exist between observations and model predictions of deliquescence and efflorescence transitions and the hygroscopic growth of salt nanoparticles. Here we show that these discrepancies can be resolved by consideration of particle size effects with consistent thermodynamic data. We present a new method for the determination of water and solute activities and interfacial energies in highly supersaturated aqueous solution droplets (Differential Köhler Analysis). Our analysis reveals that particle size can strongly alter the characteristic concentration of phase separation in mixed systems, resembling the influence of temperature. Owing to similar effects, atmospheric secondary organic aerosol particles at room temperature are expected to be always liquid at diameters below ~20 nm. We thus propose and demonstrate that particle size should be included as an additional dimension in the equilibrium phase diagram of aerosol nanoparticles.
Mitogen-activated protein kinase (MAPK)-mediated responses are in part regulated by the repertoire of MAPK substrates, which is still poorly elucidated in plants. Here, the in vivo enzyme-substrate ...interaction of the Arabidopsis thaliana MAP kinase, MPK6, with an ethylene response factor (ERF104) is shown by fluorescence resonance energy transfer. The interaction was rapidly lost in response to flagellin-derived flg22 peptide. This complex disruption requires not only MPK6 activity, which also affects ERF104 stability via phosphorylation, but also ethylene signaling. The latter points to a novel role of ethylene in substrate release, presumably allowing the liberated ERF104 to access target genes. Microarray data show enrichment of GCC motifs in the promoters of ERF104-up-regulated genes, many of which are stress related. ERF104 is a vital regulator of basal immunity, as altered expression in both erf104 and overexpressors led to more growth inhibition by flg22 and enhanced susceptibility to a non-adapted bacterial pathogen.
Proteins contained in pollen and other biological particles are nitrated by ozone and nitrogen dioxide in polluted air. The nitration can enhance the allergenic potential of proteins, which may ...contribute to the increasing prevalence of allergic diseases. The reactive uptake of NO2 by aerosolized protein (bovine serum albumin) was investigated in an aerosol flow tube using the short-lived radioactive tracer 13N. In the absence of O3, the NO2 uptake coefficient was below detection limit (γNO2 < 10–6), but with 20–160 ppb O3 γNO2 increased from ∼10–6 to ∼10–4. Using the kinetic multilayer model of surface and bulk chemistry (KM-SUB), the observed time and concentration dependence can be well reproduced by a multiphase chemical mechanism involving ozone-generated reactive oxygen intermediates (ROIs), but not by NO3 radicals formed in the gas phase. Product studies show the formation of protein dimers, suggesting that the ROIs are phenoxy radical derivatives of the amino acid tyrosine (tyrosyl radicals) which are also involved in physiological protein nitration processes. Our results imply that proteins on the surface of aerosol particles undergo rapid nitration in polluted air, while the rate of nitration in bulk material may be low depending on phase state and surface-to-volume ratio.
The CALICE Collaboration is conducting R&D for highly granular calorimeters with an emphasis on detectors for Linear Colliders. This contribution briefly summarises recent tests of large scale ...technological prototypes of a silicon tungsten electromagnetic calorimeter and hadron calorimeters featuring either a gaseous medium or scintillator with a SiPM readout as active material.
•Large prototypes with realistic technology of highly granular calorimeters.•Low noise electronics, trigger on 1/2 MIP.•Power pulsing of detectors.•Unambiguous separation of close-by particles.•High granularity allows for software compensation.
The Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) Experiment was carried out in the environs of Manaus, Brazil, in the central region of the Amazon basin for 2 years from ...1 January 2014 through 31 December 2015. The experiment focused on the complex interactions among vegetation, atmospheric chemistry, and aerosol production on the one hand and their connections to aerosols, clouds, and precipitation on the other. The objective was to understand and quantify these linked processes, first under natural conditions to obtain a baseline and second when altered by the effects of human activities. To this end, the pollution plume from the Manaus metropolis, superimposed on the background conditions of the central Amazon basin, served as a natural laboratory. The present paper, as the introduction to the special issue of GoAmazon2014/5, presents the context and motivation of the GoAmazon2014/5 Experiment. The nine research sites, including the characteristics and instrumentation of each site, are presented. The sites range from time point zero (T0) upwind of the pollution, to T1 in the midst of the pollution, to T2 just downwind of the pollution, to T3 furthest downwind of the pollution (70 km). In addition to the ground sites, a low-altitude G-159 Gulfstream I (G-1) observed the atmospheric boundary layer and low clouds, and a high-altitude Gulfstream G550 (HALO) operated in the free troposphere. During the 2-year experiment, two Intensive Operating Periods (IOP1 and IOP2) also took place that included additional specialized research instrumentation at the ground sites as well as flights of the two aircraft. GoAmazon2014/5 IOP1 was carried out from 1 February to 31 March 2014 in the wet season. GoAmazon2014/5 IOP2 was conducted from 15 August to 15 October 2014 in the dry season. The G-1 aircraft flew during both IOP1 and IOP2, and the HALO aircraft flew during IOP2. In the context of the Amazon basin, the two IOPs also correspond to the clean and biomass burning seasons, respectively. The Manaus plume is present year-round, and it is transported by prevailing northeasterly and easterly winds in the wet and dry seasons, respectively. This introduction also organizes information relevant to many papers in the special issue. Information is provided on the vehicle fleet, power plants, and industrial activities of Manaus. The mesoscale and synoptic meteorologies relevant to the two IOPs are presented. Regional and long-range transport of emissions during the two IOPs is discussed based on satellite observations across South America and Africa. Fire locations throughout the airshed are detailed. In conjunction with the context and motivation of GoAmazon2014/5 as presented in this introduction, research articles including thematic overview articles are anticipated in this special issue to describe the detailed results and findings of the GoAmazon2014/5 Experiment.
Cloud glaciation is critically important for the global radiation budget (albedo) and for initiation of precipitation. But the freezing of pure water droplets requires cooling to temperatures as low ...as 235 K. Freezing at higher temperatures requires the presence of an ice nucleator, which serves as a template for arranging water molecules in an ice-like manner. It is often assumed that these ice nucleators have to be insoluble particles. We point out that also free macromolecules which are dissolved in water can efficiently induce ice nucleation: the size of such ice nucleating macromolecules (INMs) is in the range of nanometers, corresponding to the size of the critical ice embryo. As the latter is temperature-dependent, we see a correlation between the size of INMs and the ice nucleation temperature as predicted by classical nucleation theory. Different types of INMs have been found in a wide range of biological species and comprise a variety of chemical structures including proteins, saccharides, and lipids. Our investigation of the fungal species Acremonium implicatum, Isaria farinosa, and Mortierella alpina shows that their ice nucleation activity is caused by proteinaceous water-soluble INMs. We combine these new results and literature data on INMs from fungi, bacteria, and pollen with theoretical calculations to develop a chemical interpretation of ice nucleation and water-soluble INMs. This has atmospheric implications since many of these INMs can be released by fragmentation of the carrier cell and subsequently may be distributed independently. Up to now, this process has not been accounted for in atmospheric models.
Bioaerosols are relevant for public health and may play an important role in the climate system, but their atmospheric abundance, properties, and sources are not well understood. Here we show that ...the concentration of airborne biological particles in a North American forest ecosystem increases significantly during rain and that bioparticles are closely correlated with atmospheric ice nuclei (IN). The greatest increase of bioparticles and IN occurred in the size range of 2–6 μm, which is characteristic for bacterial aggregates and fungal spores. By DNA analysis we found high diversities of airborne bacteria and fungi, including groups containing human and plant pathogens (mildew, smut and rust fungi, molds, Enterobacteriaceae, Pseudomonadaceae). In addition to detecting known bacterial and fungal IN (Pseudomonas sp., Fusarium sporotrichioides), we discovered two species of IN-active fungi that were not previously known as biological ice nucleators (Isaria farinosa and Acremonium implicatum). Our findings suggest that atmospheric bioaerosols, IN, and rainfall are more tightly coupled than previously assumed.
In this study we use the ECHAM/MESSy Atmospheric Chemistry (EMAC) model to simulate global fields of the effective hygroscopicity parameter κ which approximately describes the influence of chemical ...composition on the cloud condensation nucleus (CCN) activity of aerosol particles. The obtained global mean values of κ at the Earth's surface are 0.27±0.21 for continental and 0.72±0.24 for marine regions (arithmetic mean ± standard deviation). These values are the internally mixed κ calculated across the Aitken and accumulation modes. The mean κ values are in good agreement with previous estimates based on observational data, but the model standard deviation for continental regions is higher. Over the continents, the regional distribution appears fairly uniform, with κ values mostly in the range of 0.1–0.4. Lower values over large arid regions and regions of high organic loading lead to reduced continental average values for Africa and South America (0.15–0.17) compared to the other continents (0.21–0.36). Marine regions show greater variability with κ values ranging from 0.9–1.0 in remote regions to 0.4–0.6 in continental outflow regions where the highly hygroscopic sea spray aerosol mixes with less hygroscopic continental aerosol. Marine κ values as low as 0.2–0.3 are simulated in the outflow from the Sahara desert. At the top of the planetary boundary layer the κ values can deviate substantially from those at the surface (up to 30%) – especially in marine and coastal regions. In moving from the surface to the height of the planetary boundary layer, the global average marine κ value reduces by 20%. Thus, surface observations may not always be representative for the altitudes where cloud formation mostly occurs. In a pre-industrial model scenario, the κ values tend to be higher over marine regions and lower over the continents, because the anthropogenic particulate matter is on average less hygroscopic than sea-spray but more hygroscopic than the natural continental background aerosol (dust and organic matter). In regions influenced by desert dust the particle hygroscopicity has increased strongly as the mixing of air pollutants with mineral particles typically enhances the κ values by a factor of 2–3 above the initial value of ≈0.005.
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