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Li X., Rohrer F., Hofzumahaus A., Brauers T., Häseler R., Bohn B., Broch S., Fuchs H., Gomm S., Holland F., Jäger J., Kaiser J., Keutsch F. N., Lohse I., Lu K., Tillmann R., Wegener R., Wolfe G. M., Mentel T. F., Kiendler-Scharr A., Wahner A. (2014): Missing Gas-Phase Source of HONO Inferred from Zeppelin Measurements in the Troposphere, Science, 344 (6181), 292-296, DOI:10.1126/science.1248999 .

ABSTRACT
Gaseous nitrous acid (HONO) is an important precursor of tropospheric hydroxyl radicals (OH). OH is responsible for atmospheric self-cleansing and controls the concentrations of greenhouse gases like methane and ozone. Due to lack of measurements, vertical distributions of HONO and its sources in the troposphere remain unclear. Here, we present a set of observations of HONO and its budget made onboard a Zeppelin airship. In a sunlit layer separated from Earth’s surface processes by temperature inversion, we found high HONO concentrations providing evidence for a strong gas-phase source of HONO consuming nitrogen oxides and potentially hydrogen oxide radicals. The observed properties of this production process suggest that the generally assumed impact of HONO on the abundance of OH in the troposphere is substantially overestimated.

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Oswald, R., Behrendt, T., Ermel, M., Wu, D., Su, H., Cheng, Y., Breuninger, C., Moravek, A., Mougin, E., Delon, C., Loubet, B., Pommerening-Röser, A., Sorgel, M., Pöschl, U., Hoffmann, T., Andreae, M. O., Meixner, F. X., and Trebs, I.(2013): HONO emissions from soil bacteria as a major source of atmospheric reactive nitrogen, Science, 341, 1233–1235, DOI:10.1126/science.1242266.

ABSTRACT
Abiotic release of nitrous acid (HONO) in equilibrium with soil nitrite (NO2) was suggested as an important contributor to the missing source of atmospheric HONO and hydroxyl radicals (OH). The role of total soil-derived HONO in the biogeochemical and atmospheric nitrogen cycles, however, has remained unknown. In laboratory experiments, we found that for nonacidic soils from arid and arable areas, reactive nitrogen emitted as HONO is comparable with emissions of nitric oxide (NO). We show that ammonia-oxidizing bacteria can directly release HONO in quantities larger than expected from the acid-base and Henry’s law equilibria of the aqueous phase in soil. This component of the nitrogen cycle constitutes an additional loss term for fixed nitrogen in soils and a source for reactive nitrogen in the atmosphere.



Pöhlker, C., Wiedemann, K. T., Sinha, B., Shiraiwa, M., Gunthe, S. S., Smith, M., Su, H., Artaxo, P., Chen, Q., Cheng, Y., Elbert, W., Gilles, M. K., Kilcoyne, A. L. D., Moffet, R. C., Weigand, M., Martin, S. T., Pöschl, U., and Andreae, M. O.(2012): Biogenic Potassium Salt Particles as Seeds for Secondary Organic Aerosol in the Amazon, Science, 337, 1075-1078, DOI:10.1126/science.1223264.

ABSTRACT
The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt–rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest.



Su, H., Cheng, Y., Oswald, R., Behrendt, T., Trebs, I., Meixner, F. X., Andreae, M. O., Cheng, P., Zhang, Y., and Pöschl, U.(2011): Soil nitrite as a source of atmospheric HONO and OH radicals, Science, 333, 1616-1618, DOI:10.1126/science.1207687.

ABSTRACT
Hydroxyl radicals (OH) are a key species in atmospheric photochemistry. In the lower atmosphere, up to ~30% of the primary OH radical production is attributed to the photolysis of nitrous acid (HONO), and field observations suggest a large missing source of HONO. We show that soil nitrite can release HONO and explain the reported strength and diurnal variation of the missing source. Fertilized soils with low pH appear to be particularly strong sources of HONO and OH. Thus, agricultural activities and land-use changes may strongly influence the oxidizing capacity of the atmosphere. Because of the widespread occurrence of nitrite-producing microbes, the release of HONO from soil may also be important in natural environments, including forests and boreal regions.



Carslaw, K. S., Lee, L. A., Reddington, C. L., Pringle, K. J., Rap, A., Forster, P. M., Mann, G. W., Spracklen, D. V., Woodhouse, M. T., Regayre, L. A., and Pierce, J. R.(2013): Large contribution of natural aerosols to uncertainty in indirect forcing, Nature, 503, 67–71, DOI:10.1038/nature12674.

ABSTRACT
The effect of anthropogenic aerosols on cloud droplet concentrations and radiative properties is the source of one of the largest uncertainties in the radiative forcing of climate over the industrial period. This uncertainty affects our ability to estimate how sensitive the climate is to greenhouse gas emissions. Here we perform a sensitivity analysis on a global model to quantify the uncertainty in cloud radiative forcing over the industrial period caused by uncertainties in aerosol emissions and processes. Our results show that 45 per cent of the variance of aerosol forcing since about 1750 arises from uncertainties in natural emissions of volcanic sulphur dioxide, marine dimethylsulphide, biogenic volatile organic carbon, biomass burning and sea spray. Only 34 per cent of the variance is associated with anthropogenic emissions. The results point to the importance of understanding pristine pre-industrial-like environments, with natural aerosols only, and suggest that improved measurements and evaluation of simulated aerosols in polluted present-day conditions will not necessarily result in commensurate reductions in the uncertainty of forcing estimates.


Ehn, M., Thornton, J. A., Kleist, E., Sipila, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I. H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurten, T., Nielsen, L. B., Jorgensen, S., Kjaergaard, H. G., Canagaratna, M., Dal Maso, M., Berndt, T., Petaja, T., Wahner, A., Kerminen, V. M., Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476–479, DOI:10.1038/nature13032.

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.




Elbert, W., Weber, B., Burrows, S., Steinkamp, J., Budel, B., Andreae, M. O., and Pöschl, U.(2012): Contribution of cryptogamic covers to the global cycles of carbon and nitrogen, Nature Geoscience, 5, 459-462, DOI:10.1038/ngeo1486.

ABSTRACT
Many terrestrial surfaces, including soils, rocks and plants, are covered by photoautotrophic communities, capable of synthesizing their own food from inorganic substances using sunlight as an energy source. These communities, known as cryptogamic covers, comprise variable proportions of cyanobacteria, algae, fungi, lichens and bryophytes, and are able to fix carbon dioxide and nitrogen from the atmosphere. However, their influence on global and regional biogeochemical cycling of carbon and nitrogen has not yet been assessed. Here, we analyse previously published data on the spatial coverage of cryptogamic communities, and the associated fluxes of carbon and nitrogen, in different types of ecosystem across the globe. We estimate that globally, cryptogamic covers take up around 3.9 Pg carbon per year, corresponding to around 7% of net primary production by terrestrial vegetation. We derive a nitrogen uptake by cryptogamic covers of around 49 Tg per year, suggesting that cryptogamic covers account for nearly half of the biological nitrogen fixation on land. We suggest that nitrogen fixation by cryptogamic covers may be crucial for carbon sequestration by plants.



Fuchs, H., Hofzumahaus, A., Rohrer, F., Bohn, B., Brauers, T., Dorn, H-P., Häseler, R., Holland, F., Kaminski, M., Li, X., Lu, K., Nehr, S., Tillmann, R., Wegener, R. and Wahner, A. (2013) : Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation, Nature Geoscience, 6, 1023–1026, DOI:10.1038/ngeo1964.

ABSTRACT
Most pollutants in the Earth’s atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene. Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed. Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain. Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations. Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.



Paasonen, P., Asmi, A., Petaja, T., Kajos, M. K., Aijala, M., Junninen, H., Holst, T., Abbatt, J. P. D., Arneth, A., Birmili, W., van der Gon, H. D., Hamed, A., Hoffer, A., Laakso, L., Laaksonen, A., Richard Leaitch, W., Plass-Dulmer, C., Pryor, S. C., Raisanen, P., Swietlicki, E., Wiedensohler, A., Worsnop, D. R., Kerminen, V.-M., and Kulmala, M.(2013): Warming-induced increase in aerosol number concentration likely to moderate climate change, Nature Geoscience, 6, 438–442, DOI:10.1038/ngeo1800.

ABSTRACT
Atmospheric aerosol particles influence the climate system directly by scattering and absorbing solar radiation, and indirectly by acting as cloud condensation nuclei. Apart from black carbon aerosol, aerosols cause a negative radiative forcing at the top of the atmosphere and substantially mitigate the warming caused by greenhouse gases. In the future, tightening of controls on anthropogenic aerosol and precursor vapour emissions to achieve higher air quality may weaken this beneficial effect. Natural aerosols, too, might affect future warming. Here we analyse long-term observations of concentrations and compositions of aerosol particles and their biogenic precursor vapours in continental mid- and high-latitude environments. We use measurements of particle number size distribution together with boundary layer heights derived from reanalysis data to show that the boundary layer burden of cloud condensation nuclei increases exponentially with temperature. Our results confirm a negative feedback mechanism between the continental biosphere, aerosols and climate: aerosol cooling effects are strengthened by rising biogenic organic vapour emissions in response to warming, which in turn enhance condensation on particles and their growth to the size of cloud condensation nuclei. This natural growth mechanism produces roughly 50% of particles at the size of cloud condensation nuclei across Europe. We conclude that biosphere–atmosphere interactions are crucial for aerosol climate effects and can significantly influence the effects of anthropogenic aerosol emission controls, both on climate and air quality.



Riipinen I., Yli-Juuti T., Pierce J. R., Petäjä T., Worsnop D. R., Kulmala M., Donahue N. M.(2012): The contribution of organics to atmospheric nanoparticle growth, Nature Geoscience, 5, 453–458, DOI:10.1038/ngeo1499.

ABSTRACT
Aerosols have a strong, yet poorly quantified, effect on climate. The growth of the smallest atmospheric particles from diameters in the nanometre range to sizes at which they may act as seeds for cloud droplets is a key step linking aerosols to clouds and climate. In many environments, atmospheric nanoparticles grow by taking up organic compounds that are derived from biogenic hydrocarbon emissions. Several mechanisms may control this uptake. Condensation of low-volatility vapours and formation of organic salts probably dominate the very first steps of growth in particles close to 1 nm in diameter. As the particles grow further, formation of organic polymers and effects related to the phase of the particle probably become increasingly important. We suggest that dependence of particle growth mechanisms on particle size needs to be investigated more systematically.



Adler Katz G., T. Koop, C. Haspel, I. Traniuk, T. Moise, Yinon Rudich (2013): Formation of Highly Porous Aerosol Particles by Atmospheric Freeze-Drying in Ice Clouds. Proc. Natl. Acad. Sci., 101 (51), 20414–20419, DOI:10.1073/pnas.1317209110.

ABSTRACT

The cycling of atmospheric aerosols through clouds can change their chemical and physical properties and thus modify how aerosols affect cloud microphysics and, subsequently, precipitation and climate. Current knowledge about aerosol processing by clouds is rather limited to chemical reactions within water droplets in warm low-altitude clouds. However, in cold high-altitude cirrus clouds and anvils of high convective clouds in the tropics and midlatitudes, humidified aerosols freeze to form ice, which upon exposure to subsaturation conditions with respect to ice can sublimate, leaving behind residual modified aerosols. This freeze-drying process can occur in various types of clouds. Here we simulate an atmospheric freeze-drying cycle of aerosols in laboratory experiments using proxies for atmospheric aerosols. We find that aerosols that contain organic material that undergo such a process can form highly porous aerosol particles with a larger diameter and a lower density than the initial homogeneous aerosol. We attribute this morphology change to phase separation upon freezing followed by a glass transition of the organic material that can preserve a porous structure after ice sublimation. A porous structure may explain the previously observed enhancement in ice nucleation efficiency of glassy organic particles. We find that highly porous aerosol particles scatter solar light less efficiently than nonporous aerosol particles. Using a combination of satellite and radiosonde data, we show that highly porous aerosol formation can readily occur in highly convective clouds, which are widespread in the tropics and midlatitudes. These observations may have implications for subsequent cloud formation cycles and aerosol albedo near cloud edges.



Dupart Y., S. M. King, B. Nekat, A. Nowak, A. Wiedensohler, H. Herrmann, G. David, B. Thomas, A. Miffre, P. Rairoux, B. D’Anna, C. George (2012): Mineral dust photochemistry induces nucleation events in the presence of SO2, Proc. Natl. Acad. Sci., 109 (51),20842-20847, DOI:10.1073/pnas.1212297109.

ABSTRACT
Large quantities of mineral dust particles are frequently ejected into the atmosphere through the action of wind. The surface of dust particles acts as a sink for many gases, such as sulfur dioxide. It is well known that under most conditions, sulfur dioxide reacts on dust particle surfaces, leading to the production of sulfate ions. In this report, for specific atmospheric conditions, we provide evidence for an alternate pathway in which a series of reactions under solar UV light produces first gaseous sulfuric acid as an intermediate product before surface-bound sulfate. Metal oxides present in mineral dust act as atmospheric photocatalysts promoting the formation of gaseous OH radicals, which initiate the conversion of SO2 to H2SO4 in the vicinity of dust particles. Under low dust conditions, this process may lead to nucleation events in the atmosphere. The laboratory findings are supported by recent field observations near Beijing, China, and Lyon, France.



Monge M. E., Rosenørn, T., Favez, O., Müller, M., Adler, G., Riziq, A. A., Rudich, Y., Herrmann, H., George, C., and D’Anna, B.(2012): An alternative pathway for atmospheric particles growth, Proc. Natl. Acad. Sci., 109 (18),6840–6844, DOI:10.1073/pnas.1120593109.

ABSTRACT
Credible climate change predictions require reliable fundamental scientific knowledge of the underlying processes. Despite extensive observational data accumulated to date, atmospheric aerosols still pose key uncertainties in the understanding of Earth’s radiative balance due to direct interaction with radiation and because they modify clouds’ properties. Specifically, major gaps exist in the understanding of the physicochemical pathways that lead to aerosol growth in the atmosphere and to changes in their properties while in the atmosphere. Traditionally, the driving forces for particle growth are attributed to condensation of low vapor pressure species following atmospheric oxidation of volatile compounds by gaseous oxidants. The current study presents experimental evidence of an unaccounted-for new photoinduced pathway for particle growth. We show that heterogeneous reactions activated by light can lead to fast uptake of noncondensable Volatile Organic Compounds (VOCs) at the surface of particles when only traces of a photosensitizer are present in the seed aerosol. Under such conditions, size and mass increase; changes in the chemical composition of the aerosol are also observed upon exposure to volatile organic compounds such as terpenes and near-UV irradiation. Experimentally determined growth rate values match field observations, suggesting that this photochemical process can provide a new, unaccounted-for pathway for atmospheric particle growth and should be considered by models.



Shiraiwa, M., Ammann, M., Koop, T., and Pöschl, U.(2011): Gas uptake and chemical aging of semisolid organic aerosol particles, Proc. Natl. Acad. Sci., 108 (27), 11003–11008, DOI:10.1073/pnas.1103045108.

ABSTRACT
Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.

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PEGASOS project funded by the European Commission under the Framework Programme 7 (FP7-ENV-2010-265148)