Atmospheric nucleation is the dominant source of aerosol particles in the global atmosphere and an important player in aerosol climatic effects. The key steps of this process occur in the sub-2-nanometer (nm) size range, in which direct size-segregated observations have not been possible until very recently. Here, we present detailed observations of atmospheric nanoparticles and clusters down to 1-nm mobility diameter. We identified three separate size regimes below 2-nm diameter that build up a physically, chemically, and dynamically consistent framework on atmospheric nucleation--more specifically, aerosol formation via neutral pathways. Our findings emphasize the important role of organic compounds in atmospheric aerosol formation, subsequent aerosol growth, radiative forcing and associated feedbacks between biogenic emissions, clouds, and climate.

Abstract. Atmospheric chemistry in background areas is strongly influenced by natural vegetation. Coniferous forests are known to produce large quantities of volatile vapors, especially terpenes. These compounds are reactive in the atmosphere, and contribute to the formation and growth of atmospheric new particles.Our aim was to analyze the variability of mono-and sesquiterpene emissions between Scots pine trees, in order to clarify the potential errors caused by using emission data obtained from only a few trees in atmospheric chemistry models. We also aimed at testing if stand history and seed origin has an influence on the chemotypic diversity. The inherited, chemotypic variability in mono-and sesquiterpene emission was studied in a seemingly homogeneous 48 yr-old stand in Southern Finland, where two areas differing in their stand regeneration history could be distinguished. Sampling was conducted in August 2009. Terpene concentrations in the air had been measured at the same site for seven years prior to branch sampling for chemotypes.Two main compounds, α-pinene and 3 -carene formed together 40-97 % of the monoterpene proportions in both the branch emissions and in the air concentrations. The data showed a bimodal distribution in emission composition, in particular in 3 -carene emission within the studied population. 10 % of the trees emitted mainly α-pinene and no 3 -carene at all, whereas 20 % of the trees where characterized as high 3 -carene emitters ( 3 -carene forming >80 % of total emitted monoterpene spectrum). An intermediate group of trees emitted equal amounts of both α-pinene and 3 -carene. The emission pattern of trees at the area established using seeding as the artificial regeneration method differed from the naturally regenerated or planted trees, being mainly high 3 -carene emitters. Some differences were also seen in e.g. camphene and limonene emissions between chemotypes, but sesquiterpene emissions did not differ significantly between trees. The atmospheric concentrations at the site were found to reflect the species and/or chemodiversity rather than the emissions measured from any single tree, and were strongly dominated by α-pinene. We also tested the effect of chemodiversity on modeled monoterpene concentrations at the site and found out that since it significantly influences the distributions and hence the chemical reactions in the atmosphere, it should be taken into account in atmospheric modeling.

Abstract. This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiälä, Finland from 12 July-12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer Correspondence to: J. Williams (jonathan.williams@mpic.de) of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urbanPublished by Copernicus Publications on behalf of the European Geosciences Union. 10600 J. Williams et al.: An overview of meteorological and chemical influences anthropogenic pollution (pentane and SO 2 ) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures.

SignificanceCarbonyl sulfide (COS) measurements enable quantification of terrestrial photosynthesis, which cannot be directly measured at scales greater than the leaf level. The accuracy of COS-based estimates of gross primary production (GPP) depends on how we relate the COS uptake to that of CO2. This study shows that COS-based GPP estimates will be significantly overestimated if the different environmental responses of COS and CO2 uptake are not taken into account. These findings are relevant for studies that rely on COS to quantify ecosystem to regional scale GPP, and support the use of a COS-based approach to constrain ecosystem flux partitioning. Moreover, the strong stomatal control on COS uptake shown in this study makes COS a suitable tracer for stomatal diffusion.

Organic compounds are important constituents of fine particulate matter (PM) in the troposphere. In this study, we applied direct infusion nanoelectrospray (nanoESI) ultrahigh resolution mass spectrometry (UHR-MS) and liquid chromatography LC/ESI-UHR-MS for the analysis of the organic fraction of PM1 aerosol samples collected over a two week period at a boreal forest site (Hyytiälä), southern Finland. Elemental formulas (460-730 in total) were identified with nanoESI-UHR-MS in the negative ionization mode and attributed to organic compounds with a molecular weight below 400. Kendrick Mass Defect and Van Krevelen approaches were used to identify compound classes and mass distributions of the detected species. The molecular composition of the aerosols strongly varied between samples with different air mass histories. An increased number of nitrogen, sulfur, and highly oxygenated organic compounds was observed during the days associated with continental air masses. However, the samples with Atlantic air mass history were marked by a presence of homologous series of unsaturated and saturated C12-C20 fatty acids suggesting their marine origin. To our knowledge, we show for the first time that the highly detailed chemical composition obtained from UHR-MS analyses can be clearly linked to meteorological parameters and trace gases concentrations that are relevant to atmospheric oxidation processes. The additional LC/ESI-UHR-MS analysis revealed 29 species, which were mainly attributed to oxidation products of biogenic volatile compounds BVOCs (i.e., α,β-pinene, Δ3-carene, limonene, and isoprene) supporting the results from the direct infusion analysis.

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Abstract. Estimates of volatile organic compound (VOC)emissions from forests are based on the assumption that foliage has a steady emission potential over its lifetime, and that emissions are mainly modified by short-term variations in light and temperature. However, in many field studies this has been challenged, and high emissions and atmospheric concentrations have been measured during periods of low biological activity, such as in springtime. We conducted measurements during three years, using an online gas-exchange monitoring system to observe volatile organic emissions from a mature (1 year-old) and a growing Scots pine shoot. The emission rates of organic vapors from vegetative buds of Scots pine during the dehardening and rapid shoot growth stages were one to two orders of magnitude higher than those from mature foliage; this difference decreased and finally disappeared when the new shoot was maturing in late summer. On average, the springtime monoterpene emission rate of the bud was about 500 times higher than that of the mature needles; during the most intensive needle elongation period, the monoterpene emission rate of the growing needles was 3.5 higher than that of the mature needles, and in September the monoterpene emission rate of the same years' needles was even lower (50 %) than that of the previous years' needles. For other measured compounds (methanol, acetone and methylbutenol) the values were of the same order of magnitude, except before bud break in spring, when the emission rates of buds for those compounds were on average about 20-30 times higher than that of mature needles. During spring and early summer the buds and growing shoots are a strong source of several VOCs, and if they are not accounted for in emission modeling a significant proportion of the emissions -from a few percent to even half of the annual cumulative emissions -will remain concealed. The diurnal emission pattern of growing shoots differed from the diurnal cycle in temperature as well as from the diurnal emission pattern of mature shoots, which may be related to processes involved in shoot or needle elongation. Our findings imply that global estimations of monoterpene emission rates from forests are in need of revision, and that the physiological state of the plants should be taken into account when emissions of the reactive gases such as monoterpenes are estimated.

Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.