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Recently, the number and amount of biogenically emitted volatile organic compounds (VOCs) has been discussed vigorously. Depending on the ecosystem the published number varies between a dozen and several hundred compounds. We present ecosystem exchange fluxes from a mixed oak-hornbeam forest in the Po Valley, Italy. The fluxes were measured by a proton transfer reaction-time-of-flight (PTR-ToF) mass spectrometer and calculated by the eddy covariance (EC) method. Detectable fluxes were observed for twelve compounds, dominated by isoprene, which comprised over 65% of the total flux emission. The daily average of the total VOC emission was 9.5 nmol m-2 s-1. Methanol had the highest concentration and accounted for the largest deposition. Methanol seemed to be deposited to dew, as the deposition happened in the early morning, right after the calculated surface temperature came closest to the calculated dew point temperature. We estimated that up to 27% of the upward flux of methyl vinyl ketone (MVK) and methacrolein (MACR) originated from atmospheric oxidation of isoprene. A comparison between two flux detection methods (classical/visual and automated) was made. Their respective advantages and disadvantages were discussed and the differences in their results shown. Both provide comparable results; however we recommend the automated method with a compound filter, which combines the fast analysis and better flux detection, without the overestimation due to double counting. [ABSTRACT FROM AUTHOR]

Numerous laboratory experiments have been performed in an attempt to mimic atmospheric secondary organic aerosol (SOA) formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. In this study, we generated SOA in a simulation chamber from the ozonolysis of α-pinene and a biogenic volatile organic compound (BVOC) mixture containing α- and β-pinene, Δ³-carene, and isoprene. The detailed molecular composition of laboratory-generated SOA was compared with that of background ambient aerosol collected at a boreal forest site (Hyytiälä, Finland) and an urban location (Cork, Ireland) using direct infusion nanoelectrospray ultrahigh resolution mass spectrometry. Kendrick Mass Defect and Van Krevelen approaches were used to identify and compare compound classes and distributions of the detected species. The laboratory-generated SOA contained a distinguishable group of dimers that was not observed in the ambient samples. The presence of dimers was found to be less pronounced in the SOA from the VOC mixtures when compared to the one component precursor system. The elemental composition of the compounds identified in the monomeric region from the ozonolysis of both α-pinene and VOC mixtures represented the ambient organic composition of particles collected at the boreal forest site reasonably well, with about 70% of common molecular formulae. In contrast, large differences were found between the laboratory-generated BVOC samples and the ambient urban sample. To our knowledge this is the first direct comparison of molecular composition of laboratory-generated SOA from BVOC mixtures and ambient samples. [ABSTRACT FROM AUTHOR]

An overview of acetaldehyde exchange above a managed temperate mountain grassland in Austria over four growing seasons is presented. The meadow acted as a net source of acetaldehyde in all four years, emitting between 7 and 28 mg Cm-2 over the whole growing period. The cutting of the meadow resulted in huge acetaldehyde emission bursts on the day of harvesting or one day later. During undisturbed conditions, both uptake and emission fluxes were recorded. The bidirectional nature of acetaldehyde fluxes was also reflected by clear diurnal cycles during certain time periods, indicating strong deposition processes before the 1st cut and emission towards the end of the growing season. The analysis of acetaldehyde compensation points revealed a complex relationship between ambient acetaldehyde mixing ratios and respective fluxes, significantly influenced by multiple environmental parameters and variable throughout the year. As a major finding of this study, we identified both a positive and negative correlation betweenconcentration and flux on a daily scale, where soil temperature and soil water content were the most significant factors in determining the direction of the slope. In turn, this bidirectional relationship on a daily scale resulted in compensation points between 0.40 ppbv and 0.54 ppbv, which could be well explained by collected ancillary data. We conclude that in order to model acetaldehyde fluxes at the site in Neustift on a daily scale over longer time periods, it is crucial to know the type of relationship, i.e. the direction of the slope, between mixing ratios and fluxes on a given day. [ABSTRACT FROM AUTHOR]

In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the emission at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPACOPEC- 2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters. [ABSTRACT FROM AUTHOR]

Monoterpene emissions from Scots pine have traditionally been assumed to originate as evaporation from specialized storage pools. More recently, the significance of de novo emissions, originating directly from monoterpene biosynthesis, has been recognized. To study the role of biosynthesis in the ecosystem scale, we measured monoterpene emissions from a Scots pine dominated forest in southern Finland using the disjunct eddy covariance method combined with proton transfer reaction mass spectrometry. The interpretation of the measurements was based on a hybrid emission algorithm describing both de novo and pool emissions. During the measurement period May-August 2007, the monthly medians of daytime emissions were 170, 280, 180, and 180 μgm-2 h-1. The emission potential for both de novo and pool emissions exhibited a decreasing summertime trend. The ratio of the de novo emission potential to the total emission potential varied between 30% and 46%. Although the monthly changes were not significant, the ratio always differed statistically from zero, i.e., the role of denovo biosynthesis was evident. The hybrid approach showed promising potential for the improvement of the ecosystem scale emission modelling. Given this feature and the significant role of biosynthesis, we recommend incorporating both de novo and pool emissions into the monoterpene emission algorithms for Scots pine dominated forests. [ABSTRACT FROM AUTHOR]