Atmospheric benzenoid emissions from plants rival those from fossil fuels.

Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y(-1)), pointing to the importance of these natural emissions in atmospheric physics and chemistry.

Acetaldehyde exchange above a managed temperate mountain grassland.

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 C m-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 between concentration 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.

Eddy covariance VOC emission and deposition fluxes above grassland using PTR-TOF.

Eddy covariance (EC) is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5-20 Hz). For volatile organic compounds (VOC) soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF) for 10 Hz EC measurements of full mass spectra up to m/z 315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H+ - water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C6 leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes. The smallest reliable fluxes we determined were less than 0.1 nmol m-2 s-1, as in the case of sesquiterpene emissions from freshly cut grass. Terpenoids, including mono- and sesquiterpenes, were also deposited to the grassland before and after the harvesting. During cutting, total VOC emission fluxes up to 200 nmolC m-2 s-1 were measured. Methanol emissions accounted for half of the emissions of oxygenated VOCs and a third of the carbon of all measured VOC emissions during harvesting.

Deposition Fluxes of Terpenes over Grassland.

Eddy covariance flux measurements were carried out for two subsequent vegetation periods above a temperate mountain grassland in an alpine valley using a proton-transfer-reaction - mass spectrometer (PTR-MS) and a PTR-time of flight - mass spectrometer (PTR-TOF). In 2008 and during the first half of the vegetation period 2009 the volume mixing ratios (VMRs) for the sum of monoterpenes (MTs) were typically well below 1 ppbv and neither MT emission nor deposition was observed. After a hailstorm in July 2009 an order of magnitude higher amount of terpenes was transported to the site from nearby coniferous forests causing elevated VMRs. As a consequence, deposition fluxes of terpenes to the grassland, which continued over a time period of several weeks without significant re-emission, were observed. For days without precipitation the deposition occurred at velocities close to the aerodynamic limit. In addition to monoterpene uptake, deposition fluxes of the sum of sesquiterpenes (SQTs) and the sum of oxygenated terpenes (OTs) were detected. Considering an entire growing season for the grassland (i.e., 1st of April to 1st of November), the cumulative carbon deposition of monoterpenes reached 276 mg C m-2. This is comparable to the net carbon emission of methanol (329 mg C m-2), which is the dominant non methane volatile organic compound (VOC) emitted from this site, during the same time period. It is suggested that deposition of monoterpenes to terrestrial ecosystems could play a more significant role in the reactive carbon budget than previously assumed.

BVOC fluxes above mountain grassland.

Grasslands comprise natural tropical savannah over managed temperate fields to tundra and cover one quarter of the Earth's land surface. Plant growth, maintenance and decay result in volatile organic compound (VOCs) emissions to the atmosphere. Furthermore, biogenic VOCs (BVOCs) are emitted as a consequence of various environmental stresses including cutting and drying during harvesting. Fluxes of BVOCs were measured with a proton-transfer-reaction-mass-spectrometer (PTR-MS) over temperate mountain grassland in Stubai Valley (Tyrol, Austria) over one growing season (2008). VOC fluxes were calculated from the disjunct PTR-MS data using the virtual disjunct eddy covariance method and the gap filling method. Methanol fluxes obtained with the two independent flux calculation methods were highly correlated (y = 0.95×-0.12, R2 = 0.92). Methanol showed strong daytime emissions throughout the growing season - with maximal values of 9.7 nmol m-2 s-1, methanol fluxes from the growing grassland were considerably higher at the beginning of the growing season in June compared to those measured during October (2.5 nmol m-2 s-1). Methanol was the only component that exhibited consistent fluxes during the entire growing periods of the grass. The cutting and drying of the grass increased the emissions of methanol to up to 78.4 nmol m-2 s-1. In addition, emissions of acetaldehyde (up to 11.0 nmol m-2 s-1), and hexenal (leaf aldehyde, up to 8.6 nmol m-2 s-1) were detected during/after harvesting.

First eddy covariance flux measurements by PTR-TOF.

The recently developed PTR-TOF instrument was evaluated to measure methanol fluxes emitted from grass land using the eddy covariance method. The high time resolution of the PTR-TOF allowed storing full mass spectra up to m/z 315 with a frequency of 10 Hz. Three isobaric ions were found at a nominal mass of m/z 33 due to the high mass resolving power of the PTR-TOF. Only one of the three peaks contributed to eddy covariance fluxes. The exact mass of this peak agrees well with the exact mass of protonated methanol (m/z 33.0335). The eddy covariance methanol fluxes measured with PTR-TOF were compared to virtual disjunct eddy covariance methanol fluxes simultaneously measured with a conventional PTR-MS. The methanol fluxes from both instruments show excellent agreement.