Tethered balloon measurements of biogenic volatile organic compounds at a Boreal forest site

Measurements of biogenic volatile organic compounds (VOCs) were performed at Hyytiälä, a Boreal forest site in Southern Finland as part of the OSOA (origin and formation of secondary organic aerosol) project in August 2001. At this site, frequent formation of new particles has been observed and the role of biogenic VOCs in this process is still unclear. Tethered balloons served as platforms to collect VOC samples within the planetary boundary layer at heights up to 1.2 km above ground during daytime. Mean mixed layer concentrations of total monoterpenes varied between 10 and 170 pptv, with <font face='Symbol'>a</font>-pinene, limonene and <font face='Symbol'>D</font>³-carene as major compounds, isoprene was detected at levels of 2-35 pptv. A mixed layer gradient technique and a budget approach are applied to derive surface fluxes representative for areas of tens to hundreds of square kilometres. Effects of spatial heterogeneity in surface emissions are examined with a footprint analysis. Depending on the source area considered, mean afternoon emissions of the sum of terpenes range between 180 and 300 <font face='Symbol'>m</font>g m^-2 h^-1 for the period of 2-12 August 2001. Surface fluxes close to Hyytiälä were higher than the regional average, and agree well with mean emissions predicted by a biogenic VOC emission model. Total rates of monoterpene oxidation were calculated with a photochemical model. The rates did not correlate with the occurrence of new particle formation, but the ozone pathway was of more importance on days with particle formation. Condensable vapour production from the oxidation of monoterpenes throughout the mixed layer can only account for a fraction of the increase in aerosol mass observed at the surface

Methanol exchange between grassland and the atmosphere

International audienceConcentrations and fluxes of methanol were measured above two differently managed grassland fields (intensive and extensive) in central Switzerland during summer 2004. The measurements were performed with a proton-transfer-reaction mass-spectrometer and fluxes were determined by the eddy covariance method. The observed methanol emission showed a distinct diurnal cycle and was strongly correlated with global radiation and water vapour flux. Mean and maximum daily emissions were found to depend on grassland species composition and, for the intensive field, also on the growing state. The extensive field with a more complex species composition had higher emissions than the graminoid-dominated intensive field, both on an area and on a biomass basis. A simple parameterisation depending on the water vapour flux and the leaf area index allowed a satisfying simulation of the temporal variation of methanol emissions over the growing phase. Accumulated carbon losses due to methanol emissions accounted for 0.024 and 0.048% of net primary productivity for the intensive and extensive field, respectively. The integral methanol emissions over the growing periods were more than one order of magnitude higher than the emissions related to cut and drying events

Technical note: Water vapour concentration and flux measurements with PTR-MS

International audienceThe most direct approach for measuring the exchange of biogenic volatile organic compounds between terrestrial ecosystems and the atmosphere is the eddy covariance technique. It has been applied several times in the last few years using fast response proton-transfer-reaction mass spectrometry (PTR-MS). We present an independent validation of this technique by applying it to measure the water vapour flux in comparison to a common reference system comprising an infra-red gas analyser (IRGA). Water vapour was detected in the PTR-MS at mass 37 (atomic mass units) corresponding to the cluster ion H3O+·H2O. During a five-week field campaign at a grassland site, we obtained a non-linear but stable calibration function between the mass 37 signal and the reference water vapour concentration. With a correction of the high-frequency damping loss based on empirical ogive analysis, the eddy covariance water vapour flux obtained with the PTR-MS showed a very good agreement with the flux of the reference system. The application of the empirical ogive method for high-frequency correction led to significantly better results than using a correction based on theoretical spectral transfer functions. This finding is attributed to adsorption effects on the tube walls that are presently not included in the theoretical correction approach. The proposed high-frequency correction method can also be used for other trace gases with different adsorption characteristics

The annual ammonia budget of fertilised cut grassland – Part 1: Micrometeorological flux measurements and emissions after slurry application

Two commercial ammonia (NH&lt;sub&gt;3&lt;/sub&gt;) analysers were customised to allow continuous measurements of vertical concentration gradients. The gradients were used to derive ammonia exchange fluxes above a managed grassland site at Oensingen (Switzerland) by application of the aerodynamic gradient method. The measurements from July 2006 to October 2007 covered five complete growth-cut cycles and included six applications of liquid cattle slurry. The average accuracy of the flux measurements during unstable and near-neutral conditions was 20% and the detection limit was 10 ng NH&lt;sub&gt;3&lt;/sub&gt; m&lt;sup&gt;&amp;minus;2&lt;/sup&gt; s&lt;sup&gt;&amp;minus;1&lt;/sup&gt;. Hence the flux measurements are considered sufficiently accurate for studying typical NH&lt;sub&gt;3&lt;/sub&gt; deposition rates over growing vegetation. Quantifying the overall emissions after slurry applications required the application of elaborate interpolations because of difficulties capturing the initial emissions during broadspreading of liquid manure. The emissions were also calculated with a mass balance method yielding similar fluxes. NH&lt;sub&gt;3&lt;/sub&gt; losses after slurry application expressed as percentage of emitted nitrogen versus applied total ammoniacal nitrogen (TAN) varied between 4 and 19%, which is roughly a factor of three lower than the values for broadspreading of liquid manure in emission inventories. The comparatively low emission factors appear to be a consequence of the low dry matter content of the applied slurry and soil properties favouring ammonium adsorption

The annual ammonia budget of fertilised cut grassland – Part 2: Seasonal variations and compensation point modeling

The net annual NH&lt;sub&gt;3&lt;/sub&gt; exchange budget of a fertilised, cut grassland in Central Switzerland is presented. The observation-based budget was computed from semi-continuous micrometeorological fluxes over a time period of 16 months and using a process-based gap-filling procedure. The data for emission peak events following the application of cattle slurry and for background exchange were analysed separately to distinguish short-term perturbations from longer-term ecosystem functioning. A canopy compensation point model of background exchange is parameterised on the basis of measured data and applied for the purposes of gap-filling. The data show that, outside fertilisation events, grassland behaves as a net sink for atmospheric NH&lt;sub&gt;3&lt;/sub&gt; with an annual dry deposition flux of &amp;minus;3.0 kg N ha&lt;sup&gt;&amp;minus;1&lt;/sup&gt; yr&lt;sup&gt;&amp;minus;1&lt;/sup&gt;, although small NH&lt;sub&gt;3&lt;/sub&gt; emissions by the canopy were measured in dry daytime conditions. The median &amp;Gamma;&lt;sub&gt;&lt;i&gt;s&lt;/i&gt;&lt;/sub&gt; ratio in the apoplast (=[NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;]/[H&lt;sup&gt;+&lt;/sup&gt;]) estimated from micrometeorological measurements was 620, equivalent to a stomatal compensation point of 1.3 &amp;mu;g NH&lt;sub&gt;3&lt;/sub&gt; m&lt;sup&gt;&amp;minus;3&lt;/sup&gt; at 15 &amp;deg;C. Non-stomatal resistance to deposition &lt;i&gt;R&lt;sub&gt;w&lt;/sub&gt;&lt;/i&gt; was shown to increase with temperature and decrease with surface relative humidity, and &lt;i&gt;R&lt;sub&gt;w&lt;/sub&gt;&lt;/i&gt; values were among the highest published for European grasslands, consistent with a relatively high ratio of NH&lt;sub&gt;3&lt;/sub&gt; to acid gases in the boundary layer at this site. Since the gross annual NH&lt;sub&gt;3&lt;/sub&gt; emission by slurry spreading was of the order of +20 kg N ha&lt;sup&gt;&amp;minus;1&lt;/sup&gt; yr&lt;sup&gt;&amp;minus;1&lt;/sup&gt;, the fertilised grassland was a net NH&lt;sub&gt;3&lt;/sub&gt; source of +17 kg N ha&lt;sup&gt;&amp;minus;1&lt;/sup&gt; yr&lt;sup&gt;&amp;minus;1&lt;/sup&gt;. A comparison with the few other measurement-based budget values from the literature reveals considerable variability, demonstrating both the influence of soil, climate, management and grassland type on the NH&lt;sub&gt;3&lt;/sub&gt; budget and the difficulty of scaling up to the national level

Implications of changes in seasonal mean temperature for agricultural production systems: three case studies

- The performance of dairy cows will suffer from elevated temperatures, reflecting the extent and uncertainty of projected warming in different scenarios, with a marked increase in heat stress for non-intervention scenarios (A1B and A2) toward the end of the century. This calls for the adoption of protective measures in the management of indoor and outdoor animal environments. - A substantial risk of a prolonged pest control season for the codling moth (an apple pest) is projected toward the end of the century for Northern Switzerland sites, and mid-century for the Ticino. Timely preventive programs are anticipated to represent a key ingredient of adaptation to changing risks from agricultural pests. - Results suggest that in the near future viticulture could benefit from increasing temperatures as a wider range of grape varieties could be grown. Toward the end of the century negative impacts from extreme temperatures are nevertheless expected to become important

Virtual disjunct eddy covariance measurements of organic compound fluxes from a subalpine forest using proton transfer reaction mass spectrometry

International audienceA `virtual' disjunct eddy covariance (vDEC) device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO), methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes

Flux measurements of biogenic VOCs during ECHO 2003

International audienceWithin the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany using the eddy covariance (EC) technique. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. As a consequence, a considerable fraction of the measurements did not qualify for flux calculations by EC and had to be discarded. The validated results show light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average emissions (normalised to 30°C and 1000 µmoles m?2 s?1 PAR) of 1.5 and 0.39 µg m?2 s?1, respectively. Emissions of methanol reached on average 0.087 µg m?2 s?1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were also found, being two orders of magnitude lower than those of isoprene. The observed fluxes are consistent with upscalings from leaf-level emission measurements of representative tree species in this forest and, in the case of MVK and MACR, can plausibly be explained by chemical production through oxidation of isoprene within the canopy. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement

Virtual disjunct eddy covariance measurements of organic compound fluxes from a subalpine forest using proton transfer reaction mass spectrometry

A `virtual' disjunct eddy covariance (vDEC) device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO), methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes

Subseasonal hydrometeorological ensemble predictions in small- and medium-sized mountainous catchments: benefits of the NWP approach

Traditional ensemble streamflow prediction (ESP) systems are known to provide a valuable baseline to predict streamflows at the subseasonal to seasonal timescale. They exploit a combination of initial conditions and past meteorological observations, and can often provide useful forecasts of the expected streamflow in the upcoming month. In recent years, numerical weather prediction (NWP) models for subseasonal to seasonal timescales have made large progress and can provide added value to such a traditional ESP approach. Before using such meteorological predictions two major problems need to be solved: the correction of biases, and downscaling to increase the spatial resolution. Various methods exist to overcome these problems, but the potential of using NWP information and the relative merit of the different statistical and modelling steps remain open. To address this question, we compare a traditional ESP system with a subseasonal hydrometeorological ensemble prediction system in three alpine catchments with varying hydroclimatic conditions and areas between 80 and 1700&thinsp;km2. Uncorrected and corrected (pre-processed) temperature and precipitation reforecasts from the ECMWF subseasonal NWP model are used to run the hydrological simulations and the performance of the resulting streamflow predictions is assessed with commonly used verification scores characterizing different aspects of the forecasts (ensemble mean and spread). Our results indicate that the NWP-based approach can provide superior prediction to the ESP approach, especially at shorter lead times. In snow-dominated catchments the pre-processing of the meteorological input further improves the performance of the predictions. This is most pronounced in late winter and spring when snow melting occurs. Moreover, our results highlight the importance of snow-related processes for subseasonal streamflow predictions in mountainous regions.</p