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

Inhibition of Granulopoiesis in Vivo and in Vitro by β-Lactam Antibiotics

β-Lactam antibiotics can induce severe neutropenia by a hitherto unknown mechanism. Fifty cases of β-lactam antibiotic-induced neutropenia (15% in patients treated for ⩾10 days with large doses of any β-lactam antibiotic but 95% of cases recovery occurred between one to seven days after withdrawal of β-lactam antibiotics. Bone marrow aspirates were characterized by a lack of well-differentiated myeloid elements in the presence of numerous immature granulocyte precursors. Nine penicillins and eight cephalosporins inhibited in vitro granulopoiesis in a dose-dependent manner. There was a good correlation between the inhibitory capacity of β-lactam antibiotics in vitro and the doses inducing neutropenia in vivo. These observations may be relevant for therapy in the granulocytopenic patien

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

Two commercial ammonia (NH<sub>3</sub>) 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<sub>3</sub> m<sup>−2</sup> s<sup>−1</sup>. Hence the flux measurements are considered sufficiently accurate for studying typical NH<sub>3</sub> 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<sub>3</sub> 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<sub>3</sub> 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<sub>3</sub> with an annual dry deposition flux of −3.0 kg N ha<sup>−1</sup> yr<sup>−1</sup>, although small NH<sub>3</sub> emissions by the canopy were measured in dry daytime conditions. The median Γ<sub><i>s</i></sub> ratio in the apoplast (=[NH<sub>4</sub><sup>+</sup>]/[H<sup>+</sup>]) estimated from micrometeorological measurements was 620, equivalent to a stomatal compensation point of 1.3 μg NH<sub>3</sub> m<sup>−3</sup> at 15 °C. Non-stomatal resistance to deposition <i>R<sub>w</sub></i> was shown to increase with temperature and decrease with surface relative humidity, and <i>R<sub>w</sub></i> values were among the highest published for European grasslands, consistent with a relatively high ratio of NH<sub>3</sub> to acid gases in the boundary layer at this site. Since the gross annual NH<sub>3</sub> emission by slurry spreading was of the order of +20 kg N ha<sup>−1</sup> yr<sup>−1</sup>, the fertilised grassland was a net NH<sub>3</sub> source of +17 kg N ha<sup>−1</sup> yr<sup>−1</sup>. 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<sub>3</sub> budget and the difficulty of scaling up to the national level

Large perturbations of ammonium and organic acids content in the Summit-Greenland ice core. Fingerprint from forest fires?

Biomass burning is influencing the atmospheric chemistry by emitting large amounts of reactive species such as hydrocarbons, organic acids and nitrogen compounds [Andreae et al., 1988]. Polar ice cores provide a unique record of precipitation whose chemistry reflects the atmospheric composition at the time of deposition. The analysis of such ice samples therefore allows an estimate to be made of the concentration of atmospheric impurities in the past. During the first season of the deep drill operation (GRIP) at Summit, Central Greenland (72° 34' N, 37° 38'W) continuous ammonium (NH4+) measurements were performed between 100 and 600 m depth covering the time period from 330 to 2500 years B.P. The NH4+ concentrations show seasonal variations between 1–20 ng.g−1 with some sporadic high values up to 600 ng.g−1 in narrow layers. The chemical fingerprint points to biomass burning causing the high ammonium peaks

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

Temporal variability in bioassays of the stomatal ammonia compensation point in relation to plant and soil nitrogen parameters in intensively managed grassland

The exchange of ammonia between crop canopies and the atmosphere depends on a range of plant parameters and climatic conditions. However, little is known about effects of management factors. We have here investigated the stomatal ammonia compensation point in response to cutting and fertilization of a grass sward dominated by Lolium perenne. Tall grass had a very low NH3 compensation point (around 1 nmol mol−1), reflecting the fact that leaf nitrogen (N) concentration was very low. During re-growth after cutting, leaf tissue concentrations of NO3-, NH4+, soluble N and total N increased along with apoplastic NH4+ concentrations. In contrast, apoplastic pH decreased resulting in largely unaltered NH3 compensation points. Nitrogen fertilization one week after cutting caused the apoplastic NH4+ concentration of the newly emerging leaves to increase dramatically. The NH3 compensation point peaked between 15 and 25 nmol mol−1 the day after the fertiliser was applied and thereafter decreased over the following 10 days until reaching the same level as before fertilisation. Ammonium concentrations in leaf apoplast, bulk tissue and litter were positively correlated (P=0.001) throughout the experimental period. Bulk tissue NH4+ concentrations, total plant N and soil NH4+ concentrations also showed a positive correlation. A very high potential for NH3 emission was shown by the plant litter

Trimethylamine emissions in animal husbandry

Degradation of plant material by animals is an important transformation pathway in the nitrogen (N) cycle. During the involved processes, volatile reduced alkaline nitrogen compounds, mainly ammonia (NH3) and aliphatic amines such as trimethylamine (TMA), are formed. Today, animal husbandry is estimated to constitute a main source of aliphatic amines in the atmosphere with TMA being the main emitted compound. Here, we show how the interaction between faeces and urine in animal production systems provides the primary source for agricultural TMA emissions. Excreted urine contains large quantities of urea and TMA-N-oxide, which are transformed into NH3 and TMA, respectively, via enzymatic processes provided by microbes present in faeces. TMA emissions from areas polluted with urine-faeces mixtures are on average of the order of 10 to 50 nmol m(-2) s(-1). Released amines promote secondary aerosol particle formation in the agricultural emission plume. The atmospheric lifetime of TMA, which was estimated to be of the order of 30 to 1000 s, is determined by the condensation onto aerosol particles.Peer reviewe