Abstract.A system for fast ammonia (NH 3 ) measurements with chemical ionisation mass spectrometry (CIMS) based on a commercial Proton Transfer Reaction-Mass Spectrometer (PTR-MS) is presented. It uses electron transfer reaction as ionisation pathway and features a drift tube of polyetheretherketone (PEEK) and silica-coated steel. Heating the instrumental inlet and the drift tube to 180 • C enabled an effective time resolution of ∼1 s and made it possible to apply the instrument for eddy covariance (EC) measurements. EC fluxes of NH 3 were measured over two agricultural fields in Oensingen, Switzerland, following fertilisations with cattle slurry. Air was aspirated close to a sonic anemometer at a flow of 100 STP L min −1 and was directed through a 23 m long 1/2" PFA tube heated to 150 • C to an airconditioned trailer where the gas was sub-sampled from the large bypass stream. This setup minimised damping of fast NH 3 concentration changes between the sampling point and the actual measurement. High-frequency attenuation loss of the NH 3 fluxes of 20 to 40% was quantified and corrected for using an empirical ogive method. The instrumental NH 3 background signal showed a minor interference with H 2 O which was characterised in the laboratory. The resulting correction of the NH 3 flux after slurry spreading was less than 1‰. The flux detection limit of the EC system was about 5 ng m −2 s −1 while the accuracy of individual flux measurements was estimated 16% for the high-flux regime during these experiments. The NH 3 emissions after broad spreading of the slurry showed an initial maximum of 150 µg m −2 s −1 with a fast decline in the following hours.

Abstract. The EMEP/EEA guidebook 2009 for agricultural emission inventories reports an average ammonia (NH3) emission factor (EF) by volatilisation of 55% of the applied total ammoniacal nitrogen (TAN) content for cattle slurry, and 35% losses for pig slurry, irrespective of the type of surface or slurry characteristics such as dry matter content and pH. In this review article, we compiled over 350 measurements of EFs published between 1991 and 2011. The standard slurry application technique during the early years of this period, when a large number of measurements were made, was spreading by splash plate, and as a result reference EFs given in many European inventories are predominantly based on this technique. However, slurry application practices have evolved since then, while there has also been a shift in measurement techniques and investigated plot sizes. We therefore classified the available measurements according to the flux measurement technique or measurement plot size and year of measurement. Medium size plots (usually circles between 20 to 50 m radius) generally yielded the highest EFs. The most commonly used measurement setups at this scale were based on the Integrated Horizontal Flux method (IHF or the ZINST method (a simplified IHF method)). Several empirical models were published in the years 1993 to 2003 predicting NH3 EFs as a function of meteorology and slurry characteristics (Menzi et al., 1998; Søgaard et al., 2002). More recent measurements show substantially lower EFs which calls for new measurement series in order to validate the various measurement approaches against each other and to derive revised inputs for inclusion into emission inventories.

Abstract. 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−2s−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.

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Ammonia (NH3) emission from animal manure contributes to air pollution and ecosystem degradation, and the loss of reactive nitrogen (N) from agricultural systems. Estimates of NH3 emission are necessary for national inventories and nutrient management, and NH3 emission from field-applied manure has been measured in many studies over the past few decades. In this work, we facilitate the use of these data by collecting and organizing them in the ALFAM2 database. In this paper we describe the development of the database and summarise its contents, quantify effects of application methods and other variables on emission using a data subset, and discuss challenges for data analysis and model development. The database contains measurements of emission, manure and soil properties, weather, application technique, and other variables for 1899 plots from 22 research institutes in 12 countries. Data on five manure types (cattle, pig, mink, poultry, mixed, as well as sludge and "other") applied to three types of crops (grass, small grains, maize, as well as stubble and bare soil) are included. Application methods represented in the database include broadcast, trailing hose, trailing shoe (narrow band application), and open slot injection. Cattle manure application to grassland was the most common combination, and analysis of this subset (with dry matter (DM) limited to <15%) was carried out using mixed-and fixed-effects models in order to quantify effects of management and environment on ammonia emission, and to highlight challenges for use of the database. Measured emission from cattle slurry ranged from < 1% to 130% of applied ammonia after 48 hours. Results showed clear, albeit variable, reductions in NH3 emission due to trailing hose, trailing shoe, and open slot injection of slurry compared to broadcast application. There was evidence of positive effects of air temperature and wind speed on NH3 emission, and limited evidence of effects of slurry DM. However, random-effects coefficients for differences among research institutes were among the largest model coefficients, and 4 showed a deviation from the mean response by more than 100% in some cases. The source of these institute differences could not be determined with certainty, but there is some evidence that they are related to differences in soils, or differences in application or measurement methods. The ALFAM2 database should be useful for development and evaluation of both emission factors and emission models, but users need to recognize the limitations caused by confounding variables, imbalance in the dataset, and dependence among observations from the same institute. Variation among measurements and in reported variables highlights the importance of international agreement on how NH3 emission should be measured, along with necessary types of supporting data and standard protocols for their measurement. Both are needed in order to produce more accurate and useful ammonia emission measurements. Expansion of the ALFAM2 database will continue, and readers are invited...

Despite recent evidence on an important role of volatile amines in the nucleation of particulate matter, very scarce information is available on their atmospheric abundance and source distribution. Previous measurements in animal housings had identified livestock husbandry as the main amine source, with trimethylamine (TMA) being the key component. This has led to the assumption that the agricultural sources for amines are similar as for ammonia, emitted throughout the cascade of animal excretion, storage and application in the field. In this study, we present the first micrometeorological flux measurements as well as dynamic enclosure experiments showing that the amine source strength from stored slurry is negligible, implying significant consequences for the global amine emission inventory. In the case of cattle, amine production is attributed to the animal's rumination activity and exhalation is suggested to be an important emission pathway, similar to the greenhouse gas methane. Fodder like hay and silage also emits volatile amines, potentially assigning these alkaloid compounds a key function in enhancing particle formation in remote areas.

Abstract. We present a differential optical absorption spectroscopy (DOAS) instrument, called "miniDOAS", optimised for optical open-path field-measurements of ambient ammonia (NH3) alongside nitrogen oxide (NO) and sulfur dioxide (SO2). The instrument is a further development of the miniDOAS presented by Volten et al. (2012). We use a temperature-controlled spectrometer, a deuterium light source and a modified optical arrangement. The system was set up in a robust, field-deployable, temperature-regulated housing. For the evaluation of light spectra we use a new high-pass filter routine based upon robust baseline extraction with local regression. Multiple linear regression including terms of an autoregressive–moving-average model is used to determine concentrations. For NH3 the random uncertainty is about 1.4 % of the concentration, and not better than 0.2 µg m−3. Potential biases for the slope of the calibration are given by the precision of the differential absorption cross sections (±3 %) and for the offset by the precision of the estimation of concentration offsets (cref) introduced by the reference spectrum Iref. Comparisons of miniDOAS measurements to those by NH3 acid trap devices showed good agreement. The miniDOAS can be flexibly used for a wide range of field trials, such as micrometeorological NH3 flux measurements with approaches based upon horizontal or vertical concentration differences. Results from such applications covering concentration dynamics of less than one up to several hundreds of µg m−3 are presented.

Abstract.At a cropland and a grassland site field scale ammonia (NH 3 ) emissions from slurry application were determined simultaneously by two approaches based on (i) eddy covariance (EC) flux measurements using high temperature Chemical Ionisation Mass Spectrometry (HT-CIMS) and on (ii) backward Lagrangian Stochastic (bLS) dispersion modelling using concentration measurements by three optical open path Fourier Transform Infrared (FTIR) systems. Slurry was spread on the fields in sequential tracks over a period of one to two hours. In order to calculate field emissions, measured EC/HT-CIMS fluxes were combined with flux footprint analysis of individual slurry spreading tracks to parameterise the NH 3 volatilisation with a bi-exponential time dependence. Accordingly, track-resolved concentration footprints for the FTIR measurements were calculated using bLS. A consistency test with concentrations measured by impingers showed very low systematic deviations for the EC/HT-CIMS results (<8 %) but larger deviations for the bLS/FTIR results. For both slurry application events, the period during fertilisation and the subsequent two hours contributed by more than 80 % to the total field emissions. Averaged over the two measurement methods, the cumulated emissions of the first day amounted to 17 ± 3 % loss of applied total ammoniacal nitrogen over the cropland and 16 ± 3 % over the grassland field.