A miniDOAS instrument optimised for ammonia field measurements

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

Ammonia emissions from a grazed field estimated by miniDOAS measurements and inverse dispersion modelling

Ammonia (NH3) fluxes were estimated from a field being grazed by dairy cattle during spring by applying a backward Lagrangian stochastic model (bLS) model combined with horizontal concentration gradients measured across the field. Continuous concentration measurements at field boundaries were made by open-path miniDOAS (differential optical absorption spectroscopy) instruments while the cattle were present and for 6 subsequent days. The deposition of emitted NH3 to "clean" patches on the field was also simulated, allowing both "net" and "gross" emission estimates, where the dry deposition velocity (vd) was predicted by a canopy resistance (Rc) model developed from local NH3 flux and meteorological measurements. Estimated emissions peaked during grazing and decreased after the cattle had left the field, while control on emissions was observed from covariance with temperature, wind speed and humidity and wetness measurements made on the field, revealing a diurnal emission profile. Large concentration differences were observed between downwind receptors, due to spatially heterogeneous emission patterns. This was likely caused by uneven cattle distribution and a low grazing density, where "hotspots" of emissions would arise as the cattle grouped in certain areas, such as around the water trough. The spatial complexity was accounted for by separating the model source area into sub-sections and optimising individual source area coefficients to measured concentrations. The background concentration was the greatest source of uncertainty, and based on a sensitivity/uncertainty analysis the overall uncertainty associated with derived emission factors from this study is at least 30–40 %

The ALFAM2 database on ammonia emission from field-applied manure: Description and illustrative analysis

peer-reviewedAmmonia (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 1895 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 in this subset ranged from <1% to 130% of applied ammonia after 48 h. 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 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 to contact the corresponding author for information on data submission. The latest version of the database is available at http://www.alfam.dk

Ammonia emissions from an uncovered dairy slurry storage tank over two years: Interactions with tank operations and meteorological conditions

The storage of slurry substantially contributes to the ammonia (NH3) released from livestock production. This study quantified farm-scale NH3 emissions from a circular open tank storing dairy cow slurry by means of continuous measurements over two years. Emissions were determined by scaling the product of line-integrated concentration measurements across the tank and wind speed measurements at 10 m height. The resulting data were calibrated to emissions determined using the integrated horizontal flux method. The data analysis was structured according to the main influencing factors: natural crust and meteorological conditions. The average annual emission was 0.065 g NH3 m−2 h−1 with a maximum of 1.67 g NH3 m−2 h−1. Annual emissions scaled to total ammoniacal nitrogen (TAN) were 3.3% of the TAN flow into the store. A natural crust on the slurry surface, which was strongly affected by agitation of the tank, diminished the gas release. An increasing time span after agitation led to correspondingly lower emissions. A greater filling level enhanced crust formation and induced an additional drop in emissions. Precipitation reduced emissions by 64%–86% compared to dry weather conditions. Higher wind speed and temperatures increased emissions. The emissions were highest in periods with weak or no crusting of the slurry surface, which covered 40% of the study time, but produced 61% of total emissions. The response of NH3 emissions to the interactions of influencing factors, which might vary considerably between stores, suggests that these factors require consideration for the determination of emission factors used for inventory reporting

A novel approach to estimate the abatement of ammonia emissions from mitigation techniques at farm‐scale slurry stores exemplified by a semifloating cover

Abstract Ammonia (NH3) losses from livestock slurry stores substantially contribute to agricultural emissions to the atmosphere. Gas release from slurry storage facilities is driven by interactions between store operations and meteorological conditions. This study quantifies the abating effect of an impermeable semifloating cover as an emission mitigation technique at a farm-scale slurry storage tank. Emissions were measured over 1 yr and compared with the preceding 2 yr of measurements with the uncovered tank. In this novel approach, emission data were aggregated to categories within 1 h measuring intervals according to five key factors influencing emissions (time span after agitation and tank-filling level as surrogates for natural crust occurrence; the meteorological parameters precipitation, air temperature, and wind speed) for the two consecutive measurement campaigns with and without the cover. The emission abatement effect of the cover was determined by emission modeling of the entire measuring campaign based on measuring intervals of the uncovered and the covered tank where the aggregated categories of influencing factors were equal. The resulting average emission abatement was 48%. An average abatement of 37 and 54% was achieved during periods with and without a surface crust, respectively. The emission reduction was less with low tank filling level due to higher air exchange through openings of the cover. The presented approach is applicable to evaluate emission mitigation techniques for single farm-scale stores. With adequate measurement duration, it is appropriate to produce reliable emission data reflecting the complex interactions between emissions and influencing factors occurring at real-world storage facilities

Ammonia emission after slurry application to grassland in Switzerland

Loss of ammonia (NH3) after field application of livestock slurry contributes between 30% and 50% of agricultural NH3 emissions from European countries. The objectives of this study were to re-evaluate NH3 emissions following application of cattle and pig slurry to grassland in Switzerland and to investigate the effectiveness of abatement techniques. In 17 field experiments, NH3 emissions were determined with a micrometeorological approach, relating the emission to the measured concentration by means of atmospheric dispersion modelling. The cattle slurry applied exhibited an average dry matter content of 3.3% (range between 1.0% and 6.7% dry matter). The emission after application of cattle slurry spread with a splash plate (referred to as reference technique) ranged from 10% to 47% of applied Total Ammoniacal Nitrogen (% of TAN) and averaged to 25% of TAN. This range of losses is lower by approx. a factor of two compared to measurements from earlier Swiss experiments. Applications with trailing hose and trailing shoe systems yielded an average reduction of 51% and 53%, respectively, relative to the reference technique. A regression analysis showed that the dry matter content of the slurry and the air temperature are important drivers for NH3 emission

Temporal trends in soil solution acidity indicators in European forests

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