Summertime Soil-Atmosphere Ammonia Exchange in the Colorado Rocky Mountain Front Range Pine Forest

Understanding the NH3 exchange between forest ecosystems and the atmosphere is important due to its role in the nitrogen cycle. However, NH3 exchange is dynamic and difficult to measure. The goal of this study was to characterize this exchange by measuring the atmosphere, soil, and vegetation. Compensation point modeling was used to evaluate the direction and magnitude of surface-atmosphere exchange. Measurements were performed at the Manitou Experimental Forest Observatory (MEFO) site in the Colorado Front Range by continuous online monitoring of gas and particle phase NH3-NH4+ with an ambient ion monitoring system coupled with ion chromatographs (AIM-IC), direct measurements of [NH4+] and pH in soil extracts to determine ground emission potential (Γg), and measurements of [NH4+]bulk in pine needles to derive leaf emission potential (Γst). Two different soil types were measured multiple times throughout the study, in which Γg ranged from 5 to 2122. Γst values ranged from 29 to 54. Inferred fluxes (Fg) from each soil type predicted intervals of emission and deposition. By accounting for the total [NH4+] pool in each compartment, the lifetime of NH3 with respect to the surface-atmosphere exchange in the soil is on the order of years compared to much faster naturally occurring processes, i.e., mineralization and nitrification.

Surface-atmosphere exchange of ammonia over peatland using QCL-based eddy covariance measurements and inferential modeling

Recent advances in laser spectrometry offer new opportunities to investigate ecosystem-atmosphere exchange of environmentally relevant trace gases. In this study, we demonstrate the applicability of a quantum cascade laser (QCL) absorption spectrometer to continuously measure ammonia concentrations at a high time resolution and thus to quantify the net exchange between a semi-natural peatland ecosystem and the atmosphere based on the eddy-covariance approach. Changing diurnal patterns of both ammonia concentration and fluxes were found during different periods of the campaign. We observed a clear tipping point in early spring with decreasing deposition velocities and increasingly bi-directional fluxes that occurred after the switch from dormant vegetation to CO2 uptake, but was triggered by a significant weather change. While several biophysical parameters such as temperature, radiation, and surface wetness were identified to partially regulate ammonia exchange at the site, the seasonal concentration pattern was clearly dominated by agricultural practices in the surrounding area. Comparing the results of a compensation point model with our measurement-based flux estimates showed considerable differences in some periods of the campaign due to overestimation of non-stomatal resistances caused by low acid ratios. The total cumulative campaign exchange of ammonia after nine weeks, however, differed only in a 6 % deviation with 911 and 857 g NH3-N ha−1 deposition being found by measurements and modeling, respectively. Extrapolating our findings to an entire year, ammonia deposition was lower than reported by Hurkuck et al. (2014) for the same site in previous years using denuder systems. This was likely due to a better representation of the emission component in the net signal of eddy-covariance fluxes as well as better adapted site-specific parameters in the model. Our study not only stresses the importance of high-quality measurements for studying and assessing land surface-atmosphere interactions, but also demonstrates the potential of QCL spectrometers for continuous observation of reactive nitrogen species as important additional instruments within long-term monitoring research infrastructures such as ICOS or NEON.

Review and parameterisation of bi-directional ammonia exchange between vegetation and the atmosphere

Current deposition schemes used in atmospheric chemical transport models do not generally account for bi-directional exchange of ammonia (NH3). Bi-directional exchange schemes, which have so far been applied at the plot scale, can be included in transport models, but need to be parameterised with appropriate values of the ground layer compensation point (χg), stomatal compensation point (χs) and cuticular resistance (Rw). We review existing measurements of χg, χs as well as Rw and compile a comprehensive dataset from which we then propose generalised parameterisations. χs is related to Γs, the non-dimensional ratio of [NH4+]apo and [H+]apo in the apoplast, through the temperature dependence of the combined Henry and dissociation equilibrium. The meta-analysis suggests that the nitrogen (N) input is the main driver of the apoplastic and bulk leaf concentrations of ammonium (NH4 apo

Review and parameterisation of bi-directional ammonia exchange between vegetation and the atmosphere

Current deposition schemes used in atmospheric chemical transport models do not generally account for bi-directional exchange of ammonia (NH3). Bi-directional exchange schemes, which have so far been applied at the plot scale, can be included in transport models, but need to be parameterised with appropriate values of the stomatal compensation point (χs) and cuticular resistance (Rw). We here review existing measurements of χs as well as Rw and compile a comprehensive dataset from which we then propose generalised parameterisations. χs is related to Γs, the non-dimensional ratio of [NH4+]apo and [H+]apo in the apoplast, through the temperature dependence of the combined Henry and solubility equilibrium. The meta-analysis suggests that the nitrogen (N) input is the main driver of the apoplastic and bulk leaf concentrations of ammonium (NH+4 apo, NH+4 bulk). For managed ecosystems, the main source of N is fertilisation which is reflected in a peak value of χs a few days following application, but also alters seasonal values of NH+4 apo and NH+4 bulk. We propose a parameterisation for χs which includes peak values as a function of amount and type of fertiliser application which gradually decreases to a background value. The background χs is set based on total N input to the ecosystem as a yearly fertiliser application and N deposition (Ndep). For non-managed ecosystems, χs is parameterised based solely on the link with Ndep. For Rw we propose a general parameterisation as a function of atmospheric Relative Humidity (RH), incorporating a minimum value (R w(min)), which depends on the ratio of atmospheric acid concentrations (SO2, HNO3 and HCl) to NH3 concentrations. The parameterisations are based mainly on datasets from temperate locations in northern Europe making them most suitable for up-scaling in these regions (Unified EMEP model for example). In principle, the parameterisations should be applicable to other climates, though there is a need for more underpinning data, with the uncertainties being especially large for tropical and subtropical conditions.

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

Two commercial ammonia (NH3) 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 NH3 m−2 s−1. Hence the flux measurements are considered sufficiently accurate for studying typical NH3 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. NH3 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 1: Micrometeorological flux measurements and emissions after slurry application

Two commercial ammonia (NH3) 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 (AGM). The semi-continuous measurements during 1.5 years covered five complete growth-cut cycles and included six applications of liquid cattle slurry. The average accuracy of the flux measurements during conditions of well established turbulence was 20% and the detection limit 10 ng NH3 m−2 s−1, hence sufficient for studying the background exchange of NH3. Quantifying emissions after slurry applications required the application of elaborate interpolations because of difficulties capturing the initial emissions during manure spreading in some parts of the experiments. The emissions were also calculated with a mass balance method (MBM) yielding similar fluxes. NH3 losses after slurry application expressed as percentage of emitted nitrogen versus applied total ammoniacal nitrogen (TAN) varied between 4 and 19%, which is lower than typical values for broadspreading of liquid manure. The comparatively low emission factors appear to be a consequence of the rather thin slurry applied here and soil properties favouring ammonium adsorption.