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

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

Interatomic Coulombic Decay as a New Source of Low Energy Electrons in slow Ion-Dimer Collisions

We provide the experimental evidence that the single electron capture process in slow collisions between O$^{3+}$ ions and neon dimer targets leads to an unexpected production of low-energy electrons. This production results from the interatomic Coulombic decay process, subsequent to inner shell single electron capture from one site of the neon dimer. Although pure one-electron capture from inner shell is expected to be negligible in the low collision energy regime investigated here, the electron production due to this process overtakes by one order of magnitude the emission of Auger electrons by the scattered projectiles after double-electron capture. This feature is specific to low charge states of the projectile: similar studies with Xe$^{20+}$ and Ar$^{9+}$ projectiles show no evidence of inner shell single-electron capture. The dependence of the process on the projectile charge state is interpreted using simple calculations based on the classical over the barrier model

Paul trapping of radioactive 6He+ions and direct observation of their beta-decay

We demonstrate that abundant quantities of short-lived beta unstable ions can be trapped in a novel transparent Paul trap and that their decay products can directly be detected in coincidence. Low energy 6He+ (807 ms half-life) ions were extracted from the SPIRAL source at GANIL, then decelerated, cooled and bunched by means of the buffer gas cooling technique. More than 10^8 ions have been stored over a measuring period of six days and about 10^5 decay coincidences between the beta particles and the 6Li^{++} recoiling ions have been recorded. The technique can be extended to other short-lived species, opening new possibilities for trap assisted decay experiments.Comment: 4 pages, 4 figures, submitted to Phys.Rev.Let

Effects of global change during the 21st century on the nitrogen cycle

The global nitrogen (N) cycle at the beginning of the 21st century has been shown to be strongly influenced by the inputs of reactive nitrogen (Nr) from human activities, including combustion-related NOx, industrial and agricultural N fixation, estimated to be 220 Tg N yr−1 in 2010, which is approximately equal to the sum of biological N fixation in unmanaged terrestrial and marine ecosystems. According to current projections, changes in climate and land use during the 21st century will increase both biological and anthropogenic fixation, bringing the total to approximately 600 Tg N yr−1 by around 2100. The fraction contributed directly by human activities is unlikely to increase substantially if increases in nitrogen use efficiency in agriculture are achieved and control measures on combustion-related emissions implemented. Some N-cycling processes emerge as particularly sensitive to climate change. One of the largest responses to climate in the processing of Nr is the emission to the atmosphere of NH3, which is estimated to increase from 65 Tg N yr−1 in 2008 to 93 Tg N yr−1 in 2100 assuming a change in global surface temperature of 5 °C in the absence of increased anthropogenic activity. With changes in emissions in response to increased demand for animal products the combined effect would be to increase NH3 emissions to 135 Tg N yr−1. Another major change is the effect of climate changes on aerosol composition and specifically the increased sublimation of NH4NO3 close to the ground to form HNO3 and NH3 in a warmer climate, which deposit more rapidly to terrestrial surfaces than aerosols. Inorganic aerosols over the polluted regions especially in Europe and North America were dominated by (NH4)2SO4 in the 1970s to 1980s, and large reductions in emissions of SO2 have removed most of the SO42− from the atmosphere in these regions. Inorganic aerosols from anthropogenic emissions are now dominated by NH4NO3, a volatile aerosol which contributes substantially to PM10 and human health effects globally as well as eutrophication and climate effects. The volatility of NH4NO3 and rapid dry deposition of the vapour phase dissociation products, HNO3 and NH3, is estimated to be reducing the transport distances, deposition footprints and inter-country exchange of Nr in these regions. There have been important policy initiatives on components of the global N cycle. These have been regional or country-based and have delivered substantial reductions of inputs of Nr to sensitive soils, waters and the atmosphere. To date there have been no attempts to develop a global strategy to regulate human inputs to the nitrogen cycle. However, considering the magnitude of global Nr use, potential future increases, and the very large leakage of Nr in many forms to soils, waters and the atmosphere, international action is required. Current legislation will not deliver the scale of reductions globally for recovery from the effects of Nr deposition on sensitive ecosystems, or a decline in N2O emissions to the global atmosphere. Such changes would require substantial improvements in nitrogen use efficiency across the global economy combined with optimization of transport and food consumption patterns. This would allow reductions in Nr use, inputs to the atmosphere and deposition to sensitive ecosystems. Such changes would offer substantial economic and environmental co-benefits which could help motivate the necessary actions

Carbon-nitrogen interactions in European forests and semi-natural vegetation - Part 1: Fluxes and budgets of carbon, nitrogen and greenhouse gases from ecosystem monitoring and modelling

The impact of atmospheric reactive nitrogen (N$_{r}$) deposition on carbon (C) sequestration in soils and biomass of unfertilized, natural, semi-natural and forest ecosystems has been much debated. Many previous results of this dC/dN response were based on changes in carbon stocks from periodical soil and ecosystem inventories, associated with estimates of N$_{r}$ deposition obtained from large-scale chemical transport models. This study and a companion paper (Flechard et al., 2020) strive to reduce uncertainties of N effects on C sequestration by linking multi-annual gross and net ecosystem productivity estimates from 40 eddy covariance flux towers across Europe to local measurement-based estimates of dry and wet N$_{r}$ deposition from a dedicated collocated monitoring network. To identify possible ecological drivers and processes affecting the interplay between C and N$_{r}$ inputs and losses, these data were also combined with in situ flux measurements of NO, N$_{2}$O and CH$_{4}$ fluxes; soil NO$_{3}$̅ leaching sampling; and results of soil incubation experiments for N and greenhouse gas (GHG) emissions, as well as surveys of available data from online databases and from the literature, together with forest ecosystem (BASFOR) modelling. Multi-year averages of net ecosystem productivity (NEP) in forests ranged from -70 to 826 gCm$^{-2}$ yr$^{-1}$ at total wet+dry inorganic N$_{r}$ deposition rates (N$_{dep}$) of 0.3 to 4.3 gNm$^{-2}$ yr$^{-1}$ and from -4 to 361 g Cm$^{-2}$ yr$^{-1}$ at N$_{dep}$ rates of 0.1 to 3.1 gNm$^{-2}$ yr$^{-1}$ in short semi-natural vegetation (moorlands, wetlands and unfertilized extensively managed grasslands). The GHG budgets of the forests were strongly dominated by CO$_{2}$ exchange, while CH$_{4}$ and N$_{2}$O exchange comprised a larger proportion of the GHG balance in short semi-natural vegetation. Uncertainties in elemental budgets were much larger for nitrogen than carbon, especially at sites with elevated N$_{dep}$ where N$_{r}$ leaching losses were also very large, and compounded by the lack of reliable data on organic nitrogen and N$_{2}$ losses by denitrification. Nitrogen losses in the form of NO, N$_{2}$O and especially NO$_{3}$̅ were on average 27%(range 6 %–54 %) of N$_{dep}$ at sites with N$_{dep}$ 3 gNm$^{-2}$ yr$^{-1}$. Such large levels of N$_{r}$ loss likely indicate that different stages of N saturation occurred at a number of sites. The joint analysis of the C and N budgets provided further hints that N saturation could be detected in altered patterns of forest growth. Net ecosystem productivity increased with N$_{r}$ deposition up to 2–2.5 gNm$^{-2}$ yr$^{-1}$, with large scatter associated with a wide range in carbon sequestration efficiency (CSE, defined as the NEP = GPP ratio). At elevated N$_{dep}$ levels (> 2.5 gNm$^{-2}$ yr$^{-1}$), where inorganic N$_{r}$ losses were also increasingly large, NEP levelled off and then decreased. The apparent increase in NEP at low to intermediate N$_{dep}$ levels was partly the result of geographical cross-correlations between N$_{dep}$ and climate, indicating that the actual mean dC/dN response at individual sites was significantly lower than would be suggested by a simple, straightforward regression of NEP vs. N$_{dep}$

Characteristics of ammonia, acid gases, and PM_2.5 for three typical land-use types in the North China Plain

Air pollution is one of the most serious environmental problems in China due to its rapid economic development alongside a very large consumption of fossil fuel, particularly in the North China Plain (NCP). During the period 2011–2014, we integrated active and passive sampling methods to perform continuous measurements of NH3, HNO3, NO2, and PM2.5 at two urban, one suburban, and two rural sites in the NCP. The annual average concentrations of NH3, NO2, and HNO3 across the five sites were in the ranges 8.5–23.0, 22.2–50.5, and 5.5–9.7 μg m−3, respectively, showing no significant spatial differences for NH3 and HNO3 but significantly higher NO2 concentration at the urban sites. At each site, annual average concentrations of NH3 and NO2 showed increasing and decreasing trends, respectively, while there was no obvious trend in annual HNO3 concentrations. Daily PM2.5 concentrations ranged from 11.8 to 621.0 μg m−3 at the urban site, from 19.8 to 692.9 μg m−3 at the suburban site, and from 23.9 to 754.5 μg m−3 at the two rural sites, with more than 70 % of sampling days exceeding 75 μg m−3. Concentrations of water-soluble ions in PM2.5 ranked differently between the non-rural and rural sites. The three dominant ions were NH4 +, NO3 −, and SO4 2− and mainly existed as (NH4)2SO4, NH4HSO4, and NH4NO3, and their concentrations averaged 48.6 ± 44.9, 41.2 ± 40.8, and 49.6 ± 35.9 μg m−3 at the urban, suburban, and rural sites, respectively. Ion balance calculations indicated that PM2.5 was neutral at the non-rural sites but acidic at the rural sites. Seasonal variations of the gases and aerosols exhibited different patterns, depending on source emission strength and meteorological conditions. Our results suggest that a feasible pathway to control PM2.5 pollution in the NCP should target ammonia and acid gases together

Theoretical and practical limitations of the acetylene inhibition technique to determine total denitrification losses

The loss of N2 from intensively managed agro-ecosystems is an important part of the N budget. Flux monitoring of N2 emissions at the field scale, e.g., by eddy correlation or aerodynamic gradient method, is impossible due to the large atmospheric N2 background (78%). The acetylene (C2H2) inhibition technique (AIT) is a rather simple and frequently used, albeit imperfect, method to determine N2 losses from intact soil cores. In principle, AIT allows an estimation of total denitrification at high temporal resolution and on small spatial scales, with limited workload and costs involved. To investigate its potential and limitations, a laboratory system with two different detection systems (photoacoustic IR spectroscopy and gas chromatography) is presented, which allowed simultaneous measurements of up to 7 intact soil cores in air-tight glass tubes in a temperature controlled cabinet (adjusted to field conditions) with automated C2H2 injection. A survey of total denitrification losses (N2 + N2O) over 1.5 yr in soil cores from an intensively managed, cut grassland system in central Switzerland supports previous reports on severe limitations of the AIT, which precluded reliable estimates of total denitrification losses. Further, the unavoidable sampling and transfer of soil samples to the laboratory causes unpredictable deviations from the denitrification activity in the field