N2 is one of the major gaseous nitrogen compounds released by soils due to N-transformation processes. Since it is also the major constituent of the earth's atmosphere (78.08% vol.), the determination of soil N2 release is still one of the main methodological challenges with respect to a complete evaluation of the gaseous N-loss of soils. Commonly used approaches are based either on a C2H2 inhibition technique, an artificial atmosphere or a 15N-tracer technique, and are designed either as closed systems (non-steady state) or gas flow systems (steady state). The intention of this work has been to upgrade the current gas flow technique using an artificial atmosphere for a 15N-aided determination of the soil N2 release simultaneously with N2O. A 15N-aided artificial atmosphere gas flow approach has been developed, which allows a simultaneous online determination of N2 as well as N2O fluxes from an open soil system (steady state). Fluxes of both gases can be determined continuously over long incubation periods and with high sampling frequency. The N2 selective molecular sieve Köstrolith SX6 was tested successfully for the first time for dinitrogen collection. The presented paper mainly focuses on N2 flux determination. For validation purposes soil aggregates of a Haplic Phaeozem were incubated under aerobic (21 and 6 vol.% O2) and anaerobic conditions. Significant amounts of N2 were released only during anaerobic incubation (0.4 and 640.2 pmol N2 h(-1) g(-1) dry soil). However, some N2 formation also occurred during aerobic incubation. It was also found that, during ongoing denitrification, introduced [NO3]- will be more strongly delivered to microorganisms than the original soil [NO3]-.

Abstract. The prediction of nitrous oxide (N2O) and of dinitrogen (N2) emissions formed by biotic denitrification in soil is notoriously difficult due to challenges in capturing co-occurring processes at microscopic scales. N2O production and reduction depend on the spatial extent of anoxic conditions in soil, which in turn are a function of oxygen (O2) supply through diffusion and O2 demand by respiration in the presence of an alternative electron acceptor (e.g. nitrate). This study aimed to explore controlling factors of complete denitrification in terms of N2O and (N2O + N2) fluxes in repacked soils by taking micro-environmental conditions directly into account. This was achieved by measuring microscale oxygen saturation and estimating the anaerobic soil volume fraction (ansvf) based on internal air distribution measured with X-ray computed tomography (X-ray CT). O2 supply and demand were explored systemically in a full factorial design with soil organic matter (SOM; 1.2 % and 4.5 %), aggregate size (2–4 and 4–8 mm), and water saturation (70 %, 83 %, and 95 % water-holding capacity, WHC) as factors. CO2 and N2O emissions were monitored with gas chromatography. The 15N gas flux method was used to estimate the N2O reduction to N2. N gas emissions could only be predicted well when explanatory variables for O2 demand and O2 supply were considered jointly. Combining CO2 emission and ansvf as proxies for O2 demand and supply resulted in 83 % explained variability in (N2O + N2) emissions and together with the denitrification product ratio [N2O / (N2O + N2)] (pr) 81 % in N2O emissions. O2 concentration measured by microsensors was a poor predictor due to the variability in O2 over small distances combined with the small measurement volume of the microsensors. The substitution of predictors by independent, readily available proxies for O2 demand (SOM) and O2 supply (diffusivity) reduced the predictive power considerably (60 % and 66 % for N2O and (N2O+N2) fluxes, respectively). The new approach of using X-ray CT imaging analysis to directly quantify soil structure in terms of ansvf in combination with N2O and (N2O + N2) flux measurements opens up new perspectives to estimate complete denitrification in soil. This will also contribute to improving N2O flux models and can help to develop mitigation strategies for N2O fluxes and improve N use efficiency.

Evaporation—a key process for water exchange between soil and atmosphere—is controlled by internal water fluxes and surface vapor fluxes. Recent studies demonstrated that the dynamics of the water flow in corners determine the time behavior of the evaporation rate. The internal water flux of the porous media is often described by capillary flow assuming complete wetting. Particularly, the crucial influence of partial wetting, that is, the nonlinear contact angle dependency of the capillary flow has been neglected so far. The focus of the paper is to demonstrate that SiO2‐surfaces can exhibit contact angles of about 40°. This reduces the internal capillary flow by 1 order of magnitude compared to complete wetting. First, we derived the contact angle by inverse modeling. We conducted a series of evaporation experiments in a 2‐D square lattice microstructure connected by lognormal distributed throats. We used an explicit analytical power series solution of the single square capillary model. A contact angle of 38° ± 1° was derived. Second, we directly measured the contact angle of the Si‐SiO2 wafer using the Drop Shape Analyzer Krüss 100 and obtained an averaged contact angle of 42° ± 2°. The results support the single square capillary model as an appropriate model for the description of the evaporation process in an ideal square capillary.

On the basis of the principle of reaction continuous-flow quadrupole mass spectrometry, an automated sample preparation unit for inorganic nitrogen (SPIN) species was developed and coupled to a quadrupole Mass Spectrometer (MAS). The SPINMAS technique was designed for an automated, sensitive, and rapid determination of 15N abundance and concentration of a wide variety of N-species involved in nitrogen cycling (e.g. NH4+, NO3-, NH2OH etc.). In this paper, the SPINMAS technique is evaluated with regard to the determination of 15N abundance and concentration of the most fundamental inorganic nitrogen compounds in ecosystems such as NH4+, NO2-, and NO3-. The presented paper describes the newly developed system in detail and demonstrates the general applicability of the system. For a precise determination of 15N abundance and concentration, a minimum total N-amount of 10 microg NH4+ - N, 0.03 microg NO2- - N, or 0.3 microg NO3- - N has to be supplied. Currently, the SPINMAS technique represents the most rapid and only fully automated all-round method for a simultaneous determination of 15N abundance and total N-amount of NH4+, NO2-, or NO3- in aqueous samples.

The standard method for determining the 15N abundance of total dissolved nitrogen (TDN) in aqueous samples (e.g., soil leachate, sewage, urine) is currently Kjeldahl digestion followed by steam distillation or diffusion to isolate the ammonium, and then 15N measurement using IRMS. However, this technique is both time-consuming and laborious. One way of overcoming these disadvantages could be to couple a TOC analyser to determine the TDN with a sufficient quadrupole MS to determine the 15N abundance. The high TOC analyser (Elementar Analysensysteme Hanau, Germany), which catalytically oxidises the sample's total nitrogen with a high, constant yield to nitrogen monoxide (NO), appeared particularly suitable. The quadrupole-MS ESD 100 (InProcess Instruments Bremen, Germany) proved to be a suitable mass spectrometer for the 15N determination of NO. This combination of instruments was found to provide a workable method in numerous measurements of standard and actual samples. The detection limit concerning the N amount required per analysis is 2 microg, corresponding to an N concentration of 0.7 mg/l in a maximum sample volume of 3ml. Depending on the N concentration, 15N abundances starting from 0.5 at.% can be measured with the required precision of better than 3% (simple standard deviation). For example, measuring the abundance of 0.5 at.% requires about 50 microg N, whereas for 1 at.% or more only about 5 microg N is needed per analysis.