Release of nitrous oxide and dinitrogen from a transition bog under drained and rewetted conditions due to denitrification: results from a [15N]nitrate-bromide double-tracer study.

Denitrification is well known being the most important nitrate-consuming process in water-logged peat soils, whereby the intermediate compound nitrous oxide (N(2)O) and the end product dinitrogen (N(2)) are ultimately released. The present study was aimed at evaluating the release of these gases (due to denitrification) from a nutrient-poor transition bog ecosystem under drained and three differently rewetted conditions at the field scale using a (15)N-tracer approach ([(15)N]nitrate application, 30 kg N ha(-1)) and a common closed-chamber technique. The drained site is characterized by a constant water table (WT) of -30 cm (here referred to as D30), while rewetted sites represent a constant WT of -15 cm, a constant WT of 0 cm (i.e. waterlogged), and an initial WT of 0 cm (which decreased slightly during the experiment), respectively, (here referred to as R15, R0, and R0(d), respectively). The highest N(2)O emissions were observed at D30 (291 µg N(2)O-N m(-2) h(-1)) as well as at R0d (665 µg N(2)O-N m(-2) h(-1)). At the rewetted peat sites with a constant WT (i.e. R15 and R0), considerably lower N2O emissions were observed (maximal 37 µg N(2)O-N m(-2) h(-1)). Concerning N(2) only at the initially water-logged peat site R0d considerable release rates (up to 3110 µg N(2)-N m(-2) h(-1)) were observed, while under drained conditions (D30) no N(2) emission and under rewetted conditions with a constant WT (R15 and R0) significantly lower N(2) release rates (maximal 668 µg N(2)-N m(-2) h(-1)) could be detected. In addition, it has been found that natural WT fluctuations at rewetted peat sites, in particular a rapid drop down of the WT, can induce high emission rates for both N(2)O and N(2).

Nitrate turnover in a peat soil under drained and rewetted conditions: results from a [(15)N]nitrate-bromide double-tracer study.

Under natural conditions, peatlands are generally nitrate-limited. However, recent concerns about an additional N input into peatlands by atmospheric N deposition have highlighted the risk of an increased denitrification activity and hence the likelihood of a rise of emissions of the greenhouse gas nitrous oxide. Therefore, the aim of the present study was to investigate the turnover of added nitrate in a drained and a rewetted peatland using a [(15)N]nitrate-bromide double-tracer method. The double-tracer method allows a separation between physical effects (dilution, dispersion and dislocation) and microbial and chemical nitrate transformation by comparing with the conservative Br(-) tracer. In the drained peat site, low NO3(-) consumption rates have been observed. In contrast, NO3(-) consumption at the rewetted peat site rises rapidly to about 100% within 4 days after tracer application. Concomitantly, the (15)N abundances of nitrite and ammonium in soil water increased and lead to the conclusion that, besides commonly known NO3(-) reduction to nitrite (i.e. denitrification), a dissimilatory nitrate reduction to ammonium has simultaneously taken place. The present study reveals that increasing NO3(-) inputs into rewetted peatlands via atmospheric deposition results in a rapid NO3(-) consumption, which could lead to an increase in N2O emissions into the atmosphere.

Analysis of the coexisting pathways for NO and N2O formation in Chernozem using the (15)N-tracer SimKIM-Advanced model.

The nitrogen (N) cycle consists of a variety of microbial processes. These processes often occur simultaneously in soils, but respond differently to local environmental conditions due to process-specific biochemical restrictions (e.g. oxygen levels). Hence, soil nitrogen cycling (e.g. soil N gas production through nitrification and denitrification) is individually affected through these processes, resulting in the complex and highly dynamic behaviour of total soil N turnover. The development and application of methods that facilitate the quantification of individual contributions of coexisting processes is a fundamental prerequisite for (i) understanding the dynamics of soil N turnover and (ii) implementing these processes in ecosystem models. To explain the unexpected results of the triplet tracer experiment (TTE) of Russow et al. (Role of nitrite and nitric oxide in the processes of nitrification and denitrification in soil: results from (15)N tracer experiments. Soil Biol Biochem. 2009;41:785-795) the existing SimKIM model was extended to the SimKIM-Advanced model through the addition of three separate nitrite subpools associated with ammonia oxidation, oxidation of organic nitrogen (Norg), and denitrification, respectively. For the TTE, individual treatments with (15)N ammonium, (15)N nitrate, and (15)N nitrite were conducted under oxic, hypoxic, and anoxic conditions, respectively, to clarify the role of nitric oxide as a denitrification intermediate during N2O formation. Using a split nitrite pool, this analysis model explains the observed differences in the (15)N enrichments in nitric oxide (NO) and nitrous oxide (N2O) which occurred in dependence on different oxygen concentrations. The change from oxic over hypoxic to anoxic conditions only marginally increased the NO and N2O release rates (1.3-fold). The analysis using the model revealed that, under oxic and hypoxic conditions, Norg-based N2O production was the dominant pathway, contributing to 90 and 50 % of the total soil N2O release. Under anoxic conditions, denitrification was the dominant process for soil N2O release. The relative contribution of Norg to the total soil NO release was small. Ammonia oxidation served as the major pathway of soil NO release under oxic and hypoxic conditions, while denitrification was dominant under anoxic conditions. The model parameters for soil with moderate soil organic matter (SOM) content were not scalable to an additional data set for soil with higher SOM content, indicating a strong influence of SOM content on microbial N turnover. Thus, parameter estimation had to be re-calculated for these conditions, highlighting the necessity of individual soil-dependent parameter estimations.

Automated and rapid online determination of 15N abundance and concentration of ammonium, nitrite, or nitrate in aqueous samples by the SPINMAS technique.

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.

GC-R-CF-MS method to determine the 13C abundance of gaseous combustion products in cigarette smoke.

To determine the 13C abundance of combustion and break down products formed in cigarette smoke, especially CO and CO2, a simple and fast analytical method is needed. Taking into account the knowledge about the determination of the natural 13C abundance in air, an online method - based on gas chromatography-reaction-continuous flow mass spectrometry (GC-R-CF-MS) - has been developed, which enables the determination of the 13C abundance of CO and CO2 in the vapour phase of cigarette smoke with a relative standard deviation of< or =0.5% in one analytical run. Additionally, in a second step, the 13C abundance of total volatile carbon can be determined.

Denitrification in the river estuaries of the northern Baltic Sea.

Estuaries have been suggested to have an important role in reducing the nitrogen load transported to the sea. We measured denitrification rates in six estuaries of the northern Baltic Sea. Four of them were river mouths in the Bothnian Bay (northern Gulf of Bothnia), and two were estuary bays, one in the Archipelago Sea (southern Gulf of Bothnia) and the other in the Gulf of Finland. Denitrification rates in the four river mouths varied between 330 and 905 micromol N m(-2) d(-1). The estuary bays at the Archipelago Sea and the Gulf of Bothnia had denitrification rates from 90 micromol N m(-2) d(-1) to 910 micromol N m(-2) d(-1) and from 230 micromol N m(-2) d(-1) to 320 micromol N m(-2) d(-1), respectively. Denitrification removed 3.6-9.0% of the total nitrogen loading in the river mouths and in the estuary bay in the Gulf of Finland, where the residence times were short. In the estuary bay with a long residence time, in the Archipelago Sea, up to 4.5% of nitrate loading and 19% of nitrogen loading were removed before entering the sea. According to our results, the sediments of the fast-flowing rivers and the estuary areas with short residence times have a limited capacity to reduce the nitrogen load to the Baltic Sea.

A 15N-aided artificial atmosphere gas flow technique for online determination of soil N2 release using the zeolite Köstrolith SX6.

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]-.

A natural 15N approach to determine the biological fixation of atmospheric nitrogen by biological soil crusts of the Negev Desert.

Biological soil crusts are important cryptogamic communities covering the sand dunes of the north-western Negev. The biological crusts contain cyanobacteria and other free-living N(2)-fixing bacteria and are hence able to fix atmospheric nitrogen (N). This is why they are considered to be one of the main N input pathways into the desert ecosystem. However, up to now, in situ determinations of the N(2) fixation in the field are not known to have been carried out. We examined the natural (15)N method to determine the biological N(2) fixation by these soil crusts under field conditions. This novel natural (15)N method uses the lichen Squamarina with symbiotic green algae--which are unable to fix N(2)--as a reference in order to determine N(2) fixation. Depending on the sampling location and year, the relative biological fixation of atmospheric nitrogen was estimated at 84-91% of the total N content of the biological soil crust. The cyanobacteria-containing soil lichen Collema had a fixation rate of about 88%. These fixation rates were used to derive an absolute atmospheric N input of 10-41 kg N ha(-1) year(-1). These values are reasonable results for the fixation of atmospheric N(2) by the biological crusts and cyanolichens and are in agreement with other comparable lab investigations. As far as we are aware, the results presented are the first to have been obtained from in situ field measurements, albeit only one location of the Negev with a small number of samples was investigated.

Fate and metabolism of [15N]2,4,6-trinitrotoluene in soil.

The fates of the labels from [14C] and [15N] trinitrotoluene were analyzed in bioreactors under aerobic conditions in soil treated by a fungal bioremediation process with Stropharia rugosoannulata and in control soil. Up to 17.5% of the 15N label had a different fate than the 14C label. Three N-mineralization processes were identified in detailed experiments with [15N]TNT. About 2% of the 15N label was found as NO3- and NH4+, showing simultaneous processes of direct TNT denitration (I) and reduction with cleavage of the amino groups (II). The enrichment of NO2-/NO3- (up to 7.5 atom% 15N abundance) indicates the formation of Meisenheimer complexes with a denitration of [15N]TNT. A 1.4% of the label was found distributed between N2O and N2. However, the 15N enrichment of the N2O (up to 38 atom%) demonstrated that both N atoms were generated from the labeled TNT and clearly indicates a novel formation process (III). We propose, as an explanation, the generation of N2O by cleavage from condensed azoxy metabolites. In addition, 1.7% of the 15N label was detected as biogenic amino acids in the wheat straw containing the fungus. Overall, 60 to 85% of the applied [15N]TNT was degraded and 52 to 64% was found as nonextractable residues in the soil matrix. Three percent was detected as 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene.

Using the natural 15N abundance to assess the main nitrogen inputs into the sand dune area of the north-western Negev Desert (Israel).

The variation of the natural 15N abundance is often used to evaluate the origin of nitrogen or the pathways of N input into ecosystems. We tried to use this approach to assess the main input pathways of nitrogen into the sand dune area of the north-western Negev Desert (Israel). The following two pathways are the main sources for nitrogen input into the system: i. Biological fixation of atmospheric nitrogen by cyanobacteria present in biological crusts and by N2-fixing vascular plants (e.g. the shrub Retama raetam); ii. Atmospheric input of nitrogen by wet deposition with rainfall, dry deposition of dust containing N compounds, and gaseous deposition. Samples were taken from selected environmental compartments such as biological crusts, sand underneath these crusts (down to a depth of 90 cm), N2-fixing and non-N2-fixing plants, atmospheric bulk deposition as well as soil from arable land north of the sandy area in three field campaigns in March 1998, 1999 and 2000. The delta15N values measured were in the following ranges: grass -2.5/1000 to +1.5/1000; R. reatam: +0.5/1000 to +4.5/1000; non-N2-fixing shrubs +1/1000 to +7/1000; sand beneath the biological crusts +4/1000 to +20/1000 (soil depth 2-90 cm); and arable land to the north up to 10/1000. Thus, the natural 15N abundance of the different N pools varies significantly. Accordingly, it should be feasible to assess different input pathways from the various 15N abundances of nitrogen. For example, the biological N fixation rates of the Fabaceae shrub R. reatam from the 15N abundances measured were calculated to be 46-86% of biomass N derived from the atmosphere. The biological crusts themselves generally show slight negative 15N values (-3/1000 to -0.5/1000), which can be explained by biological N fixation. However, areas with a high share of lichens, which are unable to fix atmospheric nitrogen, show very negative values down to -10/1000. The atmospheric N bulk deposition, which amounts to 1.9-3.8 kg N/hayr, has a 15N abundance between 4.4/1000 and 11.6/1000 and is likely to be caused by dust from the arable land to the north. Thus, it cannot be responsible for the very negative values of lichens measured either. There must be an additional N input from the atmosphere with negative delta15N values, e.g. gaseous N forms (NOx, NH3). To explain these conflicting findings, detailed information is still needed on the wet, particulate and gaseous atmospheric deposition of nitrogen.