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The nitrogen (N) cycle involves a set of N compounds transformed by plants and microbes. Some of these N compounds, such as nitrous oxide (N 2 O) or nitrate (NO 3-), are environmental pollutants jeopardizing biodiversity, human health or the global climate. The natural abundances of the common

Full-scale application of partial nitritation and anammox in a single suspended-growth sequencing batch (SBR) reactor presented here confirm the process suitable for removing nitrogen from ammonium-rich wastewater with low concentrations of BOD and suspended solids: details of simple and robust process control based on online ammonium or conductivity signals are discussed by describing the full-scale startup at three municipal plants (five reactors in total). Ammonium oxidation rates of up to 500 gN m(-3) d(-1) with conversion to N2 of over 90% are achieved in a full-scale plant, but pilot results indicate that significantly higher rates are feasible. With continuous aeration at dissolved oxygen concentrations <1 mgO2 x L(-1), the nitrite oxidation and the anammox reaction occur simultaneously, allowing increased overall performance and simplified process control compared to separate aerobic end anaerobic phases (segregated either temporally or in different reactors). Sedimentation of the sludge requires special attention only during startup. Although the observed N2O emissions were slightly higher than in conventional nitrogen removal, the overall greenhouse gas emissions were lower, mainly due to energy-saving.

We present measurements of site preference (SP) and bulk (15)N/(14)N ratios (δ(15)N(bulk)(N2O)) of nitrous oxide (N(2)O) by quantum cascade laser absorption spectroscopy (QCLAS) as a powerful tool to investigate N(2)O production pathways in biological wastewater treatment. QCLAS enables high-precision N(2)O isotopomer analysis in real time. This allowed us to trace short-term fluctuations in SP and δ(15)N(bulk)(N2O) and, hence, microbial transformation pathways during individual batch experiments with activated sludge from a pilot-scale facility treating municipal wastewater. On the basis of previous work with microbial pure cultures, we demonstrate that N(2)O emitted during ammonia (NH(4)(+)) oxidation with a SP of -5.8 to 5.6 ‰ derives mostly from nitrite (NO(2)(-)) reduction (e.g., nitrifier denitrification), with a minor contribution from hydroxylamine (NH(2)OH) oxidation at the beginning of the experiments. SP of N(2)O produced under anoxic conditions was always positive (1.2 to 26.1 ‰), and SP values at the high end of this spectrum (24.9 to 26.1 ‰) are indicative of N(2)O reductase activity. The measured δ(15)N(bulk)(N2O) at the initiation of the NH(4)(+) oxidation experiments ranged between -42.3 and -57.6 ‰ (corresponding to a nitrogen isotope effect Δδ(15)N = δ(15)N(substrate) - δ(15)N(bulk)(N2O) of 43.5 to 58.8 ‰), which is considerably higher than under denitrifying conditions (δ(15)N(bulk)(N2O) 2.4 to -17 ‰; Δδ(15)N = 0.1 to 19.5 ‰). During the course of all NH(4)(+) oxidation and nitrate (NO(3)(-)) reduction experiments, δ(15)N(bulk)(N2O) increased significantly, indicating net (15)N enrichment in the dissolved inorganic nitrogen substrates (NH(4)(+), NO(3)(-)) and transfer into the N(2)O pool. The decrease in δ(15)N(bulk)(N2O) during NO(2)(-) and NH(2)OH oxidation experiments is best explained by inverse fractionation during the oxidation of NO(2)(-) to NO(3)(-).

The study reveals that for future research on N2O isotopocules, standardisation against N2O reference material is essential to improve interlaboratory compatibility. For atmospheric monitoring activities, we suggest N2O in whole air as a unifying scale anchor.

The ocean is an important source of nitrous oxide (N 2 O) to the atmosphere, yet the factors controlling N 2 O production and consumption in oceanic environments are still not understood nor constrained. We measured N 2 O concentrations and isotopomer ratios, as well as O 2 , nutrient and biogenic N 2 concentrations, and the isotopic compositions of nitrate and nitrite at several coastal stations during two cruises off the Peru coast (~5-16°S, 75-81°W) in December 2012 and January 2013. N 2 O concentrations varied from below equilibrium values in the oxygen deficient zone (ODZ) to up to 190 nmol L À1 in surface waters. We used a 3-D-reaction-advection-diffusion model to evaluate the rates and modes of N 2 O production in oxic waters and rates of N 2 O consumption versus production by denitrification in the ODZ. Intramolecular site preference in N 2 O isotopomer was relatively low in surface waters (generally À3 to 14‰) and together with modeling results, confirmed the dominance of nitrifier-denitrification or incomplete denitrifier-denitrification, corresponding to an efflux of up to 0.6 Tg N yr À1 off the Peru coast. Other evidence, e.g., the absence of a relationship between ΔN 2 O and apparent O 2 utilization and significant relationships between nitrate, a substrate during denitrification, and N 2 O isotopes, suggest that N 2 O production by incomplete denitrification or nitrifier-denitrification decoupled from aerobic organic matter remineralization are likely pathways for extreme N 2 O accumulation in newly upwelled surface waters. We observed imbalances between N 2 O production and consumption in the ODZ, with the modeled proportion of N 2 O consumption relative to production generally increasing with biogenic N 2 . However, N 2 O production appeared to occur even where there was high N loss at the shallowest stations.

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The isotopic composition of nitrous oxide (N2O) provides useful information for evaluating N2O sources and budgets. Due to the co‐occurrence of multiple N2O transformation pathways, it is, however, challenging to use isotopic information to quantify the contribution of distinct processes across variable spatiotemporal scales. Here, we present an overview of recent progress in N2O isotopic studies and provide suggestions for future research, mainly focusing on: analytical techniques; production and consumption processes; and interpretation and modelling approaches. Comparing isotope‐ratio mass spectrometry (IRMS) with laser absorption spectroscopy (LAS), we conclude that IRMS is a precise technique for laboratory analysis of N2O isotopes, while LAS is more suitable for in situ/inline studies and offers advantages for site‐specific analyses. When reviewing the link between the N2O isotopic composition and underlying mechanisms/processes, we find that, at the molecular scale, the specific enzymes and mechanisms involved determine isotopic fractionation effects. In contrast, at plot‐to‐global scales, mixing of N2O derived from different processes and their isotopic variability must be considered. We also find that dual isotope plots are effective for semi‐quantitative attribution of co‐occurring N2O production and reduction processes. More recently, process‐based N2O isotopic models have been developed for natural abundance and 15N‐tracing studies, and have been shown to be effective, particularly for data with adequate temporal resolution. Despite the significant progress made over the last decade, there is still great need and potential for future work, including development of analytical techniques, reference materials and inter‐laboratory comparisons, further exploration of N2O formation and destruction mechanisms, more observations across scales, and design and validation of interpretation and modelling approaches. Synthesizing all these efforts, we are confident that the N2O isotope community will continue to advance our understanding of N2O transformation processes in all spheres of the Earth, and in turn to gain improved constraints on regional and global budgets.