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As a key biogeochemical pathway in the marine nitrogen cycle, nitrification (ammonia oxidation and nitrite oxidation) converts the most reduced form of nitrogen – ammonium/ammonia (NH4+/ NH3) into the oxidized species nitrite (NO2−) and nitrate (NO3−). In the ocean, these processes are mainly performed by ammonia-oxidizing archaea (AOA) and bacteria (AOB), and nitrite-oxidizing bacteria (NOB). By transforming nitrogen speciation and providing substrates for nitrogen removal, nitrification affects microbial community structure, marine productivity (including chemoautotrophic carbon fixation) and the production of a powerful greenhouse gas, nitrous oxide (N2O). Nitrification is hypothesized to be regulated by temperature, oxygen, light, substrate concentration, substrate flux, pH, and other environmental factors. Although the number of field observations from various oceanic regions has increased considerably over the last few decades, a global synthesis is lacking, and understanding how environmental factors control nitrification remains elusive. Therefore, we have compiled a database of nitrification rates and nitrifier abundance in the global ocean from published literature and unpublished datasets. This database includes 2393 and 1006 measurements of ammonia oxidation and nitrite oxidation rates, and 2187 and 631 quantifications of ammonia oxidizers and nitrite oxidizers, respectively. This community effort confirms and enhances our understanding of the spatial distribution of nitrification and nitrifiers, and their corresponding drivers such as the important role of substrate concentration in controlling nitrification rates and nitrifier abundance. Some conundrums are also revealed including the inconsistent observations of light limitation and high rates of nitrite oxidation reported from anoxic waters. This database can be used to constrain the distribution of marine nitrification, to evaluate and improve biogeochemical models of nitrification, and to quantify the impact of nitrification on ecosystem functions like marine productivity and N2O production. This database additionally sets a baseline for comparison with future observations and guides future exploration (e.g., measurements in the poorly sampled regions such as the Indian Ocean; method comparison/standardization). The database is publicly available at Zenodo repository: https://doi.org/10.5281/zenodo.7942922 (Tang et al., 2023).

Aquatic sediments play a critical role in moderating the availability of fixed nitrogen (N) in the biosphere. Microbial N cycling processes, such as denitrification and anammox, contribute to fixed‑N removal as N2 gas from lakes and the ocean. N‑isotopic measurements of dissolved inorganic N (e.g., nitrate (NO3-)) can provide insights into the different sources, sinks, and pathways of N, if the associated N isotope signatures/effects are constrained. While substantial work has been done to resolve N‑loss using microbial metagenomic‑based approaches and rate measurements, how nitrogen‑loss processes imprint natural‑abundance isotopes of 15N and 18O of NO3- remains largely understudied in freshwater lake sediments. Current marine evidence suggests that water column denitrification involves high NO3- isotope effects (>20‰). In contrast, the marine NO3- isotope effect of sedimentary denitrification is suppressed at the level of the sediment‑water interface (apparent N/O isotope effect, εapp

Natural and engineered nitrogen (N) removal processes in aqueous systems represent important sources of nitrogenous gas emissions, including the potent greenhouse gas nitrous dioxide (N2O). The relevance of microbial and abiotic formation pathways can be assessed using 15N tracing techniques. While 15N-N2O analysis using optical analyzers is straightforward, quantification of 15N fractions in inorganic N compounds, ammonium (NH4+), nitrite (NO2-), and nitrate (NO3-), is typically time-consuming and labor-intensive.In this study, we developed an automated sample-preparation unit coupled to a membrane-inlet quadrupole mass spectrometer (3n-ASSP-MIMS) for the online quasi-simultaneous analysis of 15N fractions in NH4+, NO2-, and NO3-. The technique was designed and validated for applications at moderate (100 - 200 μmol L-1) to high (2 – 3 mmol L-1) N, as found in sewer systems, wastewater in treatment plants, or eutrophic surface waters, and 15N spiking (f15) between 1 and 33%.The potential of 3n-ASSP-MIMS was demonstrated in a feasibility study, where the technique, in conjunction with 15N-N2O analyses by FTIR spectroscopy, was applied to pinpoint nitrifier denitrification as the primary N2O formation pathway during partial NH4+ oxidation to NO2- in a lab-scale sequencing batch reactor.

Marine and lacustrine benthic habitats represent hotspots of nitrogen (N) turnover, with many N transformation processes occurring simultaneously, and at high rates. More specifically, sedimentary microbial reduction of nitrate to dinitrogen (N2), and other modes of N2 production (e.g., anammox), are the most important sinks of fixed N in aquatic environments. Natural abundance stable isotope ratio measurements can be employed to help disentangling N-loss mechanisms, given that the isotope effects (e) associated with each process are well studied.In our study, we surveyed an array of lacustrine and marine benthic environments and assessed the isotopic composition (d15N and d18O) of porewater ammonium (NH4+) and nitrate (NO3-) – the key substrates driving the various N transformation pathways, such as denitrification, anammox, nitrification and dissimilatory nitrate reduction to ammonium (DNRA). We further examined how benthic N isotope dynamics vary in different sedimentary regimes, with distinct organic matter (OM) mineralization rates. We expect the relative importance of the various N pathways to affect the NH4+ and/or NO3- isotope pools differentially.Our preliminary porewater d15N-NH4+ results suggest a diverse pattern with regard to the isotope enrichments between oligotrophic lakes, characterized by relatively strong depth gradients, and eutrophic lakes, where no significant depth gradient was observed. We hypothesize that this distinction could be attributed to different organic N availability and/or anammox contributions in the surveyed environments. Furthermore, we compared rate measurements (based on 15N addition experiments) to the N and O nitrate isotopic signatures to quantify processes, such as denitrification and DNRA. To investigate N isotope fractionation within the narrow nitracline, we employed the whole-core squeeze method, which provided a high-resolution porewater NO3-profile. Using this method, we found that the calculated community nitrate consumption e values at the nitracline (eelim_porewater) showed strong variability among the surveyed settings. We attribute such variation to shifts in the relative importance of denitrification versus DNRA and anammox between lakes of different trophic states. Overall, eelim_porewater wasconsiderably below 25‰ – the value generally reported for the biological isotope effect of denitrification (edenit).

Oxygen minimum zones (OMZs), due to their large volumes of perennially deoxygenated waters, are critical regions for understanding how the interplay between anaerobic and aerobic nitrogen (N) cycling microbial pathways affects the marine N budget. Here, we present a suite of measurements of the most significant OMZ N cycling rates, which all involve nitrite (NO2-) as a product, reactant, or intermediate, in the eastern tropical North Pacific (ETNP) OMZ. These measurements and comparisons to data from previously published OMZ cruises present additional evidence that NO3- reduction is the predominant OMZ N flux, followed by NO2- oxidation back to NO3-. The combined rates of both of these N recycling processes were observed to be much greater (up to nearly 200 times) than the combined rates of the N loss processes of anammox and denitrification, especially in waters near the anoxic–oxic interface. We also show that NO2- oxidation can occur when O2 is maintained near 1 nM by a continuous-purge system, NO2- oxidation and O2 measurements that further strengthen the case for truly anaerobic NO2- oxidation. We also evaluate the possibility that NO2- dismutation provides the oxidative power for anaerobic NO2- oxidation. The partitioning of N loss between anammox and denitrification differed widely from stoichiometric predictions of at most 29 % anammox; in fact, N loss rates at many depths were entirely due to anammox. Our new NO3- reduction, NO2- oxidation, dismutation, and N loss data shed light on many open questions in OMZ N cycling research, especially the possibility of truly anaerobic NO2- oxidation.

RATIONALE Obtaining nitrous oxide isotopocule measurements with isotope ratio mass spectrometry (IRMS) involves analyzing the ion current ratios of the nitrous oxide parent ion (N2O+) as well as those of the NO+ fragment ion. The data analysis requires correcting for “scrambling” in the ion source, whereby the NO+ fragment ion obtains the outer N atom from the N2O molecule. While descriptions exist for this correction, and interlaboratory intercalibration efforts have been made, there has yet to be published a package of code for implementing isotopomer calibrations.METHODS We developed a user-friendly Python package (pyisotopomer) to determine two coefficients (γ and κ) that describe scrambling in the IRMS ion source, and then to use this calibration to obtain intramolecular isotope deltas in N2O samples.RESULTS With two appropriate reference materials, γ and κ can be determined robustly and accurately for a given IRMS. An additional third reference material is needed to define the zero-point of the delta scale. We show that IRMS scrambling behavior can vary with time, necessitating regular calibrations. Finally, we present an intercalibration between two IRMS laboratories, using pyisotopomer to calculate γ and κ, and to obtain intramolecular N2O isotope deltas in lake water unknowns.CONCLUSIONS Given these considerations, we discuss how to use pyisotopomer to obtain high-quality N2O isotopocule data from IRMS systems, including the use of appropriate reference materials and frequency of calibration.

Results of modern research show a relationship between emotional stress and the occurrence of autoimmune diseases as a comorbidity. The authors use EMDR therapy (Eye Movement Desensitization and Reprocessing) to treat trauma disorders. They wondered whether and to what extent this treatment also affects autoimmune processes.Parallel to the trauma-focused psychotherapy with EMDR, the thyroid hormone substitution dose was documented in patients with active Hashimoto's autoimmune thyroiditis requiring substitution. Hashimoto's autoimmune thyroiditis had already been diagnosed by a specialist and drug treatment had been initiated before starting outpatient psychotherapy.So far in five cases a decrease in autoimmune activity and a stability of the results in the follow-up between six months and one year could be observed. It is now necessary to examine whether these results can be confirmed in a larger number of patients and a diversity of therapists and whether these observations can be transferred to other somatic comorbidities.Hintergrund: Ergebnisse moderner Forschung zeigen einen Zusammenhang zwischen emotionalem Stress und dem Auftreten von Autoimmunerkrankungen als Komorbidität. Die Autorinnen setzen zur Behandlung von Traumafolgestörungen die EMDR-Therapie (Eye Movement Desensitization and Reprocessing) ein. Sie fragten sich, ob und inwieweit diese Behandlung auch auf Autoimmunprozesse wirkt.Parallel zur traumafokussierten Psychotherapie mit EMDR wurde bei Patientinnen und Patienten mit einer floriden substitutionsbedürftigen Autoimmunthyreoiditis Hashimoto die Schilddrüsenhormon-Substitutionsdosis dokumentiert. Die Autoimmunthyreoiditis Hashimoto war bereits vor Aufnahme der ambulanten Psychotherapie fachärztlicherseits diagnostiziert und eine medikamentöse Behandlung initiiert worden.Ergebnisse und Schlussfolgerung: Bisher konnte in fünf Fällen ein Rückgang der Autoimmunaktivität und eine Ergebnisstabilität in der Katamnese zwischen sechs Monaten und einem Jahr beobachtet werden. Nun gilt es zu prüfen, ob sich diese Ergebnisse bei einer größeren Anzahl von Patientinnen und Patienten und einer Diversität von Therapeutinnen und Therapeuten bestätigen lassen und ob diese Beobachtungen auf weitere somatische Komorbiditäten übertragen werden können.Schlüsselwörter: EMDR-Therapie, traumazentrierte Psychotherapie, Autoimmunthyreoiditis Hashimoto, posttraumatische BelastungsstörungEingereicht am 14.07.2022 - Revision akzeptiert am 04.10.2022.