Temporal and Vertical Oxygen Gradients Modulate Nitrous Oxide Production in a Seasonally Anoxic Fjord: Saanich Inlet, British Columbia

Nitrous oxide (N2O) is a strong greenhouse gas and an ozone depleting agent. In marine environments, N2O is produced biologically via ammonium oxidation, nitrite, and nitrate reduction. The relative importance of these principle production pathways is strongly influenced by oxygen availability. We conducted 15N tracer experiments of N2O production in parallel with measurements of N2O concentration and natural abundance isotopes/isotopomers in Saanich Inlet, a seasonally anoxic fjord, to investigate how temporal and vertical oxygen gradients regulate N2O production pathways and rates. In April, June, and August 2018, the depth of the oxic‐anoxic interface (dissolved oxygen = 2.5 μmol L−1 isoline) progressively deepened from 110 to 160 m. Within the oxygenated and suboxic water column, N2O supersaturation coincided with peak ammonium oxidation activity. Conditions in the anoxic deep water were potentially favorable to N2O production from nitrate and nitrite reduction, but N2O undersaturation was observed indicating that N2O consumption exceeded rates of production. In October, tidal mixing introduced oxygenated water from outside the inlet, displacing the suboxic and anoxic deep water. This oxygenation event stimulated N2O production from ammonium oxidation and increased water column N2O supersaturation while inhibiting nitrate and nitrite reduction to N2O. Results from 15N tracer incubation experiments and natural abundance isotopomer measurements both implicated ammonium oxidation as the dominant N2O production pathway in Saanich Inlet, fueled by high ammonium fluxes (0.6–3.5 nmol m−2 s−1) from the anoxic depths. Partial denitrification contributed little to water column N2O production because of low availability of nitrate and nitrite

Low oxygen eddies in the eastern tropical North Atlantic: Implications for N2O cycling

Nitrous oxide (N2O) is a climate relevant trace gas, and its production in the ocean generally increases under suboxic conditions. The Atlantic Ocean is well ventilated, and unlike the major oxygen minimum zones (OMZ) of the Pacific and Indian Oceans, dissolved oxygen and N2O concentrations in the Atlantic OMZ are relatively high and low, respectively. This study, however, demonstrates that recently discovered low oxygen eddies in the eastern tropical North Atlantic (ETNA) can produce N2O concentrations much higher (up to 115 nmol L−1) than those previously reported for the Atlantic Ocean, and which are within the range of the highest concentrations found in the open-ocean OMZs of the Pacific and Indian Oceans. N2O isotope and isotopomer signatures, as well as molecular genetic results, also point towards a major shift in the N2O cycling pathway in the core of the low oxygen eddy discussed here, and we report the first evidence for potential N2O cycling via the denitrification pathway in the open Atlantic Ocean. Finally, we consider the implications of low oxygen eddies for bulk, upper water column N2O at the regional scale, and point out the possible need for a reevaluation of how we view N2O cycling in the ETNA

An automated, laser‐based measurement system for nitrous oxide isotope and isotopomer ratios at nanomolar levels

Rationale: Nitrous oxide (N2O) is an atmospheric trace gas regulating Earth's climate, and is a key intermediate of many nitrogen cycling processes in aquatic ecosystems. Laser-based technology for N2O concentration and isotopic/isotopomeric analyses has potential advantages, which include high analytical specificity, low sample size requirement and reduced cost. Methods: An autosampler with a purge-and-trap module is coupled to a cavity ring-down spectrometer to achieve automated and high-throughput measurements of N2O concentrations, N2O isotope ratios (δ15Nbulk and δ18O values) and position-specific isotopomer ratios (δ15Nα and δ15Nβ values). The system provides accuracy and precision similar to those for measurements made by traditional isotope ratio mass spectrometry (IRMS) techniques. Results: The sample sizes required were 0.01–1.1 nmol-N2O. Measurements of four N2O isotopic/isotopomeric references were cross-calibrated with those obtained by IRMS. With a sample size of 0.50 nmol-N2O, the measurement precision (1σ) for δ15Nα, δ15Nβ, δ15Nbulk and δ18O values was 0.61, 0.33, 0.41 and 0.43‰, respectively. Correction schemes were developed for sample size-dependent isotopic/isotopomeric deviations. The instrumental system demonstrated consistent measurements of dissolved N2O concentrations, isotope/isotopomer ratios and production rates in seawater. Conclusions: The coupling of an autosampler with a purge-and-trap module to a cavity ring-down spectrometer not only significantly reduces sample size requirements, but also offers comprehensive investigation of N2O production pathways by the measurement of natural abundance and tracer level isotopes and isotopomers. Furthermore, the system can perform isotopic analyses of dissolved and solid nitrogen-containing samples using N2O as the analytical proxy

Nitrous Oxide Distributions in the Oxygenated Water Column of the Sargasso Sea

This study presents dissolved nitrous oxide (N2O) concentrations in the water column at the Bermuda Atlantic Time-series Study (BATS) station and uses a subset of these measurements to estimate air-to-sea flux for four specific time points between September 2018 and June 2019. N2O concentrations at BATS were in the range of 4.0 nmol L−1–16.9 nmol L−1, with vertical profiles which were the mirror inverse of dissolved oxygen. Regardless of season, N2O concentration maxima were found within the oxygen minimum zone (OMZ). The highest maximum N2O values were observed in November and lowest in October. As the water column at BATS remains consistently at dissolved oxygen concentrations greater than 140 µmol L−1, and therefore aerobic, we assume that the bulk of N2O production occurs through nitrification. A nitrification source is supported by a correlation between excess N2O (ΔN2O) below the mixed layer, apparent oxygen utilization (AOU) and nitrate concentrations. We estimate a pooled average yield of 0.027% to 0.038% N2O from nitrification at BATS. Finally, estimates of air–sea exchange of N2O using regional average monthly wind speeds indicated that this region acts as a weak source or a sink of atmospheric N2O, and varies between months.</p