Nitrous oxide (N2O) is a powerful greenhouse gas and a major cause of stratospheric ozone depletion, yet its sources and sinks remain poorly quantified in the oceans. We used isotope tracers to directly measure N2O reduction rates in the eastern tropical North Pacific. Because of incomplete denitrification, N2O cycling rates are an order of magnitude higher than predicted by current models in suboxic regions, and the spatial distribution suggests strong dependence on both organic carbon and dissolved oxygen concentrations. Furthermore, N2O turnover is 20 times higher than the net atmospheric efflux. The rapid rate of this cycling coupled to an expected expansion of suboxic ocean waters implies future increases in N2O emissions.

Biologically available nitrogen limits photosynthesis in much of the world ocean. Organic matter (OM) stoichiometry had been thought to control the balance between the two major nitrogen removal pathways-denitrification and anammox-but the expected proportion of 30% anammox derived from mean oceanic OM is rarely observed in the environment. With incubations designed to directly test the effects of stoichiometry, however, we showed that the ratio of anammox to denitrification depends on the stoichiometry of OM supply, as predicted. Furthermore, observed rates of nitrogen loss increase with the magnitude of OM supply. The variable ratios between denitrification and anammox previously observed in the ocean are thus attributable to localized variations in OM quality and quantity and do not necessitate a revision to the global nitrogen cycle.

The Eastern Tropical South Pacific oxygen minimum zone (ETSP‐OMZ) is a site of intense nitrous oxide (N2O) flux to the atmosphere. This flux results from production of N2O by nitrification and denitrification, but the contribution of the two processes is unknown. The rates of these pathways and their distributions were measured directly using 15N tracers. The highest N2O production rates occurred at the depth of peak N2O concentrations at the oxic‐anoxic interface above the oxygen deficient zone (ODZ) because slightly oxygenated waters allowed (1) N2O production from both nitrification and denitrification and (2) higher nitrous oxide production yields from nitrification. Within the ODZ proper (i.e., anoxia), the only source of N2O was denitrification (i.e., nitrite and nitrate reduction), the rates of which were reflected in the abundance of nirS genes (encoding nitrite reductase). Overall, denitrification was the dominant pathway contributing the N2O production in the ETSP‐OMZ.

[1] Nitrification rates, as well as the relationships between rates and ammonia oxidizer abundance (both archaeal and bacterial), were investigated in the Arabian Sea. Ammonia oxidation rates were measured directly using 15 N-NH 4 + stable isotope additions in gas-impermeable, trace metal clean trilaminate bags (500 mL) at in situ temperature. Tracer incubations were performed at three stations at depths above, below, and within the oxycline of the open-ocean oxygen minimum zone (OMZ). Ammonia oxidation rates were similar to previous open-ocean measurements, ranging from undetectable to 21.The highest rates at each station occurred at the primary nitrite maximum (above the OMZ), and rates were very low at depths greater than 900 m. The abundances of both ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) were estimated using the amoA gene by quantitative polymerase chain reaction (qPCR). Both AOA and AOB amoA were detected above, within, and below the OMZ, although the AOA were always more abundant than the AOB, by a factor of 35-216. Nitrification rates were not directly correlated to AOA or AOB amoA abundance. These rates offer new insight into the role of nitrification in the mesopelagic zone. The abundance of AOA amoA genes at 1000 m suggests that $50% of the microbial biomass could be autotrophic. Additionally, the integrated nitrification rate at depth implies that nitrification could consume most of the ammonium produced by the flux of organic carbon in the mesopelagic zone.

The Eastern Tropical South Pacific is one of the three major oxygen deficient zones (ODZs) in the global ocean and is responsible for approximately one third of marine water column nitrogen loss. It is the best studied of the ODZs and, like the others, features a broad nitrite maximum across the low oxygen layer. How the microbial processes that produce and consume nitrite in anoxic waters interact to sustain this feature is unknown. Here we used 15 N-tracer experiments to disentangle five of the biologically mediated processes that control the nitrite pool, including a high-resolution profile of nitrogen loss rates. Nitrate reduction to nitrite likely depended on organic matter fluxes, but the organic matter did not drive detectable rates of denitrification to N 2 . However, multiple lines of evidence show that denitrification is important in shaping the biogeochemistry of this ODZ. Significant rates of anaerobic nitrite oxidation at the ODZ boundaries were also measured. Iodate was a potential oxidant that could support part of this nitrite consumption pathway. We additionally observed N 2 production from labeled cyanate and postulate that anammox bacteria have the ability to harness cyanate as another form of reduced nitrogen rather than relying solely on ammonification of complex organic matter. The balance of the five anaerobic rates measured-anammox, denitrification, nitrate reduction, nitrite oxidation, and dissimilatory nitrite reduction to ammonium-is sufficient to reproduce broadly the observed nitrite and nitrate profiles in a simple one-dimensional model but requires an additional source of reduced nitrogen to the deeper ODZ to avoid ammonium overconsumption.

Measurements show that anaerobic ammonium oxidation with nitrite (anammox) is a major pathway of fixed nitrogen removal in the anoxic zones of the open ocean. Anammox requires a source of ammonium, which under anoxic conditions could be supplied by the breakdown of sinking organic matter via heterotrophic denitrification. However, at many locations where anammox is measured, denitrification rates are small or undetectable. Alternative sources of ammonium have been proposed to explain this paradox, for example through dissimilatory reduction of nitrate to ammonium and transport from anoxic sediments. However, the relevance of these sources in open-ocean anoxic zones is debated. Here, we bring to attention an additional source of ammonium, namely, the daytime excretion by zooplankton and micronekton migrating from the surface to anoxic waters. We use a synthesis of acoustic data to show that, where anoxic waters occur within the water column, most migrators spend the daytime within them. Although migrators export only a small fraction of primary production from the surface, they focus excretion within a confined depth range of anoxic water where particle input is small. Using a simple biogeochemical model, we suggest that, at those depths, the source of ammonium from organisms undergoing diel vertical migrations could exceed the release from particle remineralization, enhancing in situ anammox rates. The contribution of this previously overlooked process, and the numerous uncertainties surrounding it, call for further efforts to evaluate the role of animals in oxygen minimum zone biogeochemistry.anammox | denitrification | oxygen minimum zone | diel vertical migration W ater column oxygen minimum zones (OMZs), where oxygen concentrations plummet to submicromolar levels (1), are responsible for approximately one-third of the total removal of fixed nitrogen from the oceans (2, 3). Several processes mediated by specialized prokaryotes convert fixed inorganic nitrogen (NH 4 + , NO 2 − , and NO 3 − ) to N 2 in anoxic waters. Canonical denitrification, consisting of dissimilatory NO 3 − reduction to NO 2 − (DNRN) followed by the further oxidation of organic matter with NO 2 − (the denitrification step), was long considered the dominant fixed N removal pathway in anoxic waters. Over the last decade, anammox has gained attention as a major sink of fixed N in nearly anoxic waters (O 2 < 10 mmol·m −3 ) (4, 5).Stoichiometric considerations would suggest a close coupling between denitrification and anammox (6, 7). Under anoxic conditions, the NH 4 + liberated by the remineralization of organic matter through DNRN and denitrification should accumulate in the water column because conventional (aerobic) nitrification cannot proceed. However, this accumulation is not observed in the cores of anoxic waters, where observed NH 4 + concentrations are generally much less than 1 mmol·m −3 (8). In these regions, oxidation of NH 4 + with NO 2 − by anammox is thought to be the major sink of NH 4 + (9). Given that no significant NH 4 + acc...

Oceanic oxygen deficient zones (ODZs) influence global biogeochemical cycles in a variety of ways, most notably by acting as a sink for fixed nitrogen (Codispoti et al. 2001). Optimum multiparameter analysis of data from two cruises in the Eastern Tropical North Pacific (ETNP) was implemented to develop a water mass analysis for the large ODZ in this region. This analysis reveals that the most pronounced oxygen deficient conditions are within the 13 C water (13CW) mass, which is distributed via subsurface mesoscale features such as eddies branching from the California Undercurrent. Nitrite accumulates within these eddies and slightly below the core of the 13CW. This water mass analysis also reveals that the 13CW and deeper Northern Equatorial Pacific Intermediate Water (NEPIW) act as the two Pacific Equatorial source waters to the California Current System. The Equatorial Subsurface Water and Subtropical Subsurface Water are synonymous with the 13CW and this study refers to this water mass as the 13CW based on its history. Since the 13CW has been found to dominate the most pronounced oxygen deficient conditions within the Eastern Tropical South Pacific ODZ and the Peru-Chile Undercurrent, the 13CW and the NEPIW define boundaries for oxygen minimum conditions across the entire eastern Pacific Ocean.

A key challenge in origins‐of‐life studies is estimating the abundances of species relevant to the chemical pathways proposed to have contributed to the emergence of life on early Earth. Dissolved nitrogen oxide anions ( NOX−), in particular nitrate ( NO3−) and nitrite ( NO2−), have been invoked in diverse origins‐of‐life chemistry, from the oligomerization of RNA to the emergence of protometabolism. Recent work has calculated the supply of NOX− from the prebiotic atmosphere to the ocean and reported steady state [ NOX−] to be high across all plausible parameter space. These findings rest on the assumption that NOX− is stable in natural waters unless processed at a hydrothermal vent. Here, we show that NOX− is unstable in the reducing environment of early Earth. Sinks due to ultraviolet photolysis and reactions with reduced iron (Fe2+) suppress [ NOX−] by several orders of magnitude relative to past predictions. For pH = 6.5–8 and T = 0–50 °C, we find that it is most probable that [ NOX−]  <1μM in the prebiotic ocean. On the other hand, prebiotic ponds with favorable drainage characteristics may have sustained [ NOX−]  ≥1μM. As on modern Earth, most NOX− on prebiotic Earth should have been present as NO3−, due to its much greater stability. These findings inform the kind of prebiotic chemistries that would have been possible on early Earth. We discuss the implications for proposed prebiotic chemistries and highlight the need for further studies of NOX− kinetics to reduce the considerable uncertainties in predicting [ NOX−] on early Earth.