Ammonium and nitrite oxidation at nanomolar oxygen concentrations in oxygen minimum zone waters.

A major percentage of fixed nitrogen (N) loss in the oceans occurs within nitrite-rich oxygen minimum zones (OMZs) via denitrification and anammox. It remains unclear to what extent ammonium and nitrite oxidation co-occur, either supplying or competing for substrates involved in nitrogen loss in the OMZ core. Assessment of the oxygen (O2) sensitivity of these processes down to the O2 concentrations present in the OMZ core (<10 nmol⋅L(-1)) is therefore essential for understanding and modeling nitrogen loss in OMZs. We determined rates of ammonium and nitrite oxidation in the seasonal OMZ off Concepcion, Chile at manipulated O2 levels between 5 nmol⋅L(-1) and 20 µmol⋅L(-1) Rates of both processes were detectable in the low nanomolar range (5-33 nmol⋅L(-1) O2), but demonstrated a strong dependence on O2 concentrations with apparent half-saturation constants (Kms) of 333 ± 130 nmol⋅L(-1) O2 for ammonium oxidation and 778 ± 168 nmol⋅L(-1) O2 for nitrite oxidation assuming one-component Michaelis-Menten kinetics. Nitrite oxidation rates, however, were better described with a two-component Michaelis-Menten model, indicating a high-affinity component with a Km of just a few nanomolar. As the communities of ammonium and nitrite oxidizers were similar to other OMZs, these kinetics should apply across OMZ systems. The high O2 affinities imply that ammonium and nitrite oxidation can occur within the OMZ core whenever O2 is supplied, for example, by episodic intrusions. These processes therefore compete with anammox and denitrification for ammonium and nitrite, thereby exerting an important control over nitrogen loss.

A new highly sensitive method to assess respiration rates and kinetics of natural planktonic communities by use of the switchable trace oxygen sensor and reduced oxygen concentrations.

Oxygen respiration rates in pelagic environments are often difficult to quantify as the resolutions of our methods for O2 concentration determination are marginal for observing significant decreases during bottle incubations of less than 24 hours. Here we present the assessment of a new highly sensitive method, that combine Switchable Trace Oxygen (STOX) sensors and all-glass bottle incubations, where the O2 concentration was artificially lowered. The detection limit of respiration rate by this method is inversely proportional to the O2 concentration, down to <2 nmol L(-1) h(-1) for water with an initial O2 concentration of 500 nmol L(-1). The method was tested in Danish coastal waters and in oceanic hypoxic waters. It proved to give precise measurements also with low oxygen consumption rates (∼7 nmol L(-1) h(-1)), and to significantly decrease the time required for incubations (≤14 hours) compared to traditional methods. This method provides continuous real time measurements, allowing for a number of diverse possibilities, such as modeling the rate of oxygen decrease to obtain kinetic parameters. Our data revealed apparent half-saturation concentrations (Km values) one order of magnitude lower than previously reported for marine bacteria, varying between 66 and 234 nmol L(-1) O2. Km values vary between different microbial planktonic communities, but our data show that it is possible to measure reliable respiration rates at concentrations ∼0.5-1 µmol L(-1) O2 that are comparable to the ones measured at full air saturation.

Aquatic respiration rate measurements at low oxygen concentrations.

Despite its huge ecological importance, microbial oxygen respiration in pelagic waters is little studied, primarily due to methodological difficulties. Respiration measurements are challenging because of the required high resolution of oxygen concentration measurements. Recent improvements in oxygen sensing techniques bear great potential to overcome these limitations. Here we compare 3 different methods to measure oxygen consumption rates at low oxygen concentrations, utilizing amperometric Clark type sensors (STOX), optical sensors (optodes), and mass spectrometry in combination with (18-18)O2 labeling. Oxygen concentrations and consumption rates agreed well between the different methods when applied in the same experimental setting. Oxygen consumption rates between 30 and 400 nmol L(-1) h(-1) were measured with high precision and relative standard errors of less than 3%. Rate detection limits in the range of 1 nmol L(-1) h(-1) were suitable for rate determinations in open ocean water and were lowest at the lowest applied O2 concentration.