Construction of STOX oxygen sensors and their application for determination of O2 concentrations in oxygen minimum zones.
ABSTRACT Until recently, it has not been possible to measure O(2) concentrations in oxygen minimum zones (OMZs) with sufficient detection limits and accuracy to determine whether OMZs are anoxic or contain 1-2 μM O(2). With the introduction of the STOX (switchable trace oxygen) sensor, the level for accurate quantification has been lowered by a factor of 1000. By analysis with STOX sensors, O(2) can be prevented from reaching the sensing cathode by another cathode (front guard cathode), and it is the amplitude in signal by polarization/depolarization of this front guard that is used as a measure of the O(2) concentration. The STOX sensors can be used in situ, most conveniently connected to a conventional CTD (conductivity, temperature, and depth analyzer) along with a conventional oxygen sensor, and they can be used for monitoring O(2) dynamics during laboratory incubations of low-O(2) media such as OMZ water. The limiting factors for use of the STOX sensors are a relatively slow response, with measuring cycle of at least 30 s with the current design, and fragility. With improved procedures for construction, the time for a complete measuring cycle is expected to come down to about 10 s.
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ABSTRACT: Highly sensitive STOX O2 sensors were used for determination of in situ O2 distribution in the eastern tropical north and south Pacific oxygen minimum zones (ETN/SP OMZs), as well as for laboratory determination of O2 uptake rates of water masses at various depths within these OMZs. Oxygen was generally below the detection limit (few nmol L−1) in the core of both OMZs, suggesting the presence of vast volumes of functionally anoxic waters in the eastern Pacific Ocean. Oxygen was often not detectable in the deep secondary chlorophyll maximum found at some locations, but other secondary maxima contained up to ~0.4 µmol L−1. Directly measured respiration rates were high in surface and subsurface oxic layers of the coastal waters, reaching values up to 85 nmol L−1 O2 h−1. Substantially lower values were found at the depths of the upper oxycline, where values varied from 2–33 nmol L−1 O2 h−1. Where secondary chlorophyll maxima were found the rates were higher than in the oxic water just above. Incubation times longer than 20 h, in the all-glass containers, resulted in highly increased respiration rates. Addition of amino acids to the water from the upper oxycline did not lead to a significant initial rise in respiration rate within the first 20 h, indicating that the measurement of respiration rates in oligotrophic ocean water may not be severely affected by low levels of organic contamination during sampling. Our measurements indicate that aerobic metabolism proceeds efficiently at extremely low oxygen concentrations with apparent half-saturation concentrations (Km values) ranging from about 10 to about 200 nmol L−1.Deep Sea Research Part I Oceanographic Research Papers 12/2014; · 2.83 Impact Factor
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ABSTRACT: A major percentage (20 to 40%) of global marine fixed-nitrogen loss occurs in oxygen minimum zones (OMZs). Concentrations of O2 and the sensitivity of the anaerobic N2-producing processes of anammox and denitrification determine where this loss occurs. We studied experimentally how O2 at nanomolar levels affects anammox and denitrification rates and the transcription of nitrogen cycle genes in the anoxic OMZ off Chile. Rates of anammox and denitrification were reversibly suppressed, most likely at the enzyme level. Fifty percent inhibition of N2 and N2O production by denitrification was achieved at 205 and 297 nM O2, respectively, whereas anammox was 50% inhibited at 886 nM O2. Coupled metatranscriptomic analysis revealed that transcripts encoding nitrous oxide reductase (nosZ), nitrite reductase (nirS), and nitric oxide reductase (norB) decreased in relative abundance above 200 nM O2. This O2 concentration did not suppress the transcription of other dissimilatory nitrogen cycle genes, including nitrate reductase (narG), hydrazine oxidoreductase (hzo), and nitrite reductase (nirK). However, taxonomic characterization of transcripts suggested inhibition of narG transcription in gammaproteobacteria, whereas the transcription of anammox narG, whose gene product is likely used to oxidatively replenish electrons for carbon fixation, was not inhibited. The taxonomic composition of transcripts differed among denitrification enzymes, suggesting that distinct groups of microorganisms mediate different steps of denitrification. Sulfide addition (1 µM) did not affect anammox or O2 inhibition kinetics but strongly stimulated N2O production by denitrification. These results identify new O2 thresholds for delimiting marine nitrogen loss and highlight the utility of integrating biogeochemical and metatranscriptomic analyses.mBio 10/2014; 5(6):e01966-14. · 6.88 Impact Factor
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ABSTRACT: 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.PLoS ONE 08/2014; 9(8). · 3.53 Impact Factor