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Nitrite oxidation rates in the ETNPWe sampled six stations in the ETNP OMZ with DO concentrations 1 µM at 100 m (Fig. 2A). Chlorophyll concentrations were also high in the upper water column (up to 5 mg m−3 at 20 m), with an SCM spanning 70–125 m (Fig. 2B). Nitrite oxidation displayed a local maximum at the base of the EZ at Station 1 (20–30 m), and then increased to higher levels ( >100 nmol L−1 day−1; Fig. 2C). This increase at 100 and 125 m corresponded with the overlap between the bottom of the SCM and the top of the SNM. Nitrite oxidation rates then reached higher values at 150 m within the SNM at Station 1. Stations 2 and 3 displayed similar nitrite oxidation rate profiles to each other, including elevated rates in the SCM (Fig. 2G, K). Nitrite oxidation rates were similar in magnitude, and peak values at the base of the EZ and in the OMZ were also similar (69–96 nmol L−1 day−1). Depth patterns tracked oceanographic differences across the three AMZ stations, as the depth of all features increased moving offshore from Stations 1 to 2 to 3. For example, the SCM extended from 105 to 155 m at Station 2, while nitrite concentrations began to increase below 100 m; nitrite oxidation rates were elevated at 140 m and declined slightly with increasing depth (Fig. 2E–G). At Station 3, the SCM (120–180 m) and SNM ( >140 m) depths were deeper, and nitrite oxidation rates increased from 100 to 200 m (Fig. 2I–K).Fig. 2: Biogeochemical depth profiles.Profiles of A, E, I dissolved oxygen (solid lines) and nitrite (data points connected by dashed lines), B, F, J chlorophyll a, C, G, K nitrite oxidation rates, and D, H, L oxygen consumption rates (OCR; data presented as mean values of five independent replicates ±1 SD) show consistent variation across A–D Station 1, E–H Station 2, and I–L Station 3 (denoted by different colors). Black horizontal lines denote the depth of the oxygen minimum zone (OMZ), and shaded areas show the secondary chlorophyll maximum (SCM) at each station. Rates measured below the SCM should be considered potential rates (see main text). Maximum chlorophyll values at Station 1 plot off-axis.Full size imageIn contrast to these three AMZ stations (Stations 1–3), rate profiles at Stations 4–6 showed peaks at the base of the EZ followed by decreases with depth and lacked a pronounced rate increase within the OMZ (Supplementary Fig. 1). Parallel measurements of ammonia oxidation rates also showed this type of pattern at all stations (Supplementary Fig. 1). Subsurface maxima in ammonia oxidation tracked variations in the EZ across all six stations, but rates were not elevated in OMZ/AMZ waters—again contrasting with nitrite oxidation rate profiles at the AMZ stations. These data accord with earlier work in OMZs showing contrasting ammonia and nitrite oxidation rate profiles, and particularly high rates of nitrite oxidation in OMZ waters6,7,8,29,30,31.Initial DO concentrations for these measurements closely matched in situ values above the SCM (where DO concentrations are higher), and starting DO ranged from 260–1500 nM for measurements in and below the SCM. These DO concentrations are generally lower than those used for previous nitrite oxidation rate measurements in OMZs6,9, but similar to work examining the oxygen affinity of nitrite oxidation22 and overall oxygen consumption16,19. Elevated nitrite oxidation in the limited number of samples (n = 5) collected below the SCM ( >125 m at Station 1, >155 m at Station 2, and >180 m at Station 3)—where little to no DO is typically available—should be considered potential rates and could have a number of possible explanations discussed below. Within the SCM, our data support the idea that nitrite oxidation contributes to ‘cryptic’ oxygen cycling15—i.e., that DO produced via oxygenic photosynthesis is rapidly consumed.Oxygen consumption via nitrite oxidationWe determined the contribution of nitrite oxidation to overall oxygen consumption via parallel measurements of OCRs using in situ optical sensor spots—which are noninvasive, provide nearly identical results as other low-level measurement approaches32, are the only effective means of achieving substantial replication, and for which sensitivity increases as DO decreases32,33. Decreases in DO were measured in both nitrite and ammonia oxidation rate sample bottles, as well as in three additional replicates, to leverage statistical power for increased sensitivity to low-level DO consumption (see “Methods”). Water column OCR profiles at all stations showed exponential declines with depth and decreasing DO concentrations (Fig. 2D, H, L and Supplementary Fig. 1). Rates were highest in the upper water column and declined sharply within the upper portion of the OMZ above the SCM. The majority of measurements within the SCM—where DO may be produced via photosynthesis—were 100 s of nmol L−1 day−1, with an overall range of 160–1380 nmol L−1 day−1. Below the SCM, DO would be available more rarely (e.g., ref. 16), and OCR measurements represent potential rates should oxygen be supplied; OCR ranged from 120 to 390 nmol L−1 day−1. OCR also tracked variations in DO across stations, with progressively steeper declines in OCR with depth from Station 6 to Station 1.These OCR results are similar to the limited previous measurements that have been conducted in OMZ regions, with some key differences. In particular, they are consistent with previous measurements of rapid DO consumption in the SCM, with OCR rates ranging from 482 to 1520 nmol-O2 L−1 day−1 in the ETSP, and from 55 to 418 nmol-O2  L−1 day−1 in the ETNP15. Earlier OCR measurements conducted in the ETNP near Stations 1 and 3 (across a wide range of DO values) likewise ranged from 420 to 828 nmol L−1 day−1 in the SCM near Station 1, and from 101 to 269 nmol L−1 day−1 in the SCM near Station 3 (ref. 16). Above the SCM, previous OCR measurements in the ETNP spanned 2260 to 662 nmol L−1 day−1 from the EZ to the edge of the OMZ; these values are lower than our measurements at 44 and 67 m depth at Station 2, but in line with our remaining measurements above the SCM. OCR reached 1610 nmol L−1 day−1 in the SCM in Namibian shelf waters and 200–400 nmol L−1 day−1 in the SCM off Peru18. Kalvelage et al.18 furthermore observed sharp decreases with depth in the ETSP, with rates declining from >1000 nmol L−1 day−1 above the SCM.This pattern of declining OCR with increasing depth and decreasing DO was also evident in our dataset and contrasted with that of nitrite oxidation rates, which were notably elevated in the SCM at the AMZ stations (Fig. 2). We directly compared nitrite oxidation rates with OCR, assuming that each mole of nitrite is oxidized using ½ mole of O2 (ref. 5). We found that nitrite oxidation systematically increased as a proportion of overall OCR at lower DO levels (Fig. 3A, B). Nitrite oxidation was responsible for up to 69% of OCR at Station 1, although most values were closer to 10–40% at Stations 2 and 3 (Fig. 3A, B). In contrast, ammonia oxidation contributed 100 s of nM represent potential rates. For OMZ edge samples, OCR values in the µM range were higher than observed in profiles—most likely due to the effects of bubbling19, which could physically break down the organic matter present in higher concentrations at these depths (Table 1). Throughout all experiments, rate magnitudes in the 100 s of nM DO concentration range (11–820 nmol L−1 day−1) were similar to profile measurements (Fig. 2), as well as to previous measurements in OMZs15,16,18,19 (see above).DO concentrations were also continuously monitored in a subset of experimental bottles, and DO consumption was consistently linear (see “Methods”). The few exceptions occurred in several experiments conducted at DO concentrations More

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