This work presents two new methods to estimate oceanic alkalinity (A T), dissolved inorganic carbon (C T), pH, and pCO 2 from temperature, salinity, oxygen, and geolocation data. "CANYON-B" is a Bayesian neural network mapping that accurately reproduces GLODAPv2 bottle data and the biogeochemical relations contained therein. "CONTENT" combines and refines the four carbonate system variables to be consistent with carbonate chemistry. Both methods come with a robust uncertainty estimate that incorporates information from the local conditions. They are validated against independent GO-SHIP bottle and sensor data, and compare favorably to other state-of-the-art mapping methods. As "dynamic climatologies" they show comparable performance to classical climatologies on large scales but a much better representation on smaller scales (40-120 d, 500-1,500 km) compared to in situ data. The limits of these mappings are explored with pCO 2 estimation in surface waters, i.e., at the edge of the domain with high intrinsic variability. In highly productive areas, there is a tendency for pCO 2 overestimation due to decoupling of the O 2 and C cycles by air-sea gas exchange, but global surface pCO 2 estimates are unbiased compared to a monthly climatology. CANYON-B and CONTENT are highly useful as transfer functions between components of the ocean observing system (GO-SHIP repeat hydrography, BGC-Argo, underway observations) and permit the synergistic use of these highly complementary systems, both in spatial/temporal coverage and number of observations. Through easily and robotically-accessible observations they allow densification of more difficult-to-observe variables (e.g., 15 times denser A T and C T compared to direct measurements). At the same time, they give access to the complete carbonate system. This potential is demonstrated by an observation-based global analysis of the Revelle buffer factor, Bittig et al. Robust Estimation of CO 2 Variables and Nutrients which shows a significant, high latitude-intensified increase between +0.1 and +0.4 units per decade. This shows the utility that such transfer functions with realistic uncertainty estimates provide to ocean biogeochemistry and global climate change research. In addition, CANYON-B provides robust and accurate estimates of nitrate, phosphate, and silicate. Matlab and R code are available at https://github.com/HCBScienceProducts/.

Abstract.Here we present first observations, from instrumentation installed on moorings and a float, of unexpectedly low ( < 2 µmol kg −1 ) oxygen environments in the open waters of the tropical North Atlantic, a region where oxygen concentration does normally not fall much below 40 µmol kg −1 . The low-oxygen zones are created at shallow depth, just below the mixed layer, in the euphotic zone of cyclonic eddies and anticyclonic-modewater eddies. Both types of eddies are prone to high surface productivity. Net respiration rates for the eddies are found to be 3 to 5 times higher when compared with surrounding waters. Oxygen is lowest in the centre of the eddies, in a depth range where the swirl velocity, defining the transition between eddy and surroundings, has its maximum. It is assumed that the strong velocity at the outer rim of the eddies hampers the transport of properties across the eddies boundary and as such isolates their cores. This is supported by a remarkably stable hydrographic structure of the eddies core over periods of several months. The eddies propagate westward, at about 4 to 5 km day −1 , from their generation region off the West African coast into the open ocean. High productivity and accompanying respiration, paired with sluggish exchange across the eddy boundary, create the "dead zone" inside the eddies, so far only reported for coastal areas or lakes. We observe a direct impact of the open ocean dead zones on the marine ecosystem as such that the diurnal vertical migration of zooplankton is suppressed inside the eddies.

Abstract. Localized open-ocean low-oxygen "dead zones" in the eastern tropical North Atlantic are recently discovered ocean features that can develop in dynamically isolated water masses within cyclonic eddies (CE) and anticyclonic modewater eddies (ACME). Analysis of a comprehensive oxygen dataset obtained from gliders, moorings, research vessels and Argo floats reveals that "dead-zone" eddies are found in surprisingly high numbers and in a large area from about 4 to 22 • N, from the shelf at the eastern boundary to 38 • W. In total, 173 profiles with oxygen concentrations below the minimum background concentration of 40 µmol kg −1 could be associated with 27 independent eddies (10 CEs; 17 ACMEs) over a period of 10 years. Lowest oxygen concentrations in CEs are less than 10 µmol kg −1 while in ACMEs even suboxic (< 1 µmol kg −1 ) levels are observed. The oxygen minimum in the eddies is located at shallow depth from 50 to 150 m with a mean depth of 80 m. Compared to the surrounding waters, the mean oxygen anomaly in the core depth range (50 and 150 m) for CEs (ACMEs) is −38 (−79) µmol kg −1 . North of 12 • N, the oxygen-depleted eddies carry anomalously low-salinity water of South Atlantic origin from the eastern boundary upwelling region into the open ocean. Here water mass properties and satellite eddy tracking both point to an eddy generation near the eastern boundary. In contrast, the oxygen-depleted eddies south of 12 • N carry weak hydrographic anomalies in their cores and seem to be generated in the open ocean away from the boundary. In both regions a decrease in oxygen from east to west is identified supporting the en-route creation of the low-oxygen core through a combination of high productivity in the eddy surface waters and an isolation of the eddy cores with respect to lateral oxygen supply. Indeed, eddies of both types feature a cold sea surface temperature anomaly and enhanced chlorophyll concentrations in their center. The low-oxygen core depth in the eddies aligns with the depth of the shallow oxygen minimum zone of the eastern tropical North Atlantic. Averaged over the whole area an oxygen reduction of 7 µmol kg −1 in the depth range of 50 to 150 m (peak reduction is 16 µmol kg −1 at 100 m depth) can be associated with the dispersion of the eddies. Thus the locally increased oxygen consumption within the eddy cores enhances the total oxygen consumption in the open eastern tropical North Atlantic Ocean and seems to be an contributor to the formation of the shallow oxygen minimum zone.

The time response behavior of Aanderaa optodes model 3830, 4330, and 4330F, as well as a Sea-Bird SBE63 optode and a JFE Alec Co. Rinko dissolved oxygen sensor was analyzed both in the laboratory and in the field. The main factor for the time response is the dynamic regime, i.e., the water flow around the sensor that influences the boundary layer's dynamics. Response times can be drastically reduced if the sensors are pumped. Laboratory experiments under different dynamic conditions showed a close to linear relation between response time and temperature. Application of a diffusion model including a stagnant boundary layer revealed that molecular diffusion determines the temperature behavior, and that the boundary layer thickness was temperature independent. Moreover, field experiments matched the laboratory findings, with the profiling speed and mode of attachment being of prime importance. The time response was characterized for typical deployments on shipboard CTDs, gliders, and floats, and tools are presented to predict the response time as well as to quantify the effect on the data for a given water mass profile. Finally, the problem of inverse filtering optode data to recover some of the information lost by their time response is addressed.

The final published version of this manuscript will replace the preliminary version at the above DOI once it is available.If you would like to cite this EOR in a separate work, please use the following full citation:Fietzek, P., B. Fiedler, T. Steinhoff, and A. Körtzinger, 2013: In situ quality assessment of a novel underwater pCO2 sensor based on membrane equilibration and NDIR spectrometry.

In recent years, profiling floats, which form the basis of the successful international Argo observatory, are also being considered as platforms for marine biogeochemical research. This study showcases the utility of floats as a novel tool for combined gas measurements of CO 2 partial pressure ( pCO 2 ) and O 2 . These float prototypes were equipped with a small-sized and submersible pCO 2 sensor and an optode O 2 sensor for highresolution measurements in the surface ocean layer. Four consecutive deployments were carried out during November 2010 and June 2011 near the Cape Verde Ocean Observatory (CVOO) in the eastern tropical North Atlantic. The profiling float performed upcasts every 31 h while measuring pCO 2 , O 2 , salinity, temperature, and hydrostatic pressure in the upper 200 m of the water column. To maintain accuracy, regular pCO 2 sensor zeroings at depth and surface, as well as optode measurements in air, were performed for each profile. Through the application of data processing procedures (e.g., time-lag correction), accuracies of floatborne pCO 2 measurements were greatly improved (10-15 matm for the water column and 5 matm for surface measurements). O 2 measurements yielded an accuracy of 2 mmol kg 21. First results of this pilot study show the possibility of using profiling floats as a platform for detailed and unattended observations of the marine carbon and oxygen cycle dynamics.

Abstract. The temporal evolution of the physical and biogeochemical structure of an oxygen-depleted anticyclonic modewater eddy is investigated over a 2-month period using high-resolution glider and ship data. A weakly stratified eddy core (squared buoyancy frequency N 2 ∼ 0.1 × 10 −4 s −2 ) at shallow depth is identified with a horizontal extent of about 70 km and bounded by maxima in N 2 . The upper N 2 maximum (3-5 × 10 −4 s −2 ) coincides with the mixed layer base and the lower N 2 maximum (0.4 × 10 −4 s −2 ) is found at about 200 m depth in the eddy centre. The eddy core shows a constant slope in temperature/salinity (T /S) characteristic over the 2 months, but an erosion of the core progressively narrows down the T /S range. The eddy minimal oxygen concentrations decreased by about 5 µmol kg −1 in 2 months, confirming earlier estimates of oxygen consumption rates in these eddies.Separating the mesoscale and perturbation flow components reveals oscillating velocity finestructure (∼ 0.1 m s −1 ) underneath the eddy and at its flanks. The velocity finestructure is organized in layers that align with layers in properties (salinity, temperature) but mostly cross through surfaces of constant density. The largest magnitude in velocity finestructure is seen between the surface and 140 m just outside the maximum mesoscale flow but also in a layer underneath the eddy centre, between 250 and 450 m. For both regions a cyclonic rotation of the velocity finestructure with depth suggests the vertical propagation of near-inertial wave (NIW) energy. Modification of the planetary vorticity by anticyclonic (eddy core) and cyclonic (eddy periphery) relative vorticity is most likely impacting the NIW energy propagation. Below the low oxygen core salt-finger type double diffusive layers are found that align with the velocity finestructure.Apparent oxygen utilization (AOU) versus dissolved inorganic nitrate (NO − 3 ) ratios are about twice as high (16) in the eddy core compared to surrounding waters (8.1). A large NO − 3 deficit of 4 to 6 µmol kg −1 is determined, rendering denitrification an unlikely explanation. Here it is hypothesized that the differences in local recycling of nitrogen and oxygen, as a result of the eddy dynamics, cause the shift in the AOU : NO − 3 ratio. High NO − 3 and low oxygen waters are eroded by mixing from the eddy core and entrain into the mixed layer. The nitrogen is reintroduced into the core by gravitational settling of particulate matter out of the euphotic zone. The low oxygen water equilibrates in the mixed layer by air-sea gas exchange and does not participate in the gravitational sinking. Finally we propose a mesoscalesubmesoscale interaction concept where wind energy, mediated via NIWs, drives nutrient supply to the euphotic zone and drives extraordinary blooms in anticyclonic mode-water eddies.

Abstract. The eastern tropical North Atlantic (ETNA) features a mesopelagic oxygen minimum zone (OMZ) at approximately 300–600 m depth. Here, oxygen concentrations rarely fall below 40 µmol O2 kg−1, but are expected to decline under future projections of global warming. The recent discovery of mesoscale eddies that harbour a shallow suboxic (< 5 µmol O2 kg−1) OMZ just below the mixed layer could serve to identify zooplankton groups that may be negatively or positively affected by ongoing ocean deoxygenation. In spring 2014, a detailed survey of a suboxic anticyclonic modewater eddy (ACME) was carried out near the Cape Verde Ocean Observatory (CVOO), combining acoustic and optical profiling methods with stratified multinet hauls and hydrography. The multinet data revealed that the eddy was characterized by an approximately 1.5-fold increase in total area-integrated zooplankton abundance. At nighttime, when a large proportion of acoustic scatterers is ascending into the upper 150 m, a drastic reduction in mean volume backscattering (Sv) at 75 kHz (shipboard acoustic Doppler current profiler, ADCP) within the shallow OMZ of the eddy was evident compared to the nighttime distribution outside the eddy. Acoustic scatterers avoided the depth range between approximately 85 to 120 m, where oxygen concentrations were lower than approximately 20 µmol O2 kg−1, indicating habitat compression to the oxygenated surface layer. This observation is confirmed by time series observations of a moored ADCP (upward looking, 300 kHz) during an ACME transit at the CVOO mooring in 2010. Nevertheless, part of the diurnal vertical migration (DVM) from the surface layer to the mesopelagic continued through the shallow OMZ. Based upon vertically stratified multinet hauls, Underwater Vision Profiler (UVP5) and ADCP data, four strategies followed by zooplankton in response to in response to the eddy OMZ have been identified: (i) shallow OMZ avoidance and compression at the surface (e.g. most calanoid copepods, euphausiids); (ii) migration to the shallow OMZ core during daytime, but paying O2 debt at the surface at nighttime (e.g. siphonophores, Oncaea spp., eucalanoid copepods); (iii) residing in the shallow OMZ day and night (e.g. ostracods, polychaetes); and (iv) DVM through the shallow OMZ from deeper oxygenated depths to the surface and back. For strategy (i), (ii) and (iv), compression of the habitable volume in the surface may increase prey–predator encounter rates, rendering zooplankton and micronekton more vulnerable to predation and potentially making the eddy surface a foraging hotspot for higher trophic levels. With respect to long-term effects of ocean deoxygenation, we expect avoidance of the mesopelagic OMZ to set in if oxygen levels decline below approximately 20 µmol O2 kg−1. This may result in a positive feedback on the OMZ oxygen consumption rates, since zooplankton and micronekton respiration within the OMZ as well as active flux of dissolved and particulate organic matter into the OMZ will decline.