Beschreibung: Nitrous oxide (N2O) is a climate relevant trace gas, and its production in the ocean generally increases under suboxic conditions. The Atlantic Ocean is well ventilated, and unlike the major oxygen minimum zones (OMZ) of the Pacific and Indian Oceans, dissolved oxygen and N2O concentrations in the Atlantic OMZ are relatively high and low, respectively. This study, however, demonstrates that recently discovered low oxygen eddies in the eastern tropical North Atlantic (ETNA) can produce N2O concentrations much higher (up to 115 nmol L−1) than those previously reported for the Atlantic Ocean, and which are within the range of the highest concentrations found in the open-ocean OMZs of the Pacific and Indian Oceans. N2O isotope and isotopomer signatures, as well as molecular genetic results, also point towards a major shift in the N2O cycling pathway in the core of the low oxygen eddy discussed here, and we report the first evidence for potential N2O cycling via the denitrification pathway in the open Atlantic Ocean. Finally, we consider the implications of low oxygen eddies for bulk, upper water column N2O at the regional scale, and point out the possible need for a reevaluation of how we view N2O cycling in the ETNA.

Beschreibung: This work presents two new methods to estimate oceanic alkalinity (AT), dissolved inorganic carbon (CT), pH, and pCO2 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 pCO2 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 pCO2 overestimation due to decoupling of the O2 and C cycles by air-sea gas exchange, but global surface pCO2 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 AT and CT 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, 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/. Introduction

Beschreibung: The eastern tropical North Atlantic (ETNA) is characterized by a highly productive coastal upwelling system and a moderate oxygen minimum zone with lowest open ocean oxygen (O2) concentrations of around 40 μmol kg−1. Only recently, the discovery of re-occurring mesoscale eddies with sometimes close to anoxic O2 concentrations (〈1 μmol kg−1) and located just below the mixed layer challenged our understanding of O2 distribution and biogeochemical processes in this area. Here, we present the first metagenomic dataset from a deoxygenated anticyclonic modewater eddy in the open waters of the ETNA. In the eddy, we observed a significantly lower bacterial diversity compared to surrounding waters, along with a significant community shift. We detected enhanced primary productivity in the surface layer of the eddy indicated by elevated chlorophyll concentrations and increased carbon uptake rates up to three times as high as in surrounding waters. Carbon uptake below the euphotic zone correlated to the presence of a specific high-light ecotype of Prochlorococcus, which is usually underrepresented in the ETNA. Our combined data indicate that high primary production in the eddy fuels export production and the presence of a specific microbial community responsible for enhanced respiration at shallow depths, below the mixed layer base. Progressively decreasing O2 concentrations in the eddy were found to promote transcription of the key gene for denitrification, nirS, in the O2-depleted core waters. This process is usually absent from the open ETNA waters. In the light of future ocean deoxygenation our results show exemplarily that even distinct events of anoxia have the potential to alter microbial community structures and with that critically impact primary productivity and biogeochemical processes of oceanic water bodies.

Beschreibung: The role of the global surface ocean as a source and sink for atmospheric carbon dioxide and the flux strengths between the ocean and the atmosphere can be quantified by measuring the fugacity of CO2 (ƒCO2) as well as the dissolved inorganic carbon (DIC) concentration and its isotopic composition in surface seawater. In this work, the potential of continuous wave cavity ringdown spectroscopy (cw-CRDS) for autonomous underway measurements of ƒCO2 and the stable carbon isotope ratio of DIC [δ13C(DIC)] is explored. For the first time, by using a conventional air-sea equilibrator setup, both quantities were continuously and simultaneously recorded during a field deployment on two research cruises following meridional transects across the Atlantic Ocean (Bremerhaven, Germany–Punta Arenas, Chile). Data are compared against reference measurements by an established underway CO2 monitoring system and isotope ratio mass spectrometric analysis of individual water samples. Agreement within ΔƒCO2 = 0.35 μatm for atmospheric and ΔƒCO2 = 2.5 μatm and Δδ13C(DIC) =0.33‰ for seawater measurements have been achieved. Whereas “calibration-free” ƒCO2 monitoring is feasible, the measurement of accurate isotope ratios relies on running reference standards on a daily basis. Overall, the installed CRDS/equilibrator system was shown to be capable of reliable online monitoring of ƒCO2, equilibrium δ13C(CO2), δ13C(DIC), and pO2 aboard moving research vessels, thus making possible corresponding measurements with high spatial and temporal resolution.

Beschreibung: We present a detailed quality assessment of a novel underwater sensor for the measurement of CO2 partial pressure (pCO2) based on surface water field deployments carried out between 2008 and 2011. The commercially available sensor, which is based on membrane equilibration and NDIR spectrometry is small and can be integrated into mobile platforms. It is calibrated in water against a proven flow-through pCO2 instrument within a custom-built calibration setup. The aspect of highest concern with respect to achievable data quality of the sensor is the compensation for signal drift inevitably connected to absorption measurements. We use three means to correct for drift effects: (i) a filter correlation or dual-beam setup, (ii) regular zero gas measurements realized automatically within the sensor and (iii) a zero-based transformation of two sensor calibrations flanking the time of sensor deployment. Three sensors were tested against an underway pCO2 system during two major research cruises providing an in situ temperature range from 7.4 to 30.1°C and pCO2 values between 289 and 445 μatm. The average difference between sensor and reference pCO2 was found to be -0.6 ± 3 μatm with a RMSE of 3.7 μatm.

Beschreibung: 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.

Beschreibung: 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.

Beschreibung: 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 CO2 partial pressure (pCO2) and O2. These float prototypes were equipped with a small-sized and submersible pCO2 sensor and an optode O2 sensor for high resolution measurements in the surface ocean layer. Four consecutive deployments were carried out during Nov. 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 pCO2, O2, salinity, temperature and hydrostatic pressure in the upper 200 m of the water column. In order to maintain accuracy, regular pCO2 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 float-borne pCO2 measurements were greatly improved (10 – 15 μatm for water column and 5 μatm for surface measurements). O2 measurements yielded an accuracy of 2 μmol kg−1. 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.

Beschreibung: We present a laboratory calibration setup for the individual multi-point calibration of oxygen sensors. It is based on the electrochemical generation of oxygen in an electrolytic carrier solution. Under thorough control of the conditions, i.e., temperature, carrier solution flow rate, and electrolytic current, the amount of oxygen is strictly given by Faraday's laws and can be controlled to within ± 0.5 μmol L–1 (2 SD). Whereas Winkler samples can be taken for referencing with a reproducibility between triplicates of 0.8 μmol L–1 (2 SD), the calibration setup can provide a Winkler-free way of referencing with an accuracy of ± 1.2 μmol L–1 (2 SD). Thus calibrated oxygen optodes have been deployed in the Southern Ocean and the Eastern Tropical Atlantic both in profiling and underway mode and confirm the validity of the laboratory calibrations to within few μmol L–1. In two cases, the optodes drifted between deployments, which was easily identified using the calibration setup. The electrochemical calibration setup may thus facilitate accurate oxygen measurements on a large scale, and its small size makes it possible to configure as a mobile, sea-going, Winkler-free system for oxygen sensor calibrations.

Beschreibung: Highlights: • The distribution of particulate matter was studied using Argo float measurements. • Its spatio-temporal properties were analyzed in the eastern tropical North Atlantic. • Surface, subsurface, intermediate and bottom nepheloid layers were considered. • High correlations between particulate matter and phytoplankton were verified. • The depth of subsurface particle maxima correlated to the distance to shore. Abstract: The spatial and temporal distribution of particulate matter in the water column of the eastern tropical North Atlantic between 16.9–22.9°N and 16.6–29.3°W was investigated using optical measurements from transmissometers mounted on Argo floats. The corresponding profiles of beam attenuation coefficients measured from February 2008 to May 2009 were used to study particulate matter in different layers such as the surface nepheloid layer (SNL), subsurface nepheloid layer (SSNL), intermediate nepheloid layer (INL) and bottom nepheloid layer (BNL) as well as to investigate sinking particles (SP). The SNL were down to about 60 m water depth at thicknesses between 20 and 60 m. Our analyses verified high correlation between particulate matter and phytoplankton in the SNL. High offshore SNL extension of up to 750 km was found in the area of Cape Blanc filaments in January 2009. Their typical widths ranged from 11 to 72 km. Furthermore, float-borne observations even resolved atmospheric dust deposition into the surface water layer during a strong Saharan dust event in October 2008. The observed dust concentration in the mixed water layer was found to vary between 0.0021 and 0.0168 g m−3 depending on applied assumptions. An abrupt change from a SNL to a SSNL regime over distances of only 80 to 90 km was observed. The particulate matter in the SSNL showed lateral extensions from 420 to 1020 km offshore. A statistically significant correlation between the depth of subsurface particle maxima and the distance to shore was found. An averaged diameter of 30 km was determined for the sharply isolated patches of INL which was consistent with model simulations of other studies. The lateral transport of particulate matter in these INL features in the area of the giant Cape Blanc filaments was found to be more pronounced than reported in earlier studies. The distribution of particulate matter within the INL filaments reached up to 610 km off the shelf edge. The frequency of INL decreased with increasing distance to shore. The sinking velocity of particulate matter of one long-term observed INL was approximately 1.3 m day−1. Highly concentrated BNLs with beam attenuation coefficients of up to 4.530 m−1 were observed in the continental slope region. INLs appeared more frequently than SP events which lead to the conclusion that the lateral transport of particulate matter in INL features in the study area was more important than their passive vertical sinking.