ALBERT

Description: Recently, measurements of oxygen concentration in the ocean-one of the most classical parameters in chemical oceanography-are experiencing a revival. This is not surprising, given the key role of oxygen for assessing the status of the marine carbon cycle and feeling the pulse of the biological pump. The revival, however, has to a large extent been driven by the availability of robust optical oxygen sensors and their painstakingly thorough characterization. For autonomous observations, oxygen optodes are the sensors of choice: They are used abundantly on Biogeochemical-Argo floats, gliders and other autonomous oceanographic observation platforms. Still, data quality and accuracy are often suboptimal, in some part because sensor and data treatment are not always straightforward and/or sensor characteristics are not adequately taken into account. Here, we want to summarize the current knowledge about oxygen optodes, their working principle as well as their behavior with respect to oxygen, temperature, hydrostatic pressure, and response time. The focus will lie on the most widely used and accepted optodes made by Aanderaa and Sea-Bird. We revisit the essentials and caveats of in-situ in air calibration as well as of time response correction for profiling applications, and provide requirements for a successful field deployment. In addition, all required steps to post-correct oxygen optode data will be discussed. We hope this summary will serve as a comprehensive, yet concise reference to help people get started with oxygen observations, ensure successful sensor deployments and acquisition of highest quality data, and facilitate post-treatment of oxygen data. In the end, we hope that this will lead to more and higher-quality oxygen observations and help to advance our understanding of ocean biogeochemistry in a changing ocean.

Description: Changes in the ventilation of the oxygen minimum zone (OMZ) of the tropical North Atlantic are studied using oceanographic data from 18 research cruises carried out between 28.5° and 23°W during 1999–2008 as well as historical data referring to the period 1972–85. In the core of the OMZ at about 400-m depth, a highly significant oxygen decrease of about 15 μmol kg−1 is found between the two periods. During the same time interval, the salinity at the oxygen minimum increased by about 0.1. Above the core of the OMZ, within the central water layer, oxygen decreased too, but salinity changed only slightly or even decreased. The scatter in the local oxygen–salinity relations decreased from the earlier to the later period suggesting a reduced filamentation due to mesoscale eddies and/or zonal jets acting on the background gradients. Here it is suggested that latitudinally alternating zonal jets with observed amplitudes of a few centimeters per second in the depth range of the OMZ contribute to the ventilation of the OMZ. A conceptual model of the ventilation of the OMZ is used to corroborate the hypothesis that changes in the strength of zonal jets affect mean oxygen levels in the OMZ. According to the model, a weakening of zonal jets, which is in general agreement with observed hydrographic evidences, is associated with a reduction of the mean oxygen levels that could significantly contribute to the observed deoxygenation of the North Atlantic OMZ.

Description: Sub-micron marine aerosol particles (PM1) were collected over the period 22 June–21 July 2011 during the RV MARIA S. MERIAN cruise MSM 18/3, which travelled from the Cape Verdean island of São Vicente to Gabon, in the process crossing the tropical Atlantic Ocean with its equatorial upwelling regime. According to air mass origin and the chemical composition of the sampled aerosol particles, three main regimes could be established. Aerosol particles in the first part of the cruise were mainly of marine origin (Region I). In the second part of the cruise, marine influences mixed with increasing influence from biomass burning (Region II). In the final part of the cruise, which approached the African mainland, the biomass burning influence became dominant (Region III). Generally, aerosol particles were dominated by sulfate (caverage = 2.0 μg m−3) and ammonium ions (caverage = 0.7 μg m−3), which were well-correlated and increased slightly over the duration of the cruise. High concentrations of water-insoluble organic carbon (WISOC; caverage = 0.4 μg m−3) were found, most likely as a result of the high oceanic productivity in this region. Water-soluble organic carbon (WSOC) concentrations increased from 0.26 μg m−3 in Region I to 2.3 μg m−3 in Region III, most likely as a result of biomass burning influences. The major organic aerosol constituents were oxalic acid, methanesulfonic acid (MSA), and aliphatic amines. MSA concentrations were quite constant during the cruise (caverage = 42 ng m−3). Aliphatic amines were most abundant in Region I, with concentrations of ~ 20 ng m−3. Oxalic acid showed the opposite trend, with average concentrations of 12 ng m−3 in Region I and 158 ng m−3 in Region III. The α-dicarbonyl compounds glyoxal and methylglyoxal were detected in the aerosol particles in the low ng m−3 range and were closely correlated with oxalic acid. MSA and aliphatic amines arise from biogenic marine sources, whereas oxalic acid and the α-dicarbonyl compounds were attributed to biomass burning. Concentrations of n-alkanes increased from 0.8 to 4.7 ng m−3 over the duration of the cruise. PAHs and hopanes were abundant only in Region III (caverage of PAHs = 0.13 ng m−3; caverage of hopanes = 0.19 ng m−3). Levoglucosan was identified in several samples obtained in Region III, with caverage = 1.9 ng m−3, which points to (aged) biomass burning influences. The organic compounds quantified in this study could explain 8.3 % of WSOC in Regions I, where aliphatic amines and MSA dominated, 3.7 % of WSOC in Region II and 2.5 % of WSOC in Region III, where oxalic acid dominated.

Description: A yet unexplained drift of (some) oxygen optodes during storage/transport and thus significant deviations from factory/laboratory calibrations have been a major handicap for autonomous oxygen observations. Optode drift appears to be systematic and is predominantly a slope effect due to reduced oxygen sensitivity. A small contribution comes from a reduced luminophore lifetime, which causes a small positive offset. A reliable in situ reference is essential to correct such a drift. Traditionally, this called for a ship-based reference cast, which poses some challenges for opportunistic float deployments. This study presents an easily implemented alternative using near-surface/in-air measurements of an Aanderaa optode on a 10-cm stalk and compares it to the more traditional approaches (factory, laboratory, and in situ deployment calibration). In-air samples show a systematic bias depending on the water saturation, which is likely caused by occasional submersions of the standard-height stalk optode. Linear regression of measured in-air supersaturation against in-water supersaturation (using ancillary meteorological data to define the saturation level) robustly removes this bias and thus provides a precise (0.2%) and accurate (1%) in situ correction that is available throughout the entire instrument’s lifetime.

Description: We investigated the effect of hydrostatic pressure of up to 6000 dbar on Aanderaa and Sea-Bird oxygen optodes both in the laboratory and in the field. The overall pressure response is a reduction in the O2 reading by 3 – 4 % per 1000 dbar which is closely linear with pressure and increases with temperature. Closer inspection reveals two superimposed processes with opposite effect: an O2-independent pressure response on the luminophore which increases optode O2 readings and an O2-dependent change in luminescence quenching which decreases optode O2 readings. The latter process dominates and is mainly due to a shift in the equilibrium between sensing membrane and sea water under elevated pressures. If only the dominant O2-dependent process is considered, Aanderaa and Sea-Bird optodes differ in their pressure response. Compensation of the O2-independent process, however, yields a uniform O2 dependence for Aanderaa optodes with standard foil and fast-response foil as well as Sea-Bird optodes. A new scheme to calculate optode O2 from raw data is proposed to account for the two processes. The overall uncertainty of the optode pressure correction amounts to 0.3 % per 1000 dbar, mainly due to variability between sensors.

Description: Die Ozeane nehmen erhebliche Kohlendioxidmengen auf und schlucken damit einen großen Teil des vom Menschen freigesetzten Treibhausgases. Eine Entwarnung ist das trotzdem nicht, denn diese Prozesse ziehen sich über Jahrhunderte hin und werden die Folgen des Klimawandels nicht verhindern können. Zudem ist kaum abzusehen, wie der Lebensraum Meer auf die zusätzliche CO2-Aufnahme reagiert.

Description: Wissenschaftler messen den Sauerstoffgehalt im Meer seit mehr als hundert Jahren routinemäßig. Mit dem Klimawandel aber ist diese Messgröße schlagartig aktuell geworden. Denn der im Meer gelöste Sauerstoff fungiert als eine Art sensibles Frühwarnsystem für Veränderungen, die der Klimawandel im Ozean verursacht. Für die kommenden Jahre steht der Masseneinsatz von Sauerstoff-sensoren bevor, die dieser Messgröße eine Renaissance bescheren dürften.

Description: Two state-of-the-art profiling floats were equipped with novel optode-based oceanographic oxygen sensors. Both floats were simultaneously deployed in the central Labrador Sea gyre on 7 September 2003. They drift at a depth of 800 db and perform weekly profiles of temperature, salinity, and oxygen in the upper 2000 m of the water column. The initial results from the first 6 months of operation are presented. Data are compared with a small hydrographic oxygen survey of the deployment site. They are further examined for measurement quality, including precision, accuracy, and drift aspects. The first 28 profiles obtained are of high quality and show no detectable sensor drift. A method of long-term drift control is described and a few suggestions for the operation protocol are provided.

Description: 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.