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: Oxygen optode measurements on floats and gliders suffer from a slow time response and various sources of drift in the calibration coefficients. Based on two dual-O2 Argo floats, we show how to post-correct for the effect of the optode's time response and give an update on optode in situ drift stability and in-air calibration. Both floats are equipped with an unpumped Aanderaa 4330 optode and a pumped Sea-Bird SBE63 optode. Response times for the pumped SBE63 were derived following Bittig et al. (2014) and the same methods were used to correct the time response bias. Using both optodes on each float, the time response regime of the unpumped Aanderaa optode was characterized more accurately than previously possible. Response times for the pumped SBE63 on profiling floats are in the range of 25–40 s, while they are between 60 and 95 s for the unpumped 4330 optode. Our parameterization can be employed to post-correct the slow optode time response on floats and gliders. After correction, both sensors agree to within 2–3 µmol kg−1 (median difference) in the strongest gradients (120 µmol kg−1 change over 8 min or 20 dbar) and better elsewhere. However, time response correction is only possible if measurement times are known, i.e., provided by the platform as well as transmitted and stored with the data. The O2 in-air measurements show a significant in situ optode drift of −0.40 and −0.27 % yr−1 over the available 2 and 3 years of deployment, respectively. Optode in-air measurements are systematically biased high during midday surfacings compared to dusk, dawn, and nighttime. While preference can be given to nighttime surfacings to avoid this in-air calibration bias, we suggest a parameterization of the daytime effect as a function of the Sun's elevation to be able to use all data and to better constrain the result. Taking all effects into account, calibration factors have an uncertainty of 0.1 %. In addition, in-air calibration factors vary by 0.1–0.2 % when using different reanalysis models as a reference. The overall accuracy that can be achieved following the proposed correction routines is better than 1 µmol kg−1.

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 present measurements of pCO2, O2 concentration, biological oxygen saturation (ΔO2/Ar), and N2 saturation (ΔN2) in Southern Ocean surface waters during austral summer, 2010–2011. Phytoplankton biomass varied strongly across distinct hydrographic zones, with high chlorophyll a (Chl a) concentrations in regions of frontal mixing and sea ice melt. pCO2 and ΔO2/Ar exhibited large spatial gradients (range 90 to 450 µatm and −10 to 60%, respectively) and covaried strongly with Chl a. However, the ratio of biological O2 accumulation to dissolved inorganic carbon (DIC) drawdown was significantly lower than expected from photosynthetic stoichiometry, reflecting the differential time scales of O2 and CO2 air-sea equilibration. We measured significant oceanic CO2 uptake, with a mean air-sea flux (~ −10 mmol m−2 d−1) that significantly exceeded regional climatological values. N2 was mostly supersaturated in surface waters (mean ΔN2 of +2.5%), while physical processes resulted in both supersaturation and undersaturation of mixed layer O2 (mean ΔO2phys = 2.1%). Box model calculations were able to reproduce much of the spatial variability of ΔN2 and ΔO2phys along the cruise track, demonstrating significant effects of air-sea exchange processes (e.g., atmospheric pressure changes and bubble injection) and mixed layer entrainment on surface gas disequilibria. Net community production (NCP) derived from entrainment-corrected surface ΔO2/Ar data, ranged from ~ −40 to 〉 300 mmol O2 m−2 d−1 and showed good coherence with independent NCP estimates based on seasonal mixed layer DIC deficits. Elevated NCP was observed in hydrographic frontal zones and stratified regions of sea ice melt, reflecting physical controls on surface water light fields and nutrient availability.

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.