ALBERT

Description: This paper presents 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 nondispersive IR (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. Three means are used 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 ±3.0 μatm with an RMSE of 3.7 μatm.

Description: This study 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 an opposite effect: an O2-independent pressure response on the luminophore that increases optode O2 readings and an O2-dependent change in luminescence quenching that decreases optode O2 readings. The latter process dominates and is mainly due to a shift in the equilibrium between the sensing membrane and seawater under elevated pressures. If only the dominant O2-dependent process is considered, then the 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 for 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, which is mainly due to variability between the sensors.

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: 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: 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: 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: Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere – the "global carbon budget" – is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and methodology to quantify the five major components of the global carbon budget and their uncertainties. CO2 emissions from fossil fuels and industry (EFF) are based on energy statistics and cement production data, respectively, while emissions from land-use change (ELUC), mainly deforestation, are based on land-cover change data and bookkeeping models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The ocean CO2 sink (SOCEAN) and terrestrial CO2 sink (SLAND) are estimated with global process models constrained by observations. The resulting carbon budget imbalance (BIM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of imperfect data and understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the last decade available (2007–2016), EFF was 9.4 ± 0.5 GtC yr−1, ELUC 1.3 ± 0.7 GtC yr−1, GATM 4.7 ± 0.1 GtC yr−1, SOCEAN 2.4 ± 0.5 GtC yr−1, and SLAND 3.0 ± 0.8 GtC yr−1, with a budget imbalance BIM of 0.6 GtC yr−1 indicating overestimated emissions and/or underestimated sinks. For year 2016 alone, the growth in EFF was approximately zero and emissions remained at 9.9 ± 0.5 GtC yr−1. Also for 2016, ELUC was 1.3 ± 0.7 GtC yr−1, GATM was 6.1 ± 0.2 GtC yr−1, SOCEAN was 2.6 ± 0.5 GtC yr−1, and SLAND was 2.7 ± 1.0 GtC yr−1, with a small BIM of −0.3 GtC. GATM continued to be higher in 2016 compared to the past decade (2007–2016), reflecting in part the high fossil emissions and the small SLAND consistent with El Niño conditions. The global atmospheric CO2 concentration reached 402.8 ± 0.1 ppm averaged over 2016. For 2017, preliminary data for the first 6–9 months indicate a renewed growth in EFF of +2.0 % (range of 0.8 to 3.0 %) based on national emissions projections for China, USA, and India, and projections of gross domestic product (GDP) corrected for recent changes in the carbon intensity of the economy for the rest of the world. This living data update documents changes in the methods and data sets used in this new global carbon budget compared with previous publications of this data set (Le Quéré et al., 2016, 2015b, a, 2014, 2013). All results presented here can be downloaded from https://doi.org/10.18160/GCP-2017 (GCP, 2017).