Description: 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.

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.

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: The autonomous measurement of dissolved carbon dioxide (CO2) is of great and still increasing importance for addressing many scientific as well as socio-economic questions. Although there is a need for reliable, fast and easy-to-use instrumentation to measure the partial pressure of dissolved CO2 (pCO2) in situ, only few autonomous underwater sensors are available. Here we present the measuring principle as well as the latest development state of a commercial sensor (HydroC™/CO2, CONTROS Systems & Solutions GmbH, Kiel, Germany), which is optimized in a collaboration between the IFM-GEOMAR and the manufacturer. In situ tests and laboratory experiments are essential parts of the comprehensive optimization process, which aims at the successful autonomous long-term deployment on e.g. surface buoys, underwater observatories and floats.

Description: Autonomous chemical sensors are required to document the marine carbon dioxide system's evolving response to anthropogenic CO2 inputs, as well as impacts on short- and long-term carbon cycling. Observations will be required over a wide range of spatial and temporal scales, and measurements will likely need to be maintained for decades. Measurable CO2 system variables currently include total dissolved inorganic carbon (DIC), total alkalinity (AT), CO2 fugacity (fCO2), and pH, with comprehensive characterization requiring measurement of at least two variables. These four parameters are amenable to in situ analysis, but sustained deployment remains a challenge. Available methods encompass a broad range of analytical techniques, including potentiometry, spectrophotometry, conductimetry, and mass spectrometry. Instrument capabilities (precision, accuracy, endurance, reliability, etc.) are diverse and will evolve substantially over the time that the marine CO2 system undergoes dramatic changes. Different suites of measurements/parameters will be appropriate for different sampling platforms and measurement objectives.

Description: Ice sheets are currently ignored in global methane budgets1,2. Although ice sheets have been proposed to contain large reserves of methane that may contribute to a rise in atmospheric methane concentration if released during periods of rapid ice retreat3,4, no data exist on the current methane footprint of ice sheets. Here we find that subglacially produced methane is rapidly driven to the ice margin by the efficient drainage system of a subglacial catchment of the Greenland ice sheet. We report the continuous export of methane-supersaturated waters (CH4(aq)) from the ice-sheet bed during the melt season. Pulses of high CH4(aq) concentration coincide with supraglacially forced subglacial flushing events, confirming a subglacial source and highlighting the influence of melt on methane export. Sustained methane fluxes over the melt season are indicative of subglacial methane reserves that exceed methane export, with an estimated 6.3 tonnes (discharge-weighted mean; range from 2.4 to 11 tonnes) of CH4(aq) transported laterally from the ice-sheet bed. Stable-isotope analyses reveal a microbial origin for methane, probably from a mixture of inorganic and ancient organic carbon buried beneath the ice. We show that subglacial hydrology is crucial for controlling methane fluxes from the ice sheet, with efficient drainage limiting the extent of methane oxidation5 to about 17 per cent of methane exported. Atmospheric evasion is the main methane sink once runoff reaches the ice margin, with estimated diffusive fluxes (4.4 to 28 millimoles of CH4 per square metre per day) rivalling that of major world rivers6. Overall, our results indicate that ice sheets overlie extensive, biologically active methanogenic wetlands and that high rates of methane export to the atmosphere can occur via efficient subglacial drainage pathways. Our findings suggest that such environments have been previously underappreciated and should be considered in Earth’s methane budget.