ALBERT

Description: The potential of a continuous wave cavity ringdown spectrometer for monitoring the isotope ratio 13CO2/12CO2 and the partial pressure pCO2 of CO2 dissolved in water was thoroughly analyzed by quantitative measurements. Running calibration gas standards under typical operation conditions, a relative accuracy of D(d13C[CO2]) = ±0.1‰ with 120 min averaging time has been demonstrated. Absolute uncertainties were determined to be D(d13C[CO2]) = ±0.2‰ and D(xCO2) = ±0.5 ppmv. No principle problems were encountered when using the instrument in combination with a water-air equilibration setup. By contrast, when performing measurements of CO2 in gas matrices with a composition different from that of ambient air, pressure broadening linewidth effects induced significant errors in both d13C(CO2) and xCO2 values. These effects, which compromise the accessible accuracy in environmental studies, can be quantitatively taken into account by using a spectroscopically based correction procedure. Relying on linewidth analysis, the instrument was shown to be capable of continuous and simultaneous measurement of d13C(CO2), pCO2, as well as water content and O2 supersaturation, and thus holds the potential for online monitoring of these quantities aboard research vessels.

Description: 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.

Description: 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.

Description: 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.