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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.

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.

Vibrational Sum Frequency Generation (VSFG) is a surface sensitive nonlinear laser spectroscopic technique, which has been widely used in physics and physical chemistry to investigate interface processes and heterogeneous chemistry. As the technique advances from basic to applied research, we have assessed its suitability for investigations of natural air-water interfaces, which are typically covered with an organic nanolayer. Vibrational spectra of natural sea surface nanolayer samples are presented. Strong signals attributable to the alkyl chains of lipids and indications for more or less soluble carbohydrate material have been found. Furthermore, the use of VSFG spectroscopy as a time-resolved detection tool for monitoring surface layer formation and its reactive decay is demonstrated. Ozone-induced film oxidation served as an example. We successfully applied VSFG to characterize the efficiency of a surface water screen sampler as well. Overall, VSFG spectroscopy turns out to be a versatile tool that can provide valuable information about composition, structure, chemical reactivity, and film formation dynamics of the sea surface nanolayer.

The acetylene reduction assay is a common method for assessing nitrogen fixation in a variety of marine and freshwater systems. The method measures ethylene, the product of the conversion of the gas acetylene to its reduced form by nitrogenase. Knowledge of the solubility of ethylene in aqueous solution is crucial to the calculation of nitrogen fixation rates and depends on the temperature and salinity of the assay conditions. Despite the increasing interest in marine nitrogen fixation, no gas solubility (Bunsen) coefficients for ethylene in seawater are published to date. Here, we provide a set of equations and present semiempirically derived Bunsen coefficients for ethylene in water (ranging from 0.069 to 0.226) for a range of temperatures and salinities that are relevant for aquatic nitrogen fixation. We apply these data to nitrogen fixation scenarios at different temperatures and salinities and stress the importance of using accurate Bunsen coefficients in nitrogen fixation assays.