ALBERT

Description: Large-scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the water-column distribution of trace gases, including methane and nitrous oxide. Our ability as a scientific community to evaluate changes in the water-column inventories of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate concentration measurements that can be validated across different laboratory groups. This study represents the first formal international intercomparison of oceanic methane and nitrous oxide measurements whereby participating laboratories received batches of seawater samples from the subtropical Pacific Ocean and the Baltic Sea. Additionally, compressed gas standards from the same calibration scale were distributed to the majority of participating laboratories to improve the analytical accuracy of the gas measurements. The computations used by each laboratory to derive the dissolved gas concentrations were also evaluated for inconsistencies (e.g., pressure and temperature corrections, solubility constants). The results from the intercomparison and intercalibration provided invaluable insights into methane and nitrous oxide measurements. It was observed that analyses of seawater samples with the lowest concentrations of methane and nitrous oxide had the lowest precisions. In comparison, while the analytical precision for samples with the highest concentrations of trace gases was better, the variability between the different laboratories was higher: 36 % for methane and 27 % for nitrous oxide. In addition, the comparison of different batches of seawater samples with methane and nitrous oxide concentrations that ranged over an order of magnitude revealed the ramifications of different calibration procedures for each trace gas. Finally, this study builds upon the intercomparison results to develop recommendations for improving oceanic methane and nitrous oxide measurements, with the aim of precluding future analytical discrepancies between laboratories.

Description: Large scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the water-column distribution of trace gases including methane and nitrous oxide. Our ability as a scientific community to evaluate changes in the water-column inventories of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate concentration measurements which can be validated across different laboratory groups. This study represents the first formal, international, intercomparison of oceanic methane and nitrous oxide measurements whereby participating laboratories received batches of seawater samples from the subtropical Pacific and the Baltic Sea. Additionally, compressed gas standards from the same calibration scale were distributed to the majority of participating laboratories to improve the analytical accuracy of the gas measurements. The computations used by each laboratory to derive the dissolved gas concentrations were also evaluated for inconsistencies (e.g. pressure and temperature corrections, solubility constants). The results from the intercomparison and intercalibration exercises provided invaluable insights into methane and nitrous oxide measurements. It was observed that analyses of seawater samples with the lowest concentrations of methane and nitrous oxide had the lowest precisions. In comparison, while the analytical precision for samples with the highest concentrations of trace gases was better, the variability between the different laboratories was higher; 36% for methane and 27% for nitrous oxide. In addition, the comparison of different batches of seawater samples with methane and nitrous oxide concentrations that ranged over an order of magnitude revealed the ramifications of different calibration procedures for each trace gas. Overall, this paper builds upon the intercomparison results to develop a framework for improving oceanic methane and nitrous oxide measurements, with the aim of precluding future analytical discrepancies between laboratories.

Description: Autonomous measurements aboard ships of opportunity (SOOP) provide in situ data sets with high spatial and temporal coverage. In this study, we use 8 years of carbon dioxide (CO2) and methane (CH4) observations from SOOP Finnmaid to study the influence of upwelling on trace gas dynamics in the Baltic Sea. Between spring and autumn, coastal upwelling transports water masses enriched with CO2 and CH4 to the surface of the Baltic Sea. We study the seasonality, regional distribution, relaxation, and interannual variability in this process. We use reanalysed wind and modelled sea surface temperature (SST) data in a newly established statistical upwelling detection method to identify major upwelling areas and time periods. Large upwelling-induced SST decrease and trace gas concentration increase are most frequently detected around August after a long period of thermal stratification, i.e. limited exchange between surface and underlying waters. We found that these upwelling events with large SST excursions shape local trace gas dynamics and often lead to near-linear relationships between increasing trace gas levels and decreasing temperature. Upwelling relaxation is mainly driven by mixing, modulated by air–sea gas exchange, and possibly primary production. Subsequent warming through air–sea heat exchange has the potential to enhance trace gas saturation. In 2015, quasi-continuous upwelling over several months led to weak summer stratification, which directly impacted the observed trace gas and SST dynamics in several upwelling-prone areas. Trend analysis is still prevented by the observed high variability, uncertainties from data coverage, and long water residence times of 10–30 years. We introduce an extrapolation method based on trace gas–SST relationships that allows us to estimate upwelling-induced trace gas fluxes in upwelling-affected regions. In general, the surface water reverses from CO2 sink to source, and CH4 outgassing is intensified as a consequence of upwelling. We conclude that SOOP data, especially when combined with other data sets, enable flux quantification and process studies addressing the process of upwelling on large spatial and temporal scales.