Keeping an eye on all the players: The combination of bulky phosphonium tags and pressurized sample infusion transforms electrospray ionization mass spectrometry into a tool capable of producing dense data on the relative concentrations of all components of a catalytic reaction, such as the palladium‐catalyzed coupling of an aryl iodide with phenylacetylene (see graph).
We present the first field application of a N2O‐based approach to correct for vertical mixing in the estimation of net community production (NCP) from mixed layer O2 measurements. Using new ship‐based observations of N2O and biological oxygen saturation anomalies (ΔO2/Ar) from the Subarctic Northeast Pacific, we provide refined mixed layer NCP estimates across contrasting hydrographic regimes and a comprehensive assessment of the methodological considerations and limitations of the approach. Increased vertical mixing coefficients at the base of the mixed layer, derived using N2O measurements, corresponded with periods of heightened wind speed and coastal upwelling. Corrections were most significant in coastal regions where the vertical supply of low‐O2 water can otherwise falsely imply net heterotrophy from negative ΔO2/Ar measurements. After correcting for the mixing flux, all coastal stations showed autotrophic signatures, with maximum NCP exceeding 100 mmol O2 m−2 d−1 in the spring and summer. Vertical fluxes were lower in off‐shelf waters but often contributed more than 50% to corrected NCP. At some oceanic stations, however, the cooccurrence of N2O minima and O2 maxima resulted in biased (overestimated) N2O corrections. Evaluating vertical fluxes in these regions remains a challenge for ship‐based studies. Nonetheless, our refined NCP estimates show better coherence with surface chlorophyll, temperature, and mixed layer depth than uncorrected values. Potential mixed layer N2O production introduces some uncertainty in the approach, but errors are likely to be small. Ultimately, this work provides rationale for the adoption of the N2O correction to refine NCP estimates, particularly in coastal waters.
Large-scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the watercolumn 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 toPublished by Copernicus Publications on behalf of the European Geosciences Union. 5892 S. T. Wilson et al.: An intercomparison of oceanic methane and nitrous oxide measurements 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.
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