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Gas exchange between the atmosphere and ocean interior profoundly impacts global climate and biogeochemistry. However, our understanding of the relevant physical processes remains limited by a scarcity of direct observations. Dissolved noble gases in the deep ocean are powerful tracers of physical air-sea interaction due to their chemical and biological inertness, yet their isotope ratios have remained underexplored. Here, we present high-precision noble gas isotope and elemental ratios from the deep North Atlantic (~32°N, 64°W) to evaluate gas exchange parameterizations using an ocean circulation model. The unprecedented precision of these data reveal deep-ocean undersaturation of heavy noble gases and isotopes resulting from cooling-driven air-to-sea gas transport associated with deep convection in the northern high latitudes. Our data also imply an underappreciated and large role for bubble-mediated gas exchange in the global air-sea transfer of sparingly soluble gases, including O 2 , N 2 , and SF 6 . Using noble gases to validate the physical representation of air-sea gas exchange in a model also provides a unique opportunity to distinguish physical from biogeochemical signals. As a case study, we compare dissolved N 2 /Ar measurements in the deep North Atlantic to physics-only model predictions, revealing excess N 2 from benthic denitrification in older deep waters (below 2.9 km). These data indicate that the rate of fixed N removal in the deep Northeastern Atlantic is at least three times higher than the global deep-ocean mean, suggesting tight coupling with organic carbon export and raising potential future implications for the marine N cycle. 

Analyses of the isotope ratios of nitrogen (¹⁵N/¹⁴N) and oxygen (¹⁸O/¹⁶O) in nitrate (NO₃⁻) with the denitrifier method require relatively high sample volumes at low concentrations (≤1 μM) to afford sufficient analyte for mass spectrometry, resulting in isotopic offsets compared to more concentrated samples of the same isotopic composition.

To uncover the origins of isotopic offsets, we analyzed the N and O isotope ratios of NO₃⁻reference materials spanning concentrations of 0.5–20 μM. We substantiated the incidence of volume‐dependent isotopic offsets, then investigated whether they resulted from (a) incomplete sample recovery during N₂O sparging, (b) blanks – bacterial, atmospheric, or in reference material solutions – and (c) oxygen atom exchange with water during the bacterial conversion of NO₃⁻to N₂O.

Larger sample volumes resulted in modest offsets in δ¹⁵N, but substantial offsets in δ¹⁸O. N₂O recovery from sparging was less complete at higher volumes, resulting in decreases in δ¹⁵N and δ¹⁸O due to associated isotope fractionation. Blanks increased detectably with volume, whereas oxygen atom exchange with water remained constant within batch analyses, being sensitive to neither sample volume nor salinity. The sizeable offsets in δ¹⁸O with volume are only partially explained by the factors considered in our analysis.

Our observations argue for bracketing of NO₃⁻samples with reference materials that emulate sample volumes (concentrations) to achieve improved measurement accuracy and foster inter‐comparability.

 

Assessment of the global budget of the greenhouse gas nitrous oxide (${\mathrm{N}}_2$O) is limited by poor knowledge of the oceanic${\mathrm{N}}_2$O flux to the atmosphere, of which the magnitude, spatial distribution, and temporal variability remain highly uncertain. Here, we reconstruct climatological${\mathrm{N}}_2$O emissions from the ocean by training a supervised learning algorithm with over 158,000${\mathrm{N}}_2$O measurements from the surface ocean—the largest synthesis to date. The reconstruction captures observed latitudinal gradients and coastal hot spots of${\mathrm{N}}_2$O flux and reveals a vigorous global seasonal cycle. We estimate an annual mean${\mathrm{N}}_2$O flux of 4.2 ± 1.0 Tg N$\cdot {\mathrm{y}}^{-1}$, 64% of which occurs in the tropics, and 20% in coastal upwelling systems that occupy less than 3% of the ocean area. This${\mathrm{N}}_2$O flux ranges from a low of 3.3 ± 1.3 Tg N$\cdot {\mathrm{y}}^{-1}$in the boreal spring to a high of 5.5 ± 2.0 Tg N$\cdot {\mathrm{y}}^{-1}$in the boreal summer. Much of the seasonal variations in global${\mathrm{N}}_2$O emissions can be traced to seasonal upwelling in the tropical ocean and winter mixing in the Southern Ocean. The dominant contribution to seasonality by productive, low-oxygen tropical upwelling systems (>75%) suggests a sensitivity of the global${\mathrm{N}}_2$O flux to El Niño–Southern Oscillation and anthropogenic stratification of the low latitude ocean. This ocean flux estimate is consistent with the range adopted by the Intergovernmental Panel on Climate Change, but reduces its uncertainty by more than fivefold, enabling more precise determination of other terms in the atmospheric${\mathrm{N}}_2$O budget.

 

Abstract. In the current era of rapid climate change, accuratecharacterization of climate-relevant gas dynamics – namely production,consumption, and net emissions – is required for all biomes, especially thoseecosystems most susceptible to the impact of change. Marine environmentsinclude regions that act as net sources or sinks for numerous climate-activetrace gases including methane (CH4) and nitrous oxide (N2O). Thetemporal and spatial distributions of CH4 and N2O are controlledby the interaction of complex biogeochemical and physical processes. Toevaluate and quantify how these mechanisms affect marine CH4 andN2O cycling requires a combination of traditional scientificdisciplines including oceanography, microbiology, and numerical modeling.Fundamental to these efforts is ensuring that the datasets produced byindependent scientists are comparable and interoperable. Equally critical istransparent communication within the research community about the technicalimprovements required to increase our collective understanding of marineCH4 and N2O. A workshop sponsored by Ocean Carbon and Biogeochemistry (OCB)was organized to enhance dialogue and collaborations pertaining tomarine CH4 and N2O. Here, we summarize the outcomes from theworkshop to describe the challenges and opportunities for near-futureCH4 and N2O research in the marine environment. 

Recent work has suggested that the oxygen deficient zone (ODZ) and overlying surface waters of the eastern tropical South Pacific (ETSP) is a potential niche for dinitrogen (N₂) fixation. Rates of dinitrogen fixation were measured in the ETSP above and within the ODZ in July 2013 using a modified¹⁵N₂bubble addition method, wherein a bubble was added, mixed, and then removed, and the isotopic enrichment of the dissolved N₂was measured directly for each incubation. N₂fixation rates in the euphotic zone ranged from below detection to 3.9 nmol L⁻¹d⁻¹and were below detection at all depths surveyed within the ODZ. Depth‐integrated rates ranged from below detection to 289.7μmol m⁻²d⁻¹. DNA and RNA of diversenifHgenes were detected at both surface waters and in the ODZ. However, the results of this study suggest that N₂fixation rates were low and contribute little to N cycling in the ETSP.

 

Dinitrogen (N₂) fixation is an important source of biologically reactive nitrogen (N) to the global ocean. The magnitude of this flux, however, remains uncertain, in part because N₂fixation rates have been estimated following divergent protocols and because associated levels of uncertainty are seldom reported—confounding comparison and extrapolation of rate measurements. A growing number of reports of relatively low but potentially significant rates of N₂fixation in regions such as oxygen minimum zones, the mesopelagic water column of the tropical and subtropical oceans, and polar waters further highlights the need for standardized methodological protocols for measurements of N₂fixation rates and for calculations of detection limits and propagated error terms. To this end, we examine current protocols of the¹⁵N₂tracer method used for estimating diazotrophic rates, present results of experiments testing the validity of specific practices, and describe established metrics for reporting detection limits. We put forth a set of recommendations for best practices to estimate N₂fixation rates using¹⁵N₂tracer, with the goal of fostering transparency in reporting sources of uncertainty in estimates, and to render N₂fixation rate estimates intercomparable among studies.