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The oxygen (O(2)) concentration in the surface ocean is influenced by biological and physical processes. With concurrent measurements of argon (Ar), which has similar solubility properties as oxygen, we can remove the physical contribution to O(2) supersaturation and determine the biological oxygen supersaturation. Biological O(2) supersaturation in the surface ocean reflects the net metabolic balance between photosynthesis and respiration, i.e., the net community productivity (NCP). We present a new method for continuous shipboard measurements of O(2)/Ar by equilibrator inlet mass spectrometry (EIMS). From these measurements and an appropriate gas exchange parametrization, NCP can be estimated at high spatial and temporal resolution. In the EIMS configuration, seawater from the ship's continuous intake flows through a cartridge enclosing a gas-permeable microporous membrane contactor. Gases in the headspace of the cartridge equilibrate with dissolved gases in the flowing seawater. A fused-silica capillary continuously samples headspace gases, and the O(2)/Ar ratio is measured by mass spectrometry. The ion current measurements on the mass spectrometer reflect the partial pressures of dissolved gases in the water flowing through the equilibrator. Calibration of the O(2)/Ar ion current ratio (32/40) is performed automatically every 2 h by sampling ambient air through a second capillary. A conceptual model demonstrates that the ratio of gases reaching the mass spectrometer is dependent on several parameters, such as the differences in molecular diffusivities and solubilities of the gases. Laboratory experiments and field observations performed by EIMS are discussed. We also present preliminary evidence that other gas measurements, such as N(2)/Ar and pCO(2) measurements, may potentially be performed with EIMS. Finally, we compare the characteristics of the EIMS with the previously described membrane inlet mass spectrometry (MIMS) approach.

Using simultaneous sub-kilometer resolution underway measurements of surface O 2 /Ar, total O 2 and p CO 2 from annual austral summer surveys in 2012, 2013 and 2014, we explore the impacts of biological and physical processes on the O 2 and p CO 2 system spatial and interannual variability at the Western Antarctic Peninsula (WAP). In the WAP, mean O 2 /Ar supersaturation was (7.6±9.1)% and mean p CO 2 supersaturation was (−28±22)%. We see substantial spatial variability in O 2 and p CO 2 including sub-mesoscale/mesoscale variability with decorrelation length scales of ~4.5 km, consistent with the regional Rossby radius. This variability is embedded within onshore–offshore gradients. O 2 in the LTER grid region is driven primarily by biological processes as seen by the median ratio of the magnitude of biological oxygen (O 2 /Ar) to physical oxygen (Ar) supersaturation anomalies (%) relative to atmospheric equilibrium (2.6), however physical processes have a more pronounced influence in the southern onshore region of the grid where we see active sea-ice melting. Total O 2 measurements should be interpreted with caution in regions of significant sea-ice formation and melt and glacial meltwater input. p CO 2 undersaturation predominantly reflects biological processes in the LTER grid. In contrast we compare these results to the Drake Passage where gas supersaturations vary by smaller magnitudes and decorrelate at length scales of ~12 km, in line with latitudinal changes in the regional Rossby radius. Here biological processes induce smaller O 2 /Ar supersaturations (mean (0.14±1.3)%) and p CO 2 undersaturations (mean (−2.8±3.9)%) than in the WAP, and pressure changes, bubble and gas exchange fluxes drive stable Ar supersaturations. [ABSTRACT FROM AUTHOR]

Southern Ocean organic carbon export plays an important role in the global carbon cycle, yet its basin-scale climatology and variability are uncertain due to limited coverage of in situ observations. In this study, a neural network approach based on the self-organizing map (SOM) is adopted to construct weekly gridded (1° x 1°) maps of organic carbon export for the Southern Ocean from 1998 to 2009. The SOM is trained with in situ measurements of O2/Ar-derived net community production (NCP) that are tightly linked to the carbon export in the mixed layer on timescales of one to two weeks and with six potential NCP predictors: photosynthetically available radiation (PAR), particulate organic carbon (POC), chlorophyll (Chl), sea surface temperature (SST), sea surface height (SSH), and mixed layer depth (MLD). This nonparametric approach is based entirely on the observed statistical relationships between NCP and the predictors and, therefore, is strongly constrained by observations. A thorough cross-validation yields three retained NCP predictors, Chl, PAR, and MLD. Our constructed NCP is further validated by good agreement with previously published, independent in situ derived NCP of weekly or longer temporal resolution through real-time and climatological comparisons at various sampling sites. The resulting November-March NCP climatology reveals a pronounced zonal band of high NCP roughly following the Subtropical Front in the Atlantic, Indian, and western Pacific sectors, and turns south-eastward shortly after the dateline. Other regions of elevated NCP include the upwelling zones off Chile and Namibia, the Patagonian Shelf, the Antarctic coast, and areas surrounding the Islands of Kerguelen, South Georgia, and Crozet. This basin-scale NCP climatology closely resembles that of the satellite POC field and observed air-sea CO2 flux. The long-term mean area-integrated NCP south of 50° S from our dataset, 17.9mmol C m-2 d-1, falls within the range of 8.3 to 24mmol C m-2d-1 from other model estimates. A broad agreement is found in the basin-wide NCP climatology among various models but with significant spatial variations, particularly in the Patagonian Shelf. Our approach provides a comprehensive view of the Southern Ocean NCP climatology and a potential opportunity to further investigate interannual and intraseasonal variability. [ABSTRACT FROM AUTHOR]

Southern Ocean organic carbon export plays an important role in the global carbon cycle, yet its basin-scale climatology and variability are uncertain due to limited coverage of in situ observations. In this study, a neural network approach based on the self-organizing map (SOM) is adopted to construct weekly gridded (1° x 1°) maps of organic carbon export for the Southern Ocean from 1998 to 2009. The SOM is trained with in situ measurements of O2/Ar-derived net community production (NCP) that are tightly linked to the carbon export in the mixed layer on timescales of 1-2 weeks, and six potential NCP predictors: photosynthetically available radiation (PAR), particulate organic carbon (POC), chlorophyll (Chl), sea surface temperature (SST), sea surface height (SSH), and mixed layer depth (MLD). This non-parametric approach is based entirely on the observed statistical relationships between NCP and the predictors, and therefore is strongly constrained by observations. A thorough cross-validation yields three retained NCP predictors, Chl, PAR, and MLD. Our constructed NCP is further validated by good agreement with previously published independent in situ derived NCP of weekly or longer temporal resolution through real-time and climatological comparisons at various sampling sites. The resulting November--March NCP climatology reveals a pronounced zonal band of high NCP roughly following the subtropical front in the Atlantic, Indian and western Pacific sectors, and turns southeastward shortly after the dateline. Other regions of elevated NCP include the upwelling zones off Chile and Namibia, Patagonian Shelf, Antarctic coast, and areas surrounding the Islands of Kerguelen, South Georgia, and Crozet. This basin-scale NCP climatology closely resembles that of the satellite POC field and observed air-sea CO2 flux. The long-term mean area-integrated NCP south of 50° S from our dataset, 14 mmolCm-\2 d-1, falls within the range of 8.3-24 mmolCm-2 d-1 from other model estimates. A broad agreement is found in the basin-wide NCP climatology among various models but with significant spatial variations, particularly in the Patagonian Shelf. Our approach provides a comprehensive view of the Southern Ocean NCP climatology and a potential opportunity to further investigate interannual and intraseasonal variability. [ABSTRACT FROM AUTHOR]

The seasonal cycle of atmospheric potential oxygen (APO ∼ O2 + 1.1 CO2) reflects three seasonally-varying ocean processes: 1) thermal in- and outgassing, 2) mixed layer net community production (NCP) and 3) deep water ventilation. Previous studies have isolated the net biological seasonal signal (i.e., the sum of NCP and ventilation), after using air-sea heat flux data to estimate the thermal signal. In this study, we resolve all three components of the APO seasonal cycle using a methodology in which the ventilation signal is estimated based on atmospheric N2O data, the thermal signal is estimated based on heat flux or atmospheric Ar/N2 data, and the production signal is inferred as a residual. The isolation of the NCP signal in APO allows for direct comparison to estimates of NCP based on satellite ocean color data, after translating the latter into an atmospheric signal using an atmospheric transport model. When applied to ocean color data using algorithms specially adapted to the Southern Ocean and APO data at three southern monitoring sites, these two independent methods converge on a similar phase and amplitude of the seasonal NCP signal in APO and yield an estimate of annual mean NCP south of 50 °S of 0.8-1.2 Pg C/yr, with corresponding annual mean NPP of ∼ 3 Pg C/yr and a mean growing season f ratio of ∼ 0.33. These results are supported by ocean biogeochemistry model simulations, in which air-sea O2 and N2O fluxes are resolved into component thermal, ventilation and (for O2) NCP contributions. [ABSTRACT FROM AUTHOR]

A three dimensional, time-evolving field of atmospheric potential oxygen (APO ~O2/N2+CO2) was estimated using surface O2, N2 and CO2 fluxes from the WHOI ocean ecosystem model to force the MATCH atmospheric transport model. Land and fossil carbon fluxes were also run in MATCH and translated into O2 tracers using assumed O2:CO2 stoichiometries. The modeled seasonal cycles in APO agree well with the observed cycles at 13 global monitoring stations, with agreement helped by including oceanic CO2 in the APO calculation. The modeled latitudinal gradient in APO is strongly influenced by seasonal rectifier effects in atmospheric transport. An analysis of the APO-vs.-CO2 mass-balance method for partitioning land and ocean carbon sinks was performed in the controlled context of the MATCH simulation, in which the true surface carbon and oxygen fluxes were known exactly. This analysis suggests uncertainty of up to ±0.2 PgC in the inferred sinks due to variability associated with sparse atmospheric sampling. It also shows that interannual variability in oceanic O2 fluxes can cause large errors in the sink partitioning when the method is applied over short timescales. However, when decadal or longer averages are used, the variability in the oceanic O2 flux is relatively small, allowing carbon sinks to be partitioned to within a standard deviation of 0.1 Pg C/yr of the true values, provided one has an accurate estimate of longterm mean O2 outgassing. [ABSTRACT FROM AUTHOR]