What controls the distribution of dissolved organic carbon in the surface ocean?

Posted by mmaheigan 
· Friday, November 11th, 2016 

Around 662 billion tons of organic carbon are dissolved in the ocean, making the pool one of Earth’s major, exchangeable carbon reservoirs. Dissolved organic carbon (DOC) has many ecological functions. It can form complexes with metals (1); absorb UV and visible light, acting as a “sunscreen” for marine microorganisms and controlling primary production in the upper water column (2); it has antioxidant activity, reacting with free radicals in the media (3); but most importantly, it serves as substrate for the microbial loop and as a vehicle for carbon sequestration in the ocean. Therefore, DOC plays an important role in climate on geological time scales.

Because the amount of atmospheric CO2 is of the same magnitude as the DOC pool, and is closely linked to it through exchange, variations in one of these reservoirs can affect the other, impacting the carbon cycle with consequences for climate. Significant net DOC remineralization would lead to an increase of atmospheric CO2, enhancing greenhouse warming at the surface of the Earth. Net oxidation of only 1% of the seawater DOC pool within 1 year would be sufficient to generate a CO2 flux of 7 PgC/yr, comparable to that produced annually by fossil fuel combustion (4). It has also been proposed that a large-scale oxidation of DOC may have prevented a dramatic global glaciation (‘snowball earth’) in the Neoproterozoic period (5).

Despite its importance, knowledge about DOC dynamics is relatively limited; in fact, it was considered highly inert until about three decades ago when a new analytical technique for measuring it via high-temperature catalytic oxidation stimulated new interest (6). The technique eventually provided more accurate DOC values, showing that it was more involved in the carbon cycle than previously thought and that its concentrations vary with depth, time, and location. Considering DOC distributions observed in the surface Atlantic Ocean (Fig. 1), we see values in the subtropical gyres of 65-70 µmol Kg-1, the highest concentrations in the tropics (> 70 µmol Kg-1), the lowest in the Southern Ocean (< 50 µmol Kg-1), and moderate concentrations in the northern North Atlantic (55-60 µmol Kg-1); this pattern is consistent in other ocean basins. So what controls this distribution and can we predict it? Even with improved analytical techniques, DOC is not a variable that can be measured easily at sea, and the sampling must be done carefully since it is easy to contaminate. Therefore, DOC data are typically fewer than those of other more readily determined variables such as nutrients and oxygen. If we could predict DOC from variables for which much greater global ocean coverage exists, we could fill the very large spatial and temporal gaps in the DOC fields.

DOC is produced in the upper water column by phytoplankton (primary producers). Actually, half of the inorganic carbon that is fixed by phytoplankton is transformed to DOC. Heterotrophic microbes consume most of that DOC, but ~ 4% of global annual net primary production (~ 2 Pg C y-1) (7) accumulates as DOC, much of which is exported to the mesopelagic via vertical mixing and convergence, thus contributing to the biological carbon pump.

New primary production, the foundation of a system’s net community production (NCP), depends on new nutrients reaching the euphotic zone, which happens primarily via upwelling in divergence zones and winter vertical mixing. NCP is the balance of the carbon generated by primary producers minus that lost through heterotrophic respiration (prokaryotes and animals). It can be estimated either by a loss of reactants (CO2 or nutrients) or a gain in products (suspended POC, DOC, and export production) (8).

In our work, we needed to establish the fraction of NCP that was present in dissolved form (i.e., the net DOC production ratio, or NDPr). For that, we simply estimated NCP from the nitrate (NO3–) that is consumed in the euphotic zone (DNO3–):

ΔNO3– = new NO3– (introduced from deeper layers) – remaining NO3– (at surface) (Eq. 1)

In the same way, we also calculated net accumulated DOC, or ΔDOC:

ΔDOC = DOC in euphotic zone – DOC introduced from deeper layers (Eq. 2)

The ratio between ΔDOC and ΔNO3– gave us the NDPr:

NDPr = ΔDOC/ΔNO3– (Eq. 3)

NDPr was calculated throughout the Atlantic Ocean using observations of DOC and NO3– from >15 international oceanographic cruises over the last decade, including those occupied by the US Repeat Hydrography program (Fig. 1). Values of NDPr mostly varied between 0.1 and 0.4 (Fig. 2), with the exception of the North Atlantic Subtropical Gyre (NASG), where NDPr values reach >0.8 at times. After sensitivity testing, we applied a NDPr value of 0.17 to the entire basin, which yielded the smallest error between calculated and observed DOC concentrations. Applying this NDPr value to ΔNO3– (i.e. NCP) obtained from cruise data, we estimate ΔDOC (Eq. 4), in which 6.6 is the molar conversion from N to C units:

ΔDOC= ΔNO3– * 6.6 * 0.17 = NCP * 0.17 (Eq. 4)

To obtain the calculated DOC concentration (DOCcalculated), we added the DOC concentration of underlying source waters (DOCsource) to ΔDOC (Eq. 5):

DOCcalculated = DOCsource + ΔDOC (Eq. 5)

When comparing calculated vs. observed DOC (Fig. 3), we found significant agreement (R2 = 0.64; p < 0.001; n=268) throughout the Atlantic, except in the western North Atlantic, where observed DOC > estimated DOC, especially in the southern sector. After this validation of our approach using nutrients and DOC observations, we applied the method to the more extensive NO3– distributions available in the World Atlas Ocean (WOA) climatology to develop a DOCcalculated map for the entire Atlantic (Fig. 4a). The calculated values agree well with the observations, with a total error of 8.94%.

How much DOC is annually produced in the surface Atlantic Ocean? Total organic carbon export (considered equivalent to NCP) in the Atlantic has been estimated to be 4.15-4.3 Pg C y-1 (9, 10). Applying the 0.17 NDPr (equation 3) indicates that 0.70-0.75 Pg C y-1 accumulates in the Atlantic surface as DOC; as such, the Atlantic accounts for ~36% of the global net DOC production ~2 Pg C y-1.

In permanently stratified areas like the southern sectors of the NASG, our approach is invalid since there is little nutrient input from underlying depths. Also, the static view of our approach does not take into account advection that will modify the DOC distributions, nor does it account for eventual removal of accumulated and advected DOC by microbes. To account for these influences on distributions, we applied the ΔNO3– measurements to a steady-state ocean circulation model including terrestrial DOC inputs and DOC remineralization (Fig. 4b). In the model, zonal advection is evident through enrichment of DOC in the Caribbean Sea. Also, inputs of terrestrial DOC are observed near the outflow of the Amazon River. However, the model only slightly improved the match between observations and modeled DOC, with a total error of 8.71% vs. the 8.94% obtained before the model application.

The correspondence between observations and modeled values was good, considering that we are comparing observations of DOC from cruises during specific seasons with estimates based on more idealized nutrient climatology. The main mismatch is found in the western NASG, where observations can reach 13 µmol Kg-1 higher than calculated values. Local production and/or allochthonous inputs of either new nutrients or DOC must be considered. Local production of DOC could result from addition of nitrogen from sources beyond vertical mixing such as diazotrophic N2 fixation, atmospheric deposition, and river runoff. Alternatively, DOC can be concentrated by evaporation, as is sea salt. However, none of these explain the high DOC values observed in the NASG. DOC flux estimated from dissolved organic nitrogen (DON) released by N2 fixation (11) is too low to explain the extra DOC. Regarding the atmospheric deposition, aerosol optical depth data suggest higher deposition in the eastern than in the western North Atlantic (11), and no excess of DOC is observed there. According to salinity distributions from the World Ocean Atlas, advection of DOC from the closest major rivers (Amazon and Orinoco) does not extend far enough northward to explain the NASG anomaly. Salinity normalization of DOC does not erase the feature, indicating that evaporation is not the cause. Those elevated values of carbon are found during cruises from 2003 in the same area (12), so it appears to be a persistent feature. The anomaly also coincides with a DON maximum and a light stable isotope (δ15N) composition in the particulate organic carbon based on measurements recorded in 2004 (13). An explanation for these anomalies has not been confirmed.

 

Conclusions

New nutrients are the fundamental driver of net DOC accumulation in the surface Atlantic Ocean. As such, climate-driven changes in ocean dynamics, which will affect the supply of nutrients to the euphotic zone, will affect the DOC inventory. The effects of climate change on the nutrient supply to the upper water column are not well known, but they will depend on the opposing influences of thermal stratification and upwelling intensification. Some authors predict an intensification and spatial homogenization of coastal upwelling systems (14, 15). Such would increase the nutrient input to the euphotic zone and the net DOC production. In contrast, others have reported that ocean warming should intensify thermal stratification, reducing nutrient flux by vertical mixing in regions not affected by coastal upwelling systems (16, 17). Depending on which of these phenomena dominate, the nutrient supply will change, in turn changing the DOC budget and its distribution. Furthermore, the percentage of NCP accumulating as DOC (i.e. NDPr), found here to be ~17%, could change in response to a shift in the balance of autotrophs and heterotrophs. This multitude of influencing factors will undoubtedly impact the future course of the oceanic DOC budget.

 

Authors

Cristina Romera-Castillo (Univ. of Vienna) and Dennis A. Hansell (RSMAS, Univ. Miami)

Acknowledgments

The authors thank the other co-author, Robert T. Letscher, from the more extended version of this published work. Also to Dr. X.A. Álvarez-Salgado for the use of DOC data he collected during cruises supported by the Spanish government. Data collection on US CLIVAR sections and involvement by C.R.-C. and D.A.H. were supported by US National Science Foundation OCE1436748.

References

  1. Midorikawa, T., E. Tanoue, 1998. Mar. Chem. 62, 219-239.
  2. Arrigo, K. R., C. W., Brown, 1996. Mar. Ecol. Prog. Ser. 140, 207-216.
  3. Romera-Castillo, C., R. Jaffé, 2015. Mar. Chem. 177, 668–676.
  4. Hedges, J. I. 2002. In: Hansell, D., Carlson, C. (Eds.), 2002. Biogeochemistry of marine dissolved organic matter. Academic Press, San Diego, pp. 1-33.
  5. Peltier, W. R. et al., 2007. Nature 450, 813-819.
  6. Hansell, D. A., C. A. Carlson, 2015. Eos, 96, doi:10.1029/2015EO033011.
  7. Hansell, D. A., et al., 2009. Oceanography 22, 202-211.
  8. Hansell, D. A., C. A. Carlson, 1998. Global Biogeochem. Cycles 12, 443-453.
  9. Laws, E. A., et al., 2000. Global Biogeochem. Cycles 14, 1231-1246.
  10. Dunne, J. P., et al., 2007. Global Biogeochem. Cycles 21, GB4006.
  11. Benavides, M., et al., 2013. J. Geophys. Res.: Oceans 118, 3406-3415.
  12. Carlson, C. A. et al., 2010. Deep-Sea Res. Pt II 57, 1433-1445.
  13. Landolfi, A. et al., 2016. Deep-Sea Res. Part I 111, 50-60.
  14. Sydeman, W. J. et al., 2014. Science 345, 77-80.
  15. Wang, D. et al., 2015. Nature 518, 390-394.
  16. Cermeño, P. et al., 2008. PNAS 105, 20344-20349.
  17. Bopp L, et al., 2013. Biogeosciences 10, 6225-6245.
  18. Schlitzer, R., 2015. Ocean Data View. Available at https://odv.awi.de
  19. Romera-Castillo, C. et al., 2016. PNAS 113, 10497–10502.

Filter by Keyword

abundance acidification africa air-sea interactions algae alkalinity allometry ammonium AMOC anoxic Antarctic anthro impacts anthropogenic carbon aquaculture aquatic continuum aragonite saturation arctic Argo argon arsenic artificial seawater Atlantic atmospheric CO2 atmospheric nitrogen deposition authigenic carbonates autonomous platforms bacteria bathypelagic BATS BCG Argo benthic bgc argo bio-go-ship bio-optical bioavailability biogeochemical cycles biogeochemical models biogeochemistry Biological Essential Ocean Variables biological pump biophysics bloom blue carbon bottom water boundary layer buffer capacity C14 CaCO3 calcification calcite carbon carbon-climate feedback carbon-sulfur coupling carbon budget carbon cycle carbon dioxide carbon export carbon sequestration carbon storage Caribbean CCA CCS changing marine ecosystems changing marine environments changing ocean chemistry chemical oceanographic data chemical speciation chemoautotroph chesapeake bay chl a chlorophyll circulation climate change climate variability CO2 coastal darkening coastal ocean cobalt Coccolithophores community composition conservation cooling effect copepod coral reefs CTD currents cyclone daily cycles data data access data assimilation data management data product Data standards DCM dead zone decadal trends decomposers decomposition deep convection deep ocean deep sea coral deoxygenation depth diatoms DIC diel migration diffusion dimethylsulfide dinoflagellate discrete measurements DOC DOM domoic acid dust DVM ecology ecosystems eddy Education Ekman transport emissions ENSO enzyme equatorial regions ESM estuarine and coastal carbon fluxes estuary euphotic zone eutrophication evolution export export fluxes export production EXPORTS extreme events faecal pellets filter feeders filtration rates fire fish Fish carbon fisheries floats fluid dynamics fluorescence food webs forage fish forams freshening freshwater frontal zone functional role future oceans geochemistry geoengineering geologic time GEOTRACES glaciers gliders global carbon budget global ocean global warming go-ship grazing greenhouse gas Greenland ground truthing groundwater Gulf of Maine Gulf of Mexico Gulf Stream gyre harmful algal bloom high latitude human food human impact hurricane hydrogen hydrothermal hypoxia ice age ice cores ice cover industrial onset inland waters inverse circulation ions iron iron fertilization isotopes jellies katabatic winds kelvin waves krill kuroshio lab vs field land-ocean continuum larvaceans lateral transport LGM lidar ligands light light attenuation lipids machine learning mangroves marine carbon cycle marine heatwave marine particles marine snowfall marshes Mediterranean meltwater mesopelagic mesoscale metagenome metals methane methods microbes microlayer microorganisms microscale microzooplankton midwater mixed layer mixed layers mixing mixotrophy model modeling model validation mode water molecular diffusion MPT multi-decade n2o NAAMES NASA NCP net community production net primary productivity new ocean state new technology Niskin bottle nitrate nitrogen nitrogen cycle nitrogen fixation nitrous oxide north atlantic north pacific nuclear war nutricline nutrient budget nutrient cycling nutrient limitation nutrients OA ocean-atmosphere ocean acidification ocean acidification data ocean carbon uptake and storage ocean color ocean modeling ocean observatories ocean warming ODZ oligotrophic omics OMZ open ocean optics organic particles oscillation overturning circulation oxygen pacific paleoceanography parameter optimization particle flux pCO2 PDO peat pelagic PETM pH phenology phosphorus photosynthesis physical processes physiology phytoplankton PIC piezophilic piezotolerant plankton POC polar regions policy pollutants precipitation predation prediction pressure primary productivity Prochlorococcus prokaryotes proteins pteropods pycnocline radioisotopes remineralization remote sensing repeat hydrography residence time resource management respiration resuspension rivers rocky shore Rossby waves Ross Sea ROV salinity salt marsh satellite scale seafloor seagrass sea ice sea level rise seasonal patterns seasonal trends sea spray seawater collection seaweed sediments sensors shelf system shells ship-based observations shorelines silicate silicon cycle sinking particles size SOCCOM soil carbon southern ocean south pacific spatial covariations speciation SST state estimation stoichiometry subduction submesoscale subpolar subtropical sulfate surf surface surface ocean Synechococcus teleconnections temperate temperature temporal covariations thermocline thermodynamics thermohaline thorium tidal time-series time of emergence titration top predators total alkalinity trace elements trace metals trait-based transfer efficiency transient features Tris trophic transfer tropical turbulence twilight zone upper ocean upper water column upwelling US CLIVAR validation velocity gradient ventilation vertical flux vertical migration vertical transport volcano warming water clarity water mass water quality waves western boundary currents wetlands winter mixing zooplankton

Copyright © 2023 - OCB Project Office, Woods Hole Oceanographic Institution, 266 Woods Hole Rd, MS #25, Woods Hole, MA 02543 USA Phone: 508-289-2838  •  Fax: 508-457-2193  •  Email: ocb_news@us-ocb.org

link to nsflink to noaalink to WHOI

Funding for the Ocean Carbon & Biogeochemistry Project Office is provided by the National Science Foundation (NSF) and the National Aeronautics and Space Administration (NASA). The OCB Project Office is housed at the Woods Hole Oceanographic Institution.