Calculating surface ocean pCO2 from biogeochemical Argo floats equipped with pH: An uncertainty analysis

More than 74 biogeochemical profiling floats that measure water column pH, oxygen, nitrate, fluorescence, and backscattering at 10 day intervals have been deployed throughout the Southern Ocean. Calculating the surface ocean partial pressure of carbon dioxide (pCO2sw) from float pH has uncertainty contributions from the pH sensor, the alkalinity estimate, and carbonate system equilibrium constants, resulting in a relative standard uncertainty in pCO2sw of 2.7% (or 11 µatm at pCO2sw of 400 µatm). The calculated pCO2sw from several floats spanning a range of oceanographic regimes are compared to existing climatologies. In some locations, such as the subantarctic zone, the float data closely match the climatologies, but in the polar Antarctic zone significantly higher pCO2sw are calculated in the wintertime implying a greater air‐sea CO2 efflux estimate. Our results based on four representative floats suggest that despite their uncertainty relative to direct measurements, the float data can be used to improve estimates for air‐sea carbon flux, as well as to increase knowledge of spatial, seasonal, and interannual variability in this flux.

[1]  Atul K. Jain,et al.  Global Carbon Budget 2016 , 2016 .

[2]  Hervé Claustre,et al.  Bringing Biogeochemistry into the Argo Age , 2016 .

[3]  Jacqueline Boutin,et al.  A multi-decade record of high-quality fCO2 data in version 3 of the Surface Ocean CO2 Atlas (SOCAT) , 2016 .

[4]  Masao Ishii,et al.  The Global Ocean Data Analysis Project version 2 (GLODAPv2) – an internally consistent data product for the world ocean , 2016 .

[5]  Dana D. Swift,et al.  Accurate oxygen measurements on modified Argo floats using in situ air calibrations , 2016 .

[6]  S. Riser,et al.  Empirical algorithms to estimate water column pH in the Southern Ocean , 2016 .

[7]  R. Feely,et al.  Locally interpolated alkalinity regression for global alkalinity estimation , 2016 .

[8]  Todd R. Martz,et al.  Deep-Sea DuraFET: A Pressure Tolerant pH Sensor Designed for Global Sensor Networks. , 2016, Analytical chemistry.

[9]  F. Millero,et al.  Rapid anthropogenic changes in CO2 and pH in the Atlantic Ocean: 2003–2014 , 2016 .

[10]  S. Riser,et al.  Air Oxygen Calibration of Oxygen Optodes on a Profiling Float Array , 2015 .

[11]  R. Feely,et al.  Internal consistency of marine carbonate system measurements and assessments of aragonite saturation state: Insights from two U.S. coastal cruises , 2015 .

[12]  L. Talley,et al.  Quantifying anthropogenic carbon inventory changes in the Pacific sector of the Southern Ocean , 2015 .

[13]  John P. Krasting,et al.  Dominance of the Southern Ocean in Anthropogenic Carbon and Heat Uptake in CMIP5 Models , 2015 .

[14]  F. d’Ovidio,et al.  Rapid establishment of the CO 2 sink associated with Kerguelen's bloom observed during the KEOPS2/OISO20 cruise , 2014 .

[15]  P. Landschützer,et al.  Recent variability of the global ocean carbon sink , 2014 .

[16]  Taro Takahashi,et al.  Climatological distributions of pH, pCO2, total CO2, alkalinity, and CaCO3 saturation in the global surface ocean, and temporal changes at selected locations , 2014 .

[17]  J. Sarmiento,et al.  An observing system simulation for Southern Ocean carbon dioxide uptake , 2014, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[18]  Philip J. Bresnahan,et al.  Best practices for autonomous measurement of seawater pH with the Honeywell Durafet , 2014 .

[19]  L. Merlivat,et al.  Observed small spatial scale and seasonal variability of the CO 2 system in the Southern Ocean , 2013 .

[20]  B. Carter,et al.  An automated system for spectrophotometric seawater pH measurements , 2013 .

[21]  S. Doney,et al.  Detecting anthropogenic CO2 changes in the interior Atlantic Ocean between 1989 and 2005 , 2010 .

[22]  Todd R. Martz,et al.  Testing the Honeywell Durafet® for seawater pH applications , 2010 .

[23]  R. Feely,et al.  The universal ratio of boron to chlorinity for the North Pacific and North Atlantic oceans , 2010 .

[24]  W. Brechner Owens,et al.  An improved calibration method for the drift of the conductivity sensor on autonomous CTD profiling floats by θ–S climatology , 2009 .

[25]  C. S. Wong,et al.  Climatological mean and decadal change in surface ocean pCO2, and net seaair CO2 flux over the global oceans , 2009 .

[26]  Richard A. Feely,et al.  A global ocean carbon climatology: Results from Global Data Analysis Project (GLODAP) , 2004 .

[27]  C. D. Keeling,et al.  Ocean pCO2 calculated from dissolved inorganic carbon, alkalinity, and equations for K1 and K2: validation based on laboratory measurements of CO2 in gas and seawater at equilibrium , 2000 .

[28]  S. Ellison,et al.  Quantifying uncertainty in analytical measurement , 2000 .

[29]  R. Feely,et al.  The optimal carbonate dissociation constants for determining surface water pCO2 from alkalinity and total inorganic carbon , 1999 .

[30]  D. Wallace,et al.  Program developed for CO{sub 2} system calculations , 1998 .

[31]  Taro Takahashi,et al.  Seasonal variation of CO2 and nutrients in the high-latitude surface oceans: A comparative study , 1993 .

[32]  A. Dickson Standard potential of the reaction: , and and the standard acidity constant of the ion HSO4− in synthetic sea water from 273.15 to 318.15 K , 1990 .

[33]  F. F. Pérèz,et al.  Association constant of fluoride and hydrogen ions in seawater , 1987 .

[34]  J. P. Riley,et al.  The effect of analytical error on the evaluation of the components of the aquatic carbon-dioxide system , 1978 .

[35]  R. Weiss Carbon dioxide in water and seawater: the solubility of a non-ideal gas , 1974 .

[36]  C. Culberson,et al.  EFFECT OF PRESSURE ON CARBONIC ACID, BORIC ACID, AND THE pH IN SEAWATER1 , 1968 .