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Biogeosciences An interactive open-access journal of the European Geosciences Union
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Volume 14, issue 13 | Copyright
Biogeosciences, 14, 3221-3237, 2017
© Author(s) 2017. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 06 Jul 2017

Research article | 06 Jul 2017

Spatial variability in surface-water pCO2 and gas exchange in the world's largest semi-enclosed estuarine system: St. Lawrence Estuary (Canada)

Ashley Dinauer and Alfonso Mucci Ashley Dinauer and Alfonso Mucci
  • GEOTOP and Department of Earth and Planetary Sciences, McGill University, 3450 University Street, Montreal, QC H3A 0E8, Canada

Abstract. The incomplete spatial coverage of CO2 partial pressure (pCO2) measurements across estuary types represents a significant knowledge gap in current regional- and global-scale estimates of estuarine CO2 emissions. Given the limited research on CO2 dynamics in large estuaries and bay systems, as well as the sources of error in the calculation of pCO2 (carbonic acid dissociation constants, organic alkalinity), estimates of air–sea CO2 fluxes in estuaries are subject to large uncertainties. The Estuary and Gulf of St. Lawrence (EGSL) at the lower limit of the subarctic region in eastern Canada is the world's largest estuarine system, and is characterized by an exceptional richness in environmental diversity. It is among the world's most intensively studied estuaries, yet there are no published data on its surface-water pCO2 distribution. To fill this data gap, a comprehensive dataset was compiled from direct and indirect measurements of carbonate system parameters in the surface waters of the EGSL during the spring or summer of 2003–2016. The calculated surface-water pCO2 ranged from 435 to 765µatm in the shallow partially mixed upper estuary, 139–578µatm in the deep stratified lower estuary, and 207–478µatm along the Laurentian Channel in the Gulf of St. Lawrence. Overall, at the time of sampling, the St. Lawrence Estuary served as a very weak source of CO2 to the atmosphere, with an area-averaged CO2 degassing flux of 0.98 to 2.02mmolCm−2d−1 (0.36 to 0.74molCm−2yr−1). A preliminary analysis revealed that respiration (upper estuary), photosynthesis (lower estuary), and temperature (Gulf of St. Lawrence) controlled the spatial variability in surface-water pCO2. Whereas we used the dissociation constants of Cai and Wang (1998) to calculate estuarine pCO2, formulations recommended for best practices in open ocean environments may underestimate pCO2 at low salinities, while those of Millero (2010) may result in overestimates.

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Because of its large physical dimensions and unimpeded connection to the Atlantic Ocean, the St. Lawrence Gulf and Estuary encompass both estuarine and marine environments. The underlying physical and biogeochemical processes are reflected in the spatial pattern of surface-water pCO2 (139–765 µatm). The shallow partially mixed upper estuary was a CO2 source due to microbial respiration, whereas the deep stratified lower estuary was generally a CO2 sink due to phytoplankton photosynthesis.
Because of its large physical dimensions and unimpeded connection to the Atlantic Ocean, the St....