Journal cover Journal topic
Biogeosciences An interactive open-access journal of the European Geosciences Union
Biogeosciences, 14, 4949-4963, 2017
© Author(s) 2017. This work is distributed under
the Creative Commons Attribution 3.0 License.
Research article
08 Nov 2017
Seasonal variability of the inorganic carbon system in a large coastal plain estuary
Andrew Joesoef1, David L. Kirchman2, Christopher K. Sommerfield2, and Wei-Jun Cai1 1School of Marine Science and Policy, University of Delaware, Newark, DE 19716, USA
2School of Marine Science and Policy, University of Delaware, Lewes, DE 19958, USA
Abstract. Carbonate geochemistry research in large estuarine systems is limited. More work is needed to understand how changes in land-use activity influence watershed export of organic and inorganic carbon, acids, and nutrients to the coastal ocean. To investigate the seasonal variation of the inorganic carbon system in the Delaware Estuary, one of the largest estuaries along the US east coast, dissolved inorganic carbon (DIC), total alkalinity (TA), and pH were measured along the estuary from June 2013 to April 2015. In addition, DIC, TA, and pH were periodically measured from March to October 2015 in the nontidal freshwater Delaware, Schuylkill, and Christina rivers over a range of discharge conditions. There were strong negative relationships between river TA and discharge, suggesting that changes in HCO3 concentrations reflect dilution of weathering products in the drainage basin. The ratio of DIC to TA, an understudied but important property, was high (1.11) during high discharge and low (0.94) during low discharge, reflecting additional DIC input in the form of carbon dioxide (CO2), most likely from terrestrial organic matter decomposition, rather than bicarbonate (HCO3) inputs due to drainage basin weathering processes. This is also a result of CO2 loss to the atmosphere due to rapid water transit during the wet season. Our data further show that elevated DIC in the Schuylkill River is substantially different than that in the Delaware River. Thus, tributary contributions must be considered when attributing estuarine DIC sources to the internal carbon cycle versus external processes such as drainage basin mineralogy, weathering intensity, and discharge patterns. Long-term records in the Delaware and Schuylkill rivers indicate shifts toward higher alkalinity in estuarine waters over time, as has been found in other estuaries worldwide. Annual DIC input flux to the estuary and export flux to the coastal ocean are estimated to be 15.7 ± 8.2  ×  109 mol C yr−1 and 16.5 ± 10.6  ×  109 mol C yr−1, respectively, while net DIC production within the estuary including inputs from intertidal marshes is estimated to be 5.1  ×  109 mol C yr−1. The small difference between riverine input and export flux suggests that, in the case of the Delaware Estuary and perhaps other large coastal systems with long freshwater residence times, the majority of the DIC produced in the estuary by biological processes is exchanged with the atmosphere rather than exported to the sea.

Citation: Joesoef, A., Kirchman, D. L., Sommerfield, C. K., and Cai, W.-J.: Seasonal variability of the inorganic carbon system in a large coastal plain estuary, Biogeosciences, 14, 4949-4963,, 2017.
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Short summary
In this paper, we focus on key, poorly understood properties of carbonate geochemistry in one of the largest estuaries in North America. We explore how varying environmental factors impact estuarine inorganic carbon fluxes and seasonal net ecosystem production. Comparisons with long-term records highlight the significance of tributary inputs as well as a regional shift towards increased riverine bicarbonate concentrations.
In this paper, we focus on key, poorly understood properties of carbonate geochemistry in one of...