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An important biogeochemical link between organic and inorganic carbon cycling: Effects of organic alkalinity on carbonate chemistry in coastal waters influenced by intertidal salt marshes

February 19, 2020

Organic acid charge groups in dissolved organic carbon (DOC) contribute to total alkalinity (TA), i.e. organic alkalinity (OrgAlk). Its effect is often ignored or treated as a calculation uncertainty in many aquatic CO2 studies. This study evaluated the variability, sources, and characteristics of OrgAlk in estuarine waters exchanged tidally with a groundwater-influenced salt marsh in the northeast USA. Importantly, OrgAlk was found to serve as a biogeochemical medium linking organic and inorganic carbon cycling through its effects on pH, CO2 system speciation, and buffering capacity (H = -(∂pH/∂[H+])-1). Both the concentrations and characteristics of the identified organic acid charge groups, as well as water pH, influenced the magnitude and sign of the OrgAlk effects. The two main charge groups identified include carboxylic and phenolic or amine groups, with concentrations and pK values varying across tides and seasons. OrgAlk and DOC in the tidal creek were highly variable over tidal and seasonal cycles, and may be sourced from both terrestrial groundwater and in situ production in salt marsh sediments. OrgAlk seems to be more preserved over DOC in groundwater, although DOC and OrgAlk largely covaried in marsh tidal water, but with variable OrgAlk:DOC ratios. This highlights the insufficiency of using a fixed proportion of DOC to account for organic acid charge groups. OrgAlk was found to affect H+ concentrations by ~ 1 – 40 nmol kg-1 (equivalent to a pH change of ~ 0.03 – 0.26), pCO2 by ~ 30 – 1590 atm and buffering capacity by ~ 0.00 – 0.14 mmol kg-1 at relative OrgAlk contributions of 0.9 – 4.3% of TA observed in the marsh-influenced tidal water. Thus OrgAlk may have a significant influence on coastal inorganic carbon cycling. Further theoretical calculations confirm that these concentrations of OrgAlk would have sizable impacts on both carbonate speciation and, ultimately, air-sea CO2 fluxes in different coastal environments, ranging from estuarine to shelf waters. A new conceptual model linking organic and inorganic carbon cycling for coastal waters is proposed to highlight the sources and sinks of organic acid charge groups, as well as their biogeochemical behaviors and mechanistic control on the CO2 system.