The interplay of freshwater inputs and catchment geology in regulating seawater chemistry in Irish coastal areas

Open ocean carbonate chemistry is altered by the dissolution of atmospheric CO2 in seawater. Up to 40% of anthropogenic CO2 emissions have dissolved in the surface ocean since the pre-industrial era, driving changes in marine carbonate pools and promoting ocean acidification. Under open ocean conditions, Total Alkalinity (TA) generally relates with salinity and temperature due to the conservative nature of its constituents. In coastal areas, however, land-ocean interactions may greatly contribute to making TA far less predictable, since freshwater inputs can affect the chemistry of coastal water masses by increasing TA and Dissolved Inorganic Carbon (DIC) or, alternatively, lowering them through dilution. Here we analysed and compared coastal carbonate chemistry dynamics in selected coastal areas of Ireland, in order to assess whether rivers and their catchment geology can influence coastal water chemistry and to verify the occurrence of local ocean acidification processes. Data on TA, DIC, salinity, temperature, and nutrients (total nitrogen, phosphate, and silicate) collected during several surveys along the Irish coastline by The Marine Institute Foras Na Mara (MIFNM) from 2009 to 2018 were analysed against those available on the main watercourses feeding the selected coastal areas. The relationships among the different variables were scrutinized, also considering the geological characteristics of river catchments. Results showed a clear linkage between coastal water chemistry and local freshwater inputs, whereas changes in the geology of catchment areas exerted only a secondary influence. An in-depth scrutiny of the Galway Bay sector performed by comparing MIFNM data with those collected during an oceanographic cruise carried out in October 2017 further indicated remarkable effects of the interaction between river inputs and submarine groundwater discharges on seasonal variations in the water chemistry of the area. Future studies, integrating chemical data across the land-ocean boundary, may provide additional, useful information on the factors actually affecting the variation in water carbonates in coastal areas. Elucidating how land-ocean interactions influence the coastal carbonate system may ultimately provide a key for a more advanced understanding of the resilience of coastal areas to ocean acidification. •Coastal carbonate chemistry depends on land-ocean interactions.•Multiple drivers should be considered: bedrock geology, freshwater inputs typo