Dynamics of inorganic carbon and carbonate saturation in the Gulf of Cádiz (SW Spain)

The study of inorganic carbon chemistry of the coastal ocean is conducted in the Gulf of Cádiz (GoC). Here we describe observations obtained during 4 sampling cruises in March, June, September and November 2015. The primary data set consists of state-of-the-art measurements of the keystone parameters of the marine CO2 system: Total Alkalinity (TA), pH, dissolved inorganic carbon (DIC). We have then calculated aragonite and calcite saturation state. The distribution of inorganic carbon system parameters in the north eastern shelf of the Gulf of Cádiz showed temporal and spatial variability. River input, mixing, primary production, respiration and remineralization were factors that controlled such distributions. Data related to carbonate saturation of calcite and aragonite reveal the occurrence of a supersaturated water; in any case, both species increased with distance and decreased with depth. The carbon system parameters present a different behaviour close to the coast to offshore ad at deeper water. In this area six water masses are clearly identified by their different chemical properties: Surface Atlantic Water, North Atlantic Central Water (NACW) and Mediterranean Water (MOW). Moreover, with this work the measurement of calcium in seawater is optimize, allowing a better quantification for future work of the saturation state of CaCO3.

Analysis of the Variability of Carbonate System Parameters in the North-East Atlantic.

The purpose of this thesis is to analyse the spatial and temporal variability of the aragonite saturation state (ΩAR), commonly used as an indicator of ocean acidification, in the North-East Atlantic. When the aragonite saturation state decreases below a certain threshold, ΩAR <1, calcifying organisms (i.e. molluscs, pteropods, foraminifera, crabs, etc.) are subject to dissolution of shells and aragonite structures. This objective agrees with the challenge 'Ocean, climate change and acidification' of the EU COST Ocean Governance for Sustainability project, which aims to combine the information collected on the state of health of the oceans. Two open-sources data products, EMODnet and GLODAPv2, have been integrated and analysed for the first time in the North-East Atlantic region. The integrated dataset contains 1038 ΩAR vertical profiles whose time distribution spans from 1970 to 2014. The ΩAR has been computed from CO2SYS software considering different combinations of input parameters, pH, Total Alkalinity (TAlk) and Dissolved Inorganic Carbon (DIC), associated with Temperature, Salinity and Pressure at in situ conditions. A sensitivity analysis has been performed to better understand the data consistency of ΩAR computed from the different combinations of pH, Talk and DIC and to verify the difference among observed TAlk and DIC parameters and their output values from the CO2SYS tool. Maps of ΩAR have been computed with the best data coverage obtained from the two datasets, at different levels of depth in the area of investigation and they have been compared to the work of Jiang et al. (2015). The results are consistent and show similar horizontal and vertical patterns. The study highlights some aragonite undersaturated values (ΩAR <1) below 500 meters depth, suggesting a potential effect of acidification in the considered time period. This thesis aims to be a preliminary work for future studies that will be able to design the ΩAR variability on a decadal distribution based on the extended time-series acquired in this work.