A data product of 17 653 discrete samples from 3343 oceanographic stations combining measurements of pH, alkalinity and other biogeochemical parameters off the northwestern Iberian Peninsula from June 1976 to September 2018 is presented in this study. The oceanography cruises funded by 24 projects were primarily carried out in the Ría de Vigo coastal inlet but also in an area ranging from the Bay of Biscay to the Portuguese coast. The robust seasonal cycles and long-term trends were only calculated along a longitudinal section, gathering data from the coastal and oceanic zone of the Iberian upwelling system. The pH in the surface waters of these separated regions, which were highly variable due to intense photosynthesis and the remineralization of organic matter, showed an interannual acidification ranging from ?0.0012 to ?0.0039 yr?1 that grew towards the coastline. This result is obtained despite the buffering capacity increasing in the coastal waters further inland as shown by the increase in alkalinity by 1.1±0.7 and 2.6±1.0 μmol kg?1 yr?1 in the inner and outer Ría de Vigo respectively, driven by interannual changes in the surface salinity of 0.0193±0.0056 and 0.0426±0.016 psu yr?1 respectively. The loss of the vertical salinity gradient in the long-term trend in the inner ria was consistent with other significant biogeochemical changes such as a lower oxygen concentration and fertilization of the surface waters. These findings seem to be related to a growing footprint of sediment remineralization of organic matter in the surface layer of a more homogeneous water column. Data are available at https://doi.org/10.20350/digitalCSIC/12498 (Pérez et al., 2020).
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