Multidecadal accumulation of anthropogenic and remineralized dissolved inorganic carbon along the Extended Ellett Line in the northeast Atlantic Ocean

Marine carbonate chemistry measurements have been carried out annually since 2009 during UK research cruises along the Extended Ellett Line (EEL), a hydrographic transect in the northeast Atlantic Ocean. The EEL intersects several water masses that are key to the global thermohaline circulation, and therefore the cruises sample a region in which it is critical to monitor secular physical and biogeochemical changes. We have combined results from these EEL cruises with existing quality-controlled observational data syntheses to produce a hydrographic time series for the EEL from 1981 to 2013. This reveals multidecadal increases in dissolved inorganic carbon (DIC) throughout the water column, with a near-surface maximum rate of 1.80 ± 0.45 µmol kg−1 yr−1. Anthropogenic CO2 accumulation was assessed, using simultaneous changes in apparent oxygen utilization (AOU) and total alkalinity (TA) as proxies for the biogeochemical processes that influence DIC. The stable carbon isotope composition of DIC (δ13CDIC) was also determined and used as an independent test of our method. We calculated a volume-integrated anthropogenic CO2 accumulation rate of 2.8 ± 0.4 mg C m−3 yr−1 along the EEL, which is about double the global mean. The anthropogenic CO2 component accounts for only 31 ± 6% of the total DIC increase. The remainder is derived from increased organic matter remineralization, which we attribute to the lateral redistribution of water masses that accompanies subpolar gyre contraction. Output from a general circulation ecosystem model demonstrates that spatiotemporal heterogeneity in the observations has not significantly biased our multidecadal rate of change calculations and indicates that the EEL observations have been tracking distal changes in the surrounding North Atlantic and Nordic Seas

Influence of ocean acidification on the organic complexation of iron and copper in Northwest European shelf seas; a combined observational and model study

The pH of aqueous solutions is known to impact the chemical speciation of trace metals. In this study we conducted titrations of coastal seawaters with iron and copper at pH 7.91, 7.37 and 6.99 (expressed on the total pH scale). Changes in the concentration of iron and copper that complexed with the added ligands 1-nitroso-2-napthol and salicylaldoxime respectively were determined by adsorptive cathodic stripping voltammetry - competitive ligand equilibrium (AdCSV-CLE). Interpretation of the results, assuming complexation by a low concentration of discrete ligands, showed that conditional stability constants for iron complexes increased relative to inorganic iron complexation as pH decreased by approximately 1 log unit per pH unit, whilst those for copper did not change. No trend was observed for concentrations of iron and copper complexing ligands over the pH range examined. We also interpreted our titration data by describing chemical binding and polyelectrolytic effects using non-ideal competitive adsorption in Donnan-like gels (NICA-Donnan model) in a proof of concept study. The NICA-Donnan approach allows for the development of a set of model parameters that are independent of ionic strength and pH, and thus calculation of metal speciation can be undertaken at ambient sample pH or the pH of a future, more acidic ocean. There is currently a lack of basic NICA-Donnan parameters applicable to marine dissolved organic matter (DOM) so we assumed that the measured marine dissolved organic carbon could be characterized as terrestrial fulvic acids. Generic NICA-Donnan parameters were applied within the framework of the software program visual MINTEQ and the metal –added ligand concentrations [MeAL] calculated for the AdCSV-CLE conditions. For copper, calculated [MeAL] using the NICA-Donnan model for DOM were consistent with measured [MeAL], but for iron an inert fraction with kinetically inhibited dissolution was required in addition to the NICA-Donnan model in order to approximate the trends observed in measured [MeAL]. We calculated iron and copper speciation in Northwest European shelf water samples at ambient alkalinity and projected increased pCO2 concentrations as a demonstration of the potential of the approach