Marine dissolved organic matter (DOM) plays a key role in the current and future global carbon cycle, which supports life on Earth. Trace metals such as iron, an essential micronutrient, compete with protons and major ions for the binding to DOM. These competitive effects and the DOM binding capacity are related to the DOM acid-base properties, which also influence DOM transport and reactivity in marine waters. Here we present the results of a complete set of acid-base titration experiments of a pre-concentrated marine DOM sample in the range 0.01 ≤ I ≤ 0.7 M and 3 ≤ pH ≤ 10. We characterize the obtained proton binding curves using a combination of the non-ideal competitive adsorption (NICA) isotherm and Donnan electrostatic model. Within the main chemical groups of marine DOM, the carboxylic distribution was accurately characterized from the obtained data (QmaxH, 1=2.52 mol·kg-1, logk¯H,1 = 3.26, m1 = 0.69 and b = 0.70). This carboxylic mode was found to be less acidic and more homogeneous than a generic fulvic acid, but the differences are consistent with the reported variability of fulvic acids of freshwater and terrestrial origin. We find that changes in temperature (down to 5.5 °C), and the presence of calcium or magnesium (at 0.01 M) resulted in no significant modification of the proton ion binding curves obtained at 25 °C and 0.7 or 0.1 M ionic strength, respectively. We demonstrate the relevance of proton binding parameters for the modelling of the system iron/marine DOM throughout a wide range of salinity and acidity conditions in the context of different future ocean scenarios.
Keywords: Intrinsic pK(a); Marine DOM; NICA-Donnan; Proton binding; Trace metal availability.
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