Exploring the Effects of Organic Matter Characteristics on Fe(II) Oxidation Kinetics in Coastal Seawater

The iron(II) oxidation kinetic process was studied at 25 stations in coastal seawater of the Macaronesia region (9 around Cape Verde, 11 around the Canary Islands, and 5 around Madeira). In a physicochemical context, experiments were carried out to study the pseudo-first-order oxidation rate constant (k', min^-1) over a range of pH (7.8, 7.9, 8.0, and 8.1) and temperature (10, 15, 20, and 25 °C). Deviations from the calculated k_cal^' at the same T, pH, and S were observed for most of the stations. The measured t_1/2 (ln 2/k', min) values at the 25 stations ranged from 1.82 to 3.47 min (mean 1.93 ± 0.76 min) and for all but two stations were lower than the calculated t_1/2 of 3.21 ± 0.2 min. In a biogeochemical context, nutrients and variables associated with the organic matter spectral properties (CDOM and FDOM) were analyzed to explain the observed deviations. The application of a multilinear regression model indicated that k' can be described (R = 0.921 and SEE = 0.064 for pH = 8 and T = 25 °C) from a linear combination of three organic variables, k'^OM = k_cal^' -0.11* TDN + 29.9*b_DOM + 33.4*C1_humic, where TDN is the total dissolved nitrogen, b_DOM is the spectral peak obtained from colored dissolved organic matter (DOM) analysis when protein-like or tyrosine-like components are present, and C1_humic is the component associated with humic-like compounds obtained from the parallel factor analysis of the fluorescent DOM. Results show that compounds with N in their structures mainly explain the observed k' increase for most of the samples, although other components could also play a relevant role. Experimentally, k' provides the net result between the compounds that accelerate the process and those that slow it down.