Transport and cycling of iron and hydrogen peroxide in a freshwater stream: Influence of organic acids

An in‐stream injection of two dissolved organic acids (phthalic and aspartic acids) was performed in an acidic mountain stream to assess the effects of organic acids on Fe photoreduction and H₂O₂ cycling. Results indicate that the fate of Fe is dependent on a net balance of oxidative and reductive processes, which can vary over a distance of several meters due to changes in incident light and other factors. Solution phase photoreduction rates were high in sunlit reaches and were enhanced by the organic acid addition but were also limited by the amount of ferric iron present in the water column. Fe oxide photoreduction from the streambed and colloids within the water column resulted in an increase in the diurnal load of total filterable Fe within the experimental reach, which also responded to increases in light and organic acids. Our results also suggest that Fe(II) oxidation increased in response to the organic acids, with the result of offsetting the increase in Fe(II) from photoreductive processes. Fe(II) was rapidly oxidized to Fe(III) after sunset and during the day within a well‐shaded reach, presumably through microbial oxidation. H₂O₂, a product of dissolved organic matter photolysis, increased downstream to maximum concentrations of 0.25 μM midday. Kinetic calculations show that the buildup of H₂O₂ is controlled by reaction with Fe(II), but this has only a small effect on Fe(II) because of the small formation rates of H₂O₂ compared to those of Fe(II). The results demonstrate the importance of incorporating the effects of light and dissolved organic carbon into Fe reactive transport models to further our understanding of the fate of Fe in streams and lakes.