A biogeochemical budget for iron at Hubbard Brook
Iron (Fe) is abundant among trace elements in forest ecosystems and important in the development and function of soils. We constructed a biogeochemical budget for Fe to better understand the behavior of Fe and its role in the development of Spodosols (podsolization). Fluxes of reduced (ferrous, Fe(II)) and oxidized (ferric, Fe(III)) iron draining through the soil profile were calculated. Soil solution fluxes of Fe and dissolved organic carbon (DOC) decreased from the organic (Oa) horizon down through the mineral (Bh and Bs) horizons, consistent with theories of translocation of organically-complexed Fe and co-precipitation of Fe and C in the spodic horizon. The portion of total Fe as Fe(II) ranged approximately 10-60% in soil solutions, seemingly high for soils that are considered to be well-drained, oxidizing environments. Analysis of total Fe and Fe(II) in hardwood leaf litter extracts identified a source of reduced Fe to solutions draining the forest floor, as approximately 50% or more of this Fe occurred as Fe(II). Flux calculations showed that inputs of Fe to the forest floor (litterfall + throughfall) were insufficient to account for all Fe in soil solutions. The organic forest floor horizons were a net source of Fe(II) and Fe(III). Dissolved Fe draining the forest floor was either mobilized by organic compounds following organic decomposition or was leached directly from litter. The results indicate that organic complexes likely stabilized Fe(II) in solution under oxidizing conditions that would otherwise promote considerably higher Fe(III)-to-Fe(II) ratios. Fe(II) concentrations remained as a fairly constant fraction of total Fe despite fluctuations in dissolved oxygen concentrations. Our study indicates that there are organic matter-derived sources of dissolved Fe(II) as well as substantial mobilization of Fe(II), possibly the result of reduction of Fe soil minerals. The translocation of Fe(II) could have implications for redox chemistry in deeper mineral soils and downstream surface waters.