Geochemical drivers of organic matter decomposition in the active layer of Arctic tundra

Abstract:

Arctic tundra soils store large quantities of organic carbon that are susceptible to decomposition and release to the atmosphere as CO₂ and CH₄. Decomposition rates are limited by cold temperatures and widespread anoxia; however, ongoing changes in soil temperature, thaw depth, and water saturation are expected to influence rates and pathways of organic matter decomposition. In order to predict greenhouse gas releases from high-latitude ecosystems, it is necessary to identify how geochemical factors (e.g. terminal electron acceptors, carbon substrates) influence CO₂ and CH₄ production in tundra soils. This study evaluates spatial patterns of aqueous geochemistry in the active layer of low- to high-centered polygons located at the Barrow Environmental Observatory in northern Alaska. Pore waters from saturated soils were low in sulfate and nitrate but contained abundant Fe which may serve a major terminal electron acceptor for anaerobic microbial metabolism. Relatively high concentrations of soluble Fe accumulated in the middle of the active layer near the boundary between the organic and mineral horizon, and we infer that Fe-oxide reduction and dissolution in the mineral horizon produced soluble Fe that diffused upwards and was stabilized by complexation with dissolved organic matter. Fe concentrations in the bulk soil were higher in organic than mineral horizons due to the presence of these organic-Fe complexes and Fe-oxide precipitates. Dissolved CH₄ increased with increasing proportions of dissolved Fe(III) in saturated soils from transitional and low-centered polygons. The opposite trend was observed in drier soils from flat- and high-centered polygons where deeper oxidation fronts may inhibit methanogenesis. Using multiple spectroscopic and molecular methods (e.g. UV-Vis, Fourier transform infrared, ultrahigh resolution mass spectrometry), we also observed that pore waters from the middle of the active layer contained more aromatic organics than in mineral soils near the permafrost boundary, where pore waters were depleted but soils were enriched with aromatic organic moieties. The geochemical depth gradients we document for tundra soils influence organic matter degradation and are pertinent for understanding C dynamics as thaw depth and duration increase in high-latitude soils.