Manganese (Mn) is a biologically important and redox-active metal that may exert a poorly recognized control on carbon (C) cycling in terrestrial ecosystems. Manganese influences ecosystem C dynamics by mediating biochemical pathways that include photosynthesis, serving as a reactive intermediate in the breakdown of organic molecules, and binding and/or oxidizing organic molecules through organo-mineral associations. However, the potential for Mn to influence ecosystem C storage remains unresolved. Although substantial research has demonstrated the ability of Fe- and Al-oxides to stabilize organic matter, there is a scarcity of similar information regarding Mn-oxides. Furthermore, Mn-mediated reactions regulate important litter decomposition pathways, but these processes are poorly constrained across diverse ecosystems. Here, we discuss the ecological roles of Mn in terrestrial environments and synthesize existing knowledge on the multiple pathways by which biogeochemical Mn and C cycling intersect. We demonstrate that Mn has a high potential to degrade organic molecules through abiotic and microbially mediated oxidation and to stabilize organic molecules, at least temporarily, through organo-mineral associations. We outline research priorities needed to advance understanding of Mn–C interactions, highlighting knowledge gaps that may address key uncertainties in soil C predictions.

Solute concentrations in stream water vary with discharge in patterns that record complex feedbacks between hydrologic and biogeochemical processes. In a comparison of three shale-underlain headwater catchments located in Pennsylvania, USA (the forested Shale Hills Critical Zone Observatory), and Wales, UK (the peatland-dominated Upper Hafren and forest-dominated Upper Hore catchments in the Plynlimon forest), dissimilar concentration–discharge (C–Q) behaviors are best explained by contrasting landscape distributions of soil solution chemistry – especially dissolved organic carbon (DOC) – that have been established by patterns of vegetation and soil organic matter (SOM). Specifically, elements that are concentrated in organic-rich soils due to biotic cycling (Mn, Ca, K) or that form strong complexes with DOC (Fe, Al) are spatially heterogeneous in pore waters because organic matter is heterogeneously distributed across the catchments. These solutes exhibit non-chemostatic behavior in the streams, and solute concentrations either decrease (Shale Hills) or increase (Plynlimon) with increasing discharge. In contrast, solutes that are concentrated in soil minerals and form only weak complexes with DOC (Na, Mg, Si) are spatially homogeneous in pore waters across each catchment. These solutes are chemostatic in that their stream concentrations vary little with stream discharge, likely because these solutes are released quickly from exchange sites in the soils during rainfall events. Furthermore, concentration–discharge relationships of non-chemostatic solutes changed following tree harvest in the Upper Hore catchment in Plynlimon, while no changes were observed for chemostatic solutes, underscoring the role of vegetation in regulating the concentrations of certain elements in the stream. These results indicate that differences in the hydrologic connectivity of organic-rich soils to the stream drive differences in concentration behavior between catchments. As such, in catchments where SOM is dominantly in lowlands (e.g., Shale Hills), we infer that non-chemostatic elements associated with organic matter are released to the stream early during rainfall events, whereas in catchments where SOM is dominantly in uplands (e.g., Plynlimon), these non-chemostatic elements are released later during rainfall events. The distribution of SOM across the landscape is thus a key component for predictive models of solute transport in headwater catchments.

Arctic and boreal ecosystems are experiencing pronounced warming that is accelerating decomposition of soil organic matter and releasing greenhouse gases to the atmosphere. Future carbon storage in these ecosystems depends on the balance between microbial decomposition and primary production, both of which can be regulated by nutrients such as phosphorus. Phosphorus cycling in tundra and boreal regions is often assumed to occur through biological pathways with little interaction with soil minerals; that is, phosphate released from organic molecules is rapidly assimilated by plants or microorganisms. In contrast to this prevailing conceptual model, we use sequential extractions and spectroscopic techniques to demonstrate that iron (oxyhydr)oxides sequester approximately half of soil phosphate in organic soils from four arctic and boreal sites. Iron (III) (oxyhydr)oxides accumulated in shallow soils of low‐lying, saturated areas where circumneutral pH and the presence of a redox interface promoted iron oxidation and hydrolysis. Soils enriched in short‐range ordered iron oxyhydroxides, which are susceptible to dissolution under anoxic conditions, had high phosphate sorption capacities and maintained low concentrations of soluble phosphate relative to soils containing mostly organic‐bound iron or crystalline iron oxides. Thus, substantial quantities of phosphorus in these organic soils were associated with minerals that could reduce bioavailability but potentially also serve as phosphorus sources under anoxic conditions. The implication of this finding is that mineral surfaces effectively compete with biological processes for phosphate and must be considered as a nutrient regulator in these sensitive ecosystems.

Arctic tundra soils store a large quantity of organic carbon that is susceptible to decomposition and release to the atmosphere as methane (CH₄) and carbon dioxide (CO₂) under a warming climate. Anaerobic processes that generate CH₄ and CO₂ remain unclear because previous studies have focused on aerobic decomposition pathways. To predict releases of CO₂ and CH₄ from tundra soils, it is necessary to identify pathways of soil organic matter decomposition under the anoxic conditions that are prevalent in Arctic ecosystems. Here molecular and spectroscopic techniques were used to monitor biological degradation of water‐extractable organic carbon (WEOC) during anoxic incubation of tundra soils from a region of continuous permafrost in northern Alaska. Organic and mineral soils from the tundra active layer were incubated at −2, +4, or +8°C for up to 60 days to mimic the short‐term thaw season. Results suggest that, under anoxic conditions, fermentation converted complex organic molecules into simple organic acids that were used in concomitant Fe‐reduction and acetoclastic methanogenesis reactions. Nonaromatic compounds increased over time as WEOC increased. Organic acid metabolites initially accumulated in soils but were mostly depleted by day 60 because organic acids were consumed to produce Fe(II), CO₂, and CH₄. We conclude that fermentation of nonprotected organic matter facilitates methanogenesis and Fe reduction reactions, and that the proportion of organic acids consumed by methanogenesis increases relative to Fe reduction with increasing temperature. The decomposition pathways observed in this study are important to consider in numerical modeling of greenhouse gas production in the Arctic.

In permafrost peatlands, up to 20% of total organic carbon (OC) is bound to reactive iron (Fe) minerals in the active layer overlying intact permafrost, potentially protecting OC from microbial degradation and transformation into greenhouse gases (GHG) such as CO₂ and CH₄. During the summer, shifts in runoff and soil moisture influence redox conditions and therefore the balance of Fe oxidation and reduction. Whether reactive iron minerals could act as a stable sink for carbon or whether they are continuously dissolved and reprecipitated during redox shifts remains unknown. We deployed bags of synthetic ferrihydrite (FH)-coated sand in the active layer along a permafrost thaw gradient in Stordalen mire (Abisko, Sweden) over the summer (June to September) to capture changes in redox conditions and quantify the formation and dissolution of reactive Fe(III) (oxyhydr)oxides. We found that the bags accumulated Fe(III) under constant oxic conditions in areas overlying intact permafrost over the full summer season. In contrast, in fully thawed areas, conditions were continuously anoxic, and by late summer, 50.4 ± 12.8% of the original Fe(III) (oxyhydr)oxides were lost via dissolution. Periodic redox shifts (from 0 to +300 mV) were observed over the summer season in the partially thawed areas. This resulted in the dissolution and loss of 47.2 ± 20.3% of initial Fe(III) (oxyhydr)oxides when conditions are wetter and more reduced, and new formation of Fe(III) minerals (33.7 ± 8.6% gain in comparison to initial Fe) in the late summer under more dry and oxic conditions, which also led to the sequestration of Fe-bound organic carbon. Our data suggest that there is seasonal turnover of iron minerals in partially thawed permafrost peatlands, but that a fraction of the Fe pool remains stable even under continuously anoxic conditions.