Phosphorus Interactions with Iron in Undisturbed and Disturbed Arctic Tundra Ecosystems.

Phosphorus (P) limitation often constrains biological processes in Arctic tundra ecosystems. Although adsorption to soil minerals may limit P bioavailability and export from soils into aquatic systems, the contribution of mineral phases to P retention in Arctic tundra is poorly understood. Our objective was to use X-ray absorption spectroscopy to characterize P speciation and associations with soil minerals along hillslope toposequences and in undisturbed and disturbed low-lying wet sedge tundra on the North Slope, AK. Biogenic mats comprised of short-range ordered iron (Fe) oxyhydroxides were prevalent in undisturbed wet sedge meadows. Upland soils and pond sediments impacted by gravel mining or thermokarst lacked biogenic Fe mats and were comparatively iron poor. Phosphorus was primarily contained in organic compounds in hillslope soils but associated with Fe(III) oxyhydroxides in undisturbed wet sedge meadows and calcium (Ca) in disturbed pond sediments. We infer that phosphate mobilized through organic decomposition binds to Fe(III) oxyhydroxides in wet sedge, but these associations are disrupted by physical disturbance that removes Fe mats. Increasing disturbances of the Arctic tundra may continue to alter the mineralogical composition of soils at terrestrial-aquatic interfaces and binding mechanisms that could inhibit or promote transport of bioavailable P from soils to aquatic ecosystems.

Sulfur speciation in Sphagnum peat moss modified by mutualistic interactions with cyanobacteria.

Peat moss (Sphagnum spp.) develops mutualistic interactions with cyanobacteria by providing carbohydrates and S compounds in exchange for N-rich compounds, potentially facilitating N inputs into peatlands. Here, we evaluate how colonization of Sphagnum angustifolium hyaline cells by Nostoc muscorum modifies S abundance and speciation at the scales of individual cells and across whole leaves. For the first time, S K-edge X-ray Absorption Spectroscopy was used to identify bulk and micron-scale S speciation across isolated cyanobacteria colonies, and in colonized and uncolonized leaves. Uncolonized leaves contained primarily reduced organic S and oxidized sulfonate- and sulfate-containing compounds. Increasing Nostoc colonization resulted in an enrichment of S and changes in speciation, with increases in sulfate relative to reduced S and sulfonate. At the scale of individual hyaline cells, colonized cells exhibited localized enrichment of reduced S surrounded by diffuse sulfonate, similar to observations of cyanobacteria colonies cultured in the absence of leaves. We infer that colonization stimulates plant S uptake and the production of sulfate-containing metabolites that are concentrated in stem tissues. Sulfate compounds that are produced in response to colonization become depleted in colonized cells where they may be converted into reduced S metabolites by cyanobacteria.

Effects of C/Mn Ratios on the Sorption and Oxidative Degradation of Small Organic Molecules on Mn-Oxides.

Manganese (Mn) oxides have a high surface area and redox potential that facilitate sorption and/or oxidation of organic carbon (OC), but their role in regulating soil C storage is relatively unexplored. Small OC compounds with distinct structures were reacted with Mn(III/IV)-oxides to investigate the effects of OC/Mn molar ratios on Mn-OC interaction mechanisms. Dissolved and solid-phase OC and Mn were measured to quantify the OC sorption to and/or the redox reaction with Mn-oxides. Mineral transformation was evaluated using X-ray diffraction and X-ray absorption spectroscopy. Higher OC/Mn ratios resulted in higher sorption and/or redox transformation; however, interaction mechanisms differed at low or high OC/Mn ratios for some OC. Citrate, pyruvate, ascorbate, and catechol induced Mn-oxide dissolution. The average oxidation state of Mn in the solid phase did not change during the reaction with citrate, suggesting ligand-promoted mineral dissolution, but decreased significantly during reactions with the other compounds, suggesting reductive dissolution mechanisms. Phthalate primarily sorbed on Mn-oxides with no detectable formation of redox products. Mn-OC interactions led primarily to C loss through OC oxidation into inorganic C, except phthalate, which was predominantly immobilized in the solid phase. Together, these results provided detailed fundamental insights into reactions happening at organo-mineral interfaces in soils.

Seasonal Fluctuations in Iron Cycling in Thawing Permafrost Peatlands.

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.

A Critical Review on the Multiple Roles of Manganese in Stabilizing and Destabilizing Soil Organic Matter.

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.

Spectroscopic and computational investigations of organometallic complexation of group 12 transition metals by methanobactins from Methylocystis sp. SB2.

Methanotrophic bacteria catalyze the aerobic oxidation of methane to methanol using Cu-containing enzymes, thereby exerting a modulating influence on the global methane cycle. To facilitate the acquisition of Cu ions, some methanotrophic bacteria secrete small modified peptides known as "methanobactins," which strongly bind Cu and function as an extracellular Cu recruitment relay, analogous to siderophores and Fe. In addition to Cu, methanobactins form complexes with other late transition metals, including the Group 12 transition metals Zn, Cd, and Hg, although the interplay among solution-phase configurations, metal interactions, and the spectroscopic signatures of methanobactin-metal complexes remains ambiguous. In this study, the complexation of Zn, Cd, and Hg by methanobactin from Methylocystis sp. strain SB2 was studied using a combination of absorbance, fluorescence, extended x-ray absorption fine structure (EXAFS) spectroscopy, and time-dependent density functional theory (TD-DFT) calculations. We report changes in sample absorbance and fluorescence spectral dynamics, which occur on a wide range of experimental timescales and characterize a clear stoichiometric complexation dependence. Mercury L3-edge EXAFS and TD-DFT calculations suggest a linear model for HgS coordination, and TD-DFT suggests a tetrahedral model for Zn2+ and Cd2+. We observed an enhancement in the fluorescence of methanobactin upon interaction with transition metals and propose a mechanism of complexation-hindered isomerization drawing inspiration from the wild-type Green Fluorescent Protein active site. Collectively, our results represent the first combined computational and experimental spectroscopy study of methanobactins and shed new light on molecular interactions and dynamics that characterize complexes of methanobactins with Group 12 transition metals.

Iron and iron-bound phosphate accumulate in surface soils of ice-wedge polygons in arctic tundra.

Phosphorus (P) is a limiting or co-limiting nutrient to plants and microorganisms in diverse ecosystems that include the arctic tundra. Certain soil minerals can adsorb or co-precipitate with phosphate, and this mineral-bound P provides a potentially large P reservoir in soils. Iron (Fe) oxyhydroxides have a high capacity to adsorb phosphate; however, the ability of Fe oxyhydroxides to adsorb phosphate and limit P bioavailability in organic tundra soils is not known. Here, we examined the depth distribution of soil Fe and P species in the active layer (<30 cm) of low-centered and high-centered ice-wedge polygons at the Barrow Environmental Observatory on the Alaska North Slope. Soil reservoirs of Fe and P in bulk horizons and in narrower depth increments were characterized using sequential chemical extractions and synchrotron-based X-ray absorption spectroscopy (XAS). Organic horizons across all polygon features (e.g., trough, ridge, and center) were enriched in extractable Fe and P relative to mineral horizons. Soil Fe was dominated by organic-bound Fe and short-range ordered Fe oxyhydroxides, while soil P was primarily associated with oxides and organic matter in organic horizons but apatite and/or calcareous minerals in mineral horizons. Iron oxyhydroxides and Fe-bound inorganic P (Pi) were most enriched at the soil surface and decreased gradually with depth, and Fe-bound Pi was >4× greater than water-soluble Pi. These results demonstrate that Fe-bound Pi is a large and ecologically important reservoir of phosphate. We contend that Fe oxyhydroxides and other minerals may regulate Pi solubility under fluctuating redox conditions in organic surface soils on the arctic tundra.

Indexing Permafrost Soil Organic Matter Degradation Using High-Resolution Mass Spectrometry.

Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between -1 and 0 in a water-soluble fraction (WSF) demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF) did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions.

Stoichiometry and temperature sensitivity of methanogenesis and CO2 production from saturated polygonal tundra in Barrow, Alaska.

Arctic permafrost ecosystems store ~50% of global belowground carbon (C) that is vulnerable to increased microbial degradation with warmer active layer temperatures and thawing of the near surface permafrost. We used anoxic laboratory incubations to estimate anaerobic CO2 production and methanogenesis in active layer (organic and mineral soil horizons) and permafrost samples from center, ridge and trough positions of water-saturated low-centered polygon in Barrow Environmental Observatory, Barrow AK, USA. Methane (CH4 ) and CO2 production rates and concentrations were determined at -2, +4, or +8 °C for 60 day incubation period. Temporal dynamics of CO2 production and methanogenesis at -2 °C showed evidence of fundamentally different mechanisms of substrate limitation and inhibited microbial growth at soil water freezing points compared to warmer temperatures. Nonlinear regression better modeled the initial rates and estimates of Q10 values for CO2 that showed higher sensitivity in the organic-rich soils of polygon center and trough than the relatively drier ridge soils. Methanogenesis generally exhibited a lag phase in the mineral soils that was significantly longer at -2 °C in all horizons. Such discontinuity in CH4 production between -2 °C and the elevated temperatures (+4 and +8 °C) indicated the insufficient representation of methanogenesis on the basis of Q10 values estimated from both linear and nonlinear models. Production rates for both CH4 and CO2 were substantially higher in organic horizons (20% to 40% wt. C) at all temperatures relative to mineral horizons (<20% wt. C). Permafrost horizon (~12% wt. C) produced ~5-fold less CO2 than the active layer and negligible CH4 . High concentrations of initial exchangeable Fe(II) and increasing accumulation rates signified the role of iron as terminal electron acceptors for anaerobic C degradation in the mineral horizons.

Soils reveal widespread manganese enrichment from industrial inputs.

It is well-known that metals are emitted to the air by human activities and subsequently deposited to the land surface; however, we have not adequately evaluated the geographic extent and ecosystem impacts of industrial metal loading to soils. Here, we demonstrate that atmospheric inputs have widely contaminated soils with Mn in industrialized regions. Soils record elemental fluxes impacting the Earth's surface and can be analyzed to quantify inputs and outputs during pedogenesis. We use a mass balance model to interpret details of Mn enrichment by examining soil, bedrock, precipitation, and porefluid chemistry in a first-order watershed in central Pennsylvania, USA. This reveals that ∼ 53% of Mn in ridge soils can be attributed to atmospheric deposition from anthropogenic sources. An analysis of published data sets indicates that over half of the soils surveyed in Pennsylvania (70%), North America (60%), and Europe (51%) are similarly enriched in Mn. We conclude that soil Mn enrichment due to industrial inputs is extensive, yet patchy in distribution due to source location, heterogeneity of lithology, vegetation, and other attributes of the land surface. These results indicate that atmospheric transport must be considered a potentially critical component of the global Mn cycle during the Anthropocene.