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Keiluweit, Marco

Publications and source records attributed to Keiluweit, Marco.

At least 19 records

Differential Exudation Creates Biogeochemically Distinct Microenvironments during Rhizosphere Evolution

Plant roots and associated microbes release a diverse range of functionally distinct exudates into the surrounding rhizosphere with direct impacts on soil carbon storage, nutrient availability, and contaminant dynamics. Yet mechanistic linkages between root exudation and emergent biogeochemical processes remain challenging to measure nondestructively, in real soil, over time. Here we used a novel combination of in situ microsensors with high-resolution mass spectrometry to measure, nondestructively, changing exudation and associated biogeochemical dynamics along single growing plant roots (Avena sativa). We found that metabolite and dissolved organic carbon (DOC) concentrations as well as microbial growth, redox potential (EH), and pH dynamics vary significantly among bulk soil, root tip, and more mature root zones. Surprisingly, the significant spike of rhizosphere DOC upon root tip emergence did not significantly correlate with any biogeochemical parameters. However, the presence of sugars significantly correlated with declines in EH following the arrival of the root tip, likely due to enhanced microbial oxygen demand. Similarly, the presence of organic acids significantly correlated to declines in pH upon root tip emergence. Altogether, our in situ measurements highlight how different exudates released along growing roots create functionally distinct soil microenvironments that evolve over time.

54 ENVIRONMENTAL SCIENCES↗

Seasonal Controls on Microbial Depolymerization and Oxidation of Organic Matter in Floodplain Soils

Floodplain soils are vast reservoirs of organic carbon often attributed to anaerobic conditions that impose metabolic constraints on organic matter degradation. What remains elusive is how such metabolic constraints respond to dynamic flooding and drainage cycles characteristic of floodplain soils. Here, in this work, we show that microbial depolymerization and respiration of organic compounds, two rate-limiting steps in decomposition, vary spatially and temporally with seasonal flooding of mountainous floodplain soils (Gothic, Colorado, USA). Combining metabolomics and -proteomics, we found a lower abundance of oxidative enzymes during flooding coincided with the accumulation of aromatic, high-molecular weight compounds, particularly in surface soils. In subsurface soils, we found that a lower oxidation state of carbon coincided with a greater abundance of chemically reduced, energetically less favorable low-molecular weight metabolites, irrespective of flooding condition. Our results suggest that seasonal flooding temporarily constrains oxidative depolymerization of larger, potentially plant-derived compounds in surface soils; in contrast, energetic constraints on microbial respiration persist in more reducing subsurface soils regardless of flooding. Our work underscores that the potential vulnerability of these distinct anaerobic carbon storage mechanisms to changing flooding dynamics should be considered, particularly as climate change shifts both the frequency and extent of flooding in floodplains globally.

54 ENVIRONMENTAL SCIENCES↗

Deciphering controls on metal migration within floodplains: The critical role of redox environments on metal-organic complexes (Final Technical Report)

Our project elucidates the effect of differing hydrologic regimes on nutrient and contaminant dynamics within floodplains, and we explore the impact of varying sources of hydrologic extremes on nutrient-contaminant fate and transport. We use a combination of field measurements and laboratory experiments to examine the relationships between redox conditions, functionality of dissolved organic matter, metal speciation (specifically examining metal-ligand complexes), and nutrient-contaminant fate, particularly during hydrologic extremes. Floodplain biogeochemical variation through climatic extremes and beaver-induced hydrologic variation provide a unique look at controls on nutrient-contaminant fate and transport. Through our work, we have developed a novel approach that provides an unprecedented ability to resolve aqueous metal-organic complexes that reveals metal binding preferences for natural organic matter based on metal-ligand chemistry. We have developed novel methods to separate, quantify, and characterize organic-metal complexes in natural DOM that pair with field experiments comprising floodplains having systematic variation in biogeochemical conditions. We also developed a comprehensive computational approach for molecular characterization of metal-organic species that merges LC-coupled high resolution (HR) mass spectrometry and ICP-MS analysis. Importantly, we show that beaver dams have an outsized influence on hydrologic extremes, dwarfing the impact of climatic variation, that ultimate control biogeochemical conditions and water quality. Additionally, beaver dams impose a hydrologic driver that leads to improved, river water quality by divert water through soils and the hyporheic zone. We further show that iron(III) minerals have a dominant control on carbon mineralization across floodplains independent of hydrologic conditions, and that iron and aluminum associations with organic matter are a controlling factor in carbon mineralization. Ultimately, our work is helping to advancing a robust predictive understanding of how hydrologic changes in watersheds affect water quality and carbon and metal cycling in riparian zones.

54 ENVIRONMENTAL SCIENCES↗

Molecular Nature of Mineral-Organic Associations within Redox-Active Mountainous Floodplain Sediments

Floodplains are critical terrestrial-aquatic interfaces that act as hotspots of organic carbon (OC) cycling, regulating ecosystem carbon storage as well as export to riverine systems. Within floodplain sediments, regular flooding and textural gradients interact to create dynamic redox conditions. While anaerobic protection of OC upon burial is a well-recognized carbon storage mechanism in redox-active floodplain sediments, the impact of protective mineral-organic associations is relatively unknown. Here we determined the quantitative importance and chemical composition of mineral-organic associations along well-defined redox gradients emerging from textural variations and depth within meander sediments of the subalpine East River watershed (Gothic, CO). Here we characterized mineral-organic associations using a combination of sequential extractions, physical fractionation, and high-resolution mass spectrometry. Across the meander, we found that mineral-associated OC constitutes a significant fraction of total OC, and that extractable iron (Fe) and aluminum (Al) phases as well as high-density isolates were strongly correlated with total OC content, suggesting that mineral-organic associations are quantitatively important for floodplain sediment OC protection. Our mass spectrometry results showed OC associated with increasingly ordered Fe and Al phases are relatively enriched in low-molecular weight, oxidized, aromatic compounds. Surprisingly, however, total OC content showed weak or no correlation with indicators of anaerobic protection, such as relatively bioavailable OC pools (water-extractable and particulate OC) or the molecular weight and oxidation state of OC. Overall, this work highlights that protection of OC bound to reactive mineral phases-in addition to anaerobic protection-can play a quantitatively important role in controlling soil carbon storage in redox-active floodplain sediments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resolving dynamic mineral-organic interactions in the rhizosphere by combining in-situ microsensors with plant-soil reactive transport modeling

Associations between minerals and organic matter represent one of the most important carbon storage mechanisms in soils. Plant roots are major sources of soil carbon, and resolving the dynamics and dominance of microbial consumption versus mineral sorption of root-derived carbon is critical to understanding soil carbon storage. Here we integrate in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the fate of dissolved organic carbon (DOC) in the rhizosphere, particularly its microbial consumption and interaction with Fe oxide minerals. Over several days, a microdialysis probe sampling pore water at the root-soil interface of growing Vicia faba roots in live soil, revealed clear diel patterns of DOC concentration. Daytime DOC spikes coincided with peaks in leaf-level photosynthesis rates and were accompanied by declining redox potential and dissolved oxygen as well as increasing pH in the rhizosphere. Incorporating microsensor data into our modeling framework showed that the measured rapid loss of DOC after each mid-day spike could not be explained by consumption via aerobic respiration, nor via anaerobic respiration dominated by Fe oxide reduction. Rather, in the model, a large fraction of rhizosphere DOC was rapidly immobilized each day by adsorption to Fe oxides. Further, modeled microbial Fe reduction (fueled by DOC) did not mobilize significant organic carbon from Fe oxides during the day. Instead, the model predicted equilibrium desorption of organic carbon from Fe oxides at night. This new mechanistic modeling framework, which couples aboveground plant physiological measurements with non-destructive high-resolution monitoring of rhizosphere processes, has great potential for exploring the dynamics and balance of the various microbial reactions and mineral interactions controlling carbon transformations and storage in soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sticky roots--implications of widespread, cryptic, viral infection of plants in natural and managed ecosystems for soil carbon processing in the rhizosphere

Plants strongly influence soil properties through rhizodeposition, in which exudates diffuse from roots, additional secretions are actively released, and root cells are sloughed into the soil. This contribution by plants of carbon compounds belowground is at the core of soil health, water holding capacity, and the soil carbon storage that pulls carbon dioxide out of the atmosphere. Once in soil, organic matter can bind with minerals such as iron hydroxides, where it can be protected from microbial attack for millenia, preserving very large terrestrial soil carbon pools. However, those same compounds contributed by roots to soil may also destabilize the long-term protective associations of SOM with minerals, making that soil organic matter (SOM) more vulnerable to microbial attack and decomposition. Plant roots thus influence both the buildup and breakdown of soil carbon pools. DOE’s E3SM Land Model (ELM) includes a representation of soil carbon storage on minerals, but the potential vulnerability of SOM–mineral associations to effects of rhizodeposition is not yet represented in ELM. To begin testing for this effect of rhizodeposition on soil carbon storage and decomposition, we worked to develop a novel approach during this TES Exploratory project DE-SC0019142 – we harnessed the power of plant viral infection. We examined whether plant virus infection can serve as a tool to intensify rhizodeposition at the root surface, and therefore possibly intensify mobilization of SOM from minerals making it visible to our analytical techniques. Viral infection is widespread in terrestrial ecosystems; 25-70% of plants have virus infection, yet the influence of such infection on root traits and terrestrial soil carbon dynamics remains largely unexplored. We used two plant hosts: the annual Avena sativa (oats) and the genetically tractable, model grass Brachypodium distachyon. These grasses were infected with the broad host range virus Barley Yellow Dwarf Virus (BYDV) via aphids (Rhopalosiphum padi). BYDV infects at least 150 grass species in agricultural and natural ecosystems, and in previous experiments, oats infected with BYDV had roots that were very sticky to the touch, strongly suggesting that infection altered rhizodeposition. We developed this new experimental approach mostly in a one virus (Barley Yellow Dwarf Virus)–one plant (Avena sativa) system. (Several effects of infection in a Brachypodium-BYDV system were similar in nature to effects on Avena sativa, but were more variable.) In the BYDV-Avena system, we developed protocols for consistently infecting target plants (and avoiding infection of control plants) using aphid caging on leaves. We measured that infected plants exhibited reduced photosynthesis, plant (including root) biomass, and root:shoot ratio, as well as simplified root system architecture. We established procedures for sampling the organic compounds carried specifically in phloem (vascular tissue) of leaves and roots, using aphid stylectomy. We used FTICR-MS, Orbitrap GC-MS, and LC-MS/MS to analyze organic compounds in phloem, liquid around roots of plants grown hydroponically, and pore water around roots in soil, and found differences in the compounds in solution bathing roots when infected and uninfected plants were grown hydroponically. Finally, we synthesized isotopically-labeled mineral–organic matter (MAOM) associations in the lab and developed assays using them in solution and in soil. Assays quantified the extent and rate of mineralization of labeled MAOM that was mobilized by functionally distinct rhizodeposits and then attacked by microbes. Two mechanisms for MAOM mobilization emerged, with distinct dynamics. During “direct” mobilization, rhizodeposits such as the strong ligand oxalic acid could drive rapid dissolution of minerals, mobilizing MAOM. During “indirect” mobilization, rhizodeposits such as the simple sugar glucose did not attack minerals directly but instead intensified microbial activity, which led to mobilization via changes in e.g. pH, Eh, and microbial metabolite production (Li et al. 2021). Mechanistic understanding derived from these data and our ongoing experiments using these techniques will inform future development of ELM. Plant roots not only contribute newly fixed organic compounds to soils, but also root activities can drive mineralization of the carbon and nutrients mobilized off minerals via “indirect” or “direct” mechanisms. Using viral infection as a new tool, ongoing combined experimentation and modeling will explore the strength and larger-scale significance of the cascade of processes from rhizodeposition to MAOM mobilization for soil carbon storage and nutrient cycling in terrestrial ecosystems. And if viral infection leads quite generally to “sticky roots”, our perception of the potential importance of prevalent virus infection in terrestrial landscapes will be transformed.

54 ENVIRONMENTAL SCIENCES↗

Reactive iron, not fungal community, drives organic carbon oxidation potential in floodplain soils

Wetlands host ∼20% of terrestrial organic carbon and serve as a major sink for atmospheric carbon. Anoxic soils and sediments accrue soil organic carbon (SOC) partly by hampering the activity of extracellular oxidative enzymes that break down phenolic polymers. Upon aeration, fungal-driven oxidative enzymatic depolymerization and microbial respiration of released monomers ensue. Redox-active metals can simultaneously catalyze abiotic nonspecific oxidation of SOC, notable examples including Mn(III) or Fe(II) through Fenton-like, hydrogen peroxide-catalyzed oxidative radical production. However, the extent of reactive metal contributions to biotic and abiotic SOC degradation is not understood in the context of natural environments with diverse redox chemistry. We tested the relative contributions of fungi, Mn(III) and Fe(II) to phenolic substrate (L-DOPA) oxidation in floodplain soils representing a range of transient redox conditions driven by permanent vs. periodic flooding. Phenol oxidative potential was highest in permanently flooded soils with fewer fungal taxa known for observed (per)oxidase activity and instead correlated with HCl-extractable Fe(II), Fe(total) and Fe(II)/Fe(total), suggesting a specific role of Fe(II). Fe(II) additions enhanced phenol oxidative potential in sterilized and non-sterilized soils in the presence of hydrogen peroxide, indicating abiotic Fe-mediated radical chemistry could significantly enhance wetland SOC oxidative depolymerization throughout redox-active floodplain soils. Fungal community composition did not correlate to phenol oxidative potential overall and only more oxic soils adjacent to the river with diverse fungal communities showed declining oxidative potential after sterilization. Mn(III) addition did not significantly enhance phenol oxidative potential across all soils, although it appeared to drive fungal-mediated oxidative potential in the most aerated floodplain soils. Understanding how metals mediate SOC depolymerization as abiotic oxidants or microbially-harnessed enzyme cofactors and substrates in soils under variable hydrologic controls will improve our ability to represent depolymerization in terrestrial carbon models in wetland and other frequently saturated soils.

59 BASIC BIOLOGICAL SCIENCES↗

2017 Meander C sediment characterization from the East River, Colorado

This dataset includes characterization data collected on sediment samples from Meander C as part of the Watershed Function Scientific Focus Area (SFA) located in the Upper Colorado River Basin. The data were collected to investigate the nature of mineral-organic associations across the meander transect and with depth. Samples were collected in 2017, and analyzed using sequential extractions (water, pyrophosphate, HCl, and dithionite) and density fractionation. Data collected include: texture, pH, root biomass, and metals (Fe, Al, Ca, Si) of bulk sediment samples; C and N of heavy fraction; and extractable OC, Fe, and Al, and organic matter characterization using high-resolution mass spectrometry (FT-ICR-MS) of sequential extractions. Sample locations are included in the ‘sample_metadata.xlsx” file. Sediment characterization data is included in the accompanying csv files: bulk and density fractions (MCB2017_density-and-bulk-fractions.csv), sequential extractions (MCB2017_sequential-extractions.csv), and FT-ICR-MS data from sequential extractions in three files to be read by the R package ftmsRanalysis (MCB2017_FTICRMS-sequential-edata.csv, MCB2017_FTICRMS-sequential-emeta.csv, and MCB2017_FTICRMS-sequential-fdata.csv). Sediment was collected in triplicate; ID’s refer to individual samples.

54 ENVIRONMENTAL SCIENCES↗