Arbuscular mycorrhiza convey significant plant carbon to a diverse hyphosphere microbial food web and mineral-associated organic matter.

Arbuscular mycorrhizal fungi (AMF) transport substantial plant carbon (C) that serves as a substrate for soil organisms, a precursor of soil organic matter (SOM), and a driver of soil microbial dynamics. Using two-chamber microcosms where an air gap isolated AMF from roots, we 13CO2-labeled Avena barbata for 6 wk and measured the C Rhizophagus intraradices transferred to SOM and hyphosphere microorganisms. NanoSIMS imaging revealed hyphae and roots had similar 13C enrichment. SOM density fractionation, 13C NMR, and IRMS showed AMF transferred 0.77 mg C g-1 of soil (increasing total C by 2% relative to non-mycorrhizal controls); 33% was found in occluded or mineral-associated pools. In the AMF hyphosphere, there was no overall change in community diversity but 36 bacterial ASVs significantly changed in relative abundance. With stable isotope probing (SIP)-enabled shotgun sequencing, we found taxa from the Solibacterales, Sphingobacteriales, Myxococcales, and Nitrososphaerales (ammonium oxidizing archaea) were highly enriched in AMF-imported 13C (> 20 atom%). Mapping sequences from 13C-SIP metagenomes to total ASVs showed at least 92 bacteria and archaea were significantly 13C-enriched. Our results illustrate the quantitative and ecological impact of hyphal C transport on the formation of potentially protective SOM pools and microbial roles in the AMF hyphosphere soil food web.

Association between soil organic carbon and calcium in acidic grassland soils from Point Reyes National Seashore, CA.

Organo-mineral and organo-metal associations play an important role in the retention and accumulation of soil organic carbon (SOC). Recent studies have demonstrated a positive correlation between calcium (Ca) and SOC content in a range of soil types. However, most of these studies have focused on soils that contain calcium carbonate (pH > 6). To assess the importance of Ca-SOC associations in lower pH soils, we investigated their physical and chemical interaction in the grassland soils of Point Reyes National Seashore (CA, USA) at a range of spatial scales. Multivariate analyses of our bulk soil characterisation dataset showed a strong correlation between exchangeable Ca (CaExch; 5-8.3 c.molc kg-1) and SOC (0.6-4%) content. Additionally, linear combination fitting (LCF) of bulk Ca K-edge X-ray absorption near-edge structure (XANES) spectra revealed that Ca was predominantly associated with organic carbon across all samples. Scanning transmission X-ray microscopy near-edge X-ray absorption fine structure spectroscopy (STXM C/Ca NEXAFS) showed that Ca had a strong spatial correlation with C at the microscale. The STXM C NEXAFS K-edge spectra indicated that SOC had a higher abundance of aromatic/olefinic and phenolic C functional groups when associated with Ca, relative to C associated with Fe. In regions of high Ca-C association, the STXM C NEXAFS spectra were similar to the spectrum from lignin, with moderate changes in peak intensities and positions that are consistent with oxidative C transformation. Through this association, Ca thus seems to be preferentially associated with plant-like organic matter that has undergone some oxidative transformation, at depth in acidic grassland soils of California. Our study highlights the importance of Ca-SOC complexation in acidic grassland soils and provides a conceptual model of its contribution to SOC preservation, a research area that has previously been unexplored. Supplementary Information: The online version contains supplementary material available at 10.1007/s10533-023-01059-2.

The environmental controls on efficiency of enhanced rock weathering in soils.

Enhanced rock weathering (ERW) in soils is a promising carbon removal technology, but the realistically achievable efficiency, controlled primarily by in situ weathering rates of the applied rocks, is highly uncertain. Here we explored the impacts of coupled biogeochemical and transport processes and a set of primary environmental and operational controls, using forsterite as a proxy mineral in soils and a multiphase multi-component reactive transport model considering microbe-mediated reactions. For a onetime forsterite application of ~ 16 kg/m2, complete weathering within five years can be achieved, giving an equivalent carbon removal rate of ~ 2.3 kgCO2/m2/yr. However, the rate is highly variable based on site-specific conditions. We showed that the in situ weathering rate can be enhanced by conditions and operations that maintain high CO2 availability via effective transport of atmospheric CO2 (e.g. in well-drained soils) and/or sufficient biogenic CO2 supply (e.g. stimulated plant-microbe processes). Our results further highlight that the effect of increasing surface area on weathering rate can be significant-so that the energy penalty of reducing the grain size may be justified-only when CO2 supply is nonlimiting. Therefore, for ERW practices to be effective, siting and engineering design (e.g. optimal grain size) need to be co-optimized.

River thorium concentrations can record bedrock fracture processes including some triggered by distant seismic events.

Fractures are integral to the hydrology and geochemistry of watersheds, but our understanding of fracture dynamics is very limited because of the challenge of monitoring the subsurface. Here we provide evidence that long-term, high-frequency measurements of the river concentration of the ultra-trace element thorium (Th) can provide a signature of bedrock fracture processes spanning neighboring watersheds in Colorado. River Th concentrations show abrupt (subdaily) excursions and biexponential decay with approximately 1-day and 1-week time constants, concentration patterns that are distinct from all other solutes except beryllium and arsenic. The patterns are uncorrelated with daily precipitation records or seasonal trends in atmospheric deposition. Groundwater Th analyses are consistent with bedrock release and dilution upon mixing with river water. Most Th excursions have no seismic signatures that are detectable 50 km from the site, suggesting the Th concentrations can reveal aseismic fracture or fault events. We find, however, a weak statistical correlation between Th and seismic motion caused by distant earthquakes, possibly the first chemical signature of dynamic earthquake triggering, a phenomenon previously identified only through geophysical methods.

Beaver dams overshadow climate extremes in controlling riparian hydrology and water quality.

Hydrologic extremes dominate chemical exports from riparian zones and dictate water quality in major river systems. Yet, changes in land use and ecosystem services alongside growing climate variability are altering hydrologic extremes and their coupled impacts on riverine water quality. In the western U.S., warming temperatures and intensified aridification are increasingly paired with the expanding range of the American beaver-and their dams, which transform hydrologic and biogeochemical cycles in riparian systems. Here, we show that beaver dams overshadow climatic hydrologic extremes in their effects on water residence time and oxygen and nitrogen fluxes in the riparian subsurface. In a mountainous watershed in Colorado, U.S.A., we find that the increase in riparian hydraulic gradients imposed by a beaver dam is 10.7-13.3 times greater than seasonal hydrologic extremes. The massive hydraulic gradient increases hyporheic nitrate removal by 44.2% relative to seasonal extremes alone. A drier, hotter climate in the western U.S. will further expand the range of beavers and magnify their impacts on watershed hydrology and biogeochemistry, illustrating that ecosystem feedbacks to climate change will alter water quality in river systems.

Impact of sports on temporomandibular dysfunction: a comparison of competitive and recreational female athletes as well as female non-athletes.

OBJECTIVES: The present study was conducted to investigate the correlation between (competitive) sports and the occurrence of temporomandibular dysfunctions (TMD) by comparing the prevalences in competitive, recreational, and non-athletic women. MATERIALS AND METHODS: A total of 138 women between the ages of 18 and 45 were interviewed about symptoms of TMD by means of a questionnaire. Based on their athletic performance level, the participating women were classified as competitive athletes, recreational athletes, or non-athletes (each group n = 46). RESULTS: Symptoms of TMD were notably less frequent in competitive female athletes (52.2%) than in recreational female athletes (63.0%) and female non-athletes (60.9%). With increasing training load, the prevalence of TMD decreased in both the competitive and recreational female athlete groups. CONCLUSIONS: Athletic activity in general seems to have a positive effect on the occurrence of TMD. Competitive female athletes appear less likely to suffer from symptoms of TMD than recreational athletes and non-athletes. One possible explanation for this could be the better supervision by qualified trainers and physiotherapists in competitive sports. CLINICAL RELEVANCE: Patients should be motivated to engage in sports as a protective measure against symptoms of TMD. However, it is important to ensure that they are properly instructed by experienced personnel in order to avoid unphysiological strain and negative consequences.

Spectroscopic analysis reveals that soil phosphorus availability and plant allocation strategies impact feedstock quality of nutrient-limited switchgrass.

The perennial native switchgrass adapts better than other plant species do to marginal soils with low plant-available nutrients, including those with low phosphorus (P) content. Switchgrass roots and their associated microorganisms can alter the pools of available P throughout the whole soil profile making predictions of P availability in situ challenging. Plant P homeostasis makes monitoring of P limitation via measurements of plant P content alone difficult to interpret. To address these challenges, we developed a machine-learning model trained with high accuracy using the leaf tissue chemical profile, rather than P content. By applying this learned model in field trials across two sites with contrasting extractable soil P, we observed that actual plant available P in soil was more similar than expected, suggesting that adaptations occurred to alleviate the apparent P constraint. These adaptations come at a metabolic cost to the plant that have consequences for feedstock chemical components and quality. We observed that other biochemical signatures of P limitation, such as decreased cellulose-to-lignin ratios, were apparent, indicating re-allocation of carbon resources may have contributed to increased P acquisition. Plant P allocation strategies also differed across sites, and these differences were correlated with the subsequent year's biomass yields.

Production of hydrogen peroxide in an intra-meander hyporheic zone at East River, Colorado.

The traditionally held assumption that photo-dependent processes are the predominant source of H2O2 in natural waters has been recently questioned by an increrasing body of evidence showing the ubiquitiousness of H2O2 in dark water bodies and in groundwater. In this study, we conducted field measurement of H2O2 in an intra-meander hyporheic zone and in surface water at East River, CO. On-site detection using a sensitive chemiluminescence method suggests H2O2 concentrations in groundwater ranging from 6 nM (at the most reduced region) to ~ 80 nM (in a locally oxygen-rich area) along the intra-meander transect with a maxima of 186 nM detected in the surface water in an early afternoon, lagging the maximum solar irradiance by ∼ 1.5 h. Our results suggest that the dark profile of H2O2 in the hyporheic zone is closely correlated to local redox gradients, indicating that interactions between various redox sensitive elements could play an essential role. Due to its transient nature, the widespread presence of H2O2 in the hyporheic zone indicates the existence of a sustained balance between H2O2 production and consumption, which potentially involves a relatively rapid succession of various biogeochemically important processes (such as organic matter turnover, metal cycling and contaminant mobilization). More importantly, this study confirmed the occurrence of reactive oxygen species at a subsurface redox transition zone and further support our understanding of redox boundaries on reactive oxygen species generation and as key locations of biogeochemical activity.

Root Carbon Interaction with Soil Minerals Is Dynamic, Leaving a Legacy of Microbially Derived Residues.

Minerals preserve the oldest, most persistent soil carbon, and mineral characteristics appear to play a critical role in the formation of soil organic matter (SOM) associations. To test the hypothesis that roots, and differences in carbon source and microbial communities, influence mineral SOM associations over short timescales, we incubated permeable mineral bags in soil microcosms with and without plants, inside a 13CO2 labeling chamber. Mineral bags contained quartz, ferrihydrite, kaolinite, or soil minerals isolated via density separation. Using 13C-nuclear magnetic resonance, Fourier transform ion cyclotron resonance mass spectrometry, and lipidomics, we traced carbon deposition onto minerals, characterizing total carbon, 13C enrichment, and SOM chemistry over three growth stages of Avena barbata. Carbon accumulation was rapid and mineral-dependent but slowed with time; the accumulated amount was not significantly affected by root presence. However, plant roots strongly shaped the chemistry of mineral-associated SOM. Minerals incubated in a plant rhizosphere were associated with a more diverse array of compounds (with different functional groups-carbonyl, aromatics, carbohydrates, and lipids) than minerals incubated in an unplanted bulk soil control. We also found that many of the lipids that sorbed to minerals were microbially derived, including many fungal lipids. Together, our data suggest that diverse rhizosphere-derived compounds may represent a transient fraction of mineral SOM, rapidly exchanging with mineral surfaces.

Microbial Phosphorus Mobilization Strategies Across a Natural Nutrient Limitation Gradient and Evidence for Linkage With Iron Solubilization Traits.

Microorganisms have evolved several mechanisms to mobilize and mineralize occluded and insoluble phosphorus (P), thereby promoting plant growth in terrestrial ecosystems. However, the linkages between microbial P-solubilization traits and the preponderance of insoluble P in natural ecosystems are not well known. We tested the P solubilization traits of hundreds of culturable bacteria representative of the rhizosphere from a natural gradient where P concentration and bioavailability decline as soil becomes progressively more weathered. Aluminum, iron phosphate and organic P (phytate) were expected to dominate in more weathered soils. A defined cultivation medium with these chemical forms of P was used for isolation. A combination of soil chemical, spectroscopic analyses and 16S rRNA gene sequencing were used to understand the in situ ability for solubilization of these predominant forms of P. Locations with more occluded and organic P harbored the greatest abundance of P-mobilizing microorganisms, especially Burkholderiaceae (Caballeronia and Paraburkholderia spp.). Nearly all bacteria utilized aluminum phosphate, however fewer could subsist on iron phosphate (FePO4) or phytate. Microorganisms isolated from phytic acid were also most effective at solubilizing FePO4, suggesting that phytate solubilization may be linked to the ability to solubilize Fe. Significantly, we observed Fe to be co-located with P in organic patches in soil. Siderophore addition in lab experiments reinstated phytase mediated P-solubilization from Fe-phytate complexes. Taken together, these results indicate that metal-organic-P complex formation may limit enzymatic P solubilization from phytate in soil. Additionally, the linked traits of phytase and siderophore production were mostly restricted to specific clades within the Burkholderiaceae. We propose that Fe complexation of organic P (e.g., phytate) represents a major constraint on P turnover and availability in acidic soils, as only a limited subset of bacteria appear to possess the traits required to access this persistent pool of soil P.

Quantifying the effects of multiple land management practices, land cover change, and wildfire on the California landscape carbon budget with an empirical model.

The effectiveness of land-based climate mitigation strategies is generally estimated on a case-by-case basis without considering interactions with other strategies or influencing factors. Here we evaluate a new, comprehensive approach that incorporates interactions among multiple management strategies, land use/cover change, wildfire, and climate, although the potential effects of climate change are not evaluated in this study. The California natural and working lands carbon and greenhouse gas model (CALAND) indicates that summing individual practice estimates of greenhouse gas impacts may underestimate emission reduction benefits in comparison with an integrated estimate. Annual per-area estimates of the potential impact of specific management practices on landscape emissions can vary based on the estimation period, which can be problematic for extrapolating such estimates over space and time. Furthermore, the actual area of implementation is a primary factor in determining potential impacts of management on landscape emissions. Nonetheless, less intensive forest management, avoided conversion to urban land, and urban forest expansion generally create the largest annual per-area reductions, while meadow restoration and forest fuel reduction and harvest practices generally create the largest increases with respect to no management. CALAND also shows that data uncertainty is too high to determine whether California land is a source or a sink of carbon emissions, but that estimating effects of management with respect to a baseline provides valid results. Important sources of this uncertainty are initial carbon density, net ecosystem carbon accumulation rates, and land use/cover change data. The appropriate choice of baseline is critical for generating valid results.

Meanders as a scaling motif for understanding of floodplain soil microbiome and biogeochemical potential at the watershed scale.

BACKGROUND: Biogeochemical exports from watersheds are modulated by the activity of microorganisms that function over micron scales. Here, we tested the hypothesis that meander-bound regions share a core microbiome and exhibit patterns of metabolic potential that broadly predict biogeochemical processes in floodplain soils along a river corridor. RESULTS: We intensively sampled the microbiomes of floodplain soils located in the upper, middle, and lower reaches of the East River, Colorado. Despite the very high microbial diversity and complexity of the soils, we reconstructed 248 quality draft genomes representative of subspecies. Approximately one third of these bacterial subspecies was detected across all three locations at similar abundance levels, and ~ 15% of species were detected in two consecutive years. Within the meander-bound floodplains, we did not detect systematic patterns of gene abundance based on sampling position relative to the river. However, across meanders, we identified a core floodplain microbiome that is enriched in capacities for aerobic respiration, aerobic CO oxidation, and thiosulfate oxidation with the formation of elemental sulfur. Given this, we conducted a transcriptomic analysis of the middle floodplain. In contrast to predictions made based on the prominence of gene inventories, the most highly transcribed genes were relatively rare amoCAB and nxrAB (for nitrification) genes, followed by genes involved in methanol and formate oxidation, and nitrogen and CO2 fixation. Within all three meanders, low soil organic carbon correlated with high activity of genes involved in methanol, formate, sulfide, hydrogen, and ammonia oxidation, nitrite oxidoreduction, and nitrate and nitrite reduction. Overall, the results emphasize the importance of sulfur, one-carbon and nitrogen compound metabolism in soils of the riparian corridor. CONCLUSIONS: The disparity between the scale of a microbial cell and the scale of a watershed currently limits the development of genomically informed predictive models describing watershed biogeochemical function. Meander-bound floodplains appear to serve as scaling motifs that predict aggregate capacities for biogeochemical transformations, providing a foundation for incorporating riparian soil microbiomes in watershed models. Widely represented genetic capacities did not predict in situ activity at one time point, but rather they define a reservoir of biogeochemical potential available as conditions change. Video abstract.

Effects of competitive sports on temporomandibular dysfunction: a literature review.

OBJECTIVES: The German Society of Craniomandibular Function and Disorders recommends that patients suffering from temporomandibular dysfunctions should practice sports in order to compensate for everyday stress. This raises the question as to what extent competitive athletes develop temporomandibular dysfunctions or whether their athletic activities protect them. With the present literature review, the authors intend to give an overview of the currently available publications on this topic. MATERIALS AND METHODS: A literature research in the PubMed and Google Scholar databases was performed to filter out the currently available publications on the topic 'sports, and temporomandibular dysfunction. RESULTS: Out of 114 available articles, seven met the inclusion criteria. Two other relevant articles were found in the list of references, so that in total, nine publications were picked for the review. In case numbers ranging from eight to 347 subjects, a temporomandibular dysfunction was detected with a prevalence between 11.7% and 100% for athletes and between 11.11% and 14.3% for non-athletes. Different kinds of sports were evaluated, all of them contact sports: basketball, handball, wrestling, boxing, karate, mixed martial arts, field hockey, water polo, and soccer. One study compared athletes with and without consumption of anabolic steroids, regardless of the type of sport. The level of athletic performance varied across the different studies. CONCLUSIONS: Currently, studies dealing with the effect of competitive sports on temporomandibular dysfunction are scarce. Inconsistent methodological procedures permit only limited comparability. CLINICAL RELEVANCE: A general trend, however, can already be discerned: professional athletes suffer from temporomandibular dysfunctions more frequently than non-athletes.

Enzymes, Manganese, or Iron? Drivers of Oxidative Organic Matter Decomposition in Soils.

Oxidative decomposition of soil organic matter determines the proportion of carbon that is either stored or emitted to the atmosphere as CO2. Full conversion of organic matter to CO2 requires oxidative mechanisms that depolymerize complex molecules into smaller, soluble monomers that can be respired by microbes. Current models attribute oxidative depolymerization largely to the activity of extracellular enzymes. Here we show that reactive manganese (Mn) and iron (Fe) intermediates, rather than other measured soil characteristics, best predict oxidative activity in temperate forest soils. Combining bioassays, spectroscopy, and wet-chemical analysis, we found that oxidative activity in surface litters was most significantly correlated to the abundance of reactive Mn(III) species. In contrast, oxidative activity in underlying mineral soils was most significantly correlated to the abundance of reactive Fe(II/III) species. Positive controls showed that both Mn(III) and Fe(II/III) species are equally potent in generating oxidative activity, but imply conventional bioassays have a systematic bias toward Fe. Combined, our results highlight the coupled biotic-abiotic nature of oxidative mechanisms, with Mn-mediated oxidation dominating within Mn-rich organic soils and Fe-mediated oxidation dominating Fe-rich mineral soils. These findings suggest microbes rely on different oxidative strategies depending on the relative availability of Fe and Mn in a given soil environment.

Projected temperature increases may require shifts in the growing season of cool-season crops and the growing locations of warm-season crops.

Predicting the effects of climate change on where and when crops can be grown under future conditions is critical for maintaining crop production, particularly in Mediterranean ecosystems. The diverse range of Mediterranean climatic conditions in California supports high crop diversity and production, yet California also faces future increased temperatures and more frequent extreme weather events indicative of a changing climate. Evaluating the effect of temperature increase is a crucial first step in estimating future impacts of warming. We compare the temperature constraints under climate projections for five annual crops. We determine maximum and minimum monthly temperatures of historical and future projections for the mid-21st century based on four climate projections (two climate models × two climate change scenarios). We estimate where temperatures were suitable for each crop historically and in the future at two spatial scales (4 km grid-cell; statewide) and two temporal scales (monthly; for each crop's growing season). We found differences between warm- and cool-season crops: temperature affects when cool-season crops (broccoli; lettuce) could be grown more than where, but temperature affects where warm-season crops (cantaloupe; tomato; carrots) could be grown more than when. More than 99% of land where lettuce and broccoli have been grown historically will have temperatures suitable for each crop by mid-century; the increased winter temperatures will enable spring and fall growing seasons to merge in more than 75% of land where each crop has been grown. Only 34-87% of land historically used for growing tomatoes will have temperatures appropriate for tomatoes due to the increase in summer temperatures. We do not predict cantaloupes and carrots to cross their upper temperature threshold. Integration of our results with other factors that affect crops - including management, water availability and helpful and harmful insects - provides guidance for adapting Mediterranean agriculture to climate change.

Satellite-based monitoring of groundwater depletion in California's Central Valley.

Range change data, obtained from Synthetic Aperture Radar satellites, form the basis for estimates of aquifer volume change in California's Central Valley. The estimation algorithm incorporates a function penalizing changes far from known well locations, linking the aquifer volume changes to agricultural, industrial, and municipal pumping within the Tulare basin. We show that the range changes are compatible with the hypothesis that the source of aquifer volume changes are variations in effective pressure around documented wells. Specifically, inclusion of the well distance penalty does not degrade the fit to the observations, inversions with and without it both give variance reductions of 99.6%. The patterns of aquifer volume change vary significantly from the drought year, between October 2015 and October 2016, to a wet year in 2017, and into 2018, a year with near average rainfall. The 2.3 million acre-feet of estimated volume reduction, a lower bound on the amount of water extracted from the basin between October 2015 and 2016, agrees with independent estimates of 1.8 and 2.3 million acre-feet. The aquifer volume reduction is also compatible with a loss of 3.1 km3 (2.5 million acre-feet) in groundwater volume derived from Gravity Recovery and Climate Experiment (GRACE) satellite data.

Redox Fluctuations Control the Coupled Cycling of Iron and Carbon in Tropical Forest Soils.

Oscillating redox conditions are a common feature of humid tropical forest soils, driven by an ample supply and dynamics of reductants, high moisture, microbial oxygen consumption, and finely textured clays that limit diffusion. However, the net result of variable soil redox regimes on iron (Fe) mineral dynamics and associated carbon (C) forms and fluxes is poorly understood in tropical soils. Using a 44-day redox incubation experiment with humid tropical forest soils from Puerto Rico, we examined patterns in Fe and C transformations under four redox regimes: static anoxic, "flux 4-day" (4d oxic, 4d anoxic), "flux 8-day" (8d oxic, 4d anoxic) and static oxic. Prolonged anoxia promoted reductive dissolution of Fe-oxides, and led to an increase in soluble Fe(II) and amorphous Fe oxide pools. Preferential dissolution of the less-crystalline Fe pool was evident immediately following a shift in bulk redox status (oxic to anoxic), and coincided with increased dissolved organic C, presumably due to acidification or direct release of organic matter (OM) from dissolving Fe(III) mineral phases. The average nominal oxidation state of water-soluble C was lowest under persistent anoxic conditions, suggesting that more reduced organic compounds were metabolically unavailable for microbial consumption under reducing conditions. Anoxic soil compounds had high H/C values (and were similar to lignin-like compounds) whereas oxic soil compounds had higher O/C values, akin to tannin- and cellulose-like components. Cumulative respiration derived from native soil organic C was highest in static oxic soils. These results show how Fe minerals and Fe-OM interactions in tropical soils are highly sensitive to variable redox effects. Shifting soil oxygen availability rapidly impacted exchanges between mineral-sorbed and aqueous C pools, increased the dissolved organic C pool under anoxic conditions implying that the periodicity of low-redox events may control the fate of C in wet tropical soils.

Manganese-Driven Carbon Oxidation at Oxic-Anoxic Interfaces.

The formation of reactive manganese (Mn) species is emerging as a key regulator of carbon oxidation rates, and thus CO2 emissions, in soils and sediments. Many subsurface environments are characterized by steep oxygen gradients, forming oxic-anoxic interfaces that enable rapid redox cycling of Mn. Here, we examined the impact of Mn(II)aq oxidation along oxic-anoxic interfaces on carbon oxidation in soils using laboratory-based diffusion reactors. A combination of cyclic voltammetry, X-ray absorption spectroscopy, and X-ray microprobe imaging revealed a tight coupling between Mn(II)aq oxidation and carbon oxidation at the oxic-anoxic interface. Specifically, zones of Mn(II)aq oxidation across the oxic-anoxic transition also exhibited the greatest lignin oxidation potential, carbon solubilization, and oxidation. Microprobe imaging further revealed that the generation of Mn(III)-dominated precipitates coincided with carbon oxidation. Combined, our findings demonstrate that biotic Mn(II)aq oxidation, specifically the formation of Mn(III) species, contributes to carbon oxidation along oxic-anoxic interfaces in soils and sediments. Our results suggest that we should regard carbon oxidation not merely as a function of molecular composition, which insufficiently predicts rates, but in relation to microenvironments favoring the formation of critically important oxidants such as Mn(III).

Microbial community assembly differs across minerals in a rhizosphere microcosm.

Mineral-associated microbes drive many critical soil processes, including mineral weathering, soil aggregation and cycling of mineral-sorbed organic matter. To investigate the interactions between soil minerals and microbes in the rhizosphere, we incubated three types of minerals (ferrihydrite, kaolinite and quartz) and a native soil mineral fraction near roots of a common Californian annual grass, Avena barbata, growing in its resident soil. We followed microbial colonization of these minerals for up to 2.5 months - the plant's lifespan. Bacteria and fungi that colonized mineral surfaces during this experiment differed across mineral types and differed from those in the background soil, implying that microbial colonization was the result of processes in addition to passive movement with water to mineral surfaces. Null model analysis revealed that dispersal limitation was a dominant factor structuring mineral-associated microbial communities for all mineral types. Once bacteria arrived at a mineral surface, capacity for rapid growth appeared important, as ribosomal copy number was significantly correlated with relative enrichment on minerals. Glomeromycota (a phylum associated with arbuscular mycorrhizal fungi) appeared to preferentially associate with ferrihydrite surfaces. The mechanisms enabling the colonization of soil minerals may be foundational in shaping the overall soil microbiome composition and development of persistent organic matter in soils.

Cross-Scale Molecular Analysis of Chemical Heterogeneity in Shale Rocks.

The organic and mineralogical heterogeneity in shale at micrometer and nanometer spatial scales contributes to the quality of gas reserves, gas flow mechanisms and gas production. Here, we demonstrate two molecular imaging approaches based on infrared spectroscopy to obtain mineral and kerogen information at these mesoscale spatial resolutions in large-sized shale rock samples. The first method is a modified microscopic attenuated total reflectance measurement that utilizes a large germanium hemisphere combined with a focal plane array detector to rapidly capture chemical images of shale rock surfaces spanning hundreds of micrometers with micrometer spatial resolution. The second method, synchrotron infrared nano-spectroscopy, utilizes a metallic atomic force microscope tip to obtain chemical images of micrometer dimensions but with nanometer spatial resolution. This chemically "deconvoluted" imaging at the nano-pore scale is then used to build a machine learning model to generate a molecular distribution map across scales with a spatial span of 1000 times, which enables high-throughput geochemical characterization in greater details across the nano-pore and micro-grain scales and allows us to identify co-localization of mineral phases with chemically distinct organics and even with gas phase sorbents. This characterization is fundamental to understand mineral and organic compositions affecting the behavior of shales.