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At least 271 records · Page 15

Phylogenomic Analyses of Non-Dikarya Fungi Supports Horizontal Gene Transfer Driving Diversification of Secondary Metabolism in the Amphibian Gastrointestinal Symbiont, Basidiobolus

Research into secondary metabolism (SM) production by fungi has resulted in the discovery of diverse, biologically active compounds with significant medicinal applications. The fungi rich in SM production are taxonomically concentrated in the subkingdom Dikarya, which comprises the phyla Ascomycota and Basidiomycota. Here, we explore the potential for SM production in Mucoromycota and Zoopagomycota, two phyla of nonflagellated fungi that are not members of Dikarya, by predicting and identifying core genes and gene clusters involved in SM. The majority of non-Dikarya have few genes and gene clusters involved in SM production except for the amphibian gut symbionts in the genus Basidiobolus. Basidiobolus genomes exhibit an enrichment of SM genes involved in siderophore, surfactin-like, and terpene cyclase production, all these with evidence of constitutive gene expression. Gene expression and chemical assays also confirm that Basidiobolus has significant siderophore activity. Finally, the expansion of SMs in Basidiobolus are partially due to horizontal gene transfer from bacteria, likely as a consequence of its ecology as an amphibian gut endosymbiont.

59 BASIC BIOLOGICAL SCIENCES↗

Bisphenol A degradation by manganese oxides at circumneutral pH: Quantitative evaluation of dissolved Mn(III) species with pyrophosphate

Although trivalent manganese (Mn(III)) species have been recognized as crucial intermediates in the degradation of organic contaminants by Mn oxides, quantitative research on their specific roles remains scarce. Here, our study investigated the degradation processes of an organic pollutant, Bisphenol A (BPA), by dissolved Mn(III) and Mn(III)-bearing oxides, and elucidated the differences of the underlying mechanisms and reaction pathways between several Mn oxides and dissolved Mn(III). Our results indicated that BPA degradation rates with Mn(III)-bearing oxides alone follow the order: δ-MnO 2 >> γ-MnOOH > Mn 3 O 4 . Adding pyrophosphate (PP) significantly enhanced BPA degradation by promoting the formation of Mn(III)-PP complexes and exposing more reactive sites, achieved through destabilizing the crystal structure and mitigating of Mn(II) readsorption, particularly in γ-MnOOH and Mn 3 O 4 . Our kinetic model revealed that heterogeneous degradation by Mn oxides is the predominant reaction pathway, accounting for 61.4 %, 87.8 %, and 73.8 % of the total degraded BPA for δ-MnO 2 , γ-MnOOH, and Mn 3 O 4 , respectively, even in the presence of significant amount of dissolved Mn(III) intermediates due to high PP concentrations. These results offer mechanistic details on BPA degradation by Mn oxides and the influence of ligand concentration, providing helpful insights for optimizing degradation strategies of organic pollutants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phylogenetic conservation of soil bacterial responses to simulated global changes.

Soil bacterial communities are altered by anthropogenic drivers such as climate change-related warming and fertilization. However, we lack a predictive understanding of how bacterial communities respond to such global changes. Here, we tested whether phylogenetic information might be more predictive of the response of bacterial taxa to some forms of global change than others. We analysed the composition of soil bacterial communities from perturbation experiments that simulated warming, drought, elevated CO2 concentration and phosphorus (P) addition. Bacterial responses were phylogenetically conserved to all perturbations. The phylogenetic depth of these responses varied minimally among the types of perturbations and was similar when merging data across locations, implying that the context of particular locations did not affect the phylogenetic pattern of response. We further identified taxonomic groups that responded consistently to each type of perturbation. These patterns revealed that, at the level of family and above, most groups responded consistently to only one or two types of perturbations, suggesting that traits with different patterns of phylogenetic conservation underlie the responses to different perturbations. We conclude that a phylogenetic approach may be useful in predicting how soil bacterial communities respond to a variety of global changes. This article is part of the theme issue 'Conceptual challenges in microbial community ecology'.

54 ENVIRONMENTAL SCIENCES↗

Estimating the Impact of Seep Methane Oxidation on Ocean pH and Dissolved Inorganic Radiocarbon Along the U.S. Mid-Atlantic Bight

Ongoing ocean warming can release methane (CH 4 ) currently stored in ocean sediments asfree gas and gas hydrates. Once dissolved in ocean waters, this CH 4 can be oxidized to carbon dioxide(CO 2 ). While it has been hypothesized that the CO 2 produced from aerobic CH4oxidation could enhanceocean acidification, a previous study conducted in Hudson Canyon shows that CH 4 oxidation has a smallshort-term influence on ocean pH and dissolved inorganic radiocarbon. Here we expand upon thatinvestigation to assess the impact of widespread CH 4 seepage on CO 2 chemistry and possible accumulationof this carbon injection along 234 km of the U.S. Mid-Atlantic Bight. Consistent with the estimates fromHudson Canyon, we demonstrate that a small fraction of ancient CH 4 -derived carbon is being assimilatedinto the dissolved inorganic radiocarbon (mean fraction of 0.5 ± 0.4%). The areas with the highest fractionsof ancient carbon coincide with elevated CH 4 concentration and active gas seepage. This suggests thataerobic CH 4 oxidation has a greater influence on the dissolved inorganic pool in areas where CH 4 concentrations are locally elevated, instead of displaying a cumulative effect downcurrent from widespreadgroupings of CH 4 seeps. Afirst-order approximation of the input rate of ancient-derived dissolved inorganiccarbon (DIC) into the waters overlying the northern U.S. Mid-Atlantic Bight further suggests thatoxidation of ancient CH 4 -derived carbon is not negligible on the global scale and could contribute todeepwater acidification over longer time scales.

54 ENVIRONMENTAL SCIENCES↗

Microbial ecology and biogeochemistry of hypersaline sediments in Orca Basin

In deep ocean hypersaline basins, the combination of high salinity, unusual ionic composition and anoxic conditions represents significant challenges for microbial life. We used geochemical porewater characterization and DNA sequencing based taxonomic surveys to enable environmental and microbial characterization of anoxic hypersaline sediments and brines in the Orca Basin, the largest brine basin in the Gulf of Mexico. Full-length bacterial 16S rRNA gene clone libraries from hypersaline sediments and the overlying brine were dominated by the uncultured halophilic KB1 lineage, Deltaproteobacteria related to cultured sulfate-reducing halophilic genera, and specific lineages of heterotrophic Bacteroidetes. Archaeal clones were dominated by members of the halophilic methanogen genus Methanohalophilus, and the ammonia-oxidizing Marine Group I (MG-I) within the Thaumarchaeota. Illumina sequencing revealed higher phylum- and subphylum-level complexity, especially in lower-salinity sediments from the Orca Basin slope. Illumina and clone library surveys consistently detected MG-I Thaumarchaeota and halotolerant Deltaproteobacteria in the hypersaline anoxic sediments, but relative abundances of the KB1 lineage differed between the two sequencing methods. The stable isotopic composition of dissolved inorganic carbon and methane in porewater, and sulfate concentrations decreasing downcore indicated methanogenesis and sulfate reduction in the anoxic sediments. While anaerobic microbial processes likely occur at low rates near their maximal salinity thresholds in Orca Basin, long-term accumulation of reaction products leads to high methane concentrations and reducing conditions within the Orca Basin brine and sediments.

54 ENVIRONMENTAL SCIENCES↗

Scat Detection Dog Surveys for the San Joaquin Kit Fox on the Lawrence Livermore National Laboratory's Experimental Test Site (Site 300) and the Corral Hollow Ecological Reserve: 2020 Deployment

The San Joaquin kit fox (Vulpes macrotis mutica) historically occupied an extensive range in the San Joaquin Valley, California; however, their populations and habitat have since been significantly reduced by human impacts (United States Fish and Wildlife Service [USFWS] 1998). More than 95% of the potential habitat for kit foxes on the San Joaquin Valley floor has been converted to irrigated agriculture, urbanized, or industrialized lands. The San Joaquin kit fox was listed as endangered by the USFWS in 1967 and as threatened by the State of California in 1971. Records from local surveys, research projects, and incidental sightings indicate the present distribution of kit foxes extends from 1) southern Kern County north to Contra Costa, Alameda, and San Joaquin counties on the west side of the valley and to Stanislaus County on the east side; 2) into some of the larger, uncultivated valley-floor land parcels in Kern, Tulare, Kings, Fresno, Madera, and Merced counties; and 3) westward within 5 counties in the interior coastal range (USFWS 1998). Kit foxes have been denoted to occur in 3 geographically distinct core and several satellite populations in a heavily fragmented landscape, with the largest extant populations concentrated in the southern part of the range and smaller populations and isolated sightings in the central and northern portions (USFWS 1998, 2010).

54 ENVIRONMENTAL SCIENCES↗

Comparison of basin-scale in situ and meteoric 10 Be erosion and denudation rates in felsic lithologies across an elevation gradient at the George River, northeast Tasmania, Australia

Long-term erosion rates in Tasmania, at the south ern end of Australia’s Great Dividing Range, are poorly known; yet, this knowledge is critical for making informed land-use decisions and improving the ecological health of coastal ecosystems. Here, we present quantitative, geologically relevant estimates of erosion rates for the George River basin, in northeast Tasmania, based on in situ-produced 10 Be ( 10 Be i ) measured from stream sand at two trunk channel sites and seven tributaries (mean: 24.1 ± 1.4 Mg km -2 yr -1 ; 1σ). These new 10 Bei-based erosion rates are strongly related to elevation, which appears to control mean annual precipitation and temperature, suggesting that elevation-dependent surface processes influence rates of erosion in northeast Tas mania. Erosion rates are not correlated with slope in contrast to erosion rates along the mainland portions of Australia’s Great Dividing Range. We also extracted and measured meteoric 10 Be ( 10 Be m ) from grain coatings of sand-sized stream sediment at each site, which we normalize to measured concentrations of reactive 9 Be and use to estimate 10 Be m -based denudation rates for the George River. 10 Bem/ 9 Be reac denudation rates replicate 10 Be i erosion rates within a factor of 3 but are highly sensitive to the value of 9 Be that is found in bedrock ( 9 Be parent ), which was unmeasured in this study. 10 Bem/ 9 Be reac denudation rates seem sensitive to recent mining, forestry, and agricultural land use, all of which resulted in widespread topsoil disturbance. Our findings suggest that 10 Bem/ 9 Be reac denudation metrics will be most useful in drainage basins that are geologically homogeneous, where recent disturbances to topsoil profiles are minimal, and where 9 Be parent is well constrained.

58 GEOSCIENCES↗

Stratospheric aerosol injection can weaken the carbon dioxide greenhouse effect

Abstract Stratospheric aerosol injection is a proposed method for offsetting greenhouse gas-induced warming by introducing scattering aerosols into the lower stratosphere to reflect sunlight. Here we explore a potentially more efficient alternative: weakening the Earth’s greenhouse effect by deploying absorptive aerosols in the upper stratosphere (~10 hPa). These aerosols warm the carbon dioxide emission level—where outgoing longwave radiation is most sensitive to temperature—thereby enhancing top-of-atmosphere infrared emission without altering atmospheric carbon dioxide concentrations. Idealized climate model simulations indicate that this approach can reduce global temperatures an order of magnitude more efficiently per unit aerosol mass than conventional scattering-based interventions. Although based on simplified model experiments lacking interactive aerosol processes and operational constraints, our results identify a distinct physical mechanism for climate intervention, arguing for further research into the impacts—especially potential unintended side effects—of injecting absorptive aerosols into the upper stratosphere as an alternative solar radiation management strategy.

Environmental Sciences & Ecology↗

Toxicity of hydraulic fracturing wastewater from black shale natural-gas wells influenced by well maturity and chemical additives

Hydraulic fracturing of deep shale formations generates large volumes of wastewater that must be managed through treatment, reuse, or disposal. Produced wastewater liberates formation-derived radionuclides and contains previously uncharacterized organohalides thought to be generated within the shale well, both posing unknown toxicity to human and ecological health. Here, we assess the toxicity of 42 input media and produced fluid samples collected from four wells in the Utica formation and Marcellus Shale using two distinct endpoint screening assays. Broad spectrum acute toxicity was assessed using a bioluminescence inhibition assay employing the halotolerant bacterium Aliivibrio fischeri, while predictive mammalian cytotoxicity was evaluated using a N-acetylcysteine (NAC) thiol reactivity assay. The acute toxicity and thiol reactivity of early-stage flowback was higher than later produced fluids, with levels diminishing through time as the natural gas wells matured. Acute toxicity of early stage flowback and drilling muds were on par with the positive control, 3,5-dichlorophenol (6.8 mg L -1 ). Differences in both acute toxicity and thiol reactivity between paired natural gas well samples were associated with specific chemical additives. Samples from wells containing a larger diversity and concentration of organic additives resulted in higher acute toxicity, while samples from a well applying a higher composition of ammonium persulfate, a strong oxidizer, showed greater thiol reactivity, predictive of higher mammalian toxicity. Both acute toxicity and thiol reactivity are consistently detected in produced waters, in some cases present up to nine months after hydraulic fracturing. These results support that specific chemical additives, the reactions generated by the additives, or the constituents liberated from the formation by the additives contribute to the toxicity of hydraulic fracturing produced waters and reinforces the need for careful consideration of early produced fluid management.

03 NATURAL GAS↗

WHONDRS River Corridor Sediment and Water Geochemistry and In Situ Sensor Data from Machine-Learning-Informed Sites across the Contiguous United States (v6)

This dataset supports a broader study examining hyporheic zone respiration rates to improve predictive models at a contiguous United States (CONUS) scale. The CONUS-Scale Model-Sample Study (CM) was designed following ICON (integrated, coordinated, open, and networked) principles to facilitate a model-experiment (ModEx) iteration approach, leveraging crowdsourced sampling across the CONUS. New machine learning models were created every month to guide sampling locations. Data from the resulting samples were used to test and rebuild the machine learning models for the next round of sampling guidance. Sampling began in April 2022 and ended in October 2023. In addition to the widely distributed CONUS sites, a more spatially focused sampling occurred in the Yakima River Basin, WA in summer 2022. Data from this more spatially intensive sampling occurred under the label “Second Spatial Study (SSS)” and were also included in the machine learning models. Other data types collected from SSS that were not part of CM were published in a separate data package (https://data.ess-dive.lbl.gov/view/doi:10.15485/1969566). This data package was originally published in February 2023. It was updated in June 2023 (v2; new and modified files); December 2023 (v3; new and modified files); June 2024 (v4; new and modified files); April 2024 (v5; new and modified files); and September 2025 (v6; modified files). See the change history section in the readme for more details. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. This dataset is comprised of two folders of field photos and videos, one folder of raw Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) data and one main data folder containing (1) file-level metadata; (2) data dictionary; (3) field metadata; (4) readme; (5) international generic sample number (IGSN) mapping file; (6) field protocols; (7) a subfolder with sample data; and (8) a subfolder with sensor data. The sample data subfolder contains (1) surface water and sediment dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data and averages; (2) surface water and sediment total nitrogen data and averages; (3) surface water major cations and anions and averages; (4) sediment grain size data; (5) sediment iron (II) data and averages; (6) wet sediment mass, dry sediment mass, water mass, and wet sediment volume in incubation and sediment ICR vials; (7) sediment incubation respiration rate data and averages; (8) normalized respiration rate data and averages; (9) methods codes; (10) sediment specific surface area; (11) sediment percent carbon and nitrogen; (12) sediment gravimetric moisture and averages; (15) sediment X-ray diffraction (XRD) data; (16) sediment adenosine triphosphate (ATP) and averages; (17) a subfolder with sediment incubation respiration data, scripts, and plots; (18) surface water and sediment FTICR methods; and (19) a subfolder of 9.4 Tesla (9.4T) FTICR-MS data. This folder contains five subfolders, one containing the sediment .xml data files, one containing the water .xml files, one containing the sediment CoreMS output files, one containing the water CoreMS output files, and the other containing instructions and scripts for processing the files in CoreMS (https://github.com/EMSL-Computing/CoreMS).The sensor data subfolder contains (1) a subfolder with miniDOT dissolved oxygen and temperature data and plots; (2) miniDOT dissolved oxygen and temperature summary data; and (3) miniDOT installation methods. All files are .csv, .pdf, .R, .xml, .d, .html, .Rmd, .py, .cal, .json, .jpg, .jpeg, .png, .mov, or .mp4. CORRECTION: Carbon and nitrogen content are reported as percentages. The current column headers "01395_C_percent_per_mg" and "01397_N_percent_per_mg" are incorrect. These should read "01395_C_percent" and "01397_N_percent" and will be corrected in the next version of this data package. We thank the United States Forest Service, Washington Department of Fish and Wildlife, Washington Department of Natural Resources, Cowiche Canyon Conservatory, Washington State Parks and Recreation Commission (Scientific Research Permit #210901), and the Confederated Tribes and Bands of the Yakama Nation for access to field locations where the samples labeled “SSS” were collected. We also thank the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview. WHONDRS consortium members were asked to provide any acknowledgments for the collection of samples labeled “CM” and the following is a list of acknowledgments that were submitted with their corresponding Site IDs: (MART) Research activities were conducted in part on the Wind River Experimental Forest within the Gifford Pinchot National Forest; (MP- 100379) Philadelphia is part of Lenapehoking, the ancestral homelands of the Lenape peoples; (MP-102398) Land surveyed is the ancestral homelands of the Nookhose'iinenno (Arapaho), Tsis tsis'tas (Cheyenne), and Nuuchu (Ute); (MP-100749 and MP- 100747) Georgia Coastal Ecosystem LTER, OCE-1832178; (SP-70 and SP-72) Eastern Shoshone, Shoshone-Bannock; (MP- 102944) Funded by Oregon Watershed Enhancement Board. On the traditional lands of the Confederated Tribes of the Siletz, Confederated Tribes of the Grand Rhonde, and the Clatsop-Nehalem Confederated Tribe; (MP- 100607) Holiday Creek is located on the traditional territory of the Monacan Indian Nation; (SP-45) Lafayette Blue Springs State Park; (MP-102420) NSF DEB-2016749; (MP-100019) New Hampshire Agriculture Experiment Station; (SP-35) Rayonier (land owner; https://www.rayonier.com/); (MP- 101276) US Department of Energy, Office of Science, Biological and Environmental Research, Subsurface Biogeochemical Research, Watershed Dynamics and Evolution SFA at ORNL; (MP- 103224) Watershed Dynamics and Evolution SFA at ORNL; (MP- 101584) Traditional lands of the Oceti Sakowin (Dakota, Lakota, Nakoda) and Anishinaabe Peoples.

54 ENVIRONMENTAL SCIENCES↗

Nitrous oxide inhibition of methanogenesis represents an underappreciated greenhouse gas emission feedback

Methane (CH 4 ) and nitrous oxide (N 2 O) are major greenhouse gases that are predominantly generated by microbial activities in anoxic environments. N 2 O inhibition of methanogenesis has been reported, but comprehensive efforts to obtain kinetic information are lacking. Using the model methanogen Methanosarcina barkeri strain Fusaro and digester sludge-derived methanogenic enrichment cultures, we conducted growth yield and kinetic measurements and showed that micromolar concentrations of N 2 O suppress the growth of methanogens and CH 4 production from major methanogenic substrate classes. Acetoclastic methanogenesis, estimated to account for two-thirds of the annual 1 billion metric tons of biogenic CH 4 , was most sensitive to N 2 O, with inhibitory constants (K I ) in the range of 18–25 μM, followed by hydrogenotrophic (K I , 60–90 μM) and methylotrophic (K I , 110–130 μM) methanogenesis. Dissolved N 2 O concentrations exceeding these K I values are not uncommon in managed (i.e. fertilized soils and wastewater treatment plants) and unmanaged ecosystems. Future greenhouse gas emissions remain uncertain, particularly from critical zone environments (e.g. thawing permafrost) with large amounts of stored nitrogenous and carbonaceous materials that are experiencing unprecedented warming. Incorporating relevant feedback effects, such as the significant N 2 O inhibition on methanogenesis, can refine climate models and improve predictive capabilities.

54 ENVIRONMENTAL SCIENCES↗

Latent bone modelling for estimation of plutonium concentration in skeleton of former nuclear workers

Abstract The skeleton is a major plutonium retention site in the human body. Estimation of the total plutonium activity in the skeleton is a challenging problem. For most tissue donors at the United States Transuranium and Uranium Registries, a limited number of bone samples is available. The skeleton activity is calculated using plutonium activity concentration (Cskel) and skeleton weight. In this study, latent bone modelling was used to estimate Cskel from the limited number of analysed bone samples. Data from 13 non-osteoporotic whole-body donors were used to develop latent bone model (LBM) to estimate Cskel for seven cases with four to eight analysed bone samples. LBM predictions were compared to Cskel estimated using an arithmetic mean in terms of accuracy and precision. For the studied cases, LBM offered a significant reduction of uncertainty of Cskel estimate.

Environmental Sciences & Ecology↗

Potential Chemical Impacts of Subsurface CO 2 : An Integrated Experimental and Numerical Assessment for a Case Study of the Ogallala Aquifer

Leakage from geologic CO 2 sequestration (GCS) reservoirs to overlying underground sources of drinking water (USDW) is a tangible risk. This study is an integrated assessment that combines column experiments and reactive transport simulations of sediments sampled from the Ogallala aquifer above an active commercial-scale GCS site (the Farnsworth Unit in northern Texas). Experimental and simulation results suggest that carbonate mineral (calcite and dolomite) dissolution is the most significant reaction following CO 2 intrusion, and is also the dominant source of trace metal release. Cation exchange is another key mechanism controlling trace metal release by cation interference. Most of the trace metals, including Ba, Sr, As, Pb, and Zn, show a short-term release and quickly drop to the baseline values, suggesting low risk to the overlying USDW quality. Other trace metals, such as Mn and U, exhibit a tangible increase of their concentrations in the beginning, and drop to a higher level compared to the baseline, which may become a potential concern of long-term USDW quality change with CO2introduction. This study provides a comprehensive example of combining laboratory experiments and simulations for assessment of CO 2 -sediment interactions with combined release mechanisms in shallow groundwater aquifers. Data presented here provides useful insights for quantitative risk assessment and effective public education regarding CO 2 geological sequestration, and trace metal reactive transport studies in shallow groundwater aquifers.

54 ENVIRONMENTAL SCIENCES↗

Chemolithoautotroph distributions across the subsurface of a convergent margin

Subducting oceanic crusts release fluids rich in biologically relevant compounds into the overriding plate, fueling subsurface chemolithoautotrophic ecosystems. To understand the impact of subsurface geochemistry on microbial communities, we collected fluid and sediments from 14 natural springs across a ~200 km transect across the Costa Rican convergent margin and performed shotgun metagenomics. The resulting 404 metagenome-assembled genomes (MAGs) cluster into geologically distinct regions based on MAG abundance patterns: outer forearc-only (25% of total relative abundance), forearc/arc-only (38% of total relative abundance), and delocalized (37% of total relative abundance) clusters. In the outer forearc, Thermodesulfovibrionia, Candidatus Bipolaricaulia, and Firmicutes have hydrogenotrophic sulfate reduction and Wood-Ljungdahl (WL) carbon fixation pathways. In the forearc/arc, Anaerolineae, Ca. Bipolaricaulia, and Thermodesulfovibrionia have sulfur oxidation, nitrogen cycling, microaerophilic respiration, and WL, while Aquificae have aerobic sulfur oxidation and reverse tricarboxylic acid carbon fixation pathway. Transformation-based canonical correspondence analysis shows that MAG distribution corresponds to concentrations of aluminum, iron, nickel, dissolved inorganic carbon, and phosphate. While delocalized MAGs appear surface-derived, the subsurface chemolithoautotrophic, metabolic, and taxonomic landscape varies by the availability of minerals/metals and volcanically derived inorganic carbon. Furthermore, the WL pathway persists across all samples, suggesting that this versatile, energy-efficient carbon fixation pathway helps shape convergent margin subsurface ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Vapor-Fed Cathode Microbial Electrolysis Cells with Closely Spaced Electrodes Enables Greatly Improved Performance

Hydrogen can be electrochemically produced in microbial electrolysis cells (MECs) by current generated from bacterial anodes with a small added voltage. MECs typically use a liquid catholyte containing a buffer or salts. However, anions in these catholytes result in charge being balanced predominantly by ions other than hydroxide or protons, leading to anode acidification. To enhance only hydroxide ion transport to the anode, we developed a novel vapor-fed MEC configuration lacking a catholyte with closely spaced electrodes and an anion exchange membrane to limit the acidification. This MEC design produced a record-high sustained current density of 43.1 ± 0.6 A/m 2 and a H 2 production rate of 72 ± 2 LH 2 /L-d (cell voltage of 0.79 ± 0.00 V). There was minimal impact on MEC performance of increased acetate concentrations, solution conductivity, or anolyte buffer capacity at applied voltages up to 1.1 V, as shown by a nearly constant internal resistance of only 6.8 ± 0.3 mΩ m 2 . At applied external voltages >1.1 V, the buffer capacity impacted performance, with current densities increasing from 28.5 ± 0.6 A/m 2 (20 mM phosphate buffer solution (PBS)) to 51 ± 1 A/m 2 (100 mM PBS). Furthermore, these results show that a vapor-fed MEC can produce higher and more stable performance than liquid-fed cathodes by enhancing transport of hydroxide ions to the anode.

anion exchange membrane↗

Soil gas probes for monitoring trace gas messengers of microbial activity

Abstract Soil microbes vigorously produce and consume gases that reflect active soil biogeochemical processes. Soil gas measurements are therefore a powerful tool to monitor microbial activity. Yet, the majority of soil gases lack non-disruptive subsurface measurement methods at spatiotemporal scales relevant to microbial processes and soil structure. To address this need, we developed a soil gas sampling system that uses novel diffusive soil probes and sample transfer approaches for high-resolution sampling from discrete subsurface regions. Probe sampling requires transferring soil gas samples to above-ground gas analyzers where concentrations and isotopologues are measured. Obtaining representative soil gas samples has historically required balancing disruption to soil gas composition with measurement frequency and analyzer volume demand. These considerations have limited attempts to quantify trace gas spatial concentration gradients and heterogeneity at scales relevant to the soil microbiome. Here, we describe our new flexible diffusive probe sampling system integrated with a modified, reduced volume trace gas analyzer and demonstrate its application for subsurface monitoring of biogeochemical cycling of nitrous oxide (N 2 O) and its site-specific isotopologues, methane, carbon dioxide, and nitric oxide in controlled soil columns. The sampling system observed reproducible responses of soil gas concentrations to manipulations of soil nutrients and redox state, providing a new window into the microbial response to these key environmental forcings. Using site-specific N 2 O isotopologues as indicators of microbial processes, we constrain the dynamics of in situ microbial activity. Unlocking trace gas messengers of microbial activity will complement -omics approaches, challenge subsurface models, and improve understanding of soil heterogeneity to disentangle interactive processes in the subsurface biome.

04 OIL SHALES AND TAR SANDS↗