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A minor respiratory process with major global implications: is atmospheric methane oxidation in tree stems driven by stem respiration rather than microbial methanotrophy?

Tree stem surfaces are widely recognized as sites of carbon dioxide (CO₂) efflux and oxygen (O₂) influx, reflecting the dynamics of aerobic respiration of photosynthate substrates, such as sugars, delivered via the phloem. Stems are also largely considered passive conduits for methane (CH₄) produced in anoxic soils via microbial methanogenesis, where CH₄ is thought to be transported upward through the transpiration stream and/or diffusion and emitted through stem surfaces and the canopy. However, recent observations from dynamic stem chambers suggest that stems may also act as active sinks for atmospheric CH₄. Despite these findings, the extent and drivers of stem CH₄ consumption remain poorly characterized across biomes, species, and environmental gradients, and its quantitative relationship to stem respiration has not been established. Moreover, previous studies captured only snapshot fluxes, leaving diurnal patterns of CH₄ exchange uncharacterized. Here, we address these limitations by combining real-time measurements of stem CH₄ and O₂ uptake under ambient conditions in a California cherry tree, using a dynamic stem gas exchange system with three chambers receiving a continuous flow of ambient air and automated chamber and reference air sampling every 10 min. Our results confirm that stems of upland trees can actively consume both atmospheric CH₄ and O₂, but with decreasing temperature sensitivity as daily temperatures increase. Early mornings were marked by rapid influxes of both gases, followed by declining uptake as temperatures rose further. Methane uptake was tightly coupled with O₂ influx and represented a minor (0.012% ± 0.002%) fraction of stem respiratory activity, as determined by concurrent O₂ uptake. These findings suggest that while atmospheric CH₄ oxidation is a minor respiratory process in stems, it is strongly linked with stem physiological activity. This challenges the current assumption that terrestrial CH₄ uptake is driven solely by microbial methanotrophy and raises the possibility that living stem tissues may contribute to CH₄ oxidation through an as-yet-unidentified plant-based mechanism.

Atmospheric greenhouse gases↗

Illuminating the pathways to carbon liberation: a systems approach to characterizing the consequential unknowns of carbon transformation and loss from thawing permafrost peatlands (Final Report)

The IsoGenie3 Project delivered new systems-level insights into carbon cycling in thawing permafrost landscapes, with an emphasis on methane and carbon dioxide emissions. From >200 samples from the site collected over a decade, co-analyzed for geochemistry and microbiology, the team recovered ~1,500 assembled microbial genomes and ~1,900 viral population genomes, revealing appreciable genetic novelty - from a new highly abundant bacterial phylum, to novel methane consumers and their activities, to rampant viral novelty. IsoGenie3 linked these organisms to carbon compound transformations (which define the cycling of organic matter in soils, and the loss of the greenhouse gases carbon dioxide and methane), and saw that the microbes at each stage of permafrost thaw had different genetic potential to degrade categories of compounds, expressed that genetic potential differently, and actually transformed carbon compounds into greenhouse gases in different ways. IsoGenie 3 identified that some of the thaw-stage differences were due to plant-microbiome relationships; the plant species across the thaw gradient contributed different carbon compounds into the soil, and hosted distinct microbiota (differing among parts of plants as well as species). Lastly, microbes in the saturated post-thaw conditions appeared likely to contribute to the mobilization and toxification of mercury released during thaw. In parallel with ongoing field sampling and analysis, hypotheses arising from field observations were tested via lab incubation experiments. When communities are taken out of their native habitats, they behave differently, and the team first rigorously quantified the magnitude of this effect on microbiome composition and functional capacity, organic matter composition, and gas production; overall the main system processes were maintained in the lab incubations under the conditions tested. Further, the microbial data could inform geochemical reaction network models of those processes. Then, the team ran experiments with additions of compounds, varying temperature, and “live” vs. “dead” peat (the latter having been gamma irradiated, with a few additional variants to control for methodological artifacts). From these, we (a) determined the importance of plant-derived soluble phenolic compounds in bogs’ extraordinary recalcitrance of organic matter, and carbon gas emissions skewed to carbon dioxide; (b) proposed an abiotic ‘tanning’ mechanism, which could contribute to Sphagnum’s inhibitory effect on anaerobic decomposition through alteration of N availability. IsoGenie3 illuminated longer-term and landscape-scale interactions of permafrost thaw and carbon cycling, advancing knowledge of the drivers of methane dynamics not only across in the permafrost-associated peatland (where hydrology and plant communities dictate microbiomes) but also their interconnected lakes (where sediment carbon quality and resident microbiota are determined by position within lake, and lake features). By leveraging observations of site methane dynamics extending well before this project, the team was able to construct a 44-year portrait of the interplay of permafrost thaw, hydrology, vegetation dynamics, and carbon gas emissions, and the doubling of the fully-thawed fens over this time. From the detailed study of this focal site, IsoGenie3 also aimed to improve model representation of these kinds of sites and processes. To improve predictions of methane transformations, we incorporated acetate and isotope dynamics into the ‘DNDC’ biogeochemistry model. In addition, recovered genomes were grouped into ‘functional groups’, i.e. the genomes that perform a specific function of interest, then used to parameterize maximum growth rate and optimum growth temperature (via signatures in their sequence composition) for the BioCrunch model. The BioCrunch model was then in turn used to test the impact of increasing functional resolution of the microbes, on the carbon gas emissions. Lastly for modeling, the ecosys model was parameterized from the microbial and other data, and used to evaluate drivers of e.g. change in methane emissions. Finally, this project also led to the development of a range of new methods and tools, a new metric of organic matter decomposability, as well as a graph-database solution to multidisciplinary data storage and querying. This project’s ongoing analyses at our focal site also contributed to broader advancements in understanding elements of genetic plasticity and methane metabolism, climate change microbiology and community assembly, global peatland geochemistry and Arctic lakes’ roles in climate feedbacks.

54 ENVIRONMENTAL SCIENCES↗

Light element geochemistry of the Apollo 12 site

Analytical techniques of improved sensitivity have revealed details of the concentrations and isotopic compositions of light elements for a comprehensive suite of samples from the Apollo 12 regolith. These samples show a wide spread in maturity, although maximum contents observed for solar wind elements are less than observed at other sites, possibly reflecting relative recency of craters at the Apollo 12 site. Isotopic composition of nitrogen is consistent with the idea that N-15/N-14 in the solar wind has increased with time, at least a major part of this increase having occurred in the past 3.1 Gyr. Sulfur isotope systematics support a model in which sulfur is both added to the regolith, by meteoritic influx, and lost, by an isotopically selective process. Most soils from this site are heavily contaminated with terrestrial carbon.

Kerridge, J. F.↗

Potential Mars Surveyor 2001 Landing Sites: Low-Elevation Cratered "Highlands" in Central and Eastern Sinus Meridiani and Near Amenthes Fossae

The main scientific goal for the Mars Surveyor Program 2001 (MSP 01) landed mission is to collect and characterize 91 rock and 13 soil core samples using an integrated instrument suite onboard the Athena Rover. If possible, these samples will be retrieved and returned to Earth via a MSP 05 or MSP 07 mission. Preliminary engineering constraints for the MSP 01 landing site call for a location that lies between 15 S and 30 N, and below about 2 km elevation (based on Viking-era topography). Desirable landing sites for MSP 01 are to be located "in the ancient highlands where the environmental conditions may have been favorable to the preservation of evidence of possible prebiotic or biotic processes including the emergence (and, potentially, the persistence) of life". We interpret this to mean that the desirable sites include those that have evidence of aqueous sediments that might have been deposited during the Noachian and/or Hesperian Epochs of Mars' history. In addition to the search for subaqueous sedimentary deposits, we took into consideration the fact that the rover, Athena, will need to be able to access these materials. Thus, a site where aeolian deflation has occurred might be desirable because it might expose, in situ, layered sedimentary deposits. Deflated areas, of course, might include potential landing hazards in the form of meterscale buttes and mesas (e.g., Christmas Lake Valley, OR), thus careful study of such sites with high resolution images will be required before a decision is made to land. We have been examining three regions that have potential to be considered for MSP 01 landing sites. This work is based on Viking (VIS, IRTM) and Phobos 2 (Termoskan) observations and should be regarded as preliminary because we believe that the final site selection should also be based upon analysis of Mars Global Surveyor observations that help constrain mineralogy (TES) and local geomorphology (MOC, MOLA). (1) Eastern Sinus Meridiani Region (proposed by K. S. Edgett) Sinus Meridiani is a persistent low-albedo (< 0. 16) region on the martian equator that has been recognized for about 400 years. All of Sinus Meridiani is below the 2 km elevation constraint for MSP 01. The region includes cratered highlands, valley networks, aeolian dunes, and possible aqueous sedimentary deposits. The landing site study region is located in the eastern portion of Sinus Meridiani. It is bounded by latitudes 10 S to 2 N, longitudes 355 W to 345 W, and the elevations are mostly 1-2 km. The center of this area contains a medium-albedo (0.19-0.21), relatively smooth-surfaced deposit that was suggested by Rice to be a lacustrine deposit. Several potential landing areas can be suggested within this region. Based on Viking and Phobos 2 data, the favored sites so far are centered at 7.6 S, 346.9 W and 0.8 S, 349 W. Thermal inertias are 3.2-7.0 x 10(exp -3) cal /sq cm s(exp -0.5)/K; and rock abundances are around 2-6%. The site at 7.6 S, 346.9 W is at the southern end of the smooth, medium-albedo unit that might have a lacustrine origin. At this location, numerous channels appear to have drained toward the smooth unit. Viking images from orbit 747A show this area at about 15 m/pixel ground resolution. The images reveal that aeolian deflation has occurred along the deposit's margins. Bright (i.e., albedo >= 0.21) aeolian dunes are present on the channel floors and in some of the depressions on the smooth unit. The bright, apparently active dunes might consist of material (perhaps lakedeposited sands) that has been eroded from the smooth unit. The site at approximately 0.8 S, 349 W is selected because it offers an opportunity to solve a long-standing puzzle about Mars remote sensing. There are three main "color" units on Mars: "dark red, dark gray, and bright red". This landing site would allow the Athena rover an opportunity to investigate all three materials within close proximity (the best place on Mars to do so). There are no high resolution (better than 100 m/pixel) Viking or Mariner images of this site. (2) Central Sinus Meridiani Region (proposed by K. S. Edgett and T. J. Parker) Central Sinus Meridiani is characterized by two types of surfaces [4]. One is like typical martian cratered highlands elsewhere- there are old valley networks and old impact craters. The other is relatively smooth and flat. These two units are in contact around 3.1 S between 5 W and 4 E longitudes. Valley networks- including one at 6'S, 358 W that rivals the Grand Canyon of Arizona- once drained toward the smooth unit. Edgett and Parker [4] proposed that the smooth unit might consist of sediments laid down in a large Noachian-aged sea/ocean that would have covered much of the northern hemisphere. Schultz and Lutz [I I I suggested that it is a paleopolar layered deposit. Regardless, the smooth unit where it contacts the cratered terrain would make an excellent site for Athena rover to investigate. The site is best seen in Viking high resolution images from orbits 408B (about 30 m/pixel) and 746A (about 12 m/pixel). These images suggest that aeolian deflation has occurred along the margin of the smooth unit, and this deflation has exposed horizontal larrs of material. The elevation is about 0.5 km; thermal inertias are 6.5-8.0 x 10(exp -3) cal /sq cm s(exp -0.5) / K; rock abundances are 2-4%; and the surface is probably sandy with dark drifts and ripples but almost no actual dunes. We suggest a landing around 3.2 S, 3.0 W would test the aqueous sediment hypothesis and provide a potentially smooth surface on which to land. (3) Amenthes Fossae Region (proposed by S. N. Huntwork and K. S. Edgett) The Amenthes Fossae are a series of graben/fissures that are circumferential to the southeast side of Isidis Planitia. These fissures cross a variety of ancient, heavily cratered Noachian terrain and younger, Hesperian and Amazonian terrain. We focused our search on a region 0-15 N, 250 - 270 W. Elevations are -0.5 to 2 km. Depending upon whether Isidis Planitia was ever a water-rich environment, this region might have been influenced by aqueous sedimentation. Valley networks are common, and they drained toward the north and northwest. We focused our work on a set of Viking orbiter high-resolution images, 719A 1-48. These have resolutions 16-24 rri/pixel. We examined images 20-23, centered at 2 N, 258 W. This site, on the plains just southwest of a 42 km-diameter crater, includes a valley network channel, a relatively young crater ejecta deposit, a few buttes composed of presumably ancient, Noachian bedrock, and a "plains" unit. The plains might make an ideal landing surface, except for the presence of some fine-scale ridges (oriented approximately N-S). The ridges are probably yardangs, thus this site offers a place where aeolian deflation has probably exposed some of the layered rock units that comprise the "plains". Thermal inertias are 7.9-8.3 x 10(exp -3) cal/sq cm s(exp -0.5) /K and rock abundances are 10-15%. A rover traverse might include the opportunity to go down to the floor (and sample along the walls) of the valley network channel at 2 N 258.1 W.

Edgett, K. S.↗

The Impact of Freeze‐Thaw History on Soil Carbon Response to Experimental Freeze‐Thaw Cycles

Abstract Freeze‐thaw is a disturbance process in cold regions where permafrost soils are becoming vulnerable to temperature fluctuations above 0°C. Freeze‐thaw alters soil physical and biogeochemical properties with implications for carbon persistence and emissions in Arctic landscapes. We examined whether different freeze‐thaw histories in two soil systems led to contrasting biogeochemical responses under a laboratory‐controlled freeze‐thaw incubation. We investigated controls on carbon composition through Fourier‐transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS) to identify nominal carbon oxidation states and relative abundances of aliphatic‐type carbon molecules in both surface and subsurface soils. Soil cores (∼60 cm‐depth) were sampled from two sites in Alaskan permafrost landscapes with different in situ freeze‐thaw characteristics: Healy (>40 freeze‐thaw cycles annually) and Toolik (<15 freeze‐thaw cycles annually). FT‐ICR‐MS was coupled with in situ temperature data and soil properties (i.e., soil texture, mineralogy) to assess (a) differences in soil organic matter composition associated with previous freeze‐thaw history and (b) sensitivity to experimental freeze‐thaw in the extracted cores. Control (freeze‐only) samples showed greater carbon oxidation in Healy soils compared with Toolik, even in lower mineral horizons where freeze‐thaw history was comparable across both sites. Healy showed the most loss of carbon compounds following experimental freeze‐thaw in the lower mineral depths, including a decrease in aliphatics. Toolik soils responded more slowly to freeze‐thaw as shown by intermediary carbon oxidation distributed across multiple carbon compound classes. Variations in the response of permafrost carbon chemistry to freeze‐thaw is an important factor for predicting changes in soil function as permafrost thaws in high northern latitudes.

Rooney, Erin C.↗

Iron Behavior in Microcosms Simulating Bioreduction in Savannah River Site Sediments - 17389

An estimated 1.8 billion gallons of acidic low-activity waste solutions originating from the processing of uranium slugs and irradiated fuel at separation facilities at the Savannah River Site (SRS) were discharged to the unlined seepage basins located in the F/H-area. The acidic solutions of the basin influent (pH from 3.2 to 5.5) contaminated with a variety of radionuclides and dissolved metals caused groundwater contamination. In 2010, DOE funded a demonstration of the Enhanced Anaerobic Reductive Precipitation (EARP) process at the SRS F-Area that consisted of in-situ injections of a carbohydrate substrate to establish anaerobic reactive zones for metal and radionuclide remediation. The addition of the molasses substrate solution to groundwater was done to produce anaerobic conditions conducive to uranium reduction and then precipitation as uranium (IV). The SRS soil is highly weathered and features very low natural alkalinity. A microcosm study, prepared with sieved SRS sediments and augmented with a solution mixture containing molasses and sulfate, was designed to provide evidence of the capabilities of this remediation technology under SRS environmental conditions. The objective of these microcosm experiments was to replicate the anaerobic conditions created as a result of injections of molasses combined with sulfate ions, similar to the EARP process that was performed at SRS, and investigate if any mineralogical changes could occur in the soil due to the addition of molasses. Specifically, the study aimed to determine if solid phases of reduced iron such as siderite and pyrite would be formed, as this would indicate the potential to form a long-lasting bioreductive zone. An understanding of this technology will be useful in determining if it is a viable option for remediation. In the experiments, the media solution was amended with molasses and sulfate to stimulate sulfate-reducing bacteria. Sulfate reduction occurs extensively under the redox conditions occurring after iron reduction and before methanogenic conditions. These conditions are considered the second most reducing condition in natural groundwater systems. Microcosm tubes prepared in triplicate were kept inside an anaerobic glove box, which was continuously monitored to ensure that conditions remained anaerobic. The initial X-ray diffraction (XRD) analyses on the background sediment samples indicated the presence of quartz, kaolinite, montmorillonite, and goethite. In the molasses-treated samples there were no visible peaks for reduced forms of iron such as siderite and pyrite. The pH measurements suggest that all samples in either batch, including those that were brought to a neutral pH before the addition of the sediments, have followed a similar trend with a decline in the pH value to between 4 and 4.7. This can be attributed to the fermentation of molasses and the natural acidity of the SRS sediments used for the microcosm study. In the acidic iron-rich sediment, the microbial reduction of Fe (III) was the predominant electron-accepting process for oxidation of the organic substrate. The maximum iron concentration detected during the experiments was 13 mg/L. Analytical results showed that there was no sulfate reduction in any of the samples augmented with sulfate and the concentration remained level at 500 ppm as originally added to the initial solutions (518 - 542 mg/L). This is consistent with the absence of any indication of iron sulfide formation. Under the experimental conditions in these microcosms, the abundance of biologically available Fe (III) allows Fe (III)-reducers to out-compete sulfate-reducing bacteria using molasses as an electron donor. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

16s Amplicon Analysis of Soil Data for Interactive effects of depth and differential irrigation on soil microbiome composition and functioning

Genomic DNA was isolated from soil and rhizosphere samples using the Zymo Quick-DNA fecal/soil microbe miniprep kit (catalog no. D6010) according to the manufacturer’s instructions (Zymo Research; Irvine, CA) with the modification of eluting in 100 uL elution buffer. Sample concentrations were quantified using the Qubit dsDNA HS assay kit (Thermo Fisher). For rhizosphere samples only, DNA was subsequently purified using Zymo’s ZR-96 DNA Clean & Concentrator kit (catalog no. D4024) to account for low DNA concentrations of these samples. . In each replicate block, there were five drip irrigation treatments (T1 = 100% normal irrigation, T2 = 56.25%, T3 = 37.5%, T4 = 18.75% and T5=no irrigation. On July 20, the strength of the drought treatments was increased: T1 remained at 100%, whereas T2 changed from 75% to 56.25%, T2 changed from 50% to 37.5%, and T4 changed from 25% to 18.75%. Sequencing was performed as described previously (Naylor, Fansler, et al. 2020). Sequences were amplified on the MiSeq platform (Illumina, San Diego, CA) using 16S primers (515F and 806R) specific to the V4 region. Raw sequence data was processed with the pipeline Hundo for amplicon quality control and annotation. Downstream statistical analyses on 16S datasets were performed using the program R and the packages ‘phyloseq’ and ‘vegan’.

Soil microbiome, metatranscriptomics↗

Soil Moisture and Sea Surface Salinity Derived from Satellite-Borne Sensors

The monitoring of soil moisture and sea surface salinity over the Earth has been profoundly enhanced during the last thirteen years owing to new generation of satellite sensors. L-band radiometry is currently the only technology providing direct measurements of soil moisture, insensitive to surface roughness and distribution of elements in the soil, and the only technology that allows to measure sea surface salinity from space. The SMOS (Soil Moisture and Ocean Salinity) and SMAP (Soil Moisture Active Passive) satellite missions resolve global and local variability with a spatial resolution of approximately 43 km, a swath width close to 1000 km, and a sampling time, for each mission, of at least twice every 3 days. These resolutions and samplings can be increased by either merging data from the two sensors, and with complementary informations gathered with other passive or active sensors, or with in situ information at higher spatial resolution. Numerous scientific studies based on the use of this new type of measurement have led to a better understanding and constraint of the processes governing the variability of the water cycle, ocean circulation and the Earth's climate. The continuity of measurements, and the increased spatial and radiometric resolution is critical for fulfilling scientific needs. Future L-band radiometry missions currently being planned in Europe (the Copernicus Imaging Microwave Radiometer), and in China (the Ocean Salinity Mission) should provide better constraint on auxiliary parameters by combining multiple frequencies, but they will not have improved spatial resolution beyond SMOS and SMAP. The temporal continuity with SMOS and SMAP will most likely not be ensured. In parallel, new concepts are being developed to increase spatial resolution of both land and ocean parameters.

J. Boutin↗

Detecting Sub-Micron Space Weathering Effects in Lunar Grains With Synchrotron Infrared Nanospectroscopy

Space weathering processes induce changes to the physical, chemical, and optical properties of space-exposed soil grains. For the Moon, space weathering causes reddening, darkening, and diminished contrast in reflectance spectra over visible and near-infrared wavelengths. The physical and chemical changes responsible for these optical effects occur on scales below the diffraction limit of traditional far-field spectroscopic techniques. Recently developed super-resolution spectroscopic techniques provide an opportunity to understand better the optical effects of space weathering on the sub-micrometer length scale. This paper uses synchrotron infrared nanospectroscopy to examine depth-profile samples from two mature lunar soils in the mid-infrared, 1,500 –700 cm -1 (6.7–14.3 μm). Overall, our findings are broadly consistent with prior bulk observations and theoretical models of space weathered spectra of lunar materials. These results provide a direct spatial link between the physical/chemical changes in space-exposed grain surfaces and spectral changes of space weathered bodies.

79 ASTRONOMY AND ASTROPHYSICS↗

A global dataset of terrestrial biological nitrogen fixation

Biological nitrogen fixation (BNF) is the main natural source of new nitrogen inputs in terrestrial ecosystems, supporting terrestrial productivity, carbon uptake, and other Earth system processes. We assembled a comprehensive global dataset of field measurements of BNF in all major N-fixing niches across natural terrestrial biomes derived from the analysis of 376 BNF studies. The dataset comprises 32 variables, including site location, biome type, N-fixing niche, sampling year, quantification method, BNF rate (kg N ha −1 y −1 ), the percentage of nitrogen derived from the atmosphere (%N dfa ), N fixer or N-fixing substrate abundance, BNF rate per unit of N fixer abundance, and species identity. Overall, the dataset combines 1,207 BNF rates for trees, shrubs, herbs, soil, leaf litter, woody litter, dead wood, mosses, lichens, and biocrusts, 152 herb %N dfa values, 1,005 measurements of N fixer or N-fixing substrate abundance, and 762 BNF rates per unit of N fixer abundance for a total of 424 species across 66 countries. This dataset facilitates synthesis, meta-analysis, upscaling, and model benchmarking of BNF fluxes at multiple spatial scales.

Reis Ely, Carla R. [Oregon State Univ., Corvallis,↗

2015 Advanced Site Investigation and Monitoring Report Riverton, Wyoming, Processing Site September 2016

The U.S. Department of Energy conducted initial groundwater characterization of the Riverton, Wyoming, Processing Site in the 1990s. The characterization culminated in a Site Observational Work Plan in 1998 that recommended a natural flushing compliance strategy. Results of verification monitoring indicated that natural flushing was generally progressing as expected until June 2010, when significant increases in contaminant concentrations were measured in several monitoring wells downgradient of the site after the area flooded. In response to the unexpected results following the flood, an enhanced characterization of the surficial aquifer was conducted in 2012, which included installation of 103 boreholes along nine transects with a Geoprobe, collection of 103 water samples and 65 soil samples, laboratory tests on the soil samples, and additional groundwater modeling. This advanced site investigation report summarizes additional investigation in 2015 through the use of backhoe trenching, sonic drilling, multilevel monitoring wells, direct-push drilling, and temporary well points to collect soil and groundwater samples. Additional surface water measurements were made included the installation of a stilling well and the measurement of stream elevation along the Wind River to approximate upgradient groundwater heads. Groundwater sampling included the addition of geochemical constituents and isotopes that have not been sampled in the past to better understand post-flood conditions and the possibility of additional or ongoing contaminant sources. This sampling was performed to (1) better define the contaminant plumes, (2) verify the occurrence of persistent secondary contaminant sources, (3) better understand the reason for the contaminant spikes after a 2010 flood, and (4) assess contaminant plume stagnation near the Little Wind River. This report provides data analyses and interpretations for the 2015 site investigation that addresses these issues and provides recommendations for future efforts. Observations from trenches and sonic drilling indicate the general lithology of the shallow, unconsolidated sediments consists of a silt zone at the surface that ranges from 2.5 to 4.8 feet below ground surface, underlain by sand and gravel, underlain by the top of the weathered bedrock (Wind River Formation). Soil data from trenches and sonic drilling indicate (1) elevated concentrations of several constituents in the silt zone, likely due to the formation of evaporites, (2) uranium is the only measured element that appears to be concentrated in the silt over the groundwater contaminant plume, (3) in the former tailings impoundment area, there may be a thin unsaturated zone with elevated uranium in the native material just below the fill, (4) in the former tailings impoundment area, slightly higher uranium concentrations occur in the underlying saturated sand and gravel, and (5) several bedrock samples have a unique geochemical signature, generally related to a higher silt content. Assessment of groundwater flow included measuring river elevations along the Wind River and installing the temporary well points adjacent to the Little Wind River that provided additional data points to refine contours for water table elevations. These data confirm past interpretations of groundwater flow to the southeast across the site toward the Little Wind River. Hydraulic head elevations between paired surficial and semiconfined aquifer wells indicate variable vertical gradients across the site with the potential for upward and downward flow. Additional direct-push drilling and groundwater sampling confirmed the contaminant plume configuration, but it also revealed a low-sulfate-concentration zone at the edge of the former tailings impoundment. Temporary well points provided better definition of plume concentrations at the bank of the Little Wind River, and data from these wells indicate plume discharge to the river. Additional sampling in an area southwest of the plume that had elevated uranium groundwater concentrations in the past did not have any uranium concentrations above the U.S. Environmental Protection Agency maximum concentration limit for uranium. Results from multilevel monitoring wells indicate some geochemical differences with depth, but overall concentrations are similar to those in nearby conventional monitoring wells in the long-term monitoring program. Geochemistry data from these multilevel monitoring wells confirm the general increase in contaminant concentrations toward the river and toward the plume centerline for chloride, sulfate, and uranium but highlight geochemical controls on calcium. Iron data indicate slightly reducing conditions, especially near water table and bedrock surfaces, with more oxidizing conditions in the middle of the sand and gravel. Uranium activity ratios (234U/238U) confirm the uranium plume in the surficial aquifer as being mill related, and the area to the southwest outside the plume as natural, non-mill related. In the semiconfined aquifer, evidence of aquifer connection and impacts from the mill is inconclusive. Values of δD and δ 18 O suggest water is derived from different sources and tritium data confirm that the semiconfined aquifer water is generally older than the surficial aquifer water. However, these data do indicate some groundwater communication from the surficial aquifer into the semiconfined aquifer, which resulted in δD and δ 18 O and tritium values in the semiconfined aquifer that are more similar to those in the surficial aquifer. Values of δ 34 S sulfate in the semiconfined aquifer combined with sulfate concentrations indicate the potential for some mill- related sulfate in the semiconfined aquifer, albeit limited to an area near and beneath the former tailings impoundment. Uranium and molybdenum concentrations in the semiconfined aquifer are below groundwater standards in all wells. However, the elevated molybdenum concentrations at one semiconfined aquifer well underneath the former tailings impoundment suggests a mill- derived source for the uranium and molybdenum in that well. It is possible that aquifer cross- communication occurred when the tailings impoundment was active and created a higher head. Current cross-communication appears unlikely given the large differences in tritium values and an upward hydraulic head at this location. Nine domestic wells are located within the institutional control boundary (eight in the confined aquifer and one in the semiconfined aquifer). Uranium and molybdenum concentrations in all samples collected from these wells were one or two orders of magnitude below the groundwater standards. Surface water flow in the Little Wind River in September 2015 was low compared to historical averages for that time of year. As a result, the uranium concentration measured in the Little Wind River was at a historical maximum at the sampling location upstream of the site. However, the impact of uranium discharge from the groundwater plume into the Little Wind River was not measureable. Elevated sulfate concentrations were observed in an outfall ditch related to an active sulfuric acid plant. Uranium concentrations in the oxbow lake remain at concentrations above the groundwater standard. Plume contaminant concentrations had returned to levels found prior to the 2010 flood by the end of 2015. However, these concentrations still exceed model predictions for natural flushing, and the current data indicate that natural flushing to achieve remediation goals within the 100-year time period is not likely, especially with the high potential for additional floods in the update to the conceptual site model (CSM), soil data indicate additional contaminant sources, specifically uranium, in evaporites within the silt layer over the uranium plume and in naturally reduced zones (NRZs). Additional zones of slightly elevated uranium concentration are in the native sediments just above the water table but below the fill layer in the former tailings impoundment area. This area also has slightly elevated uranium in the sand and gravel below the water table. Mass balance calculations indicate that small amounts of dissolution in any of these zones with increased uranium in the solid phase can produce groundwater uranium concentrations above the groundwater standard and could account for the post-flood uranium spike. The additional uranium near the former tailings impoundment provides a mechanism for a continuing source for the uranium plume that was not considered in earlier natural flushing models. In addition, uranium released from the silt layer or the NRZs seasonally and during flooding may add uranium to the groundwater plume near the Little Wind River. These mechanisms provide a possible explanation for plume persistence, along with spikes in concentrations during floods, that creates the current plume configuration. Additional updates to the CSM include (1) chloride flushes more rapidly than uranium beneath the former mill site, (2) chloride in the silt layer provides a scenario in which chloride cannot be used as a conservative tracer (especially in areas prone to flooding), (3) uranium concentrations with depth can be variable (especially below NRZs), and (4) calcite and gypsum solubility limits appear to provide important geochemical controls on groundwater geochemistry. The conclusion of this study provides several recommendations for additional work to refine the CSM and continue assessment of the natural flushing compliance strategy. Recommendations for additional work include targeted soil and groundwater sampling to assess geochemical conditions, distribution of contaminants, and groundwater/surface water interaction; additional column tests to provide data for geochemical modeling; and development of an updated groundwater flow model, which will be used in conjunction with a geochemical model to assess the viability of the natural flushing compliance strategy.

2015 Monitoring Riverton, WY↗

Apollo 14 revisited, or breccias aren't so bad after all

A study of large Apollo 14 samples suggests that they were formed by the same processes which formed the impactites found at Apollo 16 and 17 and in terrestrial craters, especially those in crystalline targets. The abundant crystalline matrix breccias of the Apollo 14 samples generally show higher clast contents and less refractory clast populations than the clast-laden impact melts abundant at the other Apollo nonmare landing sites. The Apollo 14 characteristics are attributed to the mixing of a greater amount of cold clastic debris into the superheated melt formed during impacts. The other major lithology at Apollo 14, the vitric matrix breccias, are made in part from agglutinate-bearing soil and cannot be the protolith of crystalline matrix breccias, because of differences in structure and composition. Variations among the breccias indicate the occurrence of several impact events.

Simonds, C. H.↗

Post-fire time series of sensor and geochemistry sample data from surface water, groundwater, precipitation, soil, and vegetation across Oak Creek watershed, Washington

This dataset supports a broader study examining wildfire impacts on hydrologic connectivity across 5 sites within the Oak Creek watershed and the resulting biogeochemical impacts. Stream sites were selected using the Advanced Terrestrial Simulator (ATS) hydrologic model to identify locations with varying groundwater contributions and hydrologic responses across different burn severity scenarios. The Retreat Fire burned from July 23 to August 2 in 2024, affecting the five study sites at varying burn severities. Each site is equipped with YSI EXO2 sondes logging sub-hourly throughout the year, and grab samples are collected approximately every six weeks. YSI sondes are used to measure temporally resolved proxies for groundwater inputs (specific conductivity) and organic matter (fluorescent dissolved organic matter; fDOM) along with basic water quality and depth. Grab samples of surface water, groundwater, and precipitation are analyzed for water stable isotopes and conductivity to understand endmembers for hydrologic mixing Grab samples of surface water, groundwater, soil water, and litter/vegetation/soil leachates are analyzed for organic matter composition measured by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) to understand organic matter dynamics. Game camera photos are provided in a separate data package available at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/3018598. Future versions of this dataset will include time series data from YSI EXO2 sondes (fDOM, dissolved oxygen, temperature, depth, specific conductance, turbidity, pH), BaroTROLL sensors (air temperature and barometric pressure), rain gauges (precipitation), and data from the soil and vegetation samples. Because this study is ongoing, this data package will be updated regularly to include newly collected data and the additional data types. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions. This dataset is comprised of (1) a folder of field photos; (2) a folder of surface water sample data; (3) a folder of raw Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) data; (4) a data checks report; (5) file-level metadata; (6) data dictionary; (7) field metadata; (8) readme; (9) international generic sample number (IGSN) mapping file; and (10) field protocols. The sample data subfolder contains (1) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data and averages; (2) total dissolved nitrogen data and averages; (3) stable water isotopes and averages; (4) methods codes; (5) FTICR-MS methods; and (15) a subfolder of 9.4 Tesla (9.4T) FTICR-MS data. This folder contains the processed data and three subfolders, one containing the .xml 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). All files are .csv, .pdf, .R, .xml, .d, .html, .Rmd, .py, .cal, .json, .jpg, .jpeg, .png, .mov, or .mp4.

Biogeochemistry↗

Measurement of Volatile Compounds for Real-Time Analysis of Soil Microbial Metabolic Response to Simulated Snowmelt

Snowmelt dynamics are a significant determinant of microbial metabolism in soil and regulate global biogeochemical cycles of carbon and nutrients by creating seasonal variations in soil redox and nutrient pools. With an increasing concern that climate change accelerates both snowmelt timing and rate, obtaining an accurate characterization of microbial response to snowmelt is important for understanding biogeochemical cycles intertwined with soil. However, observing microbial metabolism and its dynamics non-destructively remains a major challenge for systems such as soil. Microbial volatile compounds (mVCs) emitted from soil represent information-dense signatures and when assayed non-destructively using state-of-the-art instrumentation such as Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-TOF-MS) provide time resolved insights into the metabolism of active microbiomes. In this study, we used PTR-TOF-MS to investigate the metabolic trajectory of microbiomes from a subalpine forest soil, and their response to a simulated wet-up event akin to snowmelt. Using an information theory approach based on the partitioning of mutual information, we identified mVC metabolite pairs with robust interactions, including those that were non-linear and with time lags. The biological context for these mVC interactions was evaluated by projecting the connections onto the Kyoto Encyclopedia of Genes and Genomes (KEGG) network of known metabolic pathways. Simulated snowmelt resulted in a rapid increase in the production of trimethylamine (TMA) suggesting that anaerobic degradation of quaternary amine osmo/cryoprotectants, such as glycine betaine, may be important contributors to this resource pulse. Unique and synergistic connections between intermediates of methylotrophic pathways such as dimethylamine, formaldehyde and methanol were observed upon wet-up and indicate that the initial pulse of TMA was likely transformed into these intermediates by methylotrophs. Increases in ammonia oxidation signatures (transformation of hydroxylamine to nitrite) were observed in parallel, and while the relative role of nitrifiers or methylotrophs cannot be confirmed, the inferred connection to TMA oxidation suggests either a direct or indirect coupling between these processes. Overall, it appears that such mVC time-series from PTR-TOF-MS combined with causal inference represents an attractive approach to non-destructively observe soil microbial metabolism and its response to environmental perturbation.

59 BASIC BIOLOGICAL SCIENCES↗

Characterizing major and trace element compositions in fallout melt glass from a near-surface nuclear test

We report the chemical and isotopic compositions of fallout melt glasses from nuclear tests contain a range of information constraining the physical conditions within the fireball and the mechanisms of fallout formation but historic studies tended to exclude the behavior of stable major and trace elements. Here, we present a large study specifically focused on major and trace element relationships within a population of macroscale fallout samples from a single event. We interpret these data to better constrain how fallout melt glass formation in near surface environments is influenced by that environment and demonstrate how major and trace element abundances can provide useful insights into chemical processes within the fireball. Data confirm that the uranium in the fallout glass population derives from two isotopically distinct endmembers: isotopically enriched uranium (presumably from the weapon), and natural composition uranium that may be a combination of anthropogenic and environmental materials from within the blast zone. The similarity between major and trace element concentrations in fallout and corresponding local soils from the event site confirm the local soils as the most probable source of entrained material into the fireball and the source of carrier material into which the bomb vapor was incorporated. The lack of correlation between major and trace element abundances with size indicates that volatility driven processes, such as condensation from the fireball, do not control the composition of macroscale fallout melt glass. Although the fallout has major and trace element chemical characteristics broadly similar to those of the local, associated soils, some systematic differences are observed between the two populations. Fallout melt glass is depleted in volatile elements such as K, Na, Tl and Pb, consistent with heating to temperatures above ~1000 °C for 3-10 s. This is supported by the results of laser heating experiments performed on rhyolitic soil at temperatures (1600-2200 °C) and timescales (1-120 s) that are broadly relevant to fallout formation conditions. Relative enrichments of metals such as Cu and Co do not correlate with the abundance of uranium, suggesting that fallout also records input of near field anthropogenic materials. Our observations suggest that major chemical features can be related to processing in the fireball and used to inform the thermal-chemical evolution of the system. Ultimately, these data are consistent with a fallout formation mechanism that involves rapid melting of surface materials to form carrier material melts with minor incorporation of bomb vapor and a degree of volumetric volatile loss due to heating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Environmental Impacts of Reclaimed Asphalt Pavement on Leaching of Metals into Groundwater

To investigate the environmental impacts of reclaimed asphalt pavement (RAP) while it was freshly processed (i.e. hot mixed asphalt or HMA) and after being subjected to weathering, three RAP materials, namely north-RAP, central-RAP, south-RAP, from three plants and one fresh HMA loose mix sample (Fresh-HMA) throughout New Jersey, USA underwent four different weathering processes including: Ultraviolet (UV) and precipitation weathering on unbounded RAP, UV and precipitation weathering on compacted RAP, weathering by heat and moisture cycles, and groundwater flow-through leaching. Batch experiments were conducted to mimic releasing of trace elements in weak acidic leachate from landfills. North-RAP and central-RAP released levels of Pb greater than the United States Environmental Protection Agency (USEPA) primary drinking water maximum contaminant level (MCL) of 15 µg/L. Novel two-column experiments (a RAP column followed by a soil column) were conducted to investigate the release of trace elements from RAP and the attenuation effect of soil on potential pollutants. The results of these experiments showed that pollutants released from RAPs such as Mn and Ni were largely attenuated in the soil. The results suggest that RAP can be used as an unbound material in environments except those acidic (i.e., pH < 5 as in mines with sulfur-containing minerals and landfills with acidic environment).

batch extraction↗

Enrichment of Phosphates, Lead, and Mixed Soil–Organic Particles in INPs at the Southern Great Plains Site

Ice nucleating particles (INPs) are rare particles that initiate primary ice formation, a critical step required for subsequent important cloud microphysical processes that ultimately govern cloud phase and cloud radiative properties. Laboratory studies have found that organic-rich dusts, such as those found in soils, are more efficient INPs compared to mineral dust. However, the atmospheric relevance of these organic-rich dusts are not well understood, particularly in regions with significant agricultural activity. The Agricultural Ice nuclei at the Southern Great Plains field campaign (AGINSGP) was conducted in rural Oklahoma to investigate how soil dusts contribute to INP populations in the Great Plains. We present chemical characterization of ambient and ice crystal residual particles from a single day of sampling, using single particle mass spectrometry (SPMS) and scanning microscopy. Ambient particles were primarily carbonaceous or secondary aerosol, while the fraction of dust particles was higher in the residual particles. We also observed an unusual particle type consisting of a carbonaceous core mixed with dust fragments on the surface, which was found in higher proportion in residuals. Dust particles measured during residual sampling contained greater proportions of phosphate $(^{63}\text{PO}^-_2$ and $^{79}\text{PO}^-_3)$ and lead ( 206 Pb + ). Strong sulfate signals were not seen in the residual dust particles measured by the SPMS, while nitrate was slightly depleted relative to ambient dust. This study shows that organic-rich soils may be important contributors to the ambient INP population in agricultural regions.

54 ENVIRONMENTAL SCIENCES↗

A Deep State Space Model for Rainfall‐Runoff Simulations

The classical way of studying the rainfall‐runoff processes in the water cycle relies on conceptual or physically‐based hydrologic models. Deep learning (DL) has recently emerged as an alternative and blossomed in the hydrology community for rainfall‐runoff simulations. However, the decades‐old Long Short‐Term Memory (LSTM) network remains the benchmark for this task, outperforming newer architectures like Transformers. In this work, we propose a State Space Model (SSM), specifically the Frequency Tuned Diagonal State Space Sequence (S4D‐FT) model, for rainfall‐runoff simulations. The proposed S4D‐FT is benchmarked against the established LSTM and a physically‐based Sacramento Soil Moisture Accounting model under in‐sample and out‐of‐sample simulation setups across 531 watersheds in the contiguous United States (CONUS). Results show that S4D‐FT is able to outperform the LSTM model across diverse regions under both simulation setups, especially for regions that feature snowmelt‐driven or intermittent flow regimes. In contrast, S4D‐FT tends to underperform in flashier, high‐magnitude flow regimes, likely due to its global state‐space convolution computation that emphasizes slow, storage‐driven dynamics, which makes it less effective at picking up short bursts and noisy spikes in the data. In summary, our pioneering introduction of the S4D‐FT for rainfall‐runoff simulations challenges the dominance of LSTM in the hydrology community and expands the arsenal of DL tools available for hydrological modeling.

Wang, Yihan [Univ. of Oklahoma, Norman, OK (United↗